JP6950536B2 - Resin composition - Google Patents

Description

The present invention relates to resin compositions. Furthermore, the present invention relates to a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.

In the printed wiring board, a solder resist is provided as a permanent protective film for suppressing the adhesion of solder to the portion where the solder is unnecessary and for suppressing the corrosion of the circuit board. As the solder resist, for example, a photosensitive resin composition as described in Patent Document 1 is generally used.

International Publication No. 2017/122717

In recent years, in response to the trend toward higher densities and thinner circuits, circuit boards have been actively mounted by coreless or FC (flip chips).

By making the circuit board coreless, it is possible to make it thinner. However, since the coreless circuit board generally has low self-supporting property, warpage may easily occur depending on the configuration of the circuit board. Therefore, as a material used for a circuit board, a resin composition that relieves stress is required.

Further, by mounting with FC, it is possible to increase the density and thickness of the circuit board, but in FC, a resin composition having excellent solder heat resistance assuming a reflow furnace is required.

In order to relieve stress, it is conceivable to add a liquid material to the resin composition, but when a liquid material is added to the resin composition, basic properties such as heat resistance, insulation reliability, and developability are exhibited. It can be difficult to be satisfied.

Further, in order to improve the heat resistance of the solder, it is conceivable to include a rigid and tough material in the resin composition, but if such a material is contained in the resin composition, the flexibility is lost and the warp is caused. It may increase.

An object of the present invention is a resin composition capable of obtaining a cured product having both insulation reliability and developability and capable of achieving both solder heat resistance and suppression of warpage; a resin obtained by using the resin composition. The purpose of the present invention is to provide a sheet, a printed wiring board, and a semiconductor device.

As a result of diligent studies to solve the above problems, the present inventors have made a resin composition contain a predetermined resin containing an ethylenically unsaturated group and a carboxyl group, a predetermined epoxy resin, and rubber particles. We have found that the above problems can be solved, and have completed the present invention.

That is, the present invention includes the following contents.
[1] (A) A resin having a bisphenol skeleton, which contains an ethylenically unsaturated group and a carboxyl group.
(B) Solid epoxy resin,
(C) Inorganic filler with an average particle size of 0.5 μm or more,
(D) Photopolymerization initiator, and (E) Rubber particles,
A resin composition containing.
[2] The resin composition according to [1], wherein the content of the component (E) is 0.3% by mass or more and 30% by mass or less when the non-volatile component in the resin composition is 100% by mass.
[3] The resin composition according to [1] or [2], which is used for forming a solder resist.
[4] The resin composition according to any one of [1] to [3], wherein the component (A) has a bisphenol A skeleton.
[5] The resin composition according to any one of [1] to [4], wherein the component (B) contains a biphenyl type epoxy resin.
[6] The resin composition according to any one of [1] to [5], wherein the content of the component (C) is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass. ..
[7] The resin composition according to any one of [1] to [6], wherein the component (C) is silica.
[8] The resin composition according to any one of [1] to [7], wherein the component (D) is an acylphosphine oxide-based photopolymerization initiator or an oxime ester-based photopolymerization initiator.
[9] The resin composition according to any one of [1] to [8], further comprising (F) a (meth) acrylic polymer having a glass transition temperature of −20 ° C. or lower.
[10] When the content mass of the component (A) is W (a) and the content mass of the component (F) is W (f), W (f) / W (a) is 0.1 or more and 3 or less. The resin composition according to [9].
[11] A resin sheet having a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [10].
[12] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [10], wherein the printed wiring board has a coreless structure.
[13] A semiconductor device including the printed wiring board according to [12].

According to the present invention, a resin composition capable of obtaining a cured product having both insulation reliability and developability and capable of achieving both solder heat resistance and suppression of warpage; a resin obtained by using the resin composition. Sheets, printed wiring boards, and semiconductor devices can be provided.

Hereinafter, the resin composition (photosensitive resin composition), the resin sheet, the printed wiring board, and the semiconductor device of the present invention will be described in detail.

[Resin composition]
The resin composition of the present invention comprises (A) a resin having a bisphenol skeleton containing an ethylenically unsaturated group and a carboxyl group, (B) a solid epoxy resin, and (C) an inorganic having an average particle size of 0.5 μm or more. It contains a filler, (D) a photopolymerization initiator, and (E) rubber particles. The desire of the present invention is that by containing the components (A) to (E) in combination, a cured product having insulation reliability and developability, and capable of achieving both solder heat resistance and suppression of warpage can be obtained. The effect of can be obtained. The cured product of this resin composition can be preferably used for solder resist forming by taking advantage of its excellent properties.

Further, the resin composition of the present invention may further contain any component in combination with the components (A) to (E). Optional components include, for example, (F) a (meth) acrylic polymer having a glass transition temperature of −20 ° C. or lower, (G) a reactive diluent, (H) an organic solvent, and (I) other additives. Can include. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Resin having a bisphenol skeleton containing an ethylenically unsaturated group and a carboxyl group>
The resin composition contains (A) a resin having a bisphenol skeleton containing an ethylenically unsaturated group and a carboxyl group. When a resin containing an ethylenically unsaturated group and a carboxyl group is contained in the resin composition, the developability is improved. The present inventors have found that when this resin has a relatively rigid bisphenol skeleton, in addition to improving developability, it is possible to suppress warpage of the obtained cured product and enhance solder heat resistance.

Examples of the bisphenol skeleton include bisphenol A skeleton, bisphenol F skeleton, bisphenol AF skeleton, bisphenol AP skeleton, bisphenol B skeleton, bisphenol BP skeleton, bisphenol C skeleton, bisphenol E skeleton, bisphenol G skeleton, bisphenol M skeleton, and bisphenol S skeleton. , Bisphenol P skeleton, bisphenol PH skeleton, bisphenol TMC skeleton, bisphenol Z skeleton and the like. Above all, from the viewpoint of obtaining a cured product particularly excellent in developability, solder heat resistance and suppression of warpage, it is preferable to have a bisphenol A skeleton and a bisphenol F skeleton, and it is more preferable to have a bisphenol A skeleton.

Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a propagyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadiimide group, a (meth) acryloyl group and the like, and a reaction of photoradical polymerization. From the viewpoint of sex, a (meth) acryloyl group is preferable. "(Meta) acryloyl group" refers to a methacryloyl group and an acryloyl group.

As the component (A), any compound having a bisphenol skeleton, an ethylenically unsaturated group and a carboxyl group, which enables photoradical polymerization and alkaline development can be used, and among them, it has a bisphenol skeleton. Further, a resin having both a carboxyl group and two or more ethylenically unsaturated groups in one molecule is preferable.

As one aspect of the component (A), an acid-modified unsaturated bisphenol skeleton-containing epoxy ester resin obtained by reacting an unsaturated carboxylic acid with a bisphenol skeleton-containing epoxy compound and further reacting with an acid anhydride can be mentioned. For details, an unsaturated carboxylic acid is reacted with a bisphenol skeleton-containing epoxy compound to obtain an unsaturated bisphenol skeleton-containing epoxy ester resin, and an unsaturated bisphenol skeleton-containing epoxy ester resin is reacted with an acid anhydride to obtain an acid-modified unsaturated epoxy. An ester resin can be obtained.

Examples of the bisphenol skeleton-containing epoxy compound include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin. Examples thereof include bisphenol type epoxy resin such as modified bisphenol F type epoxy resin modified by reacting with epichlorohydrin to have trifunctionality or higher, bisphenol A type novolac type epoxy resin, bisphenol AF type epoxy resin and the like. Among them, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable from the viewpoint of obtaining a cured product which has both developability and can achieve both solder heat resistance and suppression of warpage.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid and the like, and these may be used alone or in combination of two or more. Of these, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the resin composition. In the present specification, the epoxy ester resin which is a reaction product of the above-mentioned bisphenol skeleton-containing epoxy compound and (meth) acrylic acid may be referred to as "bisphenol skeleton-containing epoxy (meth) acrylate", and here, bisphenol. The epoxy group of the skeleton-containing epoxy compound is substantially eliminated by the reaction with (meth) acrylic acid. "(Meta) acrylate" refers to methacrylate and acrylate. Acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth) acrylic acid".

Examples of the acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic acid dianhydride. Anhydrides and the like can be mentioned, and any one of them may be used alone or two or more thereof may be used in combination. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferable from the viewpoint of improving the developability and insulation reliability of the cured product.

In obtaining the acid-modified unsaturated bisphenol skeleton-containing epoxy ester resin, a catalyst, a solvent, a polymerization inhibitor and the like may be used, if necessary.

As the acid-modified unsaturated bisphenol skeleton-containing epoxy ester resin, an acid-modified bisphenol skeleton-containing epoxy (meth) acrylate is preferable from the viewpoint of further improving the insulation reliability and developability of the cured product. The "epoxy" in the acid-modified unsaturated bisphenol skeleton-containing epoxy ester resin represents a structure derived from the above-mentioned epoxy compound. For example, the "acid-modified bisphenol skeleton-containing epoxy (meth) acrylate" refers to an acid-modified unsaturated bisphenol skeleton-containing epoxy ester resin obtained by using (meth) acrylic acid as the unsaturated carboxylic acid.

As such an acid-modified unsaturated bisphenol skeleton-containing epoxy ester resin, a commercially available product can be used. As a specific example, "ZAR-2000" (bisphenol A type epoxy resin, acrylic acid, and anhydrous) manufactured by Nippon Kayakusha Co., Ltd. can be used. (Reactant of succinic acid), "ZFR-1491H", "ZFR-1533H" (reactant of bisphenol F type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The weight average molecular weight of the component (A) is preferably 1000 or more, more preferably 1500 or more, still more preferably 2000 or more, preferably 10000 or less, more preferably 8000, from the viewpoint of remarkably obtaining the effect of the present invention. Below, it is more preferably 7500 or less. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The acid value of the component (A) is preferably 1 mgKOH / g or more, more preferably 30 mgKOH / g or more, still more preferably 50 mgKOH / g or more, from the viewpoint of improving the alkali developability of the resin composition. On the other hand, from the viewpoint of suppressing the fine pattern of the cured product from leaching out due to development and improving the insulation reliability, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less. Is. Here, the acid value is the residual acid value of the carboxyl group present in the component (A), and the acid value can be measured by the following method. First, about 1 g of the measurement resin solution is precisely weighed, and then 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein, which is an indicator, is added to the solution, and titration is performed using a 0.1 N KOH aqueous solution. Then, the acid value is calculated by the following formula.
Formula: A (a) = 10 × Vf × 56.1 / (Wp × I)

In the above formula, A (a) represents an acid value (mgKOH / g), Vf represents a titration amount (mL) of KOH, Wp represents a measurement resin solution mass (g), and I represents a measurement resin solution. Represents the proportion (mass%) of the non-volatile content of.

In the production of the component (A), the ratio of the number of moles of the epoxy group of the bisphenol skeleton-containing epoxy compound to the total number of moles of the carboxyl group of the unsaturated carboxylic acid and the acid anhydride from the viewpoint of improving the storage stability. Is preferably in the range of 1: 0.8 to 1.3, and more preferably in the range of 1: 0.9 to 1.2.

Regarding the content of the component (A), from the viewpoint of remarkably obtaining the effect of the present invention, when the total solid content of the resin composition is 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more. It is more preferably 15% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less.
In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

<(B) Solid epoxy resin>
The resin composition contains (B) a solid epoxy resin. When the resin composition contains a solid epoxy resin, the insulation reliability of the obtained cured product can be enhanced. Further, since the component (B) is in a solid state, the solder heat resistance of the cured product can be enhanced. (B) The solid epoxy resin refers to a solid epoxy resin at a temperature of 20 ° C. The component (B) preferably has two or more epoxy groups in one molecule, and more preferably has three or more epoxy groups in one molecule from the viewpoint of remarkably obtaining the effect of the present invention.

Examples of the solid epoxy resin include biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, and tris. Examples include phenol type epoxy resin, naphthol type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin, etc. Among them, insulation reliability. A biphenyl type epoxy resin is preferable from the viewpoint of obtaining a cured product having better solder heat resistance.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP-7200" (dicyclopentadiene type epoxy resin); DIC's "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000L", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayakusha; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayakusha; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin (biphenyl aralkyl type epoxy resin)) manufactured by Yakusha; "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation; "ESN485" (naphthol novolac type epoxy resin) manufactured by Sumikin Chemical Co., Ltd .; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX4000HK" (bixilenol) manufactured by Mitsubishi Chemical Co., Ltd. Type epoxy resin); Mitsubishi Chemical's "YX8800" (anthracene type epoxy resin); Osaka Gas Chemical's "PG-100", "CG-500"; Mitsubishi Chemical's "YL7760" (bisphenol AF type) Epoxy resin); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1031S" (tetraphenylethane type) manufactured by Mitsubishi Chemical Co., Ltd. Epoxy resin) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the component (B) in the resin composition is preferably 1% by mass when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining a cured product showing good mechanical strength and insulation reliability. % Or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 25% by mass or less.

<(C) Inorganic filler with an average particle size of 0.5 μm or more>
The resin composition contains (C) an inorganic filler having an average particle size of 0.5 μm or more. By containing the component (C) in the resin composition, the average linear thermal expansion coefficient of the obtained cured product can be lowered, and the developability can be improved.

The material of the inorganic filler is not particularly limited, but for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Of these, silica is particularly suitable. Further, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

If an inorganic filler having a large average particle size is contained, light is scattered and the developability is deteriorated. Therefore, it is common to include an inorganic filler having an average particle size of less than 0.5 μm in the resin composition. It was a target. However, when the present inventors can obtain a cured product having excellent developability by combining the components (A) to (E) and containing an inorganic filler having an average particle size of 0.5 μm or more. It was found that there is.

The average particle size of the inorganic filler is 0.5 μm or more, preferably 0.8 μm or more, and more preferably 1 μm or more, from the viewpoint of obtaining a cured product having excellent developability and a low average coefficient of linear thermal expansion. The upper limit of the average particle size is 2.5 μm or less, preferably 2 μm or less, more preferably 1.5 μm or less, and further preferably 1.3 μm or less from the viewpoint of obtaining excellent resolution. Commercially available products of inorganic fillers having such an average particle size include, for example, "SOC2", "SC2050", "SOC4", "SC4050", "Admafine" manufactured by Admatex Co., Ltd., and "Admafine" manufactured by Electrochemical Industry Co., Ltd. "SFP Series", "SP (H) Series" manufactured by Nippon Steel & Sumikin Materials, "Sciqas Series" manufactured by Sakai Chemical Industry Co., Ltd., "Sea Hoster Series" manufactured by Nippon Shokubai, "AZ Series" manufactured by Nippon Steel & Sumikin Materials Co., Ltd. Examples include the "AX series", the "B series" manufactured by Sakai Chemical Industry Co., Ltd., and the "BF series".

The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-960" manufactured by HORIBA, Ltd. can be used.

The inorganic filler is preferably surface-treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of the surface treatment agent include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanate-based coupling agents, and the like. Be done.

Examples of commercially available surface treatment agents include "KBM22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" manufactured by Shin-Etsu Chemical Co., Ltd. (Phenyltrimethoxysilane), "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane coupling agent) and the like can be mentioned. One type of surface treatment agent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the component (C). (C) carbon content per unit surface area of the component, from the viewpoint of improving dispersibility of the component (C), preferably from 0.02 mg / ^{m 2} or more, more preferably 0.1 mg / ^{m 2} or more, particularly preferably 0 .2 mg / m ² or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, the amount of carbon is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, particularly preferably. Is 0.5 mg / m ² or less.

The amount of carbon per unit surface area of the component (C) can be measured after the component (C) after the surface treatment is washed with a solvent (for example, methyl ethyl ketone (hereinafter, may be abbreviated as “MEK”)). Specifically, a sufficient amount of methyl ethyl ketone and the component (C) surface-treated with a surface treatment agent are mixed and ultrasonically cleaned at 25 ° C. for 5 minutes. Then, after removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the component (C) can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. can be used.

The content of the component (C) is preferably 10% by mass or more, preferably 13 when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of obtaining a cured product having a low average linear thermal expansion coefficient. By mass or more, more preferably 15% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 45% by mass or less, and more preferably 40% by mass or less or 35% by mass or less from the viewpoint of enhancing developability and suppressing warpage.

<(D) Photopolymerization Initiator>
The resin composition contains (D) a photopolymerization initiator. By containing the (D) photopolymerization initiator, the resin composition can be efficiently photocured.

The photopolymerization initiator (D) is not particularly limited, but for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. Acylphosphine oxide-based photopolymerization initiator; 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime), etanone, 1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-Carbazole-3-yl]-, 1- (O-acetyloxime) and other oxime ester-based photopolymerization initiators; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1- Butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]-[4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] Α-Aminoalkylphenone-based photopolymerization initiators such as -2-morpholinopropan-1-one; benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethyl Thioxanthone, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate, 4,4'-bis (diethylamino) benzophenone, 1-hydroxy-cyclohexyl- Phenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one , Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxand; sulfonium salt-based photopolymerization initiator and the like. One of these may be used alone, or two or more thereof may be used in combination. Among these, acylphosphine oxide-based photopolymerization initiators and oxime ester-based photopolymerization initiators are preferable, and oxime ester-based photopolymerization initiators are preferable from the viewpoint of photocuring the resin composition more efficiently and improving the resolution. The agent is more preferred.

Specific examples of the photopolymerization initiator (D) include "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819", "Omnirad TPO" manufactured by IGM, and "Irgacure OXE-01" and "Irgar" manufactured by BASF. 02 ”,“ Irgacure TPO ”,“ Irgacure 819 ”,“ N-1919 ”manufactured by ADEKA, etc. may be mentioned.

Further, the resin composition may contain a photopolymerization initiator in combination with the (D) photopolymerization initiator. Examples of the photopolymerization initiator include tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. Kind: Photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, thioxanthones and the like can be mentioned. Any one of these may be used alone or two or more thereof may be used in combination.

The content of the photopolymerization initiator (D) is preferably 0 when the non-volatile component of the resin composition is 100% by mass from the viewpoint of sufficiently photocuring the resin composition and improving the insulation reliability. It is 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.3% by mass or more. On the other hand, from the viewpoint of suppressing the decrease in resolution due to excessive sensitivity, the upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1.5% by mass or less. When the resin composition contains a photopolymerization initiator, the total content of (D) the photopolymerization initiator and the photopolymerization initiator is preferably within the above range.

<(E) Rubber particles>
The resin composition contains (E) rubber particles. Since the rubber particles (E) usually have a higher refractive index than the component (C), they are matched with the refractive index of the components containing the components (A) to (D) in combination to expose the cured product of the resin composition. The light is less likely to be scattered. Further, since the rubber particles (E) are in the form of particles, they can be easily removed with a developing solution. Further, since the rubber particles usually have a stress relaxation action, the internal stress generated at the time of forming the cured product of the resin composition is relaxed by the (E) rubber particles. Therefore, by containing the rubber particles (E) in the resin composition, the warp of the cured product can be suppressed and the developability of the cured product can be improved.

The rubber particles (E) are preferably insoluble in the organic solvent used when preparing the resin composition, incompatible with the resin component in the resin composition, and present in a dispersed state in the varnish of the resin composition. .. (E) Rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level that does not dissolve in an organic solvent or resin to form particles.

Examples of the rubber particles (E) include core-shell type rubber particles, crosslinked acrylic nitrile butadiene rubber (NBR) particles, crosslinked styrene butadiene rubber (SBR) particles, and acrylic rubber particles. Of these, core-shell type rubber particles are preferable from the viewpoint of suppressing warpage of the cured product and improving developability.

The core-shell type rubber particles are rubber particles including a shell layer on the surface of the particles and a core layer inside the shell layer, and may include an intermediate layer between the shell layer and the core layer. .. Examples of the core-shell type rubber particles include core-shell type rubber particles including a shell layer formed of a glass-like polymer and a core layer formed of a rubber-like polymer; a shell layer formed of a glass-like polymer and a rubber-like shape. Core-shell type rubber particles including an intermediate layer formed of a polymer and a core layer formed of a glassy polymer; and the like. Examples of the glassy polymer include a polymer of methyl methacrylate and the like, and examples of the rubbery polymer include a butyl acrylate polymer (butyl rubber) and the like.

Specific examples of the core-shell type rubber particles include stafyroids "AC3832" and "AC3816N" manufactured by Aica Kogyo Co., Ltd. and "Metabrene KW-4426" manufactured by Mitsubishi Chemical Corporation.

Specific examples of the crosslinked acrylonitrile butadiene rubber particles include "XER-91" (average particle size 0.5 μm) manufactured by JSR Corporation.

Specific examples of the crosslinked styrene-butadiene rubber particles include "XSK-500" (average particle diameter 0.5 μm) manufactured by JSR Corporation.

Specific examples of acrylic rubber particles include Mitsubishi Chemical's Metabrene "W300A" (average particle size 0.1 μm), "W450A" (average particle size 0.2 μm), and Dow Chemical's "EXL-2655". And so on.

(E) One type of rubber particles may be used alone, or two or more types may be used in combination.

The average particle size of the rubber particles (E) is the same as the average particle size of the component (C), and can be measured by the same method.

The content of the rubber particles (E) is preferably 0.3% by mass when the non-volatile component of the resin composition is 100% by mass from the viewpoint of suppressing the warp of the cured product and improving the developability of the cured product. % Or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less.

<(F) (Meta) acrylic polymer with a glass transition temperature of -20 ° C or less>
The resin composition may contain (F) a (meth) acrylic polymer having a glass transition temperature of −20 ° C. or lower. However, the component (F) excludes the component (A). When the resin composition contains the component (F), when the obtained cured product is developed, appropriate phase separation occurs with the developing solution, and it becomes easy to remove with the developing solution. As a result, the developability of the cured product can be further improved. Further, when the resin composition contains the component (F), the stress is relaxed, and the warpage of the obtained cured product can be further suppressed. The (meth) acrylic polymer is a polymer containing a structural unit having a structure formed by polymerizing a (meth) acrylic monomer. Examples of such a (meth) acrylic polymer include a polymer obtained by polymerizing a (meth) acrylic monomer, or a polymer obtained by copolymerizing a (meth) acrylic monomer and a monomer copolymerizable with the (meth) acrylic monomer. Can be mentioned.

The glass transition temperature (Tg) of the component (F) is preferably −20 ° C. or lower, more preferably −23 ° C. or lower, still more preferably −25 ° C. or lower, from the viewpoint of improving flexibility. From the viewpoint of improving alkali solubility, the lower limit is preferably −300 ° C. or higher, more preferably −200 ° C. or higher, still more preferably −100 ° C. or higher, −80 ° C. or higher. Here, the glass transition temperature of the component (F) is the theoretical glass transition temperature of the main chain of the component (F), and this theoretical glass transition temperature is calculated by the following FOX formula. Can be done. Since the glass transition temperature obtained by the FOX equation is almost the same as the glass transition temperature measured by differential scanning calorimetry (TMA, DSC, DTA), the glass transition temperature of the main chain of component (F) by differential scanning calorimetry. May be measured.
1 / Tg = (W1 / Tg1) + (W2 / Tg2) + ... + (Wm / Tgm)
W1 + W2 + ... + Wm = 1
Wm represents the content (mass%) of each monomer constituting the component (F), and Tgm represents the glass transition temperature (K) of each monomer constituting the component (F).

The component (F) is preferably a (meth) acrylic polymer containing an ethylenically unsaturated group and a carboxyl group, and has both a carboxyl group and two or more ethylenically unsaturated groups in one molecule (meth). Acrylic polymers are more preferred.

The ethylenically unsaturated group is the same as the ethylenically unsaturated group in the component (A), and the preferable range is also the same.

Examples of the component (F) include an acid-modified unsaturated epoxy (meth) acrylic copolymer obtained by reacting an epoxy group-containing copolymer with (meth) acrylic acid and further reacting with an acid anhydride. For details, the epoxy group-containing copolymer is reacted with (meth) acrylic acid to obtain an unsaturated epoxy (meth) acrylic copolymer, and the unsaturated epoxy (meth) acrylic copolymer is reacted with an acid anhydride. An acid-modified unsaturated epoxy (meth) acrylic copolymer can be obtained from the above. The epoxy group of the epoxy group-containing copolymer is substantially eliminated by the reaction with normal (meth) acrylic acid.

The epoxy group-containing copolymer can be obtained by polymerizing an epoxy group-containing monomer and, if necessary, an arbitrary monomer. Examples of the epoxy group-containing monomer include an epoxy group-containing monomer such as glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2-methyl-3,4-epoxycyclohexyl (meth) acrylate, and allyl glycidyl ether. Examples thereof include meta) acrylate monomers, and glycidyl (meth) acrylate is preferable. The epoxy group-containing monomer may be used alone or in combination of two or more.

Optional monomers include, for example, styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl methacrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth). ) Acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl methacrylate, nonyl ( Meta) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-tert- Butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acrylonitrile, 3- (meth) Acryloylpropyltrimethoxysilane, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, 2-hydroxyethyl (meth) acrylate, 3-Hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl ( Meta) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) ) Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth) acrylate having a hydroxyl group at the terminal, 1-adamantyl (meth) acrylate and the like, and n-butyl (meth) acrylate preferable. Any monomer may be used alone or in combination of two or more.

As the acid anhydride used for obtaining the component (F), the same acid anhydride used for obtaining the component (A) can be used.

A preferred embodiment of the component (F) is a compound obtained by reacting an epoxy group-containing monomer, an epoxy group-containing copolymer obtained by polymerizing an arbitrary monomer, (meth) acrylic acid, and an acid anhydride. The epoxy-containing monomer is glycidyl methacrylate, any monomer is butyl acrylate, and the acid anhydride is tetrahydrophthalic anhydride.

The weight average molecular weight of the component (F) is 30,000 or less, preferably 28,000 or less, and more preferably 25,000 or less, from the viewpoint of improving the developability of the cured product. The lower limit is preferably 5000 or more, more preferably 10000 or more, and further preferably 15000 or more from the viewpoint of coating film property. The weight average molecular weight can be measured according to the same method as the weight average molecular weight of the component (A).

The acid value of the component (F) is preferably 0.1 mgKOH / g or more, more preferably 0.5 mgKOH / g or more, from the viewpoint of improving the alkali developability of the cured product. It is more preferably 1 mgKOH / g or more. On the other hand, from the viewpoint of excellent removal of residues during development, the acid value is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, and further preferably 100 mgKOH / g or less. preferable. The acid value can be calculated by the same method as the acid value of the component (A).

When the resin composition contains the component (F), the content of the component (F) is 100% by mass of the non-volatile component of the resin composition from the viewpoint of obtaining a cured product having excellent developability and suppressed warpage. , It is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass. It is as follows.

The total content of the component (A) and the component (F) in the resin composition is determined when the non-volatile component of the resin composition is 100% by mass from the viewpoint of obtaining the effect of the present invention remarkably. It is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less.

When the content mass of the component (A) in the resin composition is W (a) and the content mass of the component (F) component in the resin composition is W (f), W (f) / W (a) is From the viewpoint of obtaining a cured product having better developability, it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, preferably 3 or less, more preferably 1.5 or less. More preferably, it is 1 or less. Here, the content mass of the component (A) in the resin composition represents the content of the component (A) when the non-volatile component of the resin composition is 100% by mass, and the content of the component (A) in the resin composition is (F). The content mass of the component represents the content of the component (F) when the non-volatile component of the resin composition is 100% by mass.

<(G) Reactive Diluent>
The resin composition may further contain (G) a reactive diluent. The photoreactivity can be improved by containing the (G) reactive diluent. As the (G) reactive diluent, for example, a liquid, solid or semi-solid photosensitive (meth) acrylate compound having one or more (meth) acryloyl groups in one molecule at room temperature can be used. Room temperature represents about 25 ° C.

Typical photosensitive (meth) acrylate compounds include, for example, hydroxyalkyl acrylates such as tricyclodecanedimethanol diacrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate, ethylene glycol, methoxytetraethylene glycol, and polyethylene. Glycol mono- or diacrylates such as glycol and propylene glycol, acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide, aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, trimethylolpropane, penta Polyhydric alcohols such as erythritol and dipentaerythritol or polyvalent acrylates of these ethylene oxide, propylene oxide or ε-caprolactone adducts, phenols such as phenoxyacrylate and phenoxyethyl acrylate, or ethylene oxide or propylene oxide adducts thereof. Examples thereof include acrylates such as acrylates such as, epoxy acrylates derived from glycidyl ether such as trimethylpropan triglycidyl ether, melamine acrylates, and / or methacrylates corresponding to the above-mentioned acrylate. Among these, polyhydric acrylates or polyvalent methacrylates are preferable, and for example, trivalent acrylates or methacrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylolpropane. EO-added tri (meth) acrylate, glycerin PO-added tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraflufuryl alcohol oligo (meth) acrylate, ethylcarbitol oligo (meth) acrylate, 1,4-butanediol Oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimetylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol hexa (meth) ) Acryloyl, N, N, N', N'-tetrax (β-hydroxyethyl) ethyldiamine (meth) acrylic acid ester, etc. Examples of trivalent or higher acrylates or methacrylates include tri (2-). (Meta) acryloyloxyethyl) phosphate, tri (2- (meth) acryloyloxypropyl) phosphate, tri (3- (meth) acryloyloxypropyl) phosphate, tri (3- (meth) acryloyl-2-hydroxypropyl) Phosphate, di (3- (meth) acryloyl-2-hydroxypropyl) (2- (meth) acryloyloxyethyl) phosphate, (3- (meth) acryloyl-2-hydroxypropyl) di (2- (meth)) Acryloyloxyethyl) phosphate and other phosphate triester (meth) acrylates can be mentioned. Any one of these photosensitive (meth) acrylate compounds may be used alone, or two or more thereof may be used in combination.

Commercially available products can be used as the (G) reactive diluent, and specific examples thereof include "DPHA" (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) and "DCA-P" (tricyclodecanedimethanol). Diacrylate, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

When the resin composition contains a (G) reactive diluent, the content of the (G) reactive diluent is said to promote photocuring and suppress stickiness when the resin composition is a cured product. From the viewpoint, when the total solid content of the resin composition is 100% by mass, it is preferably 0.5% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 25% by mass. Hereinafter, it is more preferably 20% by mass or less, still more preferably 15% by mass or less.

<(H) Organic solvent>
The resin composition may further contain (H) an organic solvent. (H) The viscosity of the varnish can be adjusted by containing an organic solvent. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol and propylene glycol. Glycol ethers such as monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, ethyl diglycol acetate; Aliper hydrocarbons such as octane and decane; petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha can be mentioned. These may be used alone or in combination of two or more. When an organic solvent is used, the content can be appropriately adjusted from the viewpoint of coatability of the resin composition.

<(I) Other additives>
The resin composition may further contain (I) other additives to the extent that the object of the present invention is not impaired. (I) Other additives include, for example, an ion trapping agent such as "IXEPLAS-A3" manufactured by Toa Synthetic Co., Ltd., an epoxy resin liquid at 20 ° C., a thermoplastic resin, an organic filler, melamine, an organic bentonite and the like. Colorants such as fine particles, phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol. , Benton, thickeners such as montmorillonite, silicone-based, fluorine-based, vinyl resin-based defoaming agents, brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, aromatic condensed phosphoric acid esters, halogen-containing condensed phosphorus Examples thereof include various additives such as flame-retardant agents such as acid esters, heat-curable resins such as phenol-based curing agents and cyanate ester-based curing agents.

In the resin composition, the above-mentioned components (A) to (E) are mixed as essential components, and the above-mentioned (F) to (I) components are appropriately mixed as optional components. It can be produced as a resin varnish by kneading or stirring with a kneading means such as a bead mill or a sand mill, or a stirring means such as a super mixer or a planetary mixer.

<Physical characteristics and uses of resin composition>
Since the resin composition of the present invention contains the components (A) to (E), it usually exhibits a characteristic of having a low elastic modulus at 25 ° C. Therefore, by using this resin composition, it is possible to obtain an insulating layer and a solder resist layer capable of suppressing the warp of the printed wiring board. The elastic modulus of the cured product obtained by thermosetting the resin composition at 190 ° C. for 90 minutes at 25 ° C. is preferably 4 GPa or less, more preferably 3 GPa or less, still more preferably 2 GPa or less. The lower limit is not particularly limited, but can usually be 0.1 GPa or more. The elastic modulus can be measured by a tensile / compression tester, a dynamic viscoelasticity measuring device (DMA), or the like.

For example, using the resin composition described above, a cured product layer of the resin composition is formed on a copper foil by the method described in Examples to prepare an evaluation sample. In this case, the amount of warpage measured by the method described in the examples of the evaluation sample can usually be 3.5 mm or less, 2.5 mm or less, or 2 mm or less.

Since the resin composition of the present invention contains the components (A) to (E), a cured product having excellent developability can be obtained. Therefore, by using this resin composition, an insulating layer and a solder resist layer having excellent developability can be obtained. For example, an evaluation laminate is produced by the method described in Examples. In this case, the minimum opening diameter (minimum via diameter) without residue of the evaluation laminate is preferably 100 μm or less, more preferably 90 μm or less, still more preferably 80 μm or less, 70 μm or less. The lower limit is not particularly limited, but may be 10 μm or more. Further, since the cured product of the resin composition of the present invention is excellent in developability, when the appearance of the evaluation laminate is evaluated by the method described in Examples, usually, the resin component remains in any unexposed portion. Moreover, even when observing the opening shapes of any three points having the minimum opening diameter, the opening shape is not distorted or cracks are not observed.

Since the resin composition of the present invention contains the components (A) to (E), a cured product having excellent insulation reliability can be obtained. Therefore, by using this resin composition, an insulating layer and a solder resist layer having excellent insulation reliability can be obtained. For example, when the initial resistance value of the insulating layer obtained by the method described in Examples and the HAST resistance value after the HAST test are compared, usually, almost no decrease in the HAST resistance value is observed.

Since the resin composition of the present invention contains the components (A) to (E), a cured product having excellent solder heat resistance can be obtained. Therefore, by using this resin composition, an insulating layer and a solder resist layer having excellent solder heat resistance can be obtained. For example, an evaluation laminate is produced by the method described in Examples. In this case, when the solder heat resistance is evaluated by the method measured by the method described in the examples of the evaluation laminate, usually, peeling of the insulating layer and distortion of the pattern are not observed.

The use of the resin composition of the present invention is not particularly limited, but is limited to resin sheets, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, and hole filling materials. It can be used in a wide range of applications for resin compositions such as resins and component-embedded resins. Among them, a resin composition for solder resist (printed wiring board in which a cured product of the resin composition is used as a solder resist) and a resin composition for an insulating layer of a printed wiring board (printed wiring board in which a cured product of the resin composition is used as an insulating layer). ), Resin composition for interlayer insulation layer (printed wiring board with a cured product of the resin composition as an interlayer insulating layer), and resin composition for plating formation (printed wiring with plating formed on the cured product of the resin composition). It can be suitably used as a plate).

[Resin sheet]
The resin composition of the present invention can be suitably used in the form of a resin sheet in which a resin composition layer is formed on a support. That is, the resin sheet includes a support and a resin composition layer provided on the support and formed of the resin composition of the present invention.

Examples of the support include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, triacetyl acetate film and the like, and polyethylene terephthalate film is particularly preferable.

Examples of commercially available supports include product names "Alfan MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shinetsu Film Co., Ltd., and product names "PS-25" manufactured by Teijin Limited. Examples include, but are not limited to, polyethylene terephthalate films such as PS series. These supports are preferably coated with a release agent such as a silicone coating agent on the surface in order to facilitate the removal of the resin composition layer. The thickness of the support is preferably in the range of 5 μm to 50 μm, more preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, it is possible to prevent the support from being torn when the support is peeled off before development, and by setting the thickness to 50 μm or less, when exposing from above the support. The resolution can be improved. Also, a low fisheye support is preferred. Here, fisheye means that when a film is produced by heat-melting, kneading, extruding, biaxial stretching, casting, etc., foreign substances, undissolved substances, oxidative deterioration substances, etc. of the material are incorporated into the film. It is a thing.

Further, in order to reduce the scattering of light during exposure by active energy rays such as ultraviolet rays, it is preferable that the support has excellent transparency. Specifically, the support preferably has a turbidity (haze standardized by JIS K6714), which is an index of transparency, of 0.1 to 5.

The resin composition layer may be protected by a protective film. By protecting the resin composition layer side of the resin sheet with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches. As the protective film, a film made of the same material as the above-mentioned support can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and further preferably in the range of 10 μm to 30 μm. The protective film preferably has a smaller adhesive force between the resin composition layer and the protective film than the adhesive force between the resin composition layer and the support.

For the resin sheet of the present invention, for example, a resin varnish in which the resin composition of the present invention is dissolved in an organic solvent is prepared according to a method known to those skilled in the art, and the resin varnish is applied onto a support and heated or blown with hot air. It can be produced by drying an organic solvent by soaking or the like to form a resin composition layer. Specifically, first, after completely removing bubbles in the resin composition by a vacuum defoaming method or the like, the resin composition is applied onto a support, the solvent is removed by a hot air furnace or a far-infrared furnace, and the resin composition is dried. The resin sheet can be produced by laminating a protective film on the obtained resin composition layer, if necessary. The specific drying conditions vary depending on the curability of the resin composition and the amount of the organic solvent in the resin varnish, but in the resin varnish containing 30% by mass to 60% by mass of the organic solvent, the temperature is 3 at 80 ° C. to 120 ° C. It can be dried in 1 to 13 minutes. The amount of the residual organic solvent in the resin composition layer is preferably 5% by mass or less, preferably 2% by mass or less, based on the total amount of the resin composition layer, from the viewpoint of preventing the diffusion of the organic solvent in a later step. Is more preferable. Those skilled in the art can appropriately set suitable drying conditions by a simple experiment. The thickness of the resin composition layer is preferably in the range of 5 μm to 500 μm from the viewpoint of improving handleability and suppressing deterioration of the sensitivity and resolution inside the resin composition layer, and is preferably 10 μm to 200 μm. It is more preferably in the range of 15 μm to 150 μm, further preferably in the range of 20 μm to 100 μm, and even more preferably in the range of 20 μm to 60 μm.

Examples of the coating method of the resin composition include a gravure coating method, a micro gravure coating method, a reverse coating method, a kiss reverse coating method, a die coating method, a slot die method, a lip coating method, a comma coating method, a blade coating method, and a roll coating method. Examples thereof include a method, a knife coat method, a curtain coat method, a chamber gravure coat method, a slot orifice method, a spray coat method, and a dip coat method.

The resin composition may be applied in several times, may be applied once, or may be applied in combination of a plurality of different methods. Of these, the die coat method, which is excellent in uniform coatability, is preferable. Further, in order to prevent foreign matter from being mixed in, it is preferable to carry out the coating process in an environment such as a clean room where foreign matter is less generated.

[Printed circuit board]
The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention, and has a coreless structure. The insulating layer is preferably used as a solder resist. The coreless structure is a structure of a printed wiring board that does not include a core substrate or a substrate on which a semiconductor is mounted, and the overall thickness thereof can be reduced and the signal processing time can be shortened. Specific examples of such a printed wiring board include coreless FC-BGA (Ball Grid Array), ETS (Embedded Molding Substrate), and MIS-BGA (Ball Grid Array).

Specifically, the printed wiring board of the present invention can be manufactured using the above-mentioned resin sheet. Hereinafter, a case where the insulating layer is a solder resist will be described.

<Laminating process>
The laminating step is a step of laminating the resin composition layer side of the resin sheet on one side or both sides of the support substrate using a vacuum laminator. In the laminating step, if the resin sheet has a protective film, after removing the protective film, the resin sheet and the support substrate are preheated as necessary, and the resin composition layer is supported while being pressurized and heated. Crimped to the substrate. For the resin sheet, a method of laminating on the support substrate under reduced pressure by a vacuum laminating method is preferably used.

Examples of the support substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. Further, from the viewpoint of facilitating the peeling of the support substrate, a metal layer such as a copper foil may be formed on the surface of the support substrate.

The conditions of the laminating step are not particularly limited, but for example, the crimping temperature (lamination temperature) is preferably 70 ° C. to 140 ° C., and the crimping pressure is preferably 1 kgf / cm ^{2 to} 11 kgf / cm ² (9. 8 × 10 ⁴ N / m ^{2 to} 107.9 × 10 ⁴ N / m ² ), the crimping time is preferably 5 to 300 seconds, and the air pressure is 20 mmHg (26.7 hPa) or less for laminating under reduced pressure. Is preferable. Further, the laminating step may be a batch type or a continuous type using a roll. The vacuum laminating method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Co., Ltd., a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. be able to. In this way, a resin sheet is formed on the support substrate.

<Exposure process>
After the resin sheet is provided on the support substrate by the laminating step, an exposure step of irradiating a predetermined portion of the resin composition layer with active light through a mask pattern to photocure the resin composition layer of the irradiated portion is performed. conduct. Examples of the active ray include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. Dose of ultraviolet light is approximately ^{10mJ / cm 2 ~1000mJ / cm 2} . The exposure method includes a contact exposure method in which the mask pattern is brought into close contact with the printed wiring board and a non-contact exposure method in which the mask pattern is exposed by using parallel rays without being brought into close contact with each other. Either of them may be used. When the support is present on the resin composition layer, it may be exposed from above the support, or the support may be exposed after being peeled off.

Since the solder resist uses the resin composition of the present invention, it is excellent in developability. Therefore, as an exposure pattern in the mask pattern, for example, the ratio (L / S) of the circuit width (line; L) to the width (space; S) between circuits is 100 μm / 100 μm or less (that is, the wiring pitch is 200 μm or less). , L / S = 80 μm / 80 μm or less (wiring pitch 160 μm or less), L / S = 70 μm / 70 μm or less (wiring pitch 140 μm or less), L / S = 60 μm / 60 μm or less (wiring pitch 120 μm or less), L / S = A pattern of 50 μm / 50 μm or less (wiring pitch of 100 μm or less) can be used. As the exposure pattern, for example, a round hole having an opening of 100 μm or less, a round hole of 90 μm or less, a round hole of 80 μm or less, a round hole of 70 μm or less, a round hole of 60 μm or less, and a round hole of 50 μm or less are used. It is possible. The pitch does not have to be the same throughout the circuit board.

<Development process>
After the exposure step, the support on the resin composition layer is removed, and then the non-photocured portion (unexposed portion) is removed and developed by wet development or dry development to form a pattern. can.

In the case of the above wet development, a safe, stable and easy-to-operate developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent is used as the developer, and the development step using an alkaline aqueous solution is particularly preferable. Further, as a developing method, known methods such as spraying, rocking dipping, brushing, and scraping are appropriately adopted.

Examples of the alkaline aqueous solution used as the developing solution include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and sodium bicarbonate, or bicarbonates and sodium phosphate. , An aqueous solution of an alkali metal phosphate such as potassium phosphate, an alkali metal pyrophosphate such as sodium pyrophosphate and potassium pyrophosphate, and an aqueous solution of an organic base containing no metal ion such as tetraalkylammonium hydroxide. An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable because it does not contain metal ions and does not affect the semiconductor chip.
To these alkaline aqueous solutions, a surfactant, a defoaming agent, or the like can be added to the developing solution in order to improve the developing effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8 to 12, and more preferably in the range of 9 to 11. The base concentration of the alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected according to the developability of the resin composition layer, but is preferably 20 ° C to 50 ° C.

The organic solvent used as the developing solution is, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. It is a monobutyl ether.

The concentration of such an organic solvent is preferably 2% by mass to 90% by mass with respect to the total amount of the developing solution. Further, the temperature of such an organic solvent can be adjusted according to the developability. Further, such an organic solvent can be used alone or in combination of two or more kinds. Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

In pattern formation, if necessary, the above-mentioned two or more kinds of development methods may be used in combination. Development methods include a dip method, a battle method, a spray method, a high-pressure spray method, brushing, slapping, and the like, and the high-pressure spray method is suitable for improving the resolution. When the spray method is adopted, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

<Thermosetting (post-baking) process>
After the development step is completed, a thermosetting (post-baking) step is performed to form a solder resist. The heating conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably in the range of 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, and more preferably 160 ° C. to 160 ° C. It is selected in the range of 30 minutes to 120 minutes at 200 ° C. Before heating, ultraviolet irradiation with a high-pressure mercury lamp, a heating step using a clean oven, or the like may be performed. When irradiating with ultraviolet rays, the irradiation amount can be adjusted as needed, and for example, irradiation can be performed with an irradiation amount of about ^{0.05 J / cm 2 to} 10 J / cm ^2.

<Peeling process>
The peeling step is a step of peeling the support substrate to produce a printed wiring board having a coreless structure. The method of peeling the support substrate is not particularly limited. The peeling step may be performed after any one of the laminating step, the exposure step, and the developing step.

<Other processes>
The printed wiring board may further include a drilling step and a desmear step after forming the solder resist. These steps may be carried out according to various methods known to those skilled in the art used in the manufacture of printed wiring boards.

After forming the solder resist, if desired, a hole is formed in the solder resist formed on the circuit board to form via holes and through holes. The drilling step can be performed by, for example, a known method such as a drill, a laser, or a plasma, or a combination of these methods if necessary, but a drilling step using a laser such as a carbon dioxide gas laser or a YAG laser is preferable.

The desmear process is a process of desmearing. Generally, a resin residue (smear) is attached to the inside of the opening formed in the drilling step. Since such smear causes poor electrical connection, a process for removing the smear (desmear process) is performed in this step.

The desmear treatment may be carried out by a dry desmear treatment, a wet desmear treatment or a combination thereof.

Examples of the dry desmear treatment include desmear treatment using plasma. The desmear treatment using plasma can be carried out using a commercially available plasma desmear treatment apparatus. Among commercially available plasma desmear processing devices, examples suitable for the production of printed wiring boards include a microwave plasma device manufactured by Nissin, a normal pressure plasma etching device manufactured by Sekisui Chemical Co., Ltd., and the like.

Examples of the wet desmear treatment include a desmear treatment using an oxidizing agent solution. When the desmear treatment is performed using the oxidant solution, it is preferable to perform the swelling treatment with the swelling solution, the oxidation treatment with the oxidant solution, and the neutralization treatment with the neutralizing solution in this order. Examples of the swelling liquid include "Swelling Dip Security SBU" and "Swelling Dip Security SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing a substrate on which a via hole or the like is formed in a swelling liquid heated to 60 ° C. to 80 ° C. for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganate aqueous solution, and examples thereof include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment with the oxidizing agent solution is preferably carried out by immersing the substrate after the swelling treatment in the oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 minutes to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. The neutralization treatment with the neutralizing liquid is preferably carried out by immersing the substrate after the oxidation treatment in the neutralizing liquid at 30 ° C. to 50 ° C. for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan.

When the dry desmear treatment and the wet desmear treatment are carried out in combination, the dry desmear treatment may be carried out first, or the wet desmear treatment may be carried out first.

When the insulating layer is used as the interlayer insulating layer, it can be performed in the same manner as in the case of the solder resist, and the drilling step, the desmear step, and the plating step may be performed after the thermosetting step.

The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer may be formed by combining electroless plating and electrolytic plating, or a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method for subsequent pattern formation, for example, a subtractive method, a semi-additive method, etc. known to those skilled in the art can be used.

[Semiconductor device]
The semiconductor device of the present invention includes a printed wiring board. The semiconductor device of the present invention can be manufactured by using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conduction point" is a "place for transmitting an electric signal in the printed wiring board", and the place may be a surface or an embedded place. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting the semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples thereof include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

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

(Measurement of glass transition temperature of component (F))
The glass transition temperature of the component (F) was calculated by the FOX formula shown below.
1 / Tg = (W1 / Tg1) + (W2 / Tg2) + ... + (Wm / Tgm)
W1 + W2 + ... + Wm = 1
Wm represents the content (mass%) of each monomer constituting the component (F), and Tgm represents the glass transition temperature (K) of each monomer constituting the component (F).

(Measurement of weight average molecular weight (Mw) of component (A) and component (F))
The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) was defined as the weight average molecular weight of the components (A) and (F).

(Synthesis Example 1: Synthesis of component (F))
Methyl isobutyl ketone (350 g), glycidyl methacrylate (71 g), butyl acrylate (136 g) and azobisisobutyronitrile (16 g) were added to a 5-port reaction vessel having a content of 2 liters, and the mixture was heated at 80 ° C. for 6 hours while blowing nitrogen gas. Next, 36 g of acrylic acid, 4 mg of methquinone and 4 mg of triphenylphosphine were added to the obtained reaction solution, and the mixture was heated at 100 ° C. for 24 hours while blowing air. To the obtained reaction mixture, 48 g of tetrahydropyran anhydride was added, the mixture was heated at 70 ° C. for 10 hours, and a solvent was added to obtain a polymer solution. The theoretical Tg value of the polymer was −28 ° C., solid content: 45% by mass, Mw: 18000, acid value: 52 mgKOH / g.

<Examples 1 to 5, Comparative Examples 1 to 6>
Each component was blended in the blending ratio shown in the table below, and the resin varnish was prepared using a high-speed rotary mixer. Next, a PET film (Toray Industries, Inc., "Lumilar T6AM", thickness 38 μm, softening point 130 ° C., “Release”” was released as a support with an alkyd resin-based mold release agent (lintec, “AL-5”). Mold PET ") was prepared. The prepared resin varnish is uniformly applied to the release PET with a die coater so that the thickness of the resin composition layer after drying becomes 40 μm, and the release PET is dried at 80 ° C to 110 ° C for 5 minutes. A resin sheet having a resin composition layer on top was obtained.

The abbreviations in the table are as follows.
-ZAR-2000: Bisphenol A type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, solid content concentration about 70%)
-ZFR-1491H: Bisphenol F type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, solid content concentration about 70%)
-NC3000H: Solid biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent about 272)
SC2050: Surface-treated with 0.5 parts by mass of aminosilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 parts by mass of molten silica slurry (manufactured by Admatex, average particle size 0.5 μm), and added MEK. Slurry. Solid content concentration 70%.
IrgacureOXE-02: 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (manufactured by BASF)
-AC3816N: Organic fine particles having a core-shell multilayer structure (manufactured by Ganz Kasei Co., Ltd., average particle size 0.5 μm)
-Synthesis Example 1: Component (F) synthesized in Synthesis Example 1-DCP-A: Tricyclodecanedimethanol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., acrylic equivalent about 152)
-IXEPLAS-A3: Ion scavenger (manufactured by Toagosei Co., Ltd., a mixture of hydrotalcite and zirconium phosphate)
CCR-1171H: Cresol novolac type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, solid content concentration about 70%, Tg is -20 ° C or higher)
-ZCR-1797H: Biphenyl type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, solid content concentration about 70%, Tg is -20 ° C or higher)
UN-5507: Urethane acrylate resin (manufactured by Negami Kogyo Co., Ltd., acid value 60 mgKOH / g, solid content concentration about 70%)
828: Liquid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 190)
-PB3600: Butadiene structure-containing epoxy resin (manufactured by Daicel Chemical Co., Ltd., epoxy equivalent: about 200)
-MEK: Methyl ethyl ketone-EDGAc: Ethyl diglycol acetate

<Evaluation of warpage during resin bonding>
The resin sheets produced in Examples and Comparative Examples were placed on the entire surface of one side of a copper foil (JX Nippon Mining & Metals Co., Ltd., "JTC foil", copper foil thickness 18 μm), and a vacuum laminator (manufactured by Nichigo Morton Co., Ltd., VP160) was placed. Laminated using. Then, it was cut into a size of 10 cm × 10 cm, the PET film was peeled off, and the resin sheet was heat-cured in an oven at 190 ° C. for 90 minutes to obtain an evaluation sample. The height of each of the four corners and four sides was fixed to the SUS plate with a polyimide tape on one side of the four sides, and the height of the highest point was obtained from the SUS plate to obtain the warp value (cm). If the warp value exceeds 3 cm, it is indicated as "x".

<Evaluation of developability>
(Preparation of laminate for evaluation)
A glass epoxy substrate (copper-clad laminate) on which a circuit in which a copper layer with a thickness of 18 μm is patterned is formed is prepared, and the copper layer is treated with a surface treatment agent containing an organic acid (CZ8100, manufactured by MEC). Was roughened. Next, the resin composition layer of the resin sheet obtained in Examples and Comparative Examples was arranged so as to be in contact with the surface of the copper circuit, laminated using a vacuum laminator (manufactured by Nichigo Morton, VP160), and the copper-clad laminate was laminated. And the resin composition layer and the support were laminated in this order to form a laminated body. The crimping conditions were a vacuuming time of 30 seconds, a crimping temperature of 80 ° C., a crimping pressure of 0.7 MPa, and a pressurizing time of 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or more, and exposed to ultraviolet rays from the support of the laminate using a pattern forming apparatus. Exposure patterns are apertures: 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm round holes, L / S (line / space): 50 μm / 50 μm, 60 μm / 60 μm, 70 μm / 70 μm, 80 μm / 80 μm, 90 μm / 90 μm, 100 μm. A quartz glass mask was used to draw a line and space of / 100 μm and a quadrangle of 1 cm × 2 cm. After allowing to stand at room temperature for 30 minutes, the support was peeled off from the laminate. A 1% by mass sodium carbonate aqueous solution at 30 ° C. was spray-developed on the entire surface of the resin composition layer on the laminated plate at a spray pressure of 0.2 MPa for 2 minutes. After spray development, ^{ultraviolet irradiation of 1 J / cm 2} was performed, and further heat treatment was performed at 180 ° C. for 30 minutes to form a pattern insulating layer having openings. This was used as an evaluation laminate.

(Evaluation of appearance after exposure)
The unexposed portion of the pattern insulating layer of the 1 cm × 2 cm quadrangular portion of the evaluation laminate was visually observed, and the appearance after exposure was evaluated according to the following criteria.
◯: No resin remains in any unexposed area.
Δ: A very small amount of resin residue is observed.
X: The resin component can be visually confirmed.

(Evaluation of opening shape and measurement of minimum opening diameter)
Each opening formed by exposure was observed with an SEM (manufactured by Hitachi High-Technology Co., Ltd., S-4800) (magnification: 1000 times), and the minimum opening diameter of the opening without residue was measured. Items with a large amount of residue in the unexposed area and no residue and no minimum opening diameter are marked with "x". The opening shape of the opening was evaluated according to the following criteria.
◯: Observe the openings at any three points, and no irregular shape or cracks in diameter are observed.
X: Observing the openings at any three points, irregular shapes and cracks in diameter can be seen.

<Evaluation of insulation reliability>
The resin sheets prepared in Examples and Comparative Examples were laminated on a TAB tape having L / S = 15 μm / 15 μm using a batch type vacuum laminator (VP160 manufactured by Nichigo Morton Co., Ltd.). The resin composition layer was cured by heating in a batch oven at 190 ° C. for 90 minutes to obtain an insulating layer. The resistance value of the insulating layer after curing was measured and used as the initial resistance value. Subsequently, the HAST tester (manufactured by Kusumoto Kasei Co., Ltd., "ETAC PM422") was left to stand for 50 hours and 100 hours under the conditions of 130 ° C. and 85% Rh, and the resistance value (HAST resistance value) after each time was determined. The measurement was performed, the initial resistance value, the resistance value after 50 hours, and the resistance value after 100 hours were compared, and the degree of decrease in the resistance value was evaluated according to the following criteria.
◯: No decrease in resistance is observed even after 100 hours.
Δ: The resistance value is maintained for 50 hours or more.
X: The resistance value decreases in 50 hours or less.

<Evaluation of solder heat resistance>
WF-6300 (manufactured by Senju Metal Co., Ltd., water-soluble flux) was applied to the evaluation laminate, and the mixture was put into a reflow oven (manufactured by ANTOM, HAS-6116) at 260 ° C. or higher for 1 minute or longer. After passing through the reflow oven three times, the water-soluble flux was washed with water at 60 ° C., and then visually observed, and the swelling and peeling of the insulating layer were evaluated according to the following criteria.
◯: No peeling or pattern distortion is observed.
X: Peeling or pattern distortion occurs.

From the results in the above table, it can be seen that Examples 1 to 5 are excellent in the amount of warpage, developability, insulation reliability, and solder heat resistance.

Comparative Examples 1 to 3 containing no component (A) are inferior to those of Examples in at least one of warpage amount, developability, insulation reliability, and solder heat resistance, and cannot be used as a photosensitive resin composition. You can see that.

Comparative Example 4 containing no rubber particles had a warp amount inferior to that of Example, and Comparative Example 5 containing no solid epoxy resin had developability, insulation reliability, and solder heat resistance compared to Examples. It can be seen that it is inferior and cannot be used as a photosensitive resin composition.

It can be seen that Comparative Example 6 in which a resin having a butadiene skeleton was added instead of the rubber particles (E) was inferior in developability to Examples and could not be used as a photosensitive resin composition.

It has been confirmed that even when the components (F) to (I) are not contained in each of the examples, the results are the same as those of the above-mentioned examples, although the degree is different.

Claims (12)

(A) A resin having a bisphenol skeleton, which contains an ethylenically unsaturated group and a carboxyl group.
(B) Solid epoxy resin,
(C) Inorganic filler with an average particle size of 0.5 μm or more,
(D) Photopolymerization initiator,
(E) rubber particles, and (F) (meth) acrylic polymer having a glass transition temperature of −20 ° C. or lower,
Contains ,
When the non-volatile component in the resin composition is 100% by mass,
The content of the component (A) is 5% by mass or more and 40% by mass or less.
A resin composition having a component (E) content of 0.3% by mass or more and 40% by mass or less. (E) content of the component, when the nonvolatile component in the resin composition as 100 wt%, 3 is 0 mass% or less, the resin composition of claim 1. The resin composition according to claim 1 or 2, which is used for forming a solder resist. The resin composition according to any one of claims 1 to 3, wherein the component (A) has a bisphenol A skeleton. The resin composition according to any one of claims 1 to 4, wherein the component (B) contains a biphenyl type epoxy resin. The resin composition according to any one of claims 1 to 5, wherein the content of the component (C) is 50% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 6, wherein the component (C) is silica. The resin composition according to any one of claims 1 to 7, wherein the component (D) is an acylphosphine oxide-based photopolymerization initiator or an oxime ester-based photopolymerization initiator. When the content mass of the component (A) is W (a) and the content mass of the component (F) is W (f), W (f) / W (a) is 0.1 or more and 3 or less. The resin composition according to any one of claims 1 to 8. A resin sheet having a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 9. A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 9, wherein the printed wiring board has a coreless structure. A semiconductor device including the printed wiring board according to claim 11.