JP2019119818A - Resin composition - Google Patents

Abstract

To provide a resin composition that has insulation reliability and developability and makes it possible to obtain a cured product that both has solder heat resistance and resists warpage; and a resin sheet, printed wiring board, and semiconductor device obtained by using the resin composition.SOLUTION: A resin composition contains (A) a resin having a bisphenol skeleton, containing an ethylenically unsaturated group and a carboxyl group, (B) a solid epoxy resin, (C) an inorganic filler with an average particle size of 0.5 μm or more, (D) a photopolymerization initiator, and (E) rubber particles.SELECTED DRAWING: None

Description

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

  In the printed wiring board, a solder resist is provided as a permanent protective film for suppressing adhesion of the solder to a portion not requiring the solder and suppressing corrosion of the circuit board. As a 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 of increasing the density and reducing the thickness, the circuit board has been actively used for coreless mounting and FC (flip chip) mounting.

  Although it is possible to reduce the thickness by corelessing the circuit board, in general, the coreless circuit board has low self-supportability, and therefore, warpage may easily occur depending on the configuration of the circuit board. For this reason, as a material used for a circuit board, the resin composition which relieves stress is called for.

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

  Although it is conceivable to add a liquid material to the resin composition in order to ease the stress, when the liquid material is added to the resin composition, basic characteristics such as heat resistance, insulation reliability, and developability are obtained. It can be difficult to be satisfied.

  Also, in order to improve solder heat resistance, it is conceivable to incorporate a rigid and tough material into the resin composition, but when such a material is incorporated into the resin composition, it loses flexibility and warps. It may increase.

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

  As a result of intensive investigations to solve the above problems, the present inventors include a predetermined resin containing an ethylenically unsaturated group and a carboxyl group, a predetermined epoxy resin, and rubber particles in a resin composition, It has been found that the above problems can be solved, and the present invention has been completed.

That is, the present invention includes the following contents.
[1] (A) A resin having a bisphenol skeleton, containing 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 nonvolatile component in the resin composition is 100% by mass.
[3] The resin composition according to [1] or [2], which is 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 nonvolatile 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 acyl phosphine oxide type photopolymerization initiator or an oxime ester type 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 less.
[10] Assuming that 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], which is
[11] A resin sheet comprising: a support; and a resin composition layer provided on the support and including the resin composition according to any one of [1] to [10].
[12] A printed wiring board comprising 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 comprising the printed wiring board according to [12].

  According to the present invention, a resin composition capable of obtaining a cured product capable of achieving both solder heat resistance and suppression of warpage while having insulation reliability and developability; a resin obtained using the resin composition A sheet, a printed wiring board, and a semiconductor device 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, (C) an inorganic particle having an average particle size of 0.5 μm or more. A filler, (D) a photopolymerization initiator, and (E) rubber particles are contained. It is desirable for the present invention that a cured product capable of achieving both solder heat resistance and suppression of warpage can be obtained while having insulation reliability and developability by including the components (A) to (E) in combination. You can get the effect of The hardened | cured material of this resin composition can be preferably used as a soldering resist formation use taking advantage of the outstanding characteristic.

  Moreover, the resin composition of this invention may be combined with the (A)-(E) component, and may further contain arbitrary components. As optional components, for example, (F) a (meth) acrylic polymer having a glass transition temperature of -20 ° C. or less, (G) a reactive diluent, (H) an organic solvent, and (I) other additives May be included. Hereinafter, each component contained in a resin composition is demonstrated 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, which contains 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, developability is improved. The present inventors have found that when this resin has a relatively rigid bisphenol skeleton, in addition to the improvement of the developability, it is possible to suppress the warpage of the obtained cured product and to improve the solder heat resistance.

  As a bisphenol skeleton, for example, 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, bisphenol S skeleton And bisphenol P skeleton, bisphenol PH skeleton, bisphenol TMC skeleton, bisphenol Z skeleton and the like. Among them, 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 vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadiimide group, (meth) acryloyl group, etc. Reaction of photo radical polymerization From the viewpoint of properties, a (meth) acryloyl group is preferred. The "(meth) acryloyl group" refers to a methacryloyl group and an acryloyl group.

  The component (A) has a bisphenol skeleton, an ethylenically unsaturated group and a carboxyl group, and can use any compound that enables photo radical polymerization and enables alkali development, among which a bisphenol skeleton is contained. And resins having both a carboxyl group and two or more ethylenic unsaturated groups in one molecule.

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

  As the bisphenol skeleton-containing epoxy compound, for example, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin Examples thereof include bisphenol-type epoxy resins such as a modified bisphenol F-type epoxy resin which has been modified to have three or more functions by reacting epichlorohydrin, bisphenol A-type novolac epoxy resin, bisphenol AF-type epoxy resin, and the like. Among them, a bisphenol A epoxy resin and a bisphenol F epoxy resin are preferable from the viewpoint of obtaining a cured product capable of achieving both solder heat resistance and suppression of warpage while having developability.

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

  As the acid anhydride, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid dicarboxylate Anhydride etc. are mentioned and these may be used individually by 1 type, or may use 2 or more types together. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred from the viewpoint of improving the developability and insulation reliability of the cured product.

  In order to obtain 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 the 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-described 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 using (meth) acrylic acid as the unsaturated carboxylic acid.

  A commercial item can be used for such an acid-modified unsaturated bisphenol skeleton-containing epoxy ester resin, and as a specific example, “ZAR-2000” (bisphenol A epoxy resin, acrylic acid, and anhydride) manufactured by Nippon Kayaku Co., Ltd. Reactants of succinic acid), “ZFR-1491H”, “ZFR-1533H” (reactants of bisphenol F-type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), and the like. These may be used singly or in combination of two or more.

  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 obtaining the effects of the present invention remarkably. Or less, more preferably 7500 or less. A weight average molecular weight is a weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) method.

The acid value of the component (A) is preferably 1 mg KOH / g or more, more preferably 30 mg KOH / g or more, and still more preferably 50 mg KOH / g or more from the viewpoint of improving the alkali developability of the resin composition. On the other hand, it is preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, still more preferably 120 mg KOH / g or less from the viewpoint of suppressing dissolution of the fine pattern of the cured product by development and improving insulation reliability. It is. Here, an acid value is the residual acid value of the carboxyl group which exists in (A) component, and an 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. Then, an appropriate amount of phenolphthalein which is an indicator is added to the solution, and titration is performed using a 0.1 N aqueous KOH solution. And an acid value is computed by a following formula.
Formula: A (a) = 10 x Vf x 56.1 / (Wp x I)

  In the above formula, A (a) represents the acid value (mg KOH / g), V f represents the titration amount (mL) of KOH, W p represents the mass (g) of the resin solution to be measured, and I is the resin solution to be measured Represents the proportion (% by mass) of non-volatile components of

  In the production of the component (A), the ratio of the number of moles of epoxy group of the bisphenol skeleton-containing epoxy compound to the number of moles of carboxyl group of the total of unsaturated carboxylic acid and acid anhydride from the viewpoint of improvement of 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.

The content of the component (A) is preferably 5% by mass or more, and more preferably 10% by mass or more, when the total solid content of the resin composition is 100% by mass from the viewpoint of obtaining the effects of the present invention remarkably. And more preferably 15% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and further 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. Moreover, since the component (B) is solid, it can also improve the solder heat resistance of the cured product. (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 three or more epoxy groups in one molecule from the viewpoint of significantly achieving the effects of the present invention.

  As solid epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, tris A phenol type epoxy resin, a naphthol type epoxy resin, a naphthalene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, a tetraphenylethane type epoxy resin etc. are mentioned, Among them, insulation reliability And biphenyl type epoxy resin is preferable from a viewpoint of obtaining a hardened material which is excellent by solder heat resistance.

  Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin) manufactured by DIC; “HP-4700” manufactured by DIC, “HP-4710” (naphthalene type tetrafunctional epoxy resin); “N-690” (cresol novolac epoxy resin); “N-695” (cresol novolac epoxy resin) manufactured by DIC; “HP-7200” (dicyclopentadiene type epoxy resin) manufactured by DIC; "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000L" manufactured by DIC Corporation, “HP 6000” (Naphthylene Ether Type Epoxy Resin); “EPPN-502H” manufactured by Nippon Kayaku Co., Ltd. Phenolic epoxy resin); “NC7000L” (naphthol novolac epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) Biphenyl aralkyl type epoxy resin)); “ESN 475 V” (naphthalene type epoxy resin) manufactured by Nippon Steel Sumikin Chemical Co., Ltd .; “ESN 485” (naphthol novolac type epoxy resin) manufactured by Nippon Steel Sumikin Chemical Co., Ltd. "YX4000", "YL6121" (biphenyl type epoxy resin); "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corp .; "YX 8800" manufactured by Mitsubishi Chemical Corp. (anthracene type epoxy resin); manufactured by Osaka Gas Chemical Co., Ltd. of" G-100 "," CG-500 ";" YL 7760 "(bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corp .;" YL 7800 "manufactured by Mitsubishi Chemical Corp. (fluorene type epoxy resin);" jER 1010 "manufactured by Mitsubishi Chemical Corp. (Solid bisphenol A type epoxy resin); "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation and the like can be mentioned. These may be used alone or in combination of two or more.

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

<(C) Inorganic filler having an average particle size of 0.5 μm or more>
The resin composition contains (C) an inorganic filler having an average particle diameter of 0.5 μm or more. By containing the component (C), the resin composition can lower the average linear thermal expansion coefficient of the resulting cured product, and can improve the developability.

  Although the material of the inorganic filler is not particularly limited, 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 And zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Moreover, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

  When an inorganic filler having a large average particle size is contained, light is scattered and the developability is inferior. Therefore, it is general to include an inorganic filler having an average particle size of less than 0.5 μm in a resin composition. It was However, when the present inventors combine the (A) to (E) components, it is possible to obtain a cured product having an excellent developability if the inorganic filler having an average particle diameter of 0.5 μm or more is contained. Found out that there is

  The average particle diameter of the inorganic filler is 0.5 μm or more, preferably 0.8 μm or more, more preferably 1 μm or more, from the viewpoint of obtaining a cured product having excellent developability and a low average linear thermal expansion coefficient. 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 still more preferably 1.3 μm or less from the viewpoint of obtaining excellent resolution. As a commercial item of the inorganic filler which has such an average particle diameter, for example, "SOC2" by "ADMATEX", "SC2050", "SOC4", "SC4050", "ADMA FINE", the electric chemical industry company " "SFP series", "SP (H) series" manufactured by Nippon Steel & Sumikin Materials, "Sciqas series" manufactured by Sakai Chemical Industry, "Sea Hoster series" manufactured by Nippon Shokuhin Co., and "AZ series" manufactured by Nippon Steel & Sumikin Materials Examples include "AX series", "B series" manufactured by Sakai Chemical Industry Co., Ltd., and "BF series".

  The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle diameter distribution of the inorganic filler can be created on a volume basis by a laser diffraction / scattering particle size distribution measuring device, and the median diameter can be measured as an average particle diameter. As a measurement sample, one in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, "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 the moisture resistance and the dispersibility. Examples of surface treatment agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, titanate coupling agents, and the like. Be

  As a commercial item of the surface treatment agent, for example, “KBM 22” (dimethyl dimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM 403” (3-glycidoxypropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Shin-Etsu Chemical Co., Ltd. "KBM 803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical "KBE 903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM 573" (N-phenyl-3-aminopropyltrimethoxy) Silane), Shin-Etsu Chemical "KBM5783" (N-phenyl-3-aminooctyl trimethoxysilane), Shin-Etsu Chemical "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical "KBM 103" (Phenyltrimethoxysilane), Shin-Etsu Chemical "KBM-4803" ( Chain epoxy type silane coupling agent), and the like. The surface treatment agent may be used alone or in combination of two or more 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, the amount of carbon is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, particularly preferably from the viewpoint of suppressing the melt viscosity of the resin composition and the increase in the melt viscosity in sheet form. Is less than 0.5 mg / m ² .

  The amount of carbon per unit surface area of the component (C) can be measured after washing the component (C) after the surface treatment with a solvent (for example, methyl ethyl ketone (hereinafter sometimes 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 ultrasonic cleaning is performed at 25 ° C. for 5 minutes. Thereafter, the supernatant is removed, and after the solid content is dried, the amount of carbon per unit surface area of the component (C) can be measured using a carbon analyzer. As a 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% by mass, based on 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of obtaining a cured product having a low average linear thermal expansion coefficient. The content is preferably at least 15% by mass, more preferably at least 15% by mass. 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 the developability and suppressing warping.

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

  The photopolymerization initiator (D) is not particularly limited. For example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. Acyl phosphine oxide type photopolymerization initiators: 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) Oxime ester photopolymerization initiators such as 9) R-carbazol-3-yl]-, 1- (O-acetyloxime); 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1- Butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]-[4- (4-morpholinyl) phenyl] -1-butanone, Α-Aminoalkylphenone photopolymerization initiators such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; benzophenone, methyl benzophenone, o-benzoylbenzoic acid, benzoylethyl ether 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl- (2,4,6-trimethyl benzoyl) phosphine oxide, ethyl- (2,4,6-trimethyl benzoyl) phenyl phosphinate, 4,4 '-Bis (diethylamino) benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2 -Hydroxy-2-methyl-1-propan-1-one, bis 2,4,6-trimethylbenzoyl) - phenylphosphine Oki sand; sulfonium salt-based photopolymerization initiators, and the like. One of these may be used alone, or two or more may be used in combination. Among these, from the viewpoint of more efficiently photocuring the resin composition, and from the viewpoint of improving resolution, acyl phosphine oxide type photopolymerization initiators and oxime ester type photopolymerization initiators are preferable, and oxime ester type photopolymerization initiation Agents are more preferred.

  (D) Specific examples of the photopolymerization initiator include “Omnirad 907”, “Omnirad 369”, “Omnirad 379”, “Omnirad 819”, “Omnirad TPO” manufactured by IGM, “IrgacureOXE-01” manufactured by BASF, and “IrgacureOXE- 02 "," Irgacure TPO "," Irgacure 819 "," N- 1919 "manufactured by ADEKA Corporation, and the like.

  Furthermore, the resin composition may contain a photopolymerization initiation aid in combination with the (D) photopolymerization initiator. As a photopolymerization start auxiliary agent, for example, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, tertiary amine such as pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine etc. And photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, thioxanthones and the like. Any of these may be used alone or in combination of two or more.

  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 curing the resin composition to improve the insulation reliability. The content is 0.11% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.3% by mass or more. On the other hand, the upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1.5% by mass or less from the viewpoint of suppressing a decrease in resolution due to excessive sensitivity. In addition, when a resin composition contains a photoinitiator adjuvant, it is preferable that the sum total content of (D) photoinitiator and photoinitiator adjuvant is in the said range.

<(E) rubber particles>
The resin composition contains (E) rubber particles. (E) The rubber particles generally have a refractive index higher than that of the component (C), and thus match the refractive index of the component containing the components (A) to (D) in combination, and expose the cured product of the resin composition Light is less likely to scatter. In addition, the rubber particles (E) are in the form of particles, and are easily removed by a developer. Furthermore, since the rubber particles usually have a stress relaxation action, the internal stress generated at the time of formation of the cured product of the resin composition is relieved by the (E) rubber particles. Therefore, the curvature of hardened | cured material is suppressed by containing the (E) rubber particle, and the resin composition can improve the developability of hardened | cured material.

  (E) The rubber particles do not dissolve in the organic solvent at the time of preparing the resin composition, are not compatible with the resin component in the resin composition, and preferably present in a dispersed state in the varnish of the resin composition . (E) The rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which the rubber component does not dissolve in the organic solvent or resin, and forming it into particles.

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

  The core-shell rubber particle is a rubber particle including a shell layer on the surface of the particle and a core layer on the inside of the shell layer, and may include an intermediate layer between the shell layer and the core layer. . Core-shell rubber particles include, for example, a core-shell rubber particle including a shell layer formed of a glassy polymer and a core layer formed of a rubbery polymer; a shell layer formed of a glassy polymer; 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 glassy polymers include polymers of methyl methacrylate, and examples of rubbery polymers include polymers of butyl acrylate (butyl rubber).

  Specific examples of the core-shell type rubber particles include staphyroid “AC3832” and “AC3816N” manufactured by Aika Kogyo Co., Ltd., and “Metabren KW-4426” manufactured by Mitsubishi Chemical Corporation.

  Specific examples of the crosslinked acrylonitrile butadiene rubber particles include “XER-91” (average particle diameter 0.5 μm) manufactured by JSR Corporation, and the like.

  As a specific example of a crosslinked styrene butadiene rubber particle, "XSK-500" (average particle diameter 0.5 micrometer) by JSR Corporation etc. are mentioned.

  Specific examples of the acrylic rubber particles include metabrene "W300A" (average particle size 0.1 μm), "W450A" (average particle size 0.2 μm) manufactured by Mitsubishi Chemical Corp., "EXL-2655" manufactured by Dow Chemical Co. Etc.

  (E) The rubber particles may be used alone or in combination of two or more.

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

  The content of the rubber particles (E) is preferably 0.3 mass when the non-volatile component of the resin composition is 100 mass% from the viewpoint of suppressing the warpage of the cured product and improving the developability of the cured product. % Or more, more preferably 0.5% by mass or more, further 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) (Meth) acrylic polymer having a glass transition temperature of −20 ° C. or lower>
The resin composition may contain a (meth) acrylic polymer having a (F) glass transition temperature of -20 ° C or less. However, the component (F) does not correspond to the component (A). When the resin composition contains the component (F), when the resulting cured product is developed, appropriate phase separation occurs with the developer, and it becomes easy to remove with the developer. As a result, the developability of the cured product can be further enhanced. Moreover, stress is relieved by the resin composition containing (F) component, and the curvature of the hardened | cured material obtained can be suppressed more. The (meth) acrylic polymer is a polymer containing a structural unit having a structure formed by polymerizing a (meth) acrylic monomer. As such (meth) acrylic polymer, 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 It can be mentioned.

The glass transition temperature (Tg) of the component (F) is preferably -20 ° C or less, more preferably -23 ° C or less, still more preferably -25 ° C or less, from the viewpoint of improving the flexibility. The lower limit is preferably −300 ° C. or higher, more preferably −200 ° C. or higher, and still more preferably −100 ° C. or higher and −80 ° C. or higher, from the viewpoint of improving the alkali solubility. 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 formula of FOX shown below. Can. The glass transition temperature determined by the formula of FOX substantially matches the glass transition temperature measured by differential scanning calorimetry (TMA, DSC, DTA), so the glass transition temperature of the main chain of the 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 (% by mass) of each monomer constituting the (F) component, and Tgm represents the glass transition temperature (K) of each monomer constituting the (F) component.

  The component (F) is preferably a (meth) acrylic polymer containing an ethylenically unsaturated group and a carboxyl group, and it 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 preferred 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 an acid anhydride. Specifically, an 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. Acid-modified unsaturated epoxy (meth) acrylic copolymer can be obtained. The epoxy group of the epoxy group-containing copolymer is substantially eliminated by the reaction with (meth) acrylic acid.

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

  As an optional monomer, 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, cyclohexy (Meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, acrylamide, N, N-dimethyl (meth) acrylamide, ( Meta) 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 (meth) 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 an end, 1-adamantyl (meth) ) Acrylates, etc., among which n-butyl (meth) acrylate is preferred. Arbitrary monomers may be used independently and may be used in mixture of 2 or more types.

  As the acid anhydride used to obtain the component (F), the same acid anhydride as that used to obtain the component (A) can be used.

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

  The weight average molecular weight of the component (F) is 30,000 or less, preferably 28,000 or less, 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 still more preferably 15000 or more from the viewpoint of coating film properties. 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 mg KOH / g or more, more preferably 0.5 mg KOH / g or more, from the viewpoint of improving the alkali developability of the cured product. More preferably, it is 1 mg KOH / g or more. On the other hand, the acid value is preferably 150 mg KOH / g or less, more preferably 120 mg KOH / g or less, and further preferably 100 mg KOH / g or less from the viewpoint of excellent removability of the residue during development. 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 excellent in developability and suppressing warpage. If it is, it is preferably 1% by mass or more, more preferably 3% by mass or more, still more 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 below.

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

  Assuming that the content mass of the component (A) in the resin composition is W (a) and the content mass of the component (F) in the resin composition is W (f), W (f) / W (a) is From the viewpoint of obtaining a cured product which is more excellent in 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 means the content of the component (A) when the nonvolatile component of the resin composition is 100% by mass, and the content (F) in the resin composition The content mass of a component represents content of (F) component at the time of setting the non-volatile component of a resin composition to 100 mass%.

<(G) Reactive Diluent>
The resin composition may further contain (G) a reactive diluent. (G) Photoreactivity can be improved by containing a 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 can be used. The room temperature represents about 25 ° C.

  Representative photosensitive (meth) acrylate compounds include, for example, tricyclodecanedimethanol diacrylate, 2-hydroxyethyl acrylate, hydroxyalkyl acrylates such as 2-hydroxybutyl acrylate, ethylene glycol, methoxytetraethylene glycol, polyethylene Monoglycols or glycols such as propylene glycol, acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide, aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, trimethylolpropane, penta Polyhydric alcohols such as erythritol and dipentaerythritol or ethylene oxides, propylene oxides or ε-cars of these. Polyacrylates of adducts of rolactones, phenols such as phenoxyacrylates and phenoxyethyl acrylates, or acrylates such as ethylene oxide or propylene oxide adducts thereof, epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether And melamine acrylates, and / or methacrylates corresponding to the above-mentioned acrylates. Among these, polyvalent acrylates or polyvalent methacrylates are preferable. For example, as trivalent acrylates or methacrylates, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane EO-added tri (meth) acrylate, glycerol PO-added tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetrafurfuryl alcohol oligo (meth) acrylate, ethyl carbitol oligo (meth) acrylate, 1,4-butanediol Oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate Rate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N, N ', N'-tetrakis (β-hydroxyethyl) ethyl diamine (meth) acrylate and the like. And trivalent or higher acrylates or methacrylates, tri (2- (meth) acryloyloxyethyl) phosphate, tri (2- (meth) acryloyloxypropyl) phosphate, tri (3- (meth) acryloyloxypropyl) Phosphate, tri (3- (meth) acryloyl-2-hydroxyloxypropyl) phosphate, di (3- (meth) acryloyl-2-hydroxyloxypropyl) (2- (meth) acryloyloxyethyl) phosphate, (3- (3- (meth) acryloyloxyethyl) phosphate Meta) Acri Yl-2-hydroxy propyl) and di (2- (meth) acryloyloxyethyl) phosphate triester (meth) acrylates such as phosphates. These photosensitive (meth) acrylate compounds may be used alone or in combination of two or more.

  (G) As a reactive diluent, a commercial item can be used. As a specific example, "DPHA" (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.), "DCA-P" (tricyclodecane dimethanol) Diacrylate, manufactured by Kyoeisha Chemical Co., Ltd., and the like.

  When the resin composition contains (G) a reactive diluent, the content of the (G) reactive diluent promotes photocuring and suppresses 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, preferably 25% by mass The following content 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 varnish viscosity can be adjusted by containing an organic solvent. (H) Examples of organic solvents 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, etc. Aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha and the like. These may be used alone or in combinations of two or more. The content in the case of using the organic solvent can be appropriately adjusted from the viewpoint of the 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, ion scavengers such as “IXEPLAS-A3” manufactured by Toa Gosei Co., Ltd., epoxy resin liquid at 20 ° C., thermoplastic resin, organic filler, melamine, organic bentonite, etc. Fine particles, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, coloring agents such as naphthalene black, hydroquinone, phenothiazine, methyl hydroquinone, hydroquinone monomethyl ether, catechol, polymerization inhibitors such as pyrogallol , Benton, montmorillonite, etc., silicone type, fluorine type, vinyl resin type antifoaming agent, brominated epoxy compound, acid-modified brominated epoxy compound, antimony compound, aromatic condensed phosphate, ha-containing Flame retardants such as plasminogen condensed phosphoric acid ester, a phenolic curing agent, thermosetting resins such as cyanate ester-based curing agent, various additives and the like the like.

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

<Physical Properties of Resin Composition, Applications>
Since the resin composition of the present invention contains the components (A) to (E), it usually exhibits the property of low elastic modulus at 25 ° C. Therefore, by using this resin composition, it is possible to obtain the insulating layer and the solder resist layer capable of suppressing the warpage of the printed wiring board. The elastic modulus at 25 ° C. of the cured product obtained by heat curing the resin composition at 190 ° C. for 90 minutes is preferably 4 GPa or less, more preferably 3 GPa or less, and still more preferably 2 GPa or less. The lower limit is not particularly limited, but may 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 the examples to produce an evaluation sample. In this case, the amount of warpage measured by the method described in the example of the evaluation sample can be usually 3.5 mm or less, 2.5 mm or less, or 2 mm or less.

  Since the resin composition of this invention contains (A)-(E) component, the cured | curing material which is excellent in developability can be obtained. Therefore, by using this resin composition, an insulating layer and a solder resist layer excellent in developability can be obtained. For example, a laminate for evaluation is produced by the method described in the examples. In this case, the minimum opening diameter (minimum via diameter) free of the residue of the evaluation laminate is preferably 100 μm or less, more preferably 90 μm or less, and 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. In addition, since the cured product of the resin composition of the present invention is excellent in developability, when the appearance of the laminate for evaluation is evaluated by the method described in the examples, the resin component usually remains in any unexposed area. Also, even when observing any three opening shapes having the minimum opening diameter, the opening shape is neither irregular nor cracks can be seen.

  Since the resin composition of this invention contains (A)-(E) component, the cured | curing material which is excellent in insulation reliability can be obtained. Therefore, by using this resin composition, an insulating layer and a solder resist layer excellent in insulation reliability can be obtained. For example, when the initial resistance value of the insulating layer obtained by the method described in the examples and the HAST resistance value after the HAST test are compared, generally, almost no decrease in the HAST resistance value is observed.

  Since the resin composition of this invention contains (A)-(E) component, the hardened | cured material which is excellent in solder heat resistance can be obtained. Therefore, the insulating layer and the solder resist layer which are excellent in solder heat resistance can be obtained by using this resin composition. For example, a laminate for evaluation is produced by the method described in the examples. In this case, when the solder heat resistance is evaluated by the method described in the embodiment of the evaluation laminate, the peeling of the insulating layer, the distortion of the pattern, and the like are not generally recognized.

  Although the application of the resin composition of the present invention is not particularly limited, resin sheet, circuit board (laminate board application, multilayer printed wiring board application, etc.), solder resist, underfill material, die bonding material, semiconductor sealing material, hole filling It can be used in a wide range of applications of resin compositions, such as resins and resin embedded in parts. Above all, a resin composition for solder resist (a printed wiring board using a cured product of the resin composition as a solder resist), a resin composition for an insulating layer of a printed wiring board (a printed wiring board using a cured product of the resin composition as an insulating layer) ), Resin composition for interlayer insulating layer (printed wiring board using cured product of resin composition as interlayer insulating layer), and resin composition for plating formation (printed wiring in which plating is formed on cured product of resin composition) 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.

  As a support body, a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, a triacetyl acetate film etc. are mentioned, for example, Especially a polyethylene terephthalate film is preferable.

  As a commercially available support, for example, product names "Alfan MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films such as Shin-Etsu Film Co., Ltd., product name "PS-25" manufactured by Teijin Limited And polyethylene terephthalate films such as PS series, etc., but not limited thereto. These supports should have a release agent such as a silicone coating applied to the surface to facilitate removal of the resin composition layer. The thickness of the support is preferably in the range of 5 μm to 50 μm, and more preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, it is possible to suppress breakage of the support at the time of peeling of the support performed before development, and by setting the thickness to 50 μm or less, at the time of exposing from above the support Resolution can be improved. Also, low fisheye supports are preferred. Here, when producing a film by heat melting the material, kneading, extruding, biaxial stretching, casting, etc., the fisheye is such that foreign matter, undissolved matter, oxidatively degraded material, etc. of the material is incorporated into the film. It is

  Moreover, in order to reduce scattering of the light at the time of exposure by active energy rays, such as an ultraviolet-ray, a thing excellent in transparency is preferable for a support body. Specifically, the support preferably has a turbidity (haze standardized by JIS K6714) of 0.1 to 5 as an index of transparency.

  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 adhesion of dirt and the like to the surface of the resin composition layer and scratches. As the protective film, a film composed 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 still more preferably in the range of 10 μm to 30 μm. The protective film is preferably one in which the adhesive strength between the resin composition layer and the protective film is smaller than the adhesive strength between the resin composition layer and the support.

  The resin sheet of the present invention is prepared, for example, by dissolving a resin composition of the present invention in an organic solvent according to a method known to those skilled in the art, coating the resin varnish on a support, and heating or blowing hot air. It can manufacture by drying an organic solvent by application etc. and forming a resin composition layer. Specifically, first, after the bubbles in the resin composition are completely removed by vacuum degassing method or the like, the resin composition is applied on a support, and the solvent is removed by a hot air oven or far infrared oven, and dried. Then, a protective film is laminated on the obtained resin composition layer if necessary, whereby a resin sheet can be produced. Although specific drying conditions depend on the curability of the resin composition and the amount of organic solvent in the resin varnish, in the resin varnish containing 30% by mass to 60% by mass of organic solvent, 3 at 80 ° C. to 120 ° C. It can be dried in 13 minutes. The amount of residual organic solvent in the resin composition layer is preferably 5% by mass or less, and 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 the subsequent steps. It is more preferable to Those skilled in the art can appropriately set suitable drying conditions by simple experiments. The thickness of the resin composition layer is preferably in the range of 5 μm to 500 μm from the viewpoint of improving the handleability and suppressing the decrease in sensitivity and resolution inside the resin composition layer, and preferably 10 μm to 200 μm. Is more preferably in the range of 15 μm to 150 μm, still more preferably in the range of 20 μm to 100 μm, and particularly preferably in the range of 20 μm to 60 μm.

  As a coating method of the resin composition, for example, a gravure coating method, a microgravure 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, a roll coating Examples include a method, a knife coating method, a curtain coating method, a chamber gravure coating method, a slot orifice method, a spray coating method, and a dip coating method.

  The resin composition may be applied several times, may be applied at one time, or may be applied by combining a plurality of different methods. Among them, the die coating method, which is excellent in uniform coatability, is preferable. Moreover, in order to avoid the contamination etc., it is preferable to carry out the coating process in an environment such as a clean room where the occurrence of the contamination is small.

[Printed wiring 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 can be reduced and the signal processing time can be shortened. As a specific example of such a printed wiring board, coreless FC-BGA (Ball Grid Array), ETS (Embedded Molding Substrate), MIS-BGA (Ball Grid Array) etc. are mentioned.

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

<Lamination 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, when the resin sheet has a protective film, after removing the protective film, the resin sheet and the support substrate are preheated if necessary, and the resin composition layer is supported while being pressurized and heated. Crimp on the board. In the resin sheet, a method of laminating on a support substrate under reduced pressure by vacuum lamination method is suitably used.

  As a support substrate, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting type polyphenylene ether substrate etc. are mentioned, for example. In addition, from the viewpoint of facilitating peeling of the support substrate, a metal layer such as 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 pressure bonding temperature (lamination temperature) is preferably 70 ° C. to 140 ° C., and the pressure bonding 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 ), laminating is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less with a pressure bonding time of preferably 5 seconds to 300 seconds Is preferred. In addition, the laminating process may be a batch system or a continuous system using a roll. The vacuum laminating method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum applicator made by Nikko Materials, a vacuum pressure type laminator made by Meiki Seisakusho Co., Ltd., a roll type dry coater made by Hitachi Industries, a vacuum laminator made by Hitachi AC, etc. be able to. Thus, a resin sheet is formed on the support substrate.

<Exposure process>
After the resin sheet is provided on the support substrate in the laminating step, an actinic ray is then irradiated to a predetermined portion of the resin composition layer through the mask pattern to expose the resin composition layer in the irradiated portion to a photocuring step. Do. Examples of the actinic rays 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} . As the exposure method, there are a contact exposure method in which a mask pattern is brought into close contact with a printed wiring board and a non-contact exposure method in which exposure is performed using parallel rays without being in contact with each other. Moreover, when a support body exists on a resin composition layer, you may expose from on a support body and may expose it after peeling a support body.

  The solder resist is excellent in developability because the resin composition of the present invention is used. Therefore, as an exposure pattern in the mask pattern, for example, the ratio (L / S) of the circuit width (line; L) to the width between the circuits (space; S) 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. Further, as the exposure pattern, for example, a pattern of 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, a round hole of 50 μm or less 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 a pattern is formed by removing and developing a non-photo-cured portion (unexposed portion) by wet development or dry development. it can.

  In the case of the above wet development, a safe and stable developer having good operability such as an alkaline aqueous solution, an aqueous developer, an organic solvent, etc. is used as a developer, and among them, a developing step with an alkaline aqueous solution is preferable. In addition, as the developing method, known methods such as spraying, swing immersion, brushing, scraping and the like are appropriately adopted.

As an alkaline aqueous solution used as a developing solution, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate, sodium phosphate And aqueous solutions of alkali metal phosphates such as potassium phosphate, alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and aqueous solutions of organic bases not containing metal ions such as tetraalkylammonium hydroxide and the like. An aqueous solution of tetramethyl ammonium hydroxide (TMAH) is preferred in that it contains no metal ions and does not affect the semiconductor chip.
A surfactant, an antifoaming agent, etc. can be added to these alkaline aqueous solutions for the improvement of the development 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. Moreover, it is preferable that the base concentration of the said alkaline aqueous solution shall be 0.1 mass%-10 mass%. Although the temperature of the said alkaline aqueous solution can be suitably selected according to the developability of a resin composition layer, it is preferable to set it as 20 degreeC-50 degreeC.

  Examples of the organic solvent used as a developer include 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 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 developer. In addition, the temperature of such an organic solvent can be adjusted in accordance with the developability. Furthermore, such organic solvents can be used alone or in combination of two or more. 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 the pattern formation, the two or more developing methods described above may be used in combination as needed. The developing method includes 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. As a spray pressure in the case of adopting a spray system, 0.05 MPa-0.3 MPa are preferable.

<Thermal curing (post bake) process>
After completion of the developing step, 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, and preferably in the range of 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, and more preferably 160 ° C. to It is selected in the range of 30 minutes to 120 minutes at 200 ° C. In addition, you may perform the heating process using the ultraviolet irradiation by a high pressure mercury lamp, a clean oven, etc. before heating. Case of ultraviolet irradiation can adjust its dose optionally, the irradiation can be carried out, for example 0.05J ^/ cm ² ~10J ^/ cm 2 approximately dose.

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

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

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

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

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

  As a dry desmear process, the desmear process etc. which used the plasma are mentioned, for example. Plasma desmear treatment can be carried out using a commercially available plasma desmear treatment system. Among the commercially available plasma desmear processing apparatuses, a microwave plasma apparatus manufactured by Nissin Co., a normal pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd., etc. may be mentioned as preferable examples for use for manufacturing printed wiring boards.

  As a wet desmear process, the desmear process etc. which used the oxidizing agent solution are mentioned, for example. When desmearing treatment using an oxidizing agent solution, it is preferable to perform swelling treatment with a swelling solution, oxidation treatment with an oxidizing agent solution, and neutralization treatment with a neutralizing solution in this order. Examples of the swelling liquid include "Swelling dip security P" and "Swelling dip security SBU" manufactured by Atotech Japan Co., Ltd., and the like. The swelling treatment is preferably performed by immersing the substrate having the via holes or the like in a swelling solution heated to 60 ° C. to 80 ° C. for 5 minutes to 10 minutes. As an oxidizing agent solution, an alkaline aqueous solution of permanganic acid is preferable. For example, a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be mentioned. The oxidation treatment with the oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in an oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 minutes to 30 minutes. As a commercial item of alkaline permanganic-acid aqueous solution, "Concentrate compact CP" by Atotech Japan Ltd. company, "dosing solution security G", etc. are mentioned, for example. The neutralization treatment with the neutralization solution is preferably performed by immersing the substrate after the oxidation treatment in a 30 ° C. to 50 ° C. neutralization solution for 3 minutes to 10 minutes. As a neutralization liquid, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Security G" manufactured by Atotech Japan Co., Ltd. may be mentioned.

  When the dry desmear treatment and the wet desmear treatment are performed in combination, the dry desmear treatment may be performed first, and the wet desmear treatment may be performed first.

  When the insulating layer is used as the interlayer insulating layer, it can be carried out in the same manner as in the case of the solder resist, and the hole drilling step, the desmear step and the plating step may be performed after the heat curing 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 reverse to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method of 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 using the printed wiring board of the present invention.

  Examples of the semiconductor device include various semiconductor devices provided for electric products (for example, computers, mobile phones, digital cameras, televisions and the like) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft and the like) and the like.

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

  The semiconductor chip mounting method in the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, the wire bonding mounting method, flip chip mounting method, no bump A mounting method using a buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a nonconductive film (NCF), and the like can be given. Here, "the mounting method using a bumpless build-up layer (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip and the wiring on the printed wiring board". It is.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass" unless otherwise specified.

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

(Measurement of weight average molecular weight (Mw) of (A) component and (F) component)
The weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) was made into the weight average molecular weight of (A) component and (F) component.

Synthesis Example 1: Synthesis of Component (F)
350 g of methyl isobutyl ketone, 71 g of glycidyl methacrylate, 136 g of butyl acrylate and 16 g of azobisisobutyronitrile were added to a 2-neck five-necked reaction vessel and heated at 80 ° C. for 6 hours while blowing nitrogen gas. Next, 36 g of acrylic acid, 4 mg of methoquinone 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 resulting reaction mixture, 48 g of tetrahydrophthalic anhydride was added, and 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: 18,000, and acid value: 52 mg KOH / g.

<Examples 1 to 5, Comparative Examples 1 to 6>
Each component was mix | blended by the compounding ratio shown to the following table, and the resin varnish was adjusted using the high-speed rotation mixer. Next, as a support, a PET film (Toray Industries, Inc., “Lumirror T6AM”, release 38 μm, softening point 130 ° C., release point) treated with an alkyd resin-based mold release agent (manufactured by Lintec, “AL-5”). "Type PET" was prepared. The prepared resin varnish is uniformly coated on the mold release PET with a die coater so that the thickness of the dried resin composition layer becomes 40 μm, and the mold release PET is dried at 80 ° C. to 110 ° C. for 5 minutes. A resin sheet having a resin composition layer thereon was obtained.

Abbreviations etc. in the table are as follows.
ZAR-2000: Bisphenol A epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mg KOH / g, solid content concentration about 70%)
ZFR-1491H: bisphenol F-type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mg KOH / g, solid content concentration about 70%)
· NC 3000 H: 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 ("KBM 573", manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 parts by mass of fused silica slurry (manufactured by Admatechs, average particle diameter 0.5 μm), and added MEK Slurry. Solid concentration 70%.
Irgacure OXE-02: 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (manufactured by BASF)
AC 3816 N: Organic fine particles having a core-shell multilayer structure (manufactured by Ganz Chemical 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 (Toagosei Co., Ltd., mixture of hydrotalcite and zirconium phosphate)
CCR-1171H: cresol novolac epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mg KOH / 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 mg KOH / g, solid content concentration about 70%, Tg is -20 ° C. or higher)
-UN-5507: Urethane acrylate resin, (Kotogami Kogyo Co., Ltd., acid value 60 mg KOH / g, solid content concentration about 70%)
· 828: Liquid bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., epoxy equivalent about 190)
・ PB3600: Epoxy resin containing butadiene structure (made by Daicel Chemical, epoxy equivalent: about 200)
· MEK: methyl ethyl ketone · EDGAc: ethyl diglycol acetate

<Evaluation of warpage at the time of resin lamination>
The resin sheet prepared in the examples and comparative examples is disposed on the entire surface of one side of a copper foil ("JTC foil" manufactured by JX Nippon Mining & Metals Co., Ltd., copper foil thickness 18 μm), and a vacuum laminator (VP 160, manufactured by Nichigo Morton Co.) It laminated and used. Thereafter, it was cut into a size of 10 cm × 10 cm, the PET film was peeled off, and the resin sheet was thermally cured in an oven at 190 ° C. for 90 minutes to obtain an evaluation sample. The height of each of the four corners was fixed to the SUS plate with polyimide tape on one side of the four sides, and the height of the highest point was determined from the SUS plate to determine the value of warpage (cm). When the value of warpage exceeded 3 cm, it was described as "x".

<Evaluation of developability>
(Preparation of laminate for evaluation)
Prepare a glass epoxy substrate (copper-clad laminate) on which a circuit formed by patterning a copper layer with a thickness of 18 μm is formed (copper-clad laminate), and treat it with a surface treatment agent containing an organic acid (CZ8100, manufactured by Mec) And roughened. Next, the resin composition layer of the resin sheet obtained by the example and the comparative example is disposed so as to be in contact with the copper circuit surface, and laminated using a vacuum laminator (VP160 manufactured by Nichigo Morton Co., Ltd.), and the copper clad laminate A laminate was formed in which the resin composition layer and the support were laminated in this order. The pressure bonding conditions were a vacuum pressure of 30 seconds, a pressure bonding temperature of 80 ° C., a pressure bonding pressure of 0.7 MPa, and a pressure time of 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or more, and was exposed to ultraviolet light from the support of the laminate using a pattern forming apparatus. The exposure pattern is an aperture: 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm round hole, 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 100 μm line and space, 1 cm × 2 cm square. After standing for 30 minutes at room temperature, the support was peeled off from the laminate. On the entire surface of the resin composition layer on the laminate, 1% by mass sodium carbonate aqueous solution at 30 ° C. was spray-developed at a spray pressure of 0.2 MPa for 2 minutes as a developing solution. After spray development, 1 J / cm ² ultraviolet irradiation was performed, and heat treatment was further performed at 180 ° C. for 30 minutes to form a pattern insulating layer having an opening. This was used as a laminate for evaluation.

(Evaluation of appearance after exposure)
The unexposed part of the pattern insulation layer of the 1 cm x 2 cm square part of the laminate for evaluation was visually observed, and the appearance after exposure was evaluated based on the following criteria.
○: no resin remains in any unexposed area.
Fair: resin residue is observed only slightly.
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 SEM (S-4800, manufactured by Hitachi High-Technologies Corporation) (magnification: 1000 times), and the minimum opening diameter of the opening without residue was measured. When there were not many residual residues in the unexposed area and no minimum opening diameter was found, it was indicated as "x". Further, the shape of the opening was evaluated according to the following criteria.
○: Arbitrary three points of openings were observed, and no irregular shape or crack of diameter was observed.
X: Arbitrary three points of openings are observed, and irregular shapes and cracks of diameter can be seen.

<Evaluation of insulation reliability>
The resin sheet produced in the example and the comparative example was laminated on a TAB tape of L / S = 15 μm / 15 μm using a batch-type vacuum laminator (VP 160, manufactured by Nichigo Morton Co.). The resin composition layer was cured by heating at 190 ° C. for 90 minutes in a batch type oven to obtain an insulating layer. The resistance value of the insulating layer after curing was measured and used as the initial resistance value. Then, it was left for 50 hours under the conditions of 130 ° C. and 85% Rh for 50 hours and 100 hours in a HAST tester (manufactured by Enomoto Chemical Co., Ltd., “ETAC PM422”), and the resistance value (HAST resistance value) after each time was measured. The initial resistance value, the resistance value after 50 hours, and the resistance value after 100 hours were compared, and the condition of the decrease in resistance value was evaluated based on the following criteria.
:: No drop in resistance observed even after 100 hours.
Δ: Hold the resistance value for 50 hours or more.
X: The resistance 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 laminate for evaluation, and was placed in a reflow furnace (manufactured by ANTOM, HAS-6116) in heat history of 260 ° C. or more for 1 minute or more. After passing through the inside of a reflow furnace three times, the water-soluble flux was washed with water at 60 ° C., and then visually observed, and swelling and peeling of the insulating layer were evaluated according to the following criteria.
○: No peeling or distortion of pattern was observed.
X: peeling or distortion of pattern occurs.

  From the results of the above table, it is understood that Examples 1 to 5 are excellent in the warp amount, the developability, the insulation reliability, and the solder heat resistance.

  In Comparative Examples 1 to 3 which do not contain the component (A), at least one of the warp amount, the developability, the insulation reliability, and the solder heat resistance is inferior to that of the example, and can not be used as a photosensitive resin composition. I understand that.

  (E) Comparative Example 4 which does not contain rubber particles has a warp amount inferior to that of Examples, and (B) Comparative Example 5 which does not contain solid epoxy resin has developability, insulation reliability and solder heat resistance that are higher than those of Examples. It is also inferior, and it can be seen that it can not be used as a photosensitive resin composition.

  (E) Comparative Example 6 in which a resin having a butadiene skeleton was added instead of the rubber particles was found to be inferior in developability to the examples and not usable as a photosensitive resin composition.

  In each of the examples, even when the components (F) to (I) and the like are not contained, it is confirmed that the results are similar to those of the above examples although there is a difference in degree.

Claims (13)

(A) A resin having a bisphenol skeleton, containing 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   The resin composition according to claim 1, wherein the content of the component (E) is 0.3% by mass or more and 30% by mass or less when the nonvolatile component in the resin composition is 100% by mass.   The resin composition according to claim 1, which is 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 nonvolatile 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 acyl phosphine oxide photopolymerization initiator or an oxime ester photopolymerization initiator.   The resin composition according to any one of claims 1 to 8, further comprising (F) a (meth) acrylic polymer having a glass transition temperature of -20 ° C or less.   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 claim 9.   The resin sheet which has a support body and the resin composition layer containing the resin composition of any one of Claims 1-10 provided on this support body.   A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 10, wherein the printed wiring board has a coreless structure.   A semiconductor device comprising the printed wiring board according to claim 12.