JP2022118633A - Photosensitive resin composition - Google Patents

Abstract

To provide a photosensitive resin composition or the like that has excellent developability, and can obtain a cured product in which occurrence of crack is suppressed.SOLUTION: A photosensitive resin composition contains: (A) resin containing ethylenic unsaturated group and carboxyl group; (B) inorganic filler; (C) photopolymerization initiator; (D) epoxy resin; and (E) photopolymerizable compound, where the content of component (B) is 30 mass% or more when the total solid content in photosensitive resin composition is 100 mass%, 10% grain diameter (D10) of component (B) in grain diameter distribution is 0.06 μm or more and 0.6 μm or less, 50% grain diameter (D50) is 0.11 μm or more and 1.10 μm or less, 90% grain diameter (D90) is 0.22 μm or more and 2.20 μm or less, and a refraction index of component (E) is 1.45 or more and 1.51 or less.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition. Furthermore, it relates to a support-attached photosensitive film, a printed wiring board, and a semiconductor device obtained by using the photosensitive resin composition.

A printed wiring board is sometimes provided with a solder resist as a permanent protective film to prevent solder from adhering to areas where solder is not required and to prevent corrosion of the circuit board. As a solder resist, for example, a photosensitive resin composition as described in Patent Document 1 is generally used.

JP 2014-115672 A

A photosensitive resin composition is generally required to have developability during development. Moreover, in recent years, the photosensitive resin composition is required to suppress the generation of cracks. In order to suppress the occurrence of cracks, a method of increasing the content of the inorganic filler is conceivable. However, when the content of the inorganic filler is increased, the adhesion between the layer formed from the photosensitive resin composition and the conductor layer tends to decrease. In addition, when a via hole is formed in a layer formed from a photosensitive resin composition, the light transmission is insufficient and the sensitivity at the bottom of the via hole is lowered, resulting in undercut, and light halation may cause the via hole to have a small diameter. It may become impossible to form, and resolution may fall.

An object of the present invention is to provide a photosensitive resin composition that is excellent in developability and that can obtain a cured product with adhesion between conductor layers and crack generation suppressed; obtained using the photosensitive resin composition, An object of the present invention is to provide a support-attached photosensitive film, a printed wiring board, and a semiconductor device.

As a result of intensive studies by the present inventors, it was found that by adjusting the particle size distribution of a predetermined amount of an inorganic filler and using it in combination with a photopolymerizable compound having a predetermined refractive index, excellent developability can be obtained, and the gap between the conductor layers can be improved. The present inventors have found that it is possible to obtain a cured product with adhesion and crack generation suppressed, and have completed the present invention.

［６］ （Ａ）成分が、クレゾールノボラック骨格、ナフタレン骨格、及びナフトールアラルキル骨格のいずれかを有する、［１］～［５］のいずれかに記載の感光性樹脂組成物。
［７］ （Ａ）成分が、酸変性ナフトールアラルキル骨格含有エポキシ（メタ）アクリレートを含む、［１］～［６］のいずれかに記載の感光性樹脂組成物。
［８］ （Ｄ）成分が、（Ｄ－１）軟化点が３０℃未満のエポキシ樹脂、及び（Ｄ－２）軟化点が３０℃以上のエポキシ樹脂を含む、［１］～［７］のいずれかに記載の感光性樹脂組成物。
［９］ 支持体と、該支持体上に設けられた、［１］～［８］のいずれかに記載の感光性樹脂組成物を含む感光性樹脂組成物層と、を有する支持体付き感光性フィルム。
［１０］ ［１］～［８］のいずれかに記載の感光性樹脂組成物の硬化物により形成された絶縁層を含むプリント配線板。
［１１］ 絶縁層が、層間絶縁材、及びソルダーレジストのいずれかである、［１０］に記載のプリント配線板。
［１２］ ［１０］又は［１１］に記載のプリント配線板を含む、半導体装置。 That is, the present invention includes the following contents.
[1] (A) a resin containing an ethylenically unsaturated group and a carboxyl group;
(B) an inorganic filler,
(C) a photoinitiator,
(D) an epoxy resin, and (E) a photopolymerizable compound,
A photosensitive resin composition containing
(B) The content of the component is 30% by mass or more when the total solid content in the photosensitive resin composition is 100% by mass,
The 10% particle size (D ₁₀ ) in the particle size distribution of the component (B) is 0.06 μm or more and 0.6 μm or less, the 50% particle size (D ₅₀ ) is 0.11 μm or more and 1.10 μm or less, and 90 % particle size (D ₉₀ ) is 0.22 μm or more and 2.20 μm or less,
The photosensitive resin composition, wherein the component (E) has a refractive index of 1.45 or more and 1.51 or less.
[2] When a via hole having a minimum opening diameter of R (μm) is formed in the cured product of the photosensitive resin composition, the particle diameter exposed on the wall surface of the via hole is (0.1 × R) μm or more (B) The photosensitive resin composition according to [1], wherein the number of components is 10 or less.
[3] The photosensitive resin composition according to [1] or [2], wherein the component (E) has a divalent cyclic structure.
[4] The photosensitive resin composition according to [3], wherein the divalent cyclic group has a heteroatom-containing alicyclic skeleton.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (E) contains a compound represented by the following formula (E-1).

[6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (A) has any one of a cresol novolac skeleton, a naphthalene skeleton, and a naphtholaralkyl skeleton.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein component (A) contains an epoxy (meth)acrylate containing an acid-modified naphthol aralkyl skeleton.
[8] Component (D) comprises (D-1) an epoxy resin having a softening point of less than 30°C, and (D-2) an epoxy resin having a softening point of 30°C or higher. The photosensitive resin composition according to any one of the above.
[9] A photosensitive material with a support, comprising a support and a photosensitive resin composition layer containing the photosensitive resin composition according to any one of [1] to [8] provided on the support. sex film.
[10] A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of [1] to [8].
[11] The printed wiring board according to [10], wherein the insulating layer is either an interlayer insulating material or a solder resist.
[12] A semiconductor device comprising the printed wiring board according to [10] or [11].

According to the present invention, a photosensitive resin composition capable of obtaining a cured product with excellent developability, adhesion between conductor layers, and suppressed crack generation; obtained using the photosensitive resin composition, A support-attached photosensitive film, a printed wiring board, and a semiconductor device can be provided.

The photosensitive resin composition, photosensitive film with support, printed wiring board, and semiconductor device of the present invention are described in detail below.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention includes (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler, (C) a photopolymerization initiator, (D) an epoxy resin, and (E ) A photosensitive resin composition containing a photopolymerizable compound, wherein the content of component (B) is 30% by mass or more when the total solid content in the photosensitive resin composition is 100% by mass. 10% particle size (D ₁₀ ) in the particle size distribution of component (B) is 0.06 μm or more and 0.6 μm or less, and 50% particle size (D ₅₀ ) is 0.11 μm or more and 1.10 μm or less , a 90% particle diameter (D ₉₀ ) of 0.22 μm or more and 2.20 μm or less, and a refractive index of the component (E) of 1.45 or more and 1.51 or less.

In the present invention, the particle size distribution of a predetermined amount of inorganic filler is adjusted as the component (B), a photopolymerizable compound having a predetermined refractive index is used as the component (E), and the components (A) and (C ) to (D) in combination, it is possible to obtain a photosensitive resin composition that is excellent in developability, has good adhesion to the conductor layer, and can give a cured product with suppressed cracking. can. In addition, it is usually possible to obtain a cured product with excellent average linear thermal expansion coefficient (CTE), dielectric constant, dielectric loss tangent, laser via opening property, and surface shape, and usually has a low minimum melt viscosity. It is possible to obtain a flexible resin composition, and it is also possible to improve the film form of the support-attached photosensitive film.

The photosensitive resin composition may further contain optional components such as (F) a curing accelerator, (G) a solvent, and (H) other additives, if necessary. Each component contained in the photosensitive resin composition will be described in detail below.

<(A) Resin Containing Ethylenically Unsaturated Group and Carboxyl Group>
The photosensitive resin composition contains (A) a resin containing an ethylenically unsaturated group and a carboxyl group. Developability can be improved by including the component (A) in the photosensitive resin composition.

Ethylenically unsaturated groups have a carbon-carbon double bond, and examples include vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide, nadimide, and (meth)acryloyl groups. and a (meth)acryloyl group is preferable from the viewpoint of the reactivity of photoradical polymerization. A "(meth)acryloyl group" includes a methacryloyl group, an acryloyl group, and combinations thereof. Since the component (A) contains an ethylenically unsaturated group, photoradical polymerization is possible. The number of ethylenically unsaturated groups per molecule of component (A) may be one or two or more. Moreover, when the component (A) contains two or more ethylenically unsaturated groups per molecule, those ethylenically unsaturated groups may be the same or different.

In addition, since the component (A) contains a carboxyl group, the photosensitive resin composition containing the component (A) is soluble in an alkaline solution (for example, a 1% by mass sodium carbonate aqueous solution as an alkaline developer). indicates The number of carboxyl groups per molecule of component (A) may be one or two or more.

Component (A) is not particularly limited as long as it is a compound that has an ethylenically unsaturated group and a carboxyl group and enables photoradical polymerization and alkali development. Resins that also have one or more ethylenically unsaturated groups are preferred.

One aspect of the resin containing an ethylenically unsaturated group and a carboxyl group includes an acid-modified unsaturated epoxy ester resin obtained by reacting an epoxy compound with an unsaturated carboxylic acid and further with an acid anhydride. Specifically, an unsaturated epoxy ester resin is obtained by reacting an epoxy compound with an unsaturated carboxylic acid, and an acid-modified unsaturated epoxy ester resin can be obtained by reacting the unsaturated epoxy ester resin with an acid anhydride.

As the epoxy compound, any compound having an epoxy group in the molecule can be used. For example, 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, bisphenol type epoxy resin such as modified bisphenol F type epoxy resin obtained by reacting epichlorohydrin with bisphenol F type epoxy resin to modify it to be trifunctional or higher; biphenol type epoxy resin, tetramethylbiphenol type, etc. Novolac epoxy resins such as phenol novolak epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, and alkylphenol novolac epoxy resins; bisphenol AF epoxy resins, and perfluoroalkyl epoxy resins Fluorine-containing epoxy resins such as resins; naphthalene type epoxy resin, dihydroxynaphthalene type epoxy resin, polyhydroxy binaphthalene type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, binaphthol type epoxy resin, naphthylene ether type epoxy resin naphthol Epoxy resins having a naphthalene skeleton (naphthalene skeleton-containing epoxy resins) such as novolac-type epoxy resins, naphthalene-type epoxy resins obtained by condensation reaction of polyhydroxynaphthalene and aldehydes; bixylenol-type epoxy resins; dicyclopentadiene-type epoxy resins trisphenol type epoxy resin; tert-butyl-catechol type epoxy resin; epoxy resin containing condensed ring skeleton such as anthracene type epoxy resin; glycidylamine type epoxy resin; glycidyl ester type epoxy resin; biphenyl type epoxy resin; Aliphatic epoxy resin; epoxy resin having a butadiene structure; alicyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexane dimethanol type epoxy resin; trimethylol type epoxy resin; Glycidyl group-containing acrylic resins such as polyglycidyl (meth)acrylate, copolymers of glycidyl methacrylate and acrylic acid ester; fluorene type epoxy resins; halogenated epoxy resins and the like.

From the viewpoint of reducing the average coefficient of linear thermal expansion, the epoxy compound is preferably an epoxy resin containing an aromatic skeleton. Here, the aromatic skeleton is a concept including polycyclic aromatics and aromatic heterocycles. Among them, naphthol aralkyl type epoxy resin, naphthalene skeleton-containing epoxy resin, epoxy resin containing condensed ring skeleton, biphenyl type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type Epoxy resins are preferred, and since the rigidity of the molecules is increased, the movement of the molecules is suppressed, and as a result, the average coefficient of linear thermal expansion of the cured product of the resin composition is further lowered. Epoxy resins and novolak-type epoxy resins are more preferred, and cresol novolak-type epoxy resins, naphthalene skeleton-containing epoxy resins, and naphthol aralkyl-type epoxy resins are even more preferred. As the naphthalene skeleton-containing epoxy resin, a dihydroxynaphthalene-type epoxy resin, a polyhydroxybinaphthalene-type epoxy resin, and a naphthalene-type epoxy resin obtained by a condensation reaction of polyhydroxynaphthalene and an aldehyde are preferable.

Dihydroxynaphthalene type epoxy resins include, for example, 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, 2,3-di glycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene and the like.

Examples of polyhydroxy binaphthalene type epoxy resins include 1,1′-bi-(2-glycidyloxy)naphthyl, 1-(2,7-diglycidyloxy)-1′-(2′-glycidyloxy)binaphthyl, 1,1'-bi-(2,7-diglycidyloxy) naphthyl and the like.

Examples of naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1′-bis(2,7-diglycidyloxynaphthyl)methane and 1-(2,7-diglycidyloxynaphthyl). )-1′-(2′-glycidyloxynaphthyl)methane and 1,1′-bis(2-glycidyloxynaphthyl)methane.

Among these, polyhydroxybinaphthalene-type epoxy resins having two or more naphthalene skeletons in one molecule and naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes are preferred, and in particular epoxy 1,1′-bis(2,7-diglycidyloxynaphthyl)methane having 3 or more groups, 1-(2,7-diglycidyloxynaphthyl)-1′-(2′-glycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxy)-1'-(2'-glycidyloxy) binaphthyl and 1,1'-bis-(2,7-diglycidyloxy) naphthyl have 1,1′-bis(2,7-diglycidyloxynaphthyl)methane is more preferable because of its excellent heat resistance.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, cinnamic acid and crotonic acid, and 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 photosensitive resin composition. In this specification, the epoxy ester resin that is the reaction product of the above epoxy compound and (meth)acrylic acid may be referred to as "epoxy (meth)acrylate", where the epoxy group of the epoxy compound is It is substantially extinguished by the reaction with (meth)acrylic acid. "(Meth)acrylate" refers to methacrylate and acrylate. Acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth)acrylic acid".

Examples of acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid di Anhydrides, etc., may be mentioned, and any one of these may be used alone, or two or more thereof may be used in combination. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferred from the viewpoint of improving the resolution and insulation reliability of the cured product, and tetrahydrophthalic anhydride is more preferred.

In obtaining an acid-modified unsaturated epoxy ester resin, an unsaturated carboxylic acid and an epoxy resin are reacted in the presence of a catalyst to obtain an unsaturated epoxy ester resin, and then the unsaturated epoxy ester resin is reacted with an acid anhydride. good too. Moreover, you may use a solvent and a polymerization inhibitor as needed.

The acid-modified unsaturated epoxy ester resin preferably has a cresol novolac skeleton, a naphthalene skeleton, or a naphthol aralkyl skeleton. Acid-modified epoxy (meth)acrylate is preferable as the acid-modified unsaturated epoxy ester resin. The “epoxy” in the acid-modified unsaturated epoxy ester resin represents a structure derived from the epoxy compound described above. For example, "acid-modified bisphenol-type epoxy (meth)acrylate" is an acid-modified unsaturated epoxy ester resin obtained by using a bisphenol-type epoxy resin as an epoxy compound and using (meth)acrylic acid as an unsaturated carboxylic acid. point to The preferred range of acid-modified epoxy (meth)acrylates is derived from the preferred range of epoxy compounds. That is, from the viewpoint of lowering the average coefficient of linear thermal expansion of the cured product of the resin composition, the acid-modified unsaturated epoxy ester resin includes an acid-modified naphthalene skeleton-containing epoxy (meth)acrylate and an acid-modified cresol novolak skeleton-containing epoxy (meth)acrylate. Acrylates and epoxy (meth)acrylates containing an acid-modified naphthol aralkyl skeleton are preferred, and epoxy (meth)acrylates containing an acid-modified naphthalene skeleton are more preferred. Acid-modified naphthalene skeleton-containing epoxy (meth)acrylate is a compound obtained by reacting a reaction product of naphthalene-type epoxy resin and (meth)acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. . Acid-modified cresol novolak skeleton-containing epoxy (meth)acrylate is a compound obtained by reacting an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride with a reaction product of a cresol novolac-type epoxy resin and (meth)acrylate. is. Acid-modified naphthol aralkyl skeleton-containing epoxy (meth) acrylate is a compound obtained by reacting a reaction product of naphthol aralkyl epoxy resin and (meth) acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. is.

Such an acid-modified unsaturated epoxy ester resin can be a commercially available product, and a specific example is "ZAR-2000" manufactured by Nippon Kayaku Co., Ltd. reaction product), “ZFR-1491H”, “ZFR-1533H” (bisphenol F type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride reaction product), Showa Denko “PR-300CP” (cresol novolac type epoxy reaction product of resin, acrylic acid, and acid anhydride), Nippon Kayaku Co., Ltd. “CCR-1179” (cresol novolac F type epoxy acrylate), “ZCR-1569H” (acid-modified biphenyl type epoxy acrylate: biphenyl type epoxy reaction product of resin, acrylic acid, and acid anhydride), Nippon Kayaku Co., Ltd. “CCR-1171H” (cresol novolak type epoxy acrylate), 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 component (A) is preferably 1000 or more, more preferably 1500 or more, and even more preferably 2000 or more, from the viewpoint of film-forming properties. From the viewpoint of developability, the upper limit is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,500 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 0.1 mgKOH/g or more, more preferably 0.5 mgKOH/g or more, from the viewpoint of improving the alkali developability of the photosensitive resin composition. is more preferable, and 1 mgKOH/g or more is even more preferable. On the other hand, the acid value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, from the viewpoint of suppressing the elution of the fine pattern of the cured product by development and improving the insulation reliability. It is preferably 100 mgKOH/g or less, and more preferably 100 mgKOH/g or less. Here, the acid value is the residual acid value of the carboxyl groups present in the component (A), and the acid value can be measured by the following method. First, about 1 g of the resin solution to be measured is accurately 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 as an indicator is added to the solution, and titration is performed using a 0.1N aqueous ethanol solution. Then, the acid value is calculated by the following formula.
Formula: A = 10 x (Vf-BL) x F x 56.11 / (Wp x I)

In the above formula, A represents the acid value (mgKOH / g), Vf is the titration amount of KOH (mL), BL is the blank, F is the factor (potency), and Wp is the measured resin solution mass (g). and I represents the non-volatile content (% by mass) of the measured resin solution.

In the production of component (A), from the viewpoint of improving storage stability, the ratio of the number of moles of epoxy groups in the epoxy resin to the number of moles of the total carboxyl groups of the unsaturated carboxylic acid and the acid anhydride is 1. : It is preferably in the range of 0.8 to 1.3, more preferably in the range of 1:0.9 to 1.2.

From the viewpoint of improving alkali developability, the content of component (A) is preferably 5% by mass or more, and 8% by mass or more, when the non-volatile component of the photosensitive resin composition is 100% by mass. more preferably 10% by mass or more. From the viewpoint of improving heat resistance, the upper limit is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. In the present invention, the content of each component in the photosensitive resin composition is a value when the non-volatile component in the photosensitive resin composition is 100% by mass, unless otherwise specified.

<(B) Inorganic filler>
The photosensitive resin composition contains (B) an inorganic filler as the (B) component. Component (B) has a 10% particle size (D ₁₀ ) of 0.06 μm or more and 0.6 μm or less and a 50% particle size (D ₅₀ ) of 0.11 μm or more in the particle size distribution of component (B). It is 10 μm or less, and the 90% particle diameter (D ₉₀ ) is 0.22 μm or more and 2.20 μm or less. By including an inorganic filler having such a particle size distribution in the photosensitive resin composition, it is possible to suppress developability, adhesion, and crack generation even when the content of the inorganic filler is increased. In addition, the said particle size distribution represents the particle size distribution of the whole (B) inorganic filler contained in a photosensitive resin composition.

The particle size distribution of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler was created on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and 10% particle size (D ₁₀ ), 50% particle size (D ₅₀ ), and 90% Particle size ( _D90 ) can be measured. As a measurement sample, an inorganic filler dispersed in water or methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction/scattering type particle size distribution analyzer, "LA-500" manufactured by Horiba Ltd., "SALD-2200" manufactured by Shimadzu Corporation, etc. can be used.

The 10% particle size (D ₁₀ ) in the particle size distribution means that, as a result of measuring the particle size distribution by the above method, in the particle size distribution curve, the cumulative volume accumulated from the smaller particle size side is 10%. It refers to the particle size when The 50% particle size (D ₅₀ ) is the particle size at which the cumulative volume accumulated from the smaller particle size side becomes 50% in the particle size distribution curve as a result of measuring the particle size distribution by the above method. Say. In addition, the 90% particle size (D ₉₀ ) is the result of measuring the particle size distribution by the above method, and in the particle size distribution curve, when the cumulative amount of the volume accumulated from the small particle size side is 90%. Particle size. Here, the average particle size of the inorganic filler (B) means the particle size of the 50% particle size (D ₅₀ ). Hereinafter, the 10% particle size (D ₁₀ ) is sometimes referred to as D ₁₀ , the 50% particle size (D ₅₀ ) as D ₅₀ , and the 90% particle size (D ₉₀ ) as D ₉₀ .

_D10 in the particle size distribution is 0.06 μm or more, preferably 0.08 μm or more, more preferably 0.10 μm or more, from the viewpoint of suppressing actinic ray scattering and improving resolution. The upper limit is 0.6 μm or less, preferably 0.58 μm or less, more preferably 0.55 μm or less.

_D50 in the particle size distribution is 0.11 μm or more, preferably 0.13 μm or more, more preferably 0.15 μm or more, from the viewpoint of suppressing actinic ray scattering and improving resolution. The upper limit is 1.10 μm or less, preferably 1.05 μm or less, more preferably 1.00 μm or less.

_D90 in the particle size distribution is 0.22 μm or more, preferably 0.24 μm or more, more preferably 0.25 μm or more, from the viewpoint of suppressing actinic ray scattering and improving resolution. The upper limit is 2.20 μm or less, preferably 2.00 μm or less, more preferably 1.80 μm or less.

D ₅₀ -D ₁₀ is preferably 0.01 μm or more, more preferably 0.02 μm or more, still more preferably 0.03 μm or more, from the viewpoint of significantly obtaining the effects of the present invention. The upper limit is preferably 1.20 μm or less, more preferably 1.00 μm or less, and even more preferably 0.80 μm or less.

D ₉₀ -D ₁₀ is preferably 0.05 μm or more, more preferably 0.08 μm or more, still more preferably 0.10 μm or more, from the viewpoint of significantly obtaining the effects of the present invention. The upper limit is preferably 1.60 μm or less, more preferably 1.40 μm or less, still more preferably 1.20 μm or less.

D ₉₀ -D ₅₀ is preferably 0.04 μm or more, more preferably 0.06 μm or more, still more preferably 0.08 μm or more, from the viewpoint of significantly obtaining the effects of the present invention. The upper limit is preferably 2.00 μm or less, more preferably 1.50 μm or less, still more preferably 1.00 μm or less.

D ₉₀ /D ₅₀ is preferably 2.4 or less, more preferably 2.2 or less, and still more preferably 1.8 or less from the viewpoint of significantly obtaining the effects of the present invention. The lower limit is preferably 1.0 or more, more preferably 1.1 or more, and still more preferably 1.2 or more.

D ₉₀ /D ₁₀ is preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.0 or less from the viewpoint of significantly obtaining the effects of the present invention. The lower limit is preferably 1.0 or more, more preferably 1.2 or more, and still more preferably 1.5 or more.

D ₅₀ /D ₁₀ is preferably 3.0 or less, more preferably 2.5 or less, and still more preferably 2.0 or less from the viewpoint of significantly obtaining the effects of the present invention. The lower limit is preferably 1.0 or more, more preferably 1.1 or more, and still more preferably 1.2 or more.

(B) The content of the inorganic filler suppresses the occurrence of cracks, and from the viewpoint of obtaining a cured product with high adhesion and a low average linear thermal expansion coefficient, the non-volatile component in the photosensitive resin composition is 100% by mass. , it is 30% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more, and 55% by mass or more. The upper limit is 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, from the viewpoint of suppressing light reflection.

The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and 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, and zirconium tungstate phosphate. Among these, silica, alumina and barium sulfate are preferred, and silica is particularly preferred. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

(B) An inorganic filler can use a commercial item. (B) Examples of commercially available inorganic fillers include "Admafine" manufactured by Admatechs, "SFP series" manufactured by Denki Kagaku Kogyo, "SP (H) series" manufactured by Nippon Steel & Sumikin Materials, and Sakai Chemical Industry. "Sciqas Series" manufactured by Nippon Shokubai Co., Ltd., "Seahoster Series" manufactured by Nippon Shokubai Co., Ltd., and "SG-SO Series" manufactured by Sukgyuug. "AX series" and the like, and commercial products of barium sulfate include "B series" and "BF series" manufactured by Sakai Chemical Industry Co., Ltd., and the like.

(B) The inorganic filler can be obtained by classifying a plurality of inorganic fillers with a classifier or the like to obtain an inorganic filler having a desired average particle size.

From the viewpoint of obtaining excellent resolution, the specific surface area of the inorganic filler is 3.0 m ² /g or more, preferably 4.0 m ² /g or more, more preferably 5 m ² /g or more. The upper limit of the specific surface area is 40 m ² /g or less, preferably 30 m ² /g or less, more preferably 28 m ² /g or less, still more preferably 25 m ² /g or less, from the viewpoint of melt viscosity and the like. . The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. obtained by

Inorganic fillers include vinylsilane-based coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, and alkoxysilane compounds from the viewpoint of improving moisture resistance and dispersibility. , an organosilazane compound, and a titanate-based coupling agent. Examples of commercially available surface treatment agents include "KBM1003" (vinyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. methoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent) and the like.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of suppressing the melt viscosity of the resin varnish and the melt viscosity in the sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and further preferably 0.5 mg/m ² or less. preferable.

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

<(C) Photoinitiator>
The photosensitive resin composition contains (C) a photopolymerization initiator as the (C) component. By containing the component (C), the photosensitive resin composition can be efficiently photocured. (C) component may be used individually by 1 type, or may use 2 or more types together.

Component (C) is not particularly limited, but examples include 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]-2-morpholinopropan-1-one and other α-aminoalkylphenones Photopolymerization initiator; oxime ester photopolymerization initiator such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, 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-diphenylethan-1-one, 1 -[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2, 4,6-trimethylbenzoyl)-phenylphosphine oxide and the like, and sulfonium salt photopolymerization initiators and the like can also be used. Any one of these may be used alone, or two or more thereof may be used in combination.

Further, the photosensitive resin composition contains, in combination with the component (C), N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4- It may contain tertiary amines such as dimethylaminobenzoate, triethylamine, triethanolamine, etc., and may contain photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, thioxanthones, etc. good too. Any one of these may be used alone, or two or more thereof may be used in combination.

Specific examples of the component (C) include "Omnirad907", "Omnirad369", "Omnirad379", "Omnirad819" and "OmniradTPO" manufactured by IGM, and "IrgacureTPO", "IrgacureOXE-01" and "IrgacureOXE" manufactured by BASF. -02”, and “N-1919” manufactured by ADEKA.

From the viewpoint of sufficiently photocuring the photosensitive resin composition and improving insulation reliability, the content of the component (C) is preferably 0 when the non-volatile component of the photosensitive resin composition is 100% by mass. 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. On the other hand, the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less, from the viewpoint of suppressing deterioration in resolution due to excessive sensitivity.

<(D) epoxy resin>
The photosensitive resin composition contains (D) an epoxy resin as the (D) component. Insulation reliability can be improved by including the component (D). However, the component (D) here does not include epoxy resins containing ethylenically unsaturated groups and carboxyl groups. (D) component may be used individually by 1 type, or may use 2 or more types together.

Epoxy resin (D) can be an epoxy resin other than an epoxy resin containing an ethylenically unsaturated group and a carboxyl group. It preferably contains an epoxy resin with a softening point of less than 30°C and (D-2) an epoxy resin with a softening point of 30°C or higher.

The softening point of component (D-1) is preferably less than 30° C., more preferably 25° C. or less, still more preferably 20° C. or less, from the viewpoint of significantly obtaining the effects of the present invention. Although the lower limit is not particularly limited, it is preferably 0° C. or higher, more preferably 5° C. or higher, and still more preferably 10° C. or higher. A softening point can be measured according to JIS K7234.

Component (D-1) preferably has one or more epoxy groups in one molecule, and preferably has two or more epoxy groups in one molecule, from the viewpoint of significantly obtaining the effects of the present invention. More preferably, it has 3 or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile components of the component (D-1) is preferably 50. % by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

Component (D-1) includes a component that is liquid at a temperature of 20°C and a component that is solid at a temperature of 20°C. Component (D-1) is preferably in a liquid form from the viewpoint of significantly obtaining the effects of the present invention.

Component (D-1) preferably has a cyclic structure from the viewpoint of obtaining the effects of the present invention remarkably. The cyclic structure includes an aromatic ring structure, an alicyclic structure, and the like. Aromatic ring structures include benzene ring, naphthalene ring, anthracene ring and the like. The alicyclic structure includes cyclohexane ring, cyclopentane ring, cycloheptane ring, cyclooctane ring and the like. Among them, the cyclic structure is preferably an aromatic ring structure, more preferably a naphthalene ring or a benzene ring, and still more preferably a naphthalene ring.

Examples of component (D-1) include naphthalene-type epoxy resins, glycidylamine-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol AF-type epoxy resins, glycidyl ester-type epoxy resins, and phenol novolak. type epoxy resins, glycidylcyclohexane type epoxy resins, isocyanuric ring type epoxy resins, naphthylene ether type epoxy resins, and the like. Naphthalene type epoxy resins and glycidylamine type epoxy resins are preferred, and naphthalene type epoxy resins are more preferred.

Specific examples of the component (D-1) include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC; "ELM-434L" (glycidylamine type epoxy resin) manufactured by Sumitomo Chemical Co., Ltd.; ); "630" manufactured by Mitsubishi Chemical Corporation (glycidylamine type epoxy resin); "ZX1658GS" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (liquid 1,4-glycidylcyclohexane type epoxy resin); "EP-3980S" manufactured by ADEKA Corporation ( Bifunctional glycidylamine type epoxy resin); ADEKA "EP-3950L" (trifunctional glycidylamine type epoxy resin); Nissan Chemical Co., Ltd. "TEPIC-VL" (isocyanuric ring type epoxy resin); Sumitomo Chemical Co., Ltd. "ELM-100H" (N-[2-methyl-4-(oxiranylmethoxy)phenyl]-N-(oxiranylmethyl)oxiranemethanamine); DIC's "EXA-7311-G4" (naphth lene ether type 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 epoxy equivalent of component (D-1) is preferably 150 g/eq. from the viewpoint of significantly obtaining the effects of the present invention. Below, more preferably 148 g/eq. Below, more preferably 145 g/eq. or less, preferably 10 g/eq. above, more preferably 50 g/eq. above, more preferably 100 g/eq. That's it. The epoxy equivalent of component (D) is the mass of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of component (D-1) is preferably 100 or more, more preferably 200 or more, still more preferably 250 or more, and preferably 5000, from the viewpoint of significantly obtaining the desired effects of the present invention. Below, more preferably 3000 or less, still more preferably 1500 or less. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of component (D-1) is preferably 10% by mass or more, more preferably 10% by mass or more, and more preferably 20% by mass or more, more preferably 30% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, 60% by mass or less, 50% by mass or less, or 40% by mass or less % by mass or less.

The content of the component (D-1) is such that the non-volatile component in the photosensitive resin composition is 100% by mass from the viewpoint of obtaining a cured product excellent in insulation, dielectric constant and dielectric loss tangent in addition to developability. is preferably 1% by mass or more, more preferably 1.5% by mass or more, still more preferably 2% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass. It is below.

The softening point of component (D-2) is preferably 30° C. or higher, more preferably 35° C. or higher, and even more preferably 40° C. or higher, from the viewpoint of significantly obtaining the effects of the present invention. The upper limit is less than 59°C, preferably 57°C or less, and more preferably 55°C or less, from the viewpoint of significantly obtaining the effects of the present invention. The softening point can be measured by the same method as for component (D-1).

Component (D-2) preferably has one or more epoxy groups in one molecule, and preferably has two or more epoxy groups in one molecule, from the viewpoint of significantly obtaining the effects of the present invention. More preferably, it has 3 or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile components of the component (D-2) is preferably 50. % by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

Component (D-2) is preferably solid at a temperature of 20°C.

As component (D-2), an epoxy resin having a softening point of 30° C. or higher can be used. Such an epoxy resin preferably has a cyclic structure from the viewpoint of significantly obtaining the effects of the present invention. The cyclic structure includes an aromatic ring structure, an alicyclic structure, and the like. Aromatic ring structures include benzene ring, naphthalene ring, anthracene ring, biphenyl and the like. The alicyclic structure includes cyclohexane ring, cyclopentane ring, cycloheptane ring, cyclooctane ring and the like. Among them, the cyclic structure is preferably an aromatic ring structure, more preferably a benzene ring or a biphenyl ring, and still more preferably a biphenyl ring.

Further, the (D-2) component includes, for example, biphenyl-type epoxy resins, dicyclopentadiene-type epoxy resins, naphthylene ether-type epoxy resins, etc. Biphenyl-type epoxy resins are more preferable.

Specific examples of the component (D-2) include "NC3000L" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku; "HP-7200L" (dicyclopentadiene-type epoxy resin) and "HP-6000L" manufactured by DIC. (naphthylene ether type epoxy resin); Nippon Kayaku's "NC3000" (biphenyl type 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 epoxy equivalent of component (D-2) is preferably 50 g/eq. ~5000g/eq. , more preferably 50 g/eq. ~3000g/eq. , more preferably 80 g/eq. ~2000 g/eq. , even more preferably 110 g/eq. ~1000g/eq. is. Within this range, the crosslink density of the cured product of the photosensitive resin composition layer is sufficient, and an insulating layer with a small surface roughness can be obtained.

The weight average molecular weight (Mw) of component (D-2) is preferably 100 or more, more preferably 200 or more, still more preferably 250 or more, and preferably 5000, from the viewpoint of significantly obtaining the desired effects of the present invention. Below, more preferably 3000 or less, still more preferably 1500 or less.

The content of component (D-2) is preferably 10% by mass or more, more preferably 20% by mass or more, when the entire component (D) is 100% by mass, from the viewpoint of obtaining adhesion in addition to insulation. , More preferably 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less .

From the viewpoint of obtaining adhesion in addition to insulation, the content of component (D-2) is preferably 1% by mass or more, more preferably 1% by mass or more, when the non-volatile component in the photosensitive resin composition is 100% by mass. It is 1.5% by mass or more, more preferably 2% by mass or more, preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less.

The content of the component (D) is preferably 1% by mass or more, more preferably 3% by mass, based on 100% by mass of the non-volatile components in the photosensitive resin composition, from the viewpoint of significantly obtaining the effects of the present invention. Above, more preferably 5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.

(D-1) The content when the non-volatile component in the photosensitive resin composition of component (D-1) is 100% by mass is D1, and the non-volatile component in the photosensitive resin composition of component (D-2) is 100% by mass. When the content is D2, D2/D1 is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.2 or more, preferably 3.5 or less, and more It is preferably 3.0 or less, more preferably 2.5 or less. The desired effect of the present invention can be remarkably obtained by setting the amount ratio of the component (D-1) to the component (D-2) within such a range.

<(E) Photopolymerizable compound>
The photosensitive resin composition contains (E) a photopolymerizable compound as the (E) component. However, those corresponding to the (A) component are excluded. Photoreactivity can be improved by including the component (E). Component (E) may be used alone or in combination of two or more.

Component (E) has a refractive index of 1.45 or higher, preferably 1.46 or higher, and more preferably 1.47 or higher. The upper limit of the refractive index is 1.51 or less, preferably 1.508 or less, more preferably 1.505 or less. Generally, the refractive index of (B) the inorganic filler is 1.45 or more and 1.51 or less. The present inventors found that by bringing the refractive index of the component (E) close to the refractive index of the inorganic filler (B), it is possible to suppress the deterioration of the shape of the via hole, thereby making it possible to open a via hole with a small diameter. I found that it is possible. The refractive index can be measured according to the method described in Examples below.

As the component (E), a compound that can be photopolymerized by irradiation with actinic rays can be used. As such a compound, for example, a liquid, solid or semi-solid photosensitive (meth)acrylate compound at room temperature having one or more (meth)acryloyl groups in one molecule can be used. Room temperature represents about 25°C. A "(meth)acryloyl group" refers to an acryloyl group and a methacryloyl group.

A preferred embodiment of component (E) is a photosensitive (meth)acrylate compound having a divalent cyclic structure and a refractive index of 1.45 or more and 1.51 or less. The divalent cyclic group may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Among them, a cyclic group containing an alicyclic structure is preferable from the viewpoint of significantly obtaining the desired effects of the present invention.

From the viewpoint of significantly obtaining the desired effect of the present invention, the divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, still more preferably a 5-membered ring or more, and preferably a 20-membered ring. Below, it is more preferably a 15-membered ring or less, still more preferably a 10-membered ring or less. Moreover, the divalent cyclic group may have a monocyclic structure or a polycyclic structure.

The ring in the divalent cyclic group may have a ring skeleton composed of heteroatoms other than carbon atoms, and the divalent cyclic group preferably has a heteroatom-containing alicyclic skeleton. The heteroatom includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc., and an oxygen atom is preferred. The ring may have one heteroatom, or may have two or more.

２価の環状基は、置換基を有していてもよい。このような置換基としては、例えば、ハロゲン原子、アルキル基、アルコキシ基、アリール基、アリールアルキル基、シリル基、アシル基、アシルオキシ基、カルボキシ基、スルホ基、シアノ基、ニトロ基、ヒドロキシ基、メルカプト基、オキソ基等が挙げられ、アルキル基が好ましい。 Specific examples of divalent cyclic groups include the following divalent groups (i) to (x). Among them, (x) is preferable as the divalent cyclic group.

The bivalent cyclic group may have a substituent. Examples of such substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxy groups, sulfo groups, cyano groups, nitro groups, hydroxy groups, A mercapto group, an oxo group and the like can be mentioned, and an alkyl group is preferred.

The (meth)acryloyl group may be directly bonded to the divalent cyclic group, or may be bonded via a divalent linking group. Examples of divalent linking groups include alkylene groups, alkenylene groups, arylene groups, heteroarylene groups, -C(=O)O-, -O-, -NHC(=O)-, and -NC(=O). Examples include N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, and -NH-, and may be a group combining a plurality of these. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms. is more preferred. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, 1,1-dimethylethylene group and the like. - dimethylethylene group is preferred. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and even more preferably an alkenylene group having 2 to 5 carbon atoms. As the arylene group and heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferable. As the divalent linking group, an alkylene group is preferable, and a methylene group and a 1,1-dimethylethylene group are particularly preferable.

（式（Ｅ）中、Ｒ^１及びＲ^４はそれぞれ独立にアクリロイル基又はメタクリロイル基を表し、Ｒ^２及びＲ^３はそれぞれ独立に２価の連結基を表す。環Ａは、２価の環状基を表す。） The photosensitive (meth)acrylate compound having a divalent cyclic structure and a refractive index of 1.45 or more and 1.51 or less is preferably represented by the following formula (E).

(In formula (E), R ¹ and R ⁴ each independently represent an acryloyl group or a methacryloyl group, R ² and R ³ each independently represent a divalent linking group. Ring A is a divalent cyclic group. represents.)

R ¹ and R ⁴ each independently represent an acryloyl group or a methacryloyl group, preferably an acryloyl group.

R ² and R ³ each independently represent a divalent linking group. The divalent linking group is the same as the divalent linking group to which the (meth)acryloyl group may be bonded.

Ring A represents a divalent cyclic group. Ring A is the same as the divalent cyclic group described above. Ring A may have a substituent. The substituent is the same as the substituent that the divalent cyclic group may have.

Specific examples of the photosensitive (meth)acrylate compound having a divalent cyclic structure and a refractive index of 1.45 to 1.51 include compounds represented by formula (E-1). The invention is not limited to this.

Photosensitive (meth) acrylate compounds having a divalent cyclic structure and a refractive index of 1.45 to 1.51 may be commercially available products, for example, Shin-Nakamura Chemical Co., Ltd. "A- DOG” (compound represented by formula (E-1)), Nippon Kayaku Co., Ltd. “NPDGA”, “FM-400”, “R-687”, “THE-330”, “PET-30”, etc. mentioned.

Another embodiment of component (E) is a photosensitive (meth)acrylate compound that does not have a divalent cyclic structure and has a refractive index of 1.45 or more and 1.51 or less. Examples of such compounds include heterocyclic ring-containing acrylates such as dioxane glycol diacrylate and 4-acryloylmorpholine; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; Glycol mono- or diacrylates such as ethylene glycol, polyethylene glycol, propylene glycol and neopentyl glycol; acrylamides such as N,N-dimethylacrylamide and N-methylolacrylamide; aminoalkyls such as N,N-dimethylaminoethyl acrylate. Acrylates, polyhydric alcohols such as trimethylolpropane, pentaerythritol and dipentaerythritol, or polyhydric acrylates of these adducts of ethylene oxide, propylene oxide or ε-caprolactone; phenols such as phenoxy acrylate and phenoxyethyl acrylate, or acrylates such as ethylene oxide or propylene oxide adducts thereof; epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether; melamine acrylates; and/or methacrylates corresponding to the above acrylates. . Among these, alkyl acrylates and heterocyclic ring-containing acrylates are preferred.

Component (E) preferably contains a compound represented by formula (E-1) from the viewpoint of significantly obtaining the effects of the present invention.

The content of component (E) is preferably 0.5% by mass or more, more preferably 0.5% by mass or more, when the non-volatile component of the photosensitive resin composition is 100% by mass, from the viewpoint of effectively improving developability and adhesion. is 1% by mass or more, more preferably 3% by mass or more, preferably 10% by mass or less, more preferably 9% by mass or less, and even more preferably 8% by mass or less. Further, when the amount of the component (E) is within the above range, it is usually possible to accelerate the photocuring of the photosensitive resin composition and to suppress stickiness when the photosensitive resin composition is cured.

<(F) Curing accelerator>
The photosensitive resin composition may contain (F) a curing accelerator as an optional component in addition to the components described above. (F) component may be used individually by 1 type, and may be used in combination of 2 or more types.

Component (F) includes, for example, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

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

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and the like, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of guanidine curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

From the viewpoint of significantly obtaining the desired effects of the present invention, the content of component (F) is preferably 0.001% by mass or more, more preferably 0%, when the non-volatile component in the resin composition is 100% by mass. 005% by mass or more, more preferably 0.01% by mass or more, preferably 0.15% by mass or less, more preferably 0.12% by mass or less, and even more preferably 0.1% by mass or less.

<(F) Organic solvent>
The photosensitive resin composition may further contain (F) an organic solvent. The varnish viscosity can be adjusted by including the component (F). (F) Examples of organic solvents include ketones such as methyl ethyl ketone (MEK) and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, and propylene. Glycol ethers such as glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether Esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate and ethyl diglycol acetate , octane, and decane; and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These are used individually by 1 type or in combination of 2 or more types. When using an organic solvent, the content can be appropriately adjusted from the viewpoint of coating properties of the photosensitive resin composition.

<(G) Other additives>
The photosensitive resin composition may further contain (G) other additives to the extent that the object of the present invention is not impaired. (G) Other additives include, for example, thermoplastic resins, organic fillers, fine particles such as melamine and organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, Colorants such as naphthalene black, polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol and pyrogallol, thickeners such as bentone and montmorillonite, silicone-based, fluorine-based, and vinyl resin-based defoaming agents, Flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphate esters, halogen-containing condensed phosphate esters, phenolic curing agents, heat such as cyanate ester curing agents Various additives such as curable resins can be added.

The photosensitive resin composition is prepared by mixing the above (A) to (E) components as essential components, and appropriately mixing the above (F) to (G) components as optional components. The resin varnish can be produced by kneading or stirring with kneading means such as a ball mill, bead mill or sand mill, or stirring means such as a super mixer or planetary mixer.

<Physical properties and uses of the photosensitive resin composition>
The minimum melt viscosity of the photosensitive resin composition is preferably 10,000 poise or less, more preferably 8,000 poise or less, and even more preferably 5,000 poise or less. Although the lower limit is not particularly limited, it can be set to 10 poise or more. Here, the term "minimum melt viscosity" refers to the minimum melt viscosity between 60°C and 200°C. The minimum melt viscosity can be measured using a dynamic viscoelasticity measuring device. A specific example of the dynamic viscoelasticity measuring device is "Rheosol-G3000" manufactured by UBM. For the lowest melt viscosity, for example, using a dynamic viscoelasticity measuring device, a parallel plate with a diameter of 18 mm is used for 1 g of the sample, and the starting temperature is 60 ° C. to 200 ° C. at a heating rate of 5 ° C./min. It can be measured under the measurement conditions of a temperature interval of 2.5° C., a frequency of 1 Hz, and a strain of 1 deg.

A cured product obtained by photocuring the photosensitive resin composition and then thermally curing the composition at 190° C. for 90 minutes usually exhibits a low average coefficient of linear thermal expansion (CTE). That is, an insulating layer and a solder resist having a low average linear thermal expansion coefficient are obtained. The average coefficient of linear thermal expansion is preferably 55 ppm or less, more preferably 50 ppm or less, still more preferably 45 ppm or less. Although the lower limit is not particularly limited, it may be 10 ppm or more. The average linear thermal expansion coefficient can be measured according to the method described in Examples below.

A cured product obtained by photocuring the photosensitive resin composition of the present invention and then thermally curing the composition at 190° C. for 90 minutes usually exhibits a low dielectric constant. That is, it results in insulating layers and solder resists with low dielectric constants. The dielectric constant is preferably 3.5 or less, more preferably 3.4 or less, still more preferably 3.3 or less. Although the lower limit is not particularly limited, it may be 0.1 or more. The dielectric constant can be measured according to the method described in Examples below.

A cured product obtained by photocuring the photosensitive resin composition of the present invention and then thermally curing the composition at 190° C. for 90 minutes usually exhibits a low dielectric loss tangent. That is, an insulating layer and a solder resist having a low dielectric loss tangent are obtained. The dielectric loss tangent is preferably 0.03 or less, more preferably 0.020 or less, still more preferably 0.015 or less. Although the lower limit is not particularly limited, it may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in Examples below.

The photosensitive resin composition exhibits excellent developability even when the content of the inorganic filler is large. Specifically, when the photosensitive resin composition is exposed and developed, it is possible to prevent the resin from remaining in the unexposed areas. The evaluation of the residue in the unexposed area can be evaluated according to the method described in Examples below.

The photosensitive resin composition exhibits excellent developability even when the content of the inorganic filler is large. Specifically, when a via hole is formed by exposing and developing the photosensitive resin composition, the minimum opening diameter (minimum via diameter) of the via hole that can be formed without causing residue and peeling can be reduced. The minimum opening diameter is preferably 60 μm or less, more preferably 45 μm or less, and even more preferably 40 μm or less. Although the lower limit is not particularly limited, it can be, for example, 1 μm or more. The minimum aperture diameter can be measured according to the method described in Examples below.

The photosensitive resin composition exhibits excellent developability even when the content of the inorganic filler is large. Specifically, when a via hole is formed by exposing and developing a photosensitive resin composition, the number of inorganic fillers exposed from the wall of the via hole (hereinafter sometimes referred to as "via wall") is reduced. can. Specifically, let R (μm) be the minimum opening diameter of the via hole. The number of inorganic fillers having a particle diameter of (0.1×R) or more exposed from the via wall was counted. In this case, the number of inorganic fillers having a particle diameter of (0.1×R) or more exposed from the via wall is less than 10 pieces. For example, the number of component (B) having a particle size of 1 μm or more on the wall surface of a via hole with a minimum opening diameter of 10 μm is preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less. Although the lower limit is not particularly limited, it may be 0 or more. Evaluation of the via wall can be measured according to the method described in the examples below.

The photosensitive resin composition exhibits excellent developability even when the content of the inorganic filler is large. Specifically, when a via hole is formed by exposing and developing a photosensitive resin composition, a tapered via hole can be formed. Shaped via holes can be formed. A tapered shape means a shape in which the diameter of the top corresponding to the opening of the via hole is larger than the diameter of the bottom corresponding to the bottom of the via hole, unless otherwise specified. Specifically, the top radius (μm) and the bottom radius (μm) of the cross section of the via hole are measured by SEM. Find the difference between the top radius and the bottom radius (top radius - bottom radius). As a result, it is preferably 5 or less, more preferably 4.5 or less, still more preferably 4 or less. The evaluation of taper can be measured according to the method described in Examples below.

A cured product obtained by photocuring the photosensitive resin composition and then thermally curing the composition at 180° C. for 30 minutes exhibits the characteristic that a via hole can be formed using a laser. That is, it exhibits a characteristic of being excellent in laser via opening properties. Specifically, the cured product is irradiated with a UV-YAG laser under the conditions of a power of 0.25 W, a shot number of 20, and a target top diameter of 30 μm. As a result, a via hole can be formed, and no peeling occurs even when the cross section of the via hole is observed. The evaluation of laser via openability can be measured according to the method described in Examples below.

After photocuring the photosensitive resin composition, the cured product obtained by heat curing at 180° C. for 30 minutes can increase the peel strength (adhesion) between the conductor layer formed by plating. Therefore, when an insulating layer is formed from this cured product, an insulating layer having high peel strength between itself and the plated conductor layer can be obtained. Peel strength is preferably 0.20 kgf/cm or more, more preferably 0.30 kgf/cm or more. The upper limit of the peel strength is not particularly limited, but can be, for example, 10.0 kgf/cm or less. The peel strength can be measured according to the method described in the examples below.

The roughened surface after roughening the surface of the cured product obtained by photocuring the photosensitive resin composition and further heat-curing at 180 ° C. for 30 minutes usually exhibits the characteristic that the arithmetic average roughness (Ra) is low. . Thus, said cured product provides an insulating layer with a low arithmetic mean roughness. The arithmetic mean roughness is preferably 400 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less. On the other hand, the lower limit of the arithmetic mean roughness can be 1 nm or more. Evaluation of the arithmetic mean roughness (Ra) can be measured according to the method described in Examples below.

A cured product obtained by photocuring the photosensitive resin composition exhibits excellent crack resistance. That is, it provides an insulating layer and a solder resist having excellent crack resistance. For example, even if the above-mentioned cured product is subjected to a heat cycle treatment including a temperature decrease to -65°C and a temperature increase to 150°C, repeated 500 times, cracks and peeling are not observed. Evaluation of crack resistance can be evaluated according to the method described in Examples below.

Applications of the photosensitive resin composition of the present invention are not particularly limited, but include photosensitive films with supports, insulating resin sheets such as prepreg, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underlays, etc. - It can be used in a wide range of applications that require a photosensitive resin composition, such as filling materials, die bonding materials, semiconductor sealing materials, hole-filling resins, and part-embedding resins. Among them, a photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board having a cured product of a photosensitive resin composition as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a photosensitive resin composition Printed wiring board with a cured product as an interlayer insulating layer (interlayer insulating material)), photosensitive resin composition for plating (printed wiring board in which plating is formed on the cured product of the photosensitive resin composition), and solder resist (printed wiring board using a cured product of the photosensitive resin composition as a solder resist).

[Photosensitive film with support]
The photosensitive resin composition of the present invention can be suitably used in the form of a support-attached photosensitive film in which a photosensitive resin composition layer is formed on a support. That is, the support-attached photosensitive film includes a support and a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention provided on the support.

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 preferred.

Commercially available supports include, for example, product names “Alphan MA-410” and “E-200C” manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and product name “PS-25” manufactured by Teijin Limited. Polyethylene terephthalate films such as the PS series, etc., but not limited to these. In order to facilitate removal of the photosensitive resin composition layer, these supports are preferably coated with a release agent such as a silicone coating agent on the surface. 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 suppress breakage of the support when the support is peeled off before development. Resolution can be improved. Also preferred are supports with low fisheyes. Here, fisheye refers to foreign substances, undissolved substances, oxidized substances, etc. of the material being incorporated into the film when the film is produced by heat-melting the material, kneading, extruding, biaxial stretching, casting, etc. It is a thing.

In order to reduce light scattering during exposure by actinic rays such as ultraviolet rays, the support preferably has excellent transparency. Specifically, the support preferably has a turbidity (haze standardized by JIS-K6714) of 0.1 to 5, which is an index of transparency. Furthermore, the photosensitive resin composition layer may be protected with a protective film.

By protecting the photosensitive resin composition layer side of the support-attached photosensitive film with a protective film, it is possible to prevent dust from adhering to the surface of the photosensitive resin composition layer and scratches on the surface of the photosensitive resin composition layer. As the protective film, a film made of the same material as the support can be used. Although the thickness of the protective film is not particularly limited, it is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, even more preferably in the range of 10 μm to 30 μm. When the thickness is 1 μm or more, the handleability of the protective film can be improved, and when the thickness is 40 μm or less, the cost tends to be improved. The protective film preferably has a lower adhesive strength between the photosensitive resin composition layer and the protective film than the adhesive strength between the photosensitive resin composition layer and the support.

A support-attached photosensitive film can be produced, for example, by preparing a resin varnish by dissolving the photosensitive resin composition of the present invention in an organic solvent, applying the resin varnish on a support, and removing the organic solvent by heating or blowing with hot air. can be produced by drying to form a photosensitive resin composition layer. Specifically, first, after completely removing bubbles in the photosensitive resin composition by a vacuum defoaming method or the like, the photosensitive resin composition is applied onto a support, and the solvent is removed in a hot air oven or a far-infrared oven. A support-attached photosensitive film can be produced by removing, drying, and optionally laminating a protective film on the obtained photosensitive resin composition layer. Specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of organic solvent in the resin varnish. can be dried for 3 to 13 minutes. The amount of residual organic solvent in the photosensitive resin composition layer is preferably 5% by mass or less with respect to the total amount of the photosensitive resin composition layer from the viewpoint of preventing diffusion of the organic solvent in subsequent steps. It is more preferable to make it 2% by mass or less. A person skilled in the art can appropriately set suitable drying conditions by simple experiments. The thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm from the viewpoint of improving handleability and suppressing deterioration of sensitivity and resolution inside the photosensitive resin composition layer. , more preferably 10 μm to 200 μm, more preferably 15 μm to 150 μm, even more preferably 20 μm to 100 μm, and most preferably 20 μm to 60 μm.

The coating method of the photosensitive resin composition includes, for example, gravure coating, micro gravure coating, reverse coating, kiss reverse coating, die coating, slot die, lip coating, comma coating, blade coating, A roll coating method, a knife coating method, a curtain coating method, a chamber gravure coating method, a slot orifice method, a spray coating method, a dip coating method, and the like can be mentioned.

The photosensitive resin composition may be applied in several times, may be applied in one time, or may be applied by combining a plurality of different methods. Among them, the die coating method is preferable because of its excellent uniform coatability. Moreover, in order to avoid contamination by foreign substances, it is preferable to perform the coating process in an environment such as a clean room where foreign substances are less likely to occur.

The photosensitive resin composition layer of the support-attached photosensitive film of the present invention exhibits excellent flexibility. Therefore, the photosensitive resin composition can suppress resin scattering and crack generation even when stress is applied. In addition, even if the photosensitive resin composition layer is cut out with a cutter knife, it is preferable that no scattering or cracking of the photosensitive resin composition is observed. It is preferable that no scattering or cracking of the resin composition is observed. Flexibility can be measured as described in the Examples below.

The photosensitive resin composition layer of the support-attached photosensitive film of the present invention exhibits excellent tackiness. When the support-attached photosensitive film at 25° C. was evaluated with a probe tack tester, the appearance of the film was good and no mark remained on the probe. Evaluation of tackiness can be measured according to the method described in Examples below.

The photosensitive resin composition layer of the support-attached photosensitive film of the present invention is excellent in flexibility and tackiness, so that the film has a good appearance. Therefore, the photosensitive resin composition layer of the support-attached photosensitive film is prevented from repelling and unevenness. The appearance of the film can be measured according to the description in the examples below.

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer formed from a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a solder resist.

Specifically, the printed wiring board of the present invention can be produced using the support-attached photosensitive film described above. A case where the insulating layer is a solder resist will be described below.

<Lamination and drying process>
The photosensitive resin composition layer side of the support-attached photosensitive film is laminated on a circuit board and dried to form a photosensitive resin composition layer on the circuit board.

Examples of circuit substrates include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Here, the term "circuit board" refers to a board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above. In addition, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, a substrate in which one or both sides of the outermost layer of the multilayer printed wiring board is a patterned conductor layer (circuit) is also included here. included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

As one embodiment of the lamination step, the photosensitive resin composition layer side is laminated on one side or both sides of the circuit board using a vacuum laminator. In the lamination step, if the photosensitive film with a support has a protective film, after removing the protective film, preheat the photosensitive film with a support and the circuit board as necessary to obtain a photosensitive resin composition. The material layer is press-bonded to the circuit board while being pressurized and heated. In the case of the support-attached photosensitive film, a method of laminating on a circuit board under reduced pressure by a vacuum lamination method is preferably used.

The conditions of the lamination step are not particularly limited, but for example, the pressure bonding temperature (laminating 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 ), the pressure bonding time is preferably 5 seconds to 300 seconds, and the air pressure is 20 mmHg (26.7 hPa) or less. is preferred. Moreover, the lamination process may be of a batch type or a continuous type using rolls. A vacuum lamination method can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. be able to. Thus, a support-attached photosensitive film is formed on the circuit board.

Instead of laminating a photosensitive film with a support, the photosensitive resin composition is directly coated on the circuit board in a resin varnish state, and the organic solvent is dried to form a photosensitive resin composition layer on the circuit board. may be formed. As a coating method, screen printing is generally used for full surface printing, but any other coating method may be used as long as it can be applied uniformly. For example, spray coating method, hot melt coating method, bar coating method, applicator method, blade coating method, knife coating method, air knife coating method, curtain flow coating method, roll coating method, gravure coating method, offset printing method, dip coating method. , brushing, or any other conventional application method can be used. After coating, drying is performed in a hot air oven, a far infrared oven, or the like, if necessary. The drying conditions are preferably 80° C. to 120° C. for 3 minutes to 13 minutes.

<Exposure process>
After the photosensitive resin composition layer is provided on the circuit board by the above steps, then, through the mask pattern, a predetermined portion of the photosensitive resin composition layer is irradiated with actinic rays, and the photosensitive resin composition in the irradiated portion An exposure step is performed to photoharden the layer. Actinic rays include, for example, ultraviolet rays, visible rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. The dose of ultraviolet rays is about 10 mJ/cm ² to 1000 mJ/cm ² . The exposure method includes 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 a parallel light beam is used for exposure without close contact. Either method may be used. Further, when a support exists on the photosensitive resin composition layer, exposure may be performed from above the support, or exposure may be performed after peeling off the support.

Since the solder resist uses the photosensitive resin composition of the present invention, it has excellent developability (resolution). Therefore, as the exposure pattern in the mask pattern, for example, the ratio (L/S) of the circuit width (line; L) and the width (space; S) between the 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) can be used. is. Note that the pitch need not be the same across the circuit board.

<Development process>
After the exposure step, if there is a support on the photosensitive resin composition layer, the support is removed, and then wet development or dry development is performed to remove the non-photocured portion (unexposed portion). Then, a pattern can be formed by developing.

In the case of the wet development, a safe and stable developing solution with good operability such as an alkaline aqueous solution, an aqueous developer, an organic solvent, etc. is used as the developing solution. As a developing method, known methods such as spraying, rocking immersion, brushing, scraping, and the like are appropriately employed.

Examples of the alkaline aqueous solution used as the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; and sodium phosphate. , alkali metal phosphates such as potassium phosphate, aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and aqueous solutions of organic bases containing no metal ions 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.

Surfactants, antifoaming agents and the like can be added to these alkaline aqueous solutions in order to improve the developing effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8-12, more preferably in the range of 9-11. Further, 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 photosensitive resin composition layer, but is preferably 20°C to 50°C.

Organic solvents used as developers include, 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, and 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. Moreover, the temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such organic solvents can be used alone or in combination of two or more. Organic solvent-based developers used alone include, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

In pattern formation, if necessary, two or more of the above-described developing 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, etc. The high-pressure spray method is suitable for improving resolution. When the spray method is employed, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

<Thermal curing (post-baking) process>
After the development process is completed, a heat curing (post-baking) process is performed to form a solder resist. Examples of the post-baking process include an ultraviolet irradiation process using a high-pressure mercury lamp, a heating process using a clean oven, and the like. In the case of irradiating with ultraviolet rays, the irradiation amount can be adjusted as necessary, for example, irradiation can be performed at an irradiation amount of about 0.05 J/cm ² to 10 J/cm ² . The heating conditions may be appropriately selected according to the type and content of the resin component in the photosensitive resin composition, preferably 150° C. to 220° C. for 20 minutes to 180 minutes, more preferably It is selected in the range of 160° C. to 200° C. for 30 minutes to 120 minutes.

<Other processes>
After forming the solder resist, the printed wiring board may further include a drilling step and a desmear step. These steps may be carried out according to various methods known to those skilled in the art for use in manufacturing printed wiring boards.

After forming the solder resist, if desired, the solder resist formed on the circuit board is subjected to a drilling step to form via holes and through holes. The drilling step can be carried out by a known method such as drilling, laser, 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 preferred.

A desmear process is a process of desmearing. Resin residue (smear) generally adheres to the inside of the opening formed in the drilling process. Since such smears cause electrical connection failures, processing for removing smears (desmear processing) is performed in this step.

Desmearing may be performed by dry desmearing, wet desmearing, or a combination thereof.

Dry desmearing includes, for example, desmearing using plasma. Desmearing using plasma can be performed using a commercially available plasma desmearing device. Among commercially available plasma desmear treatment apparatuses, suitable examples for use in manufacturing printed wiring boards include a microwave plasma apparatus manufactured by Nissin Co., Ltd., and an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd., and the like.

Examples of wet desmear treatment include 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 liquid, the oxidation treatment with the oxidant solution, and the neutralization treatment with the neutralization solution in this order. Examples of the swelling liquid include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment is preferably carried out by immersing the substrate having via holes and the like formed therein in a swelling liquid heated to 60° C. to 80° C. for 5 to 10 minutes. As the oxidizing agent solution, an aqueous alkaline permanganate solution is preferable. For example, a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. 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 solution is preferably carried out by immersing the substrate after the oxidation treatment in the neutralizing solution at 30° C. to 50° C. for 3 to 10 minutes. As the neutralizing liquid, an acidic aqueous solution is preferable, and commercially available products include, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan.

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

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

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

[Semiconductor device]
A 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 semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, 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. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Examples include a mounting method using a buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, "a mounting method using a build-up layer without bumps (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

EXAMPLES The present invention will be specifically described below 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", respectively, unless otherwise specified.

(Preparation of inorganic filler)
Inorganic fillers B-1 to B-7 are "SFP series" manufactured by Denki Kagaku Kogyo Co., Ltd., "SP (H) series" manufactured by Nippon Steel & Sumikin Materials Co., Ltd., "Sciqas series" manufactured by Sakai Chemical Industry Co., Ltd., Nippon Shokubai Co., Ltd. "Seahoster series" and "SG-SO series" manufactured by Sukgyuug alone or in combination, subjected to surface treatment with a vinylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM1003), filtered and classified. be. The particle size distribution of inorganic fillers B-1 to B-7 was measured by the following method.

50 mg of inorganic filler B-1 powder, 2 g of a nonionic dispersant (“T208.5” manufactured by NOF Corporation), and 40 g of pure water were weighed in a vial and dispersed by ultrasonic waves for 20 minutes. Using a laser diffraction particle size distribution analyzer (LA-950, manufactured by Horiba, Ltd.), the particle size distribution was measured by a batch cell method, and D ₁₀ , D _{50 and} D ₉₀ were calculated. The average particle diameters of the inorganic fillers B-2 to B-6 were similarly calculated. For B-7, the particle size distribution was measured in the same manner except that pure water was changed to MEK.

The specific surface areas of the inorganic fillers B-1 to B-7 were measured using a BET fully automatic specific surface area measuring device (Macsorb HM-1210, manufactured by Mountech).

The D ₁₀ , D _{50 ,} D ₉₀ and specific surface area of each inorganic filler are shown in the table below.

(Measurement of refractive index)
The refractive index of component (E) was measured at 589 nm using an Abbe refractometer (manufactured by Atago Co., Ltd., DR-M2) while maintaining a temperature of 25°C.

(Synthesis Example 1: Synthesis of A-1 component)
Epoxy equivalent is 325g/eq. 325 parts of an epoxy resin having a naphthol aralkyl skeleton ("ESN-475V", manufactured by Nippon Steel Chemicals) is placed in a flask equipped with a gas inlet tube, a stirrer, a condenser tube and a thermometer, and 340 parts of carbitol acetate is added. Then, 0.46 part of hydroquinone and 1 part of triphenylphosphine were added. This mixture was heated to 95 to 105° C., 72 parts of acrylic acid was gradually added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80-90° C., 80 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, and cooled. By adjusting the amount of solvent, a resin solution (non-volatile content: 70%, hereinafter abbreviated as “A-1”) having a solid acid value of 60 mgKOH/g was obtained.

<Examples 1 to 7, Comparative Examples 1 to 9>
A resin varnish was prepared by blending each component in the blending ratio shown in the table below and using a high-speed rotating mixer. Next, as a support, a PET film (“Lumirror T6AM” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., “release type PET") was prepared. The prepared resin varnish is uniformly applied to the release PET with a die coater so that the thickness of the photosensitive resin composition layer after drying becomes 20 μm, and dried at 80 ° C. to 110 ° C. for 7 minutes to release the mold. A support-attached photosensitive film having a photosensitive resin composition layer on PET was obtained.

<Evaluation of Film Appearance, Flexibility, and Tackiness>
The appearance of the photosensitive resin composition layer of the support-attached photosensitive film produced in Examples and Comparative Examples was visually observed. Also, when the photosensitive resin composition layer was cut out with a utility knife, the scattering of the resin and the occurrence of cracks were visually observed. Furthermore, the development of cracks when the support-attached photosensitive film was bent by 180° was visually observed. In addition, the tackiness of the support-attached photosensitive film was evaluated in a thermostatic chamber at 25° C. using a probe tack tester (TE-6002). The measurement conditions were a probe with a diameter of 5 mm, a load of 1 kgf/cm ² , a contact time of 10 seconds, and a peeling speed of 0.1 mm/sec. Appearance, flexibility and tackiness of the film were evaluated as follows.
◯: No cissing or unevenness, and no resin scattering or cracks observed. In addition, the appearance of the film is good after tackiness evaluation, and the excessive tackiness prevents the resin from adhering to the probe.
x: repellency, unevenness, scattering of resin, cracks, or after evaluation of tackiness, excessive tackiness causes resin to remain on the probe and tear the film.

<Measurement of minimum melt viscosity>
Pellets for measurement (diameter 18 mm, 1.2 to 1.3 g) were prepared by peeling off only the photosensitive resin composition layer from the release PET of the support-attached photosensitive film and compressing it with a mold. Using a pellet for measurement, using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM), a parallel plate with a diameter of 18 mm is used for 1 g of the photosensitive resin composition layer of the sample. , The temperature was raised from the starting temperature of 60 ° C. to 200 ° C. at a temperature increase rate of 5 ° C./min, and the dynamic viscoelastic modulus was measured under the measurement conditions of a measurement temperature interval of 2.5 ° C., a frequency of 1 Hz, and a strain of 1 deg. Minimum melt viscosity (poise) was calculated.

<Measurement of average linear thermal expansion coefficient and dielectric properties>
(Formation of cured product for evaluation)
The photosensitive resin composition layers of the support-attached photosensitive films obtained in Examples and Comparative Examples were exposed to ultraviolet light at 100 mJ/cm ² to be photocured. After that, the entire surface of the photosensitive resin composition layer was developed by spraying a 1% by mass sodium carbonate aqueous solution at 30° C. as a developer at a spray pressure of 0.2 MPa for 2 minutes. After spray development, 1 J/cm ² ultraviolet irradiation was performed, and further heat treatment was performed at 190° C. for 90 minutes to obtain a cured product. After that, the support was peeled off to obtain a cured product for evaluation.

(Measurement of average linear thermal expansion coefficient)
The cured product for evaluation was cut into a test piece having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer (Thermo Plus, TMA8310 manufactured by Rigaku Corporation). After mounting the test piece on the apparatus, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. An average linear thermal expansion coefficient (ppm) from 25° C. to 150° C. in the second measurement was calculated.

(Measurement of dielectric properties (dielectric constant, dielectric loss tangent))
The cured product for evaluation was cut into a test piece having a width of 2 mm and a length of 80 mm to obtain a cured product B for evaluation. For each cured product B for evaluation, using "HP8362B" manufactured by Agilent Technologies, a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method. A tangent value (Df value) was measured. Three test pieces (N=3) were measured, and the average was calculated.

<Evaluation of developability>
(Formation of laminate A for evaluation)
The copper layer of a glass epoxy substrate (copper-clad laminate) on which a circuit is formed by patterning a copper layer with a thickness of 18 μm is roughened by treatment with a surface treatment agent (CZ8100, manufactured by MEC Co., Ltd.) containing an organic acid. was applied. Next, the photosensitive resin composition layer of the support-attached photosensitive film obtained in Examples and Comparative Examples was placed in contact with the surface of the copper circuit, and a vacuum laminator (VP160, manufactured by Nikko Materials Co., Ltd.) was used. Lamination was performed to form a laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order. The crimping conditions were as follows: evacuation time of 30 seconds, crimping temperature of 80° C., crimping pressure of 0.7 MPa, and pressurization time of 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or longer, and the support of the laminate was exposed to ultraviolet light using a pattern forming apparatus using a round hole pattern to form via holes. Exposure pattern: Aperture: 20 μm/25 μm/30 μm/40 μm/50 μm/60 μm/70 μm/80 μm/90 μm/100 μm round hole, L/S (line/space): 20 μm/20 μm, 25 μm/25 μm, 30 μm/30 μm, 40 μm /40 μm, 50 μm/50 μm, 60 μm/60 μm, 70 μm/70 μm, 80 μm/80 μm, 90 μm/90 μm, 100 μm/100 μm lines and spaces, and a 1 cm×2 cm square were drawn on a quartz glass mask. After standing at room temperature for 30 minutes, the support was peeled off from the laminate. Then, the entire surface of the photosensitive resin composition layer was developed by spraying a 1 mass % sodium carbonate aqueous solution at 30° C. as a developer at a spray pressure of 0.2 MPa. This substrate was used as a laminate A for evaluation.

(Residue in unexposed area)
The unexposed portion of the 1 cm×2 cm portion of the evaluation laminate A was visually observed and evaluated according to the following criteria.
◯: No resin remained in the unexposed area.
x: The resin can be visually confirmed, or film reduction has occurred.

(Evaluation of minimum opening diameter)
The formed via hole was observed by SEM (magnification: 1000), and the minimum via hole diameter free from residue and peeling was measured.

(Via wall evaluation)
The inner wall of the via hole (via wall) was evaluated by counting the number of inorganic fillers with a particle size of 0.1×R exposed from the via wall, where R was the minimum opening diameter. evaluated according to the criteria.
◯: Less than 10 inorganic fillers with a particle size of (0.1×R) or more are exposed from the via wall.
x: The number of inorganic fillers having a particle size of (0.1×R) or more exposed from the via wall is 10 or more.

(Evaluation of taper)
In the obtained via hole having the minimum opening diameter, a cross section is observed by SEM, the top radius (μm) and the bottom radius (μm) of the cross section are measured, and the difference (top radius - bottom radius ). A positive value indicates a tapered shape, and a negative value indicates an undercut shape.

<Laser Via Openability, Copper Plating Adhesion>
(Preparation of laminate B for evaluation)
The copper layer of a glass epoxy substrate (copper-clad laminate) on which a circuit is formed by patterning a copper layer with a thickness of 18 μm is roughened by treatment with a surface treatment agent (CZ8100, manufactured by MEC Co., Ltd.) containing an organic acid. was applied. Next, the photosensitive resin composition layer of the support-attached photosensitive film obtained in Examples and Comparative Examples was placed in contact with the surface of the copper circuit, and a vacuum laminator (VP160, manufactured by Nikko Materials Co., Ltd.) was used. Lamination was performed to form a laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order. The crimping conditions were as follows: evacuation time of 30 seconds, crimping temperature of 80° C., crimping pressure of 0.7 MPa, and pressurization time of 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or longer, and exposed to ultraviolet rays through quartz glass. After standing at room temperature for 30 minutes, the support was peeled off from the laminate. On the entire surface of the photosensitive resin composition layer on the laminated plate from which the support had been peeled off, development was carried out by spraying a 1% by weight sodium carbonate aqueous solution at 30° C. as a developer at a spray pressure of 0.2 MPa. After that, exposure was performed with a metal halide lamp, heat curing was performed at 180° C. for 30 minutes, and a laminate B for evaluation was obtained.

(Laser via openability)
A UV-YAG laser processing machine (“LU-2L212/M50L” manufactured by Via Mechanics Co., Ltd.) was used in the laminate B for evaluation to form via holes in the insulating layer under the following conditions, and evaluation was performed according to the following criteria. Conditions: power 0.25 W, number of shots 20, target top diameter 30 μm.
◯: A via hole can be opened, and there is no peeling even when the cross section is observed.
x: The via hole cannot be opened, or peeling occurs when the cross section is observed.

(Evaluation of copper plating adhesion)
The evaluation laminate B was immersed in a swelling liquid, Swelling Dip Securigand P containing diethylene glycol monobutyl ether manufactured by Atotech Japan Co., Ltd., at 60 ° C. for 5 minutes, and then a concentrate manufactured by Atotech Japan Co., Ltd. was used as a roughening liquid.・Immersed in Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally, as a neutralizing solution, 40 ° C. in Reduction Shoryusin Securigant P manufactured by Atotech Japan Co., Ltd. for 5 minutes. The laminate B for evaluation after the roughening treatment is called the laminate C for evaluation.

Next, this evaluation laminate C was immersed in an electroless plating solution containing PdCl ₂ and then in an electroless copper plating solution. After annealing by heating at 150° C. for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 20±5 μm. Annealing was then performed at 180° C. for 60 minutes. A cut with a width of 10 mm and a length of 100 mm was made in this plated conductor layer with a cutter, and one end was peeled off and gripped with a gripper (Autocom type tester AC-50C-SL manufactured by TSE Co., Ltd.). Inside, the load when peeling off 35 mm in the vertical direction at a rate of 50 mm/min was measured and evaluated according to the following criteria.
◎: load is 0.30 kgf/cm or more ○: load is less than 0.30 kgf/cm 0.20 kgf/cm or more ×: load is less than 0.20 kgf/cm

(Measurement of surface shape (arithmetic mean roughness Ra))
The average value of the arithmetic mean roughness Ra of 10 points randomly selected on the surface of the laminate C for evaluation was measured as the arithmetic mean roughness Ra of the laminate C for evaluation. The arithmetic average roughness Ra at each point is measured using a non-contact surface roughness meter ("WYKO NT3300" manufactured by Bcoinstruments) in VSI contact mode with a 50x lens, with a measurement range of 121 µm × 92 µm. , was evaluated according to the following criteria.
◎: Ra is 200 nm or less ○: Ra is greater than 200 nm and 400 nm or less ×: Ra is greater than 400 nm

<Evaluation of cracks>
By treating the copper layer of a glass epoxy substrate (copper-clad laminate) on which a circuit is formed by patterning a copper pad of 18 μm in thickness and 100 μm in diameter with a surface treatment agent (CZ8100, manufactured by MEC Co., Ltd.) containing an organic acid. Roughened. Otherwise, a laminate D for evaluation was produced in the same process as for the laminate A for evaluation. After exposing this substrate to the atmosphere of −65° C. for 15 minutes, the temperature was raised at a rate of 180° C./min. A test was conducted in which the heat cycle treatment was repeated 500 times. After the test, the degree of cracks and peeling of the substrate for evaluation was observed with an optical microscope (manufactured by Nikon Corporation, "ECLIPSE LV100ND") and evaluated according to the following criteria.
◯: No cracks and peeling are observed.
x: Cracks and peeling are observed.

Abbreviations, etc. in the table are as follows.
・ (ACA) Z-251: acrylic polymer, cyclomer P (manufactured by Daicel Ornex, acid value 66 mgKOH / g, solid content concentration about 46%)
・ CCR-1171H: cresol novolac epoxy acrylate (manufactured by Nippon Kayaku, acid value 99 mgKOH / g, solid content concentration about 60%)
· A-1: A-1 component synthesized in Synthesis Example 1 (non-volatile content 70%)
・ B-1: Inorganic filler B-1
・ B-2: Inorganic filler B-2
・ B-3: Inorganic filler B-3
· B-4: inorganic filler B-4
· B-5: inorganic filler B-5
・ B-6: Inorganic filler B-6
· B-7: inorganic filler B-7
・Irgacure TPO: Bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide, manufactured by BASF ・HP4032: Naphthalene type epoxy resin (manufactured by DIC, epoxy equivalent 144 g / eq., softening point less than 30 ° C.)
· NC3000L: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 271 g / eq., softening point 53 ° C.)
・NPGDA: neopentyl glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd., refractive index 1.452)
· A-DOG: dioxane glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., refractive index 1.472)
· ACMO: 4-acryloylmorpholine (manufactured by KJ Chemicals, refractive index 1.508)
・ NOAA: normal octyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., refractive index 1.433)
· R-551: Bisphenol A tetraethoxy diacrylate (manufactured by Nippon Kayaku Co., Ltd., refractive index 1.538)
· 1B2PZ: 2-phenyl-1-benzyl-1H-imidazole, manufactured by Shikoku Kasei Co., Ltd. · EDGAc: ethyl diglycol acetate · MEK: methyl ethyl ketone

From the results in the above table, Examples 1 to 7 are excellent in film appearance, resin viscosity, average linear thermal expansion coefficient, electrical properties, and crack resistance, and are resin compositions capable of forming via holes having fine openings. was found to be low.

On the other hand, in Comparative Examples 1 and 2 in which the refractive index of the resin of the component (E) was outside the predetermined range, formation of the via hole itself was possible, but compared with Examples 1 to 7, the shape of the via hole deteriorated. , the plating adhesion was poor. In Comparative Examples 3 to 7, in which the particle size distribution of the inorganic filler was out of range, the resolution was greatly deteriorated. Moreover, Comparative Example 8, in which the content of the inorganic filler was less than 30% by mass, had a high average coefficient of linear thermal expansion and deteriorated crack resistance. Comparative Example 8, in which an acrylic polymer was used instead of the component (A), deteriorated via hole shape, laser opening property, copper plating adhesion, surface shape, crack resistance, etc., and could not be used as a photosensitive resin composition. rice field.

In each example, it has been confirmed that the same results as those of the above examples are obtained even if the component (F) is not contained, although there is a difference in degree.

Claims (12)

(A) a resin containing an ethylenically unsaturated group and a carboxyl group;
(B) an inorganic filler,
(C) a photoinitiator,
(D) an epoxy resin, and (E) a photopolymerizable compound,
A photosensitive resin composition containing
(B) The content of the component is 30% by mass or more when the total solid content in the photosensitive resin composition is 100% by mass,
The 10% particle size (D ₁₀ ) in the particle size distribution of the component (B) is 0.06 μm or more and 0.6 μm or less, the 50% particle size (D ₅₀ ) is 0.11 μm or more and 1.10 μm or less, and 90 % particle size (D ₉₀ ) is 0.22 μm or more and 2.20 μm or less,
The photosensitive resin composition, wherein the component (E) has a refractive index of 1.45 or more and 1.51 or less. When a via hole having a minimum opening diameter of R (μm) is formed in the cured product of the photosensitive resin composition, the number of components (B) having a particle size of (0.1×R) μm or more exposed on the wall surface of the via hole. is 10 or less, the photosensitive resin composition according to claim 1. 3. The photosensitive resin composition according to claim 1, wherein the component (E) has a divalent cyclic structure. 4. The photosensitive resin composition according to claim 3, wherein the divalent cyclic group has a heteroatom-containing alicyclic skeleton. The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (E) contains a compound represented by the following formula (E-1).

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein component (A) has any one of a cresol novolac skeleton, a naphthalene skeleton, and a naphtholaralkyl skeleton. The photosensitive resin composition according to any one of claims 1 to 6, wherein component (A) comprises an acid-modified naphthol aralkyl skeleton-containing epoxy (meth)acrylate. (D) component contains (D-1) an epoxy resin having a softening point of less than 30°C, and (D-2) an epoxy resin having a softening point of 30°C or higher. The photosensitive resin composition described. A photosensitive film with a support, comprising a support and a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 8 provided on the support. A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of claims 1 to 8. 11. The printed wiring board according to claim 10, wherein the insulating layer is one of an interlayer insulating material and a solder resist. A semiconductor device comprising the printed wiring board according to claim 10 .