TW202239771A - Photosensitive resin composition providing a cured product having excellent developability and suppressed generation of cracks - Google Patents

Abstract

The present invention aims to provide a photosensitive resin composition and the like which can provide a cured product having excellent developability and suppressed generation of cracks. The solution of the present invention is a photosensitive resin composition containing (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 photopolymerizable compound; given that the content of non-volatile components in the photosensitive resin composition is 100% by mass, the content of the component (B) is 30 mass% or more, the 10% particle diameter (D10) in the particle diameter distribution of the component (B) is 0.06 um to 0.6 um, the 50% particle diameter (D50) is 0.11 um to 1.10 um, the 90% particle diameter (D90) is 0.22 um to 2.20 um, and the refractive index of the component (E) is 1.45 to 1.51.

Description

Photosensitive resin composition

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

On printed circuit boards, solder resist is provided as a permanent protective film to prevent solder from adhering to unnecessary parts and to prevent corrosion of circuit boards. As a solder resist, for example, a photosensitive resin composition as described in Patent Document 1 is generally used. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-115672

[Problems to be Solved by the Invention]

Generally, the photosensitive resin composition is required to have developability and the like at the time of image development. In addition, in recent years, photosensitive resin compositions are also 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 considered. However, when the content of the inorganic filler is increased, the adhesion between the layer formed of the photosensitive resin composition and the conductor layer tends to decrease. In addition, when a through hole is formed in a layer formed of a photosensitive resin composition, the transmission of light becomes insufficient, and the sensitivity of the bottom of the through hole decreases to cause an undercut, or it cannot be formed due to halo of light. Small-diameter via holes degrade resolution.

The object of the present invention is to provide a photosensitive resin composition that is excellent in image development, can obtain adhesion between conductor layers, and suppresses the occurrence of cracks; Photosensitive film, printed circuit board and semiconductor device. [means to solve the problem]

The inventors of the present invention devoted themselves to examination, and found that by adjusting the particle size distribution of a specific amount of inorganic filler and using it in combination with a photopolymerizable compound having a specific refractive index, excellent image development and adhesion between conductor layers can be obtained. properties, and to suppress the occurrence of cracks hardened, and finally completed the present invention.

。 [6] 如[1]～[5]中任一項記載之感光性樹脂組成物，其中(A)成分具有甲酚酚醛清漆骨架、萘骨架及萘酚芳烷基骨架中之任一者。 [7] 如[1]～[6]中任一項記載之感光性樹脂組成物，其中(A)成分包含酸改質含萘酚芳烷基骨架的環氧(甲基)丙烯酸酯。 [8] 如[1]～[7]中任一項記載之感光性樹脂組成物，其中(D)成分包含(D-1)軟化點未達30℃的環氧樹脂及(D-2)軟化點為30℃以上的環氧樹脂。 [9] 一種附有支撐體的感光性薄膜，其具有支撐體與設於該支撐體上的包含如[1]～[8]中任一項記載之感光性樹脂組成物的感光性樹脂組成物層。 [10] 一種印刷電路板，其包含藉由如[1]～[8]中任一項記載之感光性樹脂組成物之硬化物所形成的絕緣層。 [11] 如[10]記載之印刷電路板，其中絕緣層為層間絕緣材及阻焊劑之任一者。 [12] 一種半導體裝置，其包含如[10]或[11]記載之印刷電路板。 [發明的效果] That is, the present invention includes the following contents. [1] A photosensitive resin composition comprising (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 of a photopolymerizable compound, when the non-volatile components in the photosensitive resin composition are taken as 100% by mass, the content of (B) component is 30% by mass or more, and the particles of (B) component In the size distribution, the 10% particle size (D ₁₀ ) is 0.06 μm to 0.6 μm, the 50% particle size (D ₅₀ ) is 0.11 μm to 1.10 μm, and the 90% particle size (D ₉₀ ) is 0.22 μm or more And 2.20 μm or less, the refractive index of (E) component is 1.45 or more and 1.51 or less. [2] The photosensitive resin composition as described in [1], wherein when a through hole having a minimum opening diameter of R (μm) is formed in the cured product of the photosensitive resin composition, the particles exposed on the wall surface of the through hole are The number of objects of (B) component whose diameter is (0.1*R) micrometer or more 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 novolak skeleton, a naphthalene skeleton, and a naphthol aralkyl skeleton. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the component (A) contains an acid-modified naphthol aralkyl skeleton-containing epoxy (meth)acrylate. [8] The photosensitive resin composition according to any one of [1] to [7], wherein the component (D) contains (D-1) an epoxy resin having a softening point of less than 30°C and (D-2) Epoxy resin with a softening point above 30°C. [9] A photosensitive film with a support, comprising a support and a photosensitive resin composition comprising the photosensitive resin composition described in any one of [1] to [8] provided on the support object layer. [10] A printed circuit board including an insulating layer formed of a cured product of the photosensitive resin composition according to any one of [1] to [8]. [11] The printed circuit board described in [10], wherein the insulating layer is any one of an interlayer insulating material and a solder resist. [12] A semiconductor device including the printed circuit board according to [10] or [11]. [Effect of the invention]

According to the present invention, it is possible to provide a photosensitive resin composition that is excellent in image development, can obtain adhesiveness with a conductor layer, and suppresses occurrence of cracks; Photosensitive films of supports, printed circuit boards, and semiconductor devices.

[Mode of Carrying Out the Invention]

Hereinafter, the photosensitive resin composition, the photosensitive film with a support, the printed circuit board, and the semiconductor device of the present invention will be described in detail.

[Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) a resin containing ethylenically unsaturated groups and carboxyl groups, (B) an inorganic filler, (C) a photopolymerization initiator, (D) In the photosensitive resin composition of epoxy resin and (E) photopolymerizable compound, when the non-volatile components in the photosensitive resin composition are taken as 100% by mass, the content of (B) component is 30% by mass or more, and (B) ) in the particle size distribution of the component, the 10% particle size (D ₁₀ ) is not less than 0.06 μm and not more than 0.6 μm, the 50% particle size (D ₅₀ ) is not less than 0.11 μm and not more than 1.10 μm, and the 90% particle size (D ₉₀ ) It is 0.22 micrometers or more and 2.20 micrometers or less, and the refractive index of (E) component is 1.45 or more and 1.51 or less.

In the present invention, as (B) component, the particle size distribution of a specific amount of inorganic filler is adjusted, as (E) component, a photopolymerizable compound with a specific refractive index is used, and (A) component, (C)-( D) component is used to obtain a photosensitive resin composition that is excellent in image development, obtains adhesion to the conductor layer, and suppresses the occurrence of cracks in a cured product. In addition, it is usually possible to obtain cured products with excellent average linear thermal expansion coefficient (CTE), dielectric constant, dielectric tangent, laser through-hole opening and surface shape, and usually obtain photosensitive resin compositions with low minimum melt viscosity , It can also improve the film morphology of the photosensitive film with the support.

The photosensitive resin composition can contain arbitrary components, such as (F) hardening accelerator, (G) solvent, and (H) other additives, as needed. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

＜(A) Resins containing ethylenically unsaturated groups and carboxyl groups＞ The photosensitive resin composition contains (A) resin containing an ethylenically unsaturated group and a carboxyl group. Developability can be improved by making a photosensitive resin composition contain (A) component.

The ethylenically unsaturated group has a carbon-carbon double bond, and examples thereof include vinyl, allyl, propynyl, butenyl, ethynyl, phenylethynyl, maleimide, nadicyl The amino group and the (meth)acryl group are preferably a (meth)acryl group from the viewpoint of reactivity in photoradical polymerization. "(Meth)acryl" includes methacryl, acryl, and combinations thereof. (A) Component can photoradically polymerize since it contains an ethylenically unsaturated group. (A) The number of ethylenically unsaturated groups per 1 molecule of component may be 1, or may be 2 or more. Moreover, when (A) component contains 2 or more ethylenically unsaturated groups per 1 molecule, those ethylenically unsaturated groups may be the same or different.

Moreover, since (A) component contains a carboxyl group, the photosensitive resin composition system containing this (A) component shows solubility with respect to alkaline solution (for example, 1 mass % sodium carbonate aqueous solution as an alkaline developing solution). (A) The number of carboxyl groups per 1 molecule of component may be 1, or may be 2 or more.

The component (A) is not particularly limited as long as it has an ethylenically unsaturated group and a carboxyl group, is capable of photoradical polymerization, and is capable of alkali image development, but preferably has both a carboxyl group and two or more in one molecule. Ethylenically unsaturated resin.

As one aspect of the resin containing an ethylenically unsaturated group and a carboxyl group, an acid-modified unsaturated epoxy ester resin obtained by reacting an unsaturated carboxylic acid with an epoxy compound, and further reacting an acid anhydride, etc. are mentioned. Specifically, an epoxy compound is reacted with an unsaturated carboxylic acid to obtain an unsaturated epoxy ester resin, and an acid-modified unsaturated epoxy ester resin is obtained by reacting the unsaturated epoxy ester resin with an acid anhydride.

As the epoxy compound, any compound can be used as long as it has an epoxy group in the molecule, 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-F-type epoxy resin modified by reacting bisphenol-F-type epoxy resin with epichlorohydrin to modify more than three functions type epoxy resin; biphenol type epoxy resin, biphenol type epoxy resin such as tetramethyl biphenol type; phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolac Novolak type epoxy resins such as alkylphenol novolak type epoxy resins; fluorine-containing epoxy resins such as bisphenol AF type epoxy resins and perfluoroalkyl type epoxy resins; naphthalene type rings Oxygen resin, dihydroxynaphthalene type epoxy resin, polyhydroxybinaphthalene type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, binaphthol type epoxy resin, naphthyl ether type Epoxy resin naphthol novolak type epoxy resin, naphthalene type epoxy resin obtained by condensation reaction of polyhydroxynaphthalene and aldehydes, etc., such as epoxy resin with naphthalene skeleton (epoxy resin containing naphthalene skeleton); Xylenol-type epoxy resin; dicyclopentadiene-type epoxy resin; triphenol-type epoxy resin; tertiary butyl catechol-type epoxy resin; anthracene-type epoxy resin, etc. Oxygen resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Biphenyl type epoxy resin; Linear aliphatic epoxy resin; Epoxy resin with butadiene structure; Alicyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexanedimethanol epoxy resin; trimethylol epoxy resin; tetraphenylethane epoxy resin; poly Glycidyl (meth)acrylate, glycidyl methacrylate and acrylate copolymers, such as glycidyl-containing acrylic resins; fennel-type epoxy resins; halogenated epoxy resins, etc.

From the viewpoint of reducing the average linear thermal expansion coefficient, the epoxy compound is preferably an aromatic skeleton-containing epoxy resin. Here, the aromatic skeleton is a concept that also includes polycyclic aromatics and aromatic heterocycles. Among them, naphthol aralkyl type epoxy resin, epoxy resin containing naphthalene skeleton, epoxy resin containing condensation ring skeleton, biphenyl type epoxy resin, bisphenol F type epoxy resin, bisphenol A Type epoxy resins, cresol novolak type epoxy resins, and glycidyl ester type epoxy resins inhibit the movement of molecules due to the increase in molecular rigidity, and as a result, the average linear thermal expansion coefficient of the cured product of the resin composition From a lower point of view, naphthol aralkyl type epoxy resins, naphthalene-skeleton-containing epoxy resins, and novolak-type epoxy resins are preferred, and cresol novolac-type epoxy resins, naphthalene-skeleton-containing epoxy resins are particularly preferred. Epoxy resin, naphthol aralkyl type epoxy resin. As the epoxy resin containing a naphthalene skeleton, dihydroxynaphthalene-type epoxy resins, polyhydroxybinaphthalene-type epoxy resins, and naphthalene-type epoxy resins obtained by condensation reaction of polyhydroxynaphthalene and aldehydes are preferable.

Examples of dihydroxynaphthalene-type epoxy resins include 1,3-diglycidoxynaphthalene, 1,4-diglycidoxynaphthalene, 1,5-diglycidoxynaphthalene, 1 , 6-diecidyloxypropoxynaphthalene, 2,3-dioglycidoxynaphthalene, 2,6-dioglycidoxynaphthalene, 2,7-dioglycidoxynaphthalene, etc.

Examples of polyhydroxybinaphthyl epoxy resins include 1,1'-bis(2-glycidoxy)naphthyl, 1-(2,7-diglycidoxy)-1'- (2'-Glycidoxy)binaphthyl, 1,1'-bis(2,7-Diglycidoxy)naphthyl.

As the naphthalene-type epoxy resin obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes, for example, 1,1'-bis(2,7-diecidyloxynaphthyl)methane, 1-(2 , 7-diecidyloxynaphthyl)-1'-(2'-glycidoxynaphthyl)methane, 1,1'-bis(2-glycidoxynaphthyl)methane.

Among these, polyhydroxybinaphthalene-type epoxy resins having two or more naphthalene skeletons in one molecule, and naphthalene-type epoxy resins obtained by condensation reaction of polyhydroxynaphthalene and aldehydes are preferred, especially in 1,1'-bis(2,7-diecidyloxynaphthyl)methane, 1-(2,7-diecidyloxynaphthyl)- 1'-(2'-Glycidyloxynaphthyl)methane, 1-(2,7-Diglycidoxy)-1'-(2'-Glycidoxy)binaphthyl, 1 ,1'-bis(2,7-diecidyloxypropoxy)naphthyl is preferable in that it has excellent heat resistance in addition to the average linear thermal expansion coefficient, and 1,1'-bis( 2,7-Diglycidoxynaphthyl)methane.

As unsaturated carboxylic acid, acrylic acid, methacrylic acid, cinnamic acid, crotonic acid etc. are mentioned, for example, These may be used individually by 1 type, and may use 2 or more types together. Among these, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. Also, in this specification, the epoxy ester resin of the reaction product of the above-mentioned epoxy compound and (meth)acrylic acid may be described as "epoxy (meth)acrylate". Here, the ring of the epoxy compound Oxygen groups are substantially eliminated by reaction with (meth)acrylic acid. The so-called "(meth)acrylate" refers to methacrylate and acrylate. Sometimes acrylic acid and methacrylic acid are 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, and benzophenone. Tetracarboxylic dianhydride and the like may be used alone or in combination of two or more. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferable from the standpoint of improving the analytical properties and insulation reliability of the cured product, and tetrahydrophthalic anhydride is more preferable.

When obtaining acid-modified unsaturated epoxy ester resin, unsaturated carboxylic acid is reacted with epoxy resin in the presence of catalyst to obtain unsaturated epoxy ester resin, and unsaturated epoxy ester resin can be combined with Anhydride reaction. Moreover, a solvent and a polymerization inhibitor can also be used as needed.

The acid-modified unsaturated epoxy ester resin preferably has any one of a cresol novolak skeleton, a naphthalene skeleton, and a naphthol aralkyl skeleton. Moreover, acid-modified epoxy (meth)acrylate is preferable as an acid-modified unsaturated epoxy ester resin. The "epoxy group" in the acid-modified unsaturated epoxy ester resin means a structure derived from the above-mentioned epoxy compound. For example, the so-called "acid-modified bisphenol-type epoxy (meth)acrylate" refers to the acid obtained by using bisphenol-type epoxy resin as the epoxy compound and (meth)acrylic acid as the unsaturated carboxylic acid. Modified unsaturated epoxy ester resin. A preferable range of acid-modified epoxy (meth)acrylate is a preferable range derived from an epoxy compound. That is, the acid-modified unsaturated epoxy ester resin is preferably an acid-modified naphthalene skeleton-containing epoxy (meth)acrylate from the viewpoint of reducing the average linear thermal expansion coefficient of the cured product of the resin composition. , acid-modified epoxy (meth)acrylate containing cresol novolac skeleton, acid-modified epoxy (meth)acrylate containing naphthol aralkyl skeleton, more preferably acid-modified epoxy (meth)acrylate containing naphthalene skeleton Epoxy (meth)acrylate. The so-called acid-modified epoxy (meth)acrylate containing naphthalene skeleton refers to the reaction of naphthalene-type epoxy resin and (meth)acrylate by reacting acid anhydrides such as succinic anhydride or tetrahydrophthalic anhydride. The obtained compound. The so-called acid-modified epoxy (meth)acrylate containing cresol novolak skeleton is the reactant of cresol novolac epoxy resin and (meth)acrylate, making succinic anhydride or tetrahydrophthalic A compound obtained by reacting acid anhydrides such as formic anhydride. The so-called acid-modified epoxy (meth)acrylate containing naphthol aralkyl skeleton means that for the reactant of naphthol aralkyl type epoxy resin and (meth)acrylate, succinic anhydride or tetrahydro Compounds obtained by reacting acid anhydrides such as phthalic anhydride.

Such an acid-modified unsaturated epoxy ester resin can be a commercially available product, and as a specific example, "ZAR-2000" (a mixture of bisphenol A type epoxy resin, acrylic acid, and succinic anhydride) manufactured by Nippon Kayaku Co., Ltd. reactant), "ZFR-1491H", "ZFR-1533H" (reactant of bisphenol F epoxy resin, acrylic acid and tetrahydrophthalic anhydride), "PR-300CP" (methanol phenol novolak type epoxy resin, acrylic acid and acid anhydride), "CCR-1179" (cresol novolac F-type epoxy acrylate) manufactured by Nippon Kayaku Co., Ltd., "ZCR-1569H" (acid-modified Biphenyl-type epoxy acrylate: a reaction product of biphenyl-type epoxy resin, acrylic acid, and acid anhydride), "CCR-1171H" (cresol novolac-type epoxy acrylate) manufactured by Nippon Kayaku Co., Ltd., and the like. These may be used alone or in combination of two or more.

(A) The weight average molecular weight of a component is preferably 1,000 or more, more preferably 1,500 or more, and especially preferably 2,000 or more from the viewpoint of film forming property. From the viewpoint of image development, the upper limit is preferably at most 10,000, more preferably at most 8,000, and most preferably at most 7,500. The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

(A) The acid value of the component is preferably 0.1 mgKOH/g or more, more preferably 0.5 mgKOH/g or more, and most preferably 1 mgKOH/g from the viewpoint of improving the alkali developability of the photosensitive resin composition. more than g. On the other hand, from the viewpoint of suppressing the dissolution of the fine pattern of the hardened product due to development and improving the reliability of the insulation, the acid value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, and most preferably 100 mgKOH/g. below g. Here, an acid value is the residual acid value of the carboxyl group which exists in (A) component, and an acid value can be measured by the following method. First, after measuring about 1 g of the resin solution with a precise balance, 30 g of acetone was added to the resin solution to dissolve the resin solution uniformly. Next, an appropriate amount of phenolphthalein as an indicator was added to this solution, and titration was performed using a 0.1 N ethanol aqueous solution. Then, the acid value was calculated by the following formula. Formula: A=10×(Vf-BL)×F×56.11/(Wp×I)

Moreover, in the above formula, A represents the acid value (mgKOH/g), Vf represents the titer (mL) of KOH, BL represents a blank, F represents a factor (power value), Wp represents the measured resin solution quality (g), and I represents The ratio (mass %) of the nonvolatile matter of the resin solution was measured.

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

Component (A) is from the viewpoint of improvement of alkali developability. When the non-volatile components of the photosensitive resin composition are taken as 100% by mass, the content is preferably at least 5% by mass, more preferably at least 5% by mass. 8% by mass or more, preferably 10% by mass or more. The upper limit is preferably at most 50 mass %, more preferably at most 45 mass %, and most preferably at most 40 mass %, from the viewpoint of improvement of heat resistance. In addition, in the present invention, the content of each component in the photosensitive resin composition is a value when the non-volatile components in the photosensitive resin composition are regarded as 100% by mass unless otherwise specified.

<(B) inorganic filler> The photosensitive resin composition contains (B) inorganic filler as (B) component. (B) In the particle size distribution of component (B), the 10% particle size (D ₁₀ ) is 0.06 μm to 0.6 μm, the 50% particle size (D ₅₀ ) is 0.11 μm to 1.10 μm, and 90 The % particle size (D ₉₀ ) is not less than 0.22 μm and not more than 2.20 μm. By including the inorganic filler having such a particle size distribution in the photosensitive resin composition, even if the content of the inorganic filler is increased, it is possible to improve image development, adhesion, and suppress occurrence of cracks. In addition, the said particle size distribution shows the particle size distribution of the whole (B) inorganic filler contained in a photosensitive resin composition.

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

The so-called 10% particle size (D ₁₀ ) of the particle size distribution is the result of measuring the particle size distribution by the above method. In the particle size distribution curve, it means that the cumulative volume accumulated from the side with the smaller particle size becomes 10%. particle size at time. The so-called 50% particle size (D ₅₀ ) is the result of measuring the particle size distribution by the above method. In the particle size distribution curve, it refers to the particle size when the cumulative volume accumulated from the side of the smaller particle size becomes 50%. . In addition, the so-called 90% particle size (D ₉₀ ) is the result of measuring the particle size distribution by the above-mentioned method. In the particle size distribution curve, it refers to when the cumulative volume accumulated from the side with the smaller particle size becomes 90%. particle size. Here, the average particle diameter of (B) inorganic filler means the particle diameter of 50% particle diameter ( _D50 ). Hereinafter, the 10% particle diameter (D ₁₀ ) is also referred to as D ₁₀ , the 50% particle diameter (D ₅₀ ) is also referred to as D ₅₀ , and the 90% particle diameter (D ₉₀ ) is also referred to as D ₉₀ .

D ₁₀ of the particle size distribution is at least 0.06 μm, preferably at least 0.08 μm, more preferably at least 0.10 μm, from the viewpoint of suppressing scattering of actinic light rays 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.

D ₅₀ of the particle size distribution is at least 0.11 μm, preferably at least 0.13 μm, more preferably at least 0.15 μm, from the viewpoint of suppressing scattering of actinic light rays 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.

D ₉₀ of the particle size distribution is at least 0.22 μm, preferably at least 0.24 μm, more preferably at least 0.25 μm, from the viewpoint of suppressing scattering of actinic light rays and improving resolution. The upper limit is 2.20 μm or less, more preferably 2.00 μm or less, most preferably 1.80 μm or less.

D ₅₀ -D ₁₀ are preferably at least 0.01 μm, more preferably at least 0.02 μm, and especially preferably at least 0.03 μm, from the viewpoint of remarkably obtaining the effect of the present invention. The upper limit is preferably at most 1.20 μm, more preferably at most 1.00 μm, and most preferably at most 0.80 μm.

D ₉₀ -D ₁₀ are preferably at least 0.05 μm, more preferably at least 0.08 μm, and most preferably at least 0.10 μm, from the viewpoint of remarkably obtaining the effect of the present invention. The upper limit is preferably at most 1.60 μm, more preferably at most 1.40 μm, and most preferably at most 1.20 μm.

D ₉₀ -D ₅₀ are preferably at least 0.04 μm, more preferably at least 0.06 μm, and especially preferably at least 0.08 μm, from the viewpoint of remarkably obtaining the effects of the present invention. The upper limit is preferably at most 2.00 μm, more preferably at most 1.50 μm, and especially preferably at most 1.00 μm.

D ₉₀ /D ₅₀ is preferably at most 2.4, more preferably at most 2.2, and most preferably at most 1.8, from the viewpoint of remarkably obtaining the effects of the present invention. The lower limit is preferably at least 1.0, more preferably at least 1.1, and most preferably at least 1.2.

D ₉₀ /D ₁₀ is preferably at most 5.0, more preferably at most 4.0, and most preferably at most 3.0, from the viewpoint of remarkably obtaining the effects of the present invention. The lower limit is preferably at least 1.0, more preferably at least 1.2, and most preferably at least 1.5.

D ₅₀ /D ₁₀ is preferably at most 3.0, more preferably at most 2.5, and most preferably at most 2.0, from the viewpoint of remarkably obtaining the effect of the present invention. The lower limit is preferably at least 1.0, more preferably at least 1.1, and most preferably at least 1.2.

(B) The content of the inorganic filler, from the viewpoint of obtaining a cured product that suppresses the occurrence of cracks, has high adhesion, and a low average linear thermal expansion coefficient, regards the non-volatile components in the photosensitive resin composition as 100% by mass %, it is 30 mass % or more, preferably 45 mass % or more, more preferably 50 mass % or more, 55 mass % or more. The upper limit is at most 85% by mass, preferably at most 80% by mass, more preferably at most 70% by mass, 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 , diaspore, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, titanic acid Magnesium, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Among them, silicon dioxide, aluminum oxide, and barium sulfate are preferable, and silicon dioxide is particularly preferable. Moreover, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

(B) As the inorganic filler, commercially available items can be used. Examples of commercially available (B) inorganic fillers include "Admafine" manufactured by Admatechs Co., Ltd., "SFP series" manufactured by Denki Kagaku Kogyo Co., Ltd., "SP(H) series" manufactured by Nippon Steel & Sumikin Materials Co., Ltd., Sakai Chemical Co., Ltd. "Sciqas series" manufactured by Kogyo Co., Ltd., "Seahostar series" manufactured by Nippon Shokubai Co., Ltd., "SG-SO series" manufactured by Sukgyuug Co., Ltd., etc., as commercial products of alumina, "AZ series", "AX series" and the like, and examples of commercially available barium sulfate include "B series" and "BF series" manufactured by Sakai Chemical Industry Co., Ltd.

(B) Inorganic filler system A plurality of kinds of inorganic fillers can be classified with a classifier etc. to obtain an inorganic filler having a desired average particle diameter.

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, from the viewpoint of obtaining excellent resolution. 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, and most preferably 25 m ² /g or less from the viewpoint of melt viscosity and the like. The specific surface area of the inorganic filler can be calculated according to the BET method by using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH Co., Ltd.) to adsorb nitrogen gas on the surface of the sample and calculate the specific surface area using the BET multi-point method.

Inorganic fillers are preferably vinyl silane coupling agents, amino silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, and silane from the viewpoint of improving moisture resistance and dispersibility. Those treated with one or more surface treatment agents such as coupling agents, alkoxysilane compounds, organic silazane compounds, and titanate-based coupling agents. Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd. "KBM1003" (vinyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane) Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane) made by Shin-Etsu Chemical Co., Ltd., "KBM103" made by Shin-Etsu Chemical Co., Ltd. (phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., 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 most preferably 0.2 mg/m 2 from the viewpoint of improving the dispersibility of the inorganic filler. ^m2 or more. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish and the melt viscosity of the flake form from increasing, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and most preferably 0.5 mg/m 2 ² or less.

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

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

(C) The component system is not particularly limited, but examples include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethyl Amino)-2-[(4-methylphenyl)methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-( Methylthio)phenyl]-2-morpholinopropan-1-one and other α-aminoalkylphenone-based photopolymerization initiators; ethyl ketone, 1-[9-ethyl-6-(2 Oxime ester-based photopolymerization initiators such as -methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime); benzophenone, methyl diphenyl Methanone, o-benzoyl benzoic acid, benzoyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4 ,6-trimethylbenzoyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphinate, 4,4'-bis(diethyl Amino)benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 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 a perjuly salt-based photopolymerization initiator and the like can also be used. These may be used individually by 1 type, and may use 2 or more types together.

Furthermore, the photosensitive resin composition system can be combined with (C) component, including ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, amyl- Tertiary amines such as 4-dimethylaminobenzoate, triethylamine, and triethanolamine are used as photopolymerization initiation aids, and may also include pyrazolines, anthracenes, coumarins, and xanthenes Photosensitizers such as xanthones and thioxanthones. These may be used individually by 1 type, and may use 2 or more types together.

Specific examples of the component (C) include "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819", "Omnirad TPO" manufactured by IGM Corporation, "Irgacure TPO" manufactured by BASF Corporation, "Irgacure OXE-01", "Irgacure OXE-02", "N-1919" manufactured by ADEKA Corporation, etc.

The content of the component (C) is preferably 0.1% by mass when the non-volatile components of the photosensitive resin composition are regarded as 100% by mass from the viewpoint of sufficiently photocuring the photosensitive resin composition and improving insulation reliability. % or more, more preferably 0.5 mass % or more, especially preferably 1 mass % or more. On the other hand, the upper limit is preferably at most 10 mass %, more preferably at most 8 mass %, and especially preferably at most 6 mass %, from the viewpoint of suppressing a decrease in resolution due to excessive sensitivity.

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

(D) Epoxy resins can use epoxy resins other than epoxy resins containing ethylenically unsaturated groups and carboxyl groups, but from the viewpoint of improving image development, dielectric constant and dielectric tangent, it is preferable to include (D -1) Epoxy resin whose softening point is less than 30°C and (D-2) epoxy resin whose softening point is 30°C or higher.

The softening point of the component (D-1) is preferably less than 30°C, more preferably 25°C or lower, and most preferably 20°C or lower, from the viewpoint of remarkably obtaining the effect of the present invention. The lower limit is not particularly limited, but is preferably at least 0°C, more preferably at least 5°C, and especially preferably at least 10°C. The softening point can be measured in accordance with JIS K7234.

Component (D-1) preferably has one or more epoxy groups in one molecule, and more preferably has two or more epoxy groups in one molecule, from the viewpoint of remarkably obtaining the effect of the present invention. Those which have three or more epoxy groups in 1 molecule are especially preferable. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50 mass % or more, more preferably 60 mass % or more, especially preferably 70 mass % or more.

In (D-1) component, there exists a liquid component at a temperature of 20°C and a solid component at a temperature of 20°C. As (D-1) component, it is preferable that it is a liquid form from a viewpoint of remarkably obtaining the effect of this invention.

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

Moreover, as (D-1) component, a naphthalene type epoxy resin, a glycidylamine type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, etc. are mentioned, for example. Epoxy resin, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, glycidylcyclohexane type epoxy resin, isocyanuric acid cyclic epoxy resin, naphthyl ether type Epoxy resin, etc. are preferably naphthalene-type epoxy resins and glycidylamine-type epoxy resins, more preferably naphthalene-type epoxy resins.

Specific examples of the component (D-1) include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "ELM-434L" (epoxy resins) manufactured by Sumitomo Chemical Co., Ltd. Propylamine-type epoxy resin); Mitsubishi Chemical Corporation's "630" (glycidylamine-type epoxy resin); Nippon Steel Sumikin Chemicals' "ZX1658GS" (liquid 1,4-epoxypropylene Cyclohexane-based epoxy resin); ADEKA's "EP-3980S" (two-functional glycidylamine-type epoxy resin); ADEKA's "EP-3950L" (tri-functional glycidylamine-type epoxy resin); Nissan Chemical Corporation's "TEPIC-VL" (isocyanuric acid cyclic epoxy resin); Sumitomo Chemical Corporation's "ELM-100H" (N-[2-methyl-4-( Oxiranylmethoxy)phenyl]-N-(oxiranylmethyl)oxiranemethanamine); DIC Corporation's "EXA-7311-G4" (naphthyl ether-type ring Oxygen resin), etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The epoxy equivalent of the component (D-1) is preferably 150 g/eq. or less, more preferably 148 g/eq. or less, and most preferably 145 g/eq. And preferably at least 10 g/eq., more preferably at least 50 g/eq., most preferably at least 100 g/eq. (D) The epoxy equivalent of a component is the mass of the epoxy resin containing the epoxy group of 1 equivalent. This epoxy equivalent can be measured based on JISK7236.

The weight average molecular weight (Mw) of the component (D-1) is preferably at least 100, more preferably at least 200, particularly preferably at least 250, and more preferably at least 250 from the viewpoint of remarkably obtaining the desired effect of the present invention. Below 5000, more preferably below 3000, especially below 1500. The weight average molecular weight of resin can be measured as the value of polystyrene conversion by the gel permeation chromatography (GPC) method.

The content of the component (D-1) is preferably at least 10% by mass, more preferably at least 10% by mass, when the entirety of the component (D) is taken as 100% by mass from the standpoint of handling properties, melt viscosity, and image development properties of the resin varnish. Preferably at least 20% by mass, more preferably at least 30% by mass, more preferably at most 90% by mass, more preferably at most 80% by mass, especially preferably at most 70% by mass, at most 60% by mass, at most 50% by mass, or 40% by mass or less.

The content of the component (D-1) is based on the non-volatile components in the photosensitive resin composition from the viewpoint of obtaining a hardened product with excellent insulation, dielectric constant, and dielectric tangent in addition to the image development property. When making 100% by mass, it is preferably at least 1% by mass, more preferably at least 1.5% by mass, especially preferably at least 2% by mass, and more preferably at most 10% by mass, more preferably at most 8% by mass, especially preferably at least 8% by mass. 5% by mass or less.

The softening point of the component (D-2) is preferably at least 30°C, more preferably at least 35°C, and most preferably at least 40°C, from the viewpoint of remarkably obtaining the effect of the present invention. From the viewpoint of remarkably obtaining the effect of the present invention, the upper limit is less than 59°C, preferably 57°C or lower, more preferably 55°C or lower. The softening point can be measured by the method similar to (D-1) component.

Component (D-2) preferably has one or more epoxy groups in one molecule, and more preferably has two or more epoxy groups in one molecule, from the viewpoint of remarkably obtaining the effects of the present invention. Those which have three or more epoxy groups in 1 molecule are especially preferable. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50 mass % or more, more preferably 60 mass % or more, especially preferably 70 mass % or more.

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

As (D-2) component, the epoxy resin whose softening point is 30 degreeC or more can be used. Such an epoxy resin preferably has a ring structure from the viewpoint of remarkably obtaining the effect of the present invention. Examples of the cyclic structure include an aromatic ring structure, an alicyclic structure, and the like. Examples of the aromatic ring structure include benzene ring, naphthalene ring, anthracene ring, biphenyl and the like. Examples of the alicyclic structure include a cyclohexane ring, a cyclopentane ring, a cycloheptane ring, and a cyclooctane ring. Among them, the ring structure is preferably an aromatic ring structure, more preferably a benzene ring or a biphenyl ring, and particularly preferably a biphenyl ring.

Moreover, as (D-2) component, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthyl ether type epoxy resin etc. are mentioned, for example, Biphenyl type epoxy resin is more preferable. .

Specific examples of the component (D-2) include "NC3000L" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "HP-7200L" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; Resin), "HP-6000L" (naphthyl ether type epoxy resin); "NC3000" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The epoxy equivalent of the component (D-2) is preferably 50g/eq.～5000g/eq., more preferably 50g/eq.～3000g/eq., especially preferably 80g/eq.～2000g/eq., especially More preferably, it is 110g/eq.-1000g/eq. By setting it as this range, the crosslink density of the hardened|cured material of a photosensitive resin composition layer becomes sufficient, and the insulating layer with small surface roughness can be formed.

(D-2) The weight average molecular weight (Mw) of the component is preferably at least 100, more preferably at least 200, particularly preferably at least 250, and more preferably at least 250 from the viewpoint of remarkably obtaining the desired effect of the present invention. Below 5000, more preferably below 3000, especially below 1500.

The content of the component (D-2) is preferably at least 10% by mass, more preferably 20% by mass, from the viewpoint of obtaining adhesion in addition to insulation properties, when the entirety of the component (D) is taken as 100% by mass. % by mass or more, preferably at least 30 mass %, at least 40 mass %, at least 50 mass %, or at least 60 mass %, and preferably at most 90 mass %, more preferably at most 80 mass %, especially preferably at least 70 mass % the following.

The content of the component (D-2) is preferably at least 1% by mass when the non-volatile components in the photosensitive resin composition are regarded as 100% by mass from the viewpoint of obtaining adhesion in addition to insulation. , more preferably at least 1.5% by mass, especially preferably at least 2% by mass, and more preferably at most 15% by mass, more preferably at most 12% by mass, most preferably at most 10% by mass.

The content of the component (D) is preferably at least 1% by mass, more preferably 3% by mass, from the viewpoint of remarkably obtaining the effects of the present invention, when the non-volatile components in the photosensitive resin composition are taken as 100% by mass. % or more, preferably at least 5 mass %, and preferably at most 20 mass %, more preferably at most 15 mass %, especially preferably at most 10 mass %.

The content when the non-volatile component in the photosensitive resin composition of the component (D-1) is regarded as 100% by mass is defined as D1, and the non-volatile component in the photosensitive resin composition of the component (D-2) is defined as When the content at 100% by mass is D2, D2/D1 is preferably at least 0.5, more preferably at least 0.8, particularly preferably at least 1.2, more preferably at most 3.5, more preferably at most 3.0, and most preferably at most 2.5 . When the amount ratio of (D-1) component and (D-2) component exists in this range, the desired effect of this invention can be acquired remarkably.

＜(E) Photopolymerizable compound＞ The photosensitive resin composition contains (E) photopolymerizable compound as (E) component. However, those equivalent to (A) components are excluded. Photoreactivity can be improved by containing (E)component. (E) The component may be used individually by 1 type, and may use 2 or more types together.

(E) The refractive index of a component is 1.45 or more, Preferably it is 1.46 or more, More preferably, it is 1.47 or more. The upper limit of the refractive index is 1.51 or less, preferably 1.508 or less, more preferably 1.505 or less. Usually, the refractive index of (B) inorganic filler is 1.45 or more and 1.51 or less. The inventors of the present invention can suppress the deterioration of the shape of the through-hole by making the refractive index of the (E) component close to the refractive index of the (B) inorganic filler, thereby opening a small-diameter through-hole. The refractive index can be measured by the method described in the Examples described later.

As (E) component, the compound which can photopolymerize by irradiating active light rays can be used. As such a compound, the photosensitive (meth)acrylate compound which is liquid, solid, or semisolid at room temperature which has one or more (meth)acryloyl groups in 1 molecule, for example can be used. The so-called room temperature means about 25°C. The so-called "(meth)acryl" refers to acryl and methacryl.

(E) A suitable embodiment of a component is a photosensitive (meth)acrylate compound which has a divalent cyclic structure and has a refractive index of 1.45 or more and 1.51 or less. As a divalent cyclic group, any of the cyclic group containing an alicyclic structure and the cyclic group containing an aromatic ring structure may be sufficient. Among them, a cyclic group including an alicyclic structure is preferable from the viewpoint of remarkably 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, particularly preferably a 5-membered ring or more, and more preferably a 20-membered ring from the viewpoint of remarkably obtaining the desired effect of the present invention. Ring or less, more preferably less than 15 member rings, especially preferably less than 10 member rings. In addition, the divalent cyclic group may have a monocyclic structure or may have a polycyclic structure.

In the divalent cyclic group, the ring skeleton may be constituted by heteroatoms other than the carbon atoms in the ring system, and the divalent cyclic group preferably has an alicyclic skeleton containing a heteroatom. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom etc. are mentioned, for example, Oxygen atom is preferable. There may be one heteroatom in the aforementioned ring, or two or more heteroatoms.

2價環狀基可具有取代基。作為如此的取代基，例如可舉出鹵素原子、烷基、烷氧基、芳基、芳基烷基、矽烷基、醯基、醯氧基、羧基、磺基、氰基、硝基、羥基、巰基、側氧基等，較佳為烷基。 Specific examples of the divalent cyclic group include the following divalent groups (i) to (x). Among these, (x) is preferable as a divalent cyclic group.

The divalent 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, carboxyl groups, sulfo groups, cyano groups, nitro groups, and hydroxyl groups. , mercapto, side oxygen, etc., preferably an alkyl group.

The (meth)acryloyl group may be directly bonded to a divalent cyclic group, or may be bonded via a divalent linking group. Examples of divalent linking groups include aryl, alkenyl, aryl, heteroaryl, -C(=O)O-, -O-, -NHC(=O)-, -NC (=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, and the like may be plural groups combining them. The aryl group is preferably an aryl group with 1 to 10 carbon atoms, more preferably an aryl group with 1 to 6 carbon atoms, especially an aryl group with 1 to 5 carbon atoms, or an aryl group with 1 to 5 carbon atoms. 1-4 extended aryl groups. The aryl group may be straight chain, branched, or cyclic. Such aryl groups include, for example, methylene, ethylenyl, propylenyl, butyl, pentyl, hexyl, 1,1-dimethylethylenyl, etc., preferably ethylene Methyl, ethylidene, 1,1-dimethylethylidene. 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 particularly preferably an alkenylene group having 2 to 5 carbon atoms. The arylylene group or heteroarylylene group is preferably an arylylene group or heteroarylylene group having 6 to 20 carbon atoms, more preferably an arylylene group or heteroarylylene group having 6 to 10 carbon atoms. As the divalent linking group, an aryl group is preferable, and a methylene group and a 1,1-dimethylethylene group are preferable among them.

(式(E)中，R ¹及R ⁴各自獨立地表示丙烯醯基或甲基丙烯醯基，R ²及R ³各自獨立地表示2價連結基；環A表示2價環狀基)。 The photosensitive (meth)acrylate compound which has a divalent cyclic structure and has a refractive index of not less than 1.45 and not more than 1.51 is preferably represented by the following formula (E).

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

R ¹ and R ⁴ each independently represent acryl or methacryl, preferably acryl.

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 can 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 which the above-mentioned divalent cyclic group may have.

Specific examples of photosensitive (meth)acrylate compounds having a divalent cyclic structure and a refractive index of 1.45 to 1.51 include compounds represented by formula (E-1), but the present invention does not limited by it.

Commercially available photosensitive (meth)acrylate compounds having a divalent ring structure and a refractive index of 1.45 to 1.51 can be used, for example, "A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd. (compound represented by formula (E-1)), "NPDGA", "FM-400", "R-687", "THE-330", "PET-30" manufactured by Nippon Kayaku Co., Ltd.

(E) Another embodiment of a component is a photosensitive (meth)acrylate compound which 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 4-acrylmorpholine; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; ethylene glycol , methoxytetraethylene glycol, polyethylene glycol, propylene glycol, neopentyl glycol and other diol mono- or diacrylates; N,N-dimethylacrylamide, N-methylolacrylamide Acrylamides such as amines; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate, polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, or their rings Polyvalent acrylates of adducts of ethylene oxide, propylene oxide or ε-caprolactone; phenols such as phenoxy acrylate, phenoxyethyl acrylate, or ethylene oxide or propylene oxide Acrylates, etc.; epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether; melamine acrylates; and/or corresponding to the above-mentioned acrylates methacrylates, etc. Among these, alkyl acrylates and heterocyclic ring-containing acrylates are preferable.

As (E) component, it is preferable to contain the compound represented by a formula (E-1) from a viewpoint of remarkably acquiring the effect of this invention.

The content of the component (E) is preferably 0.5% by mass or more when the non-volatile components of the photosensitive resin composition are regarded as 100% by mass from the viewpoint of effective improvement of image development and adhesiveness. More preferably, it is at least 1% by mass, especially preferably at least 3% by mass, and more preferably at most 10% by mass, more preferably at most 9% by mass, and especially preferably at most 8% by mass. Moreover, when the quantity of (E) component exists in the said range, the photocuring of a photosensitive resin composition can be promoted normally, or stickiness can be suppressed when hardening a photosensitive resin composition.

＜(F) Hardening Accelerator＞ The photosensitive resin composition may contain (F) a hardening accelerator as an optional component in addition to the above components. (F) A component may be used individually by 1 type, or may use it in combination of 2 or more types.

As (F) component, phosphorus type hardening accelerator, amine type hardening accelerator, imidazole type hardening accelerator, guanidine type hardening accelerator, metal type hardening accelerator etc. are mentioned, for example.

Examples of phosphorus-based hardening accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4 -Methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutylphosphonium decanoic acid Salt.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-ginseng ( Dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-diaza Bicyclo(5,4,0)-undecene.

Examples of imidazole-based hardening 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-phenylimidazole Onium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-trimethanium, 2,4-diamino-6- ( 1')]-Ethyl-s-trimethazolium, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-trimethazolium isocyanuric acid Adducts, 2-phenylimidazole isocyanuric acid adducts, 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 -Imidazole compounds such as phenylimidazoline and adducts of imidazole compounds and epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As an imidazole type hardening accelerator, a commercial item can also be used, for example, "P200-H50" by Mitsubishi Chemical Corporation etc. are mentioned.

Examples of guanidine hardening accelerators include cyanoguanidine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethyl Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1, 5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1- Dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., preferably cyanoguanidine, 1 ,5,7-Triazabicyclo[4.4.0]dec-5-ene.

Examples of metal-based hardening accelerators include 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, and organocopper complexes such as copper(II) acetylacetonate , organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, manganese acetylacetonate (II) Organic manganese complexes, etc. Examples of organic metal salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

The content of the component (F) is preferably at least 0.001% by mass, more preferably 0.005% by mass, from the viewpoint of remarkably obtaining the desired effect of the present invention, when the non-volatile components in the resin composition are regarded as 100% by mass. % or more, preferably at least 0.01% by mass, and preferably at most 0.15% by mass, more preferably at most 0.12% by mass, especially preferably at most 0.1% by mass.

＜(G)Organic solvent＞ The photosensitive resin composition may further contain (G) an organic solvent. By containing the component (G), the viscosity of the varnish can be adjusted. (G) Organic solvents include, for example, ketones such as methyl ethyl ketone (MEK) and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methylcylonol, Diols such as butyl cellosu, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Ethers, esters of ethyl acetate, butyl acetate, butyl cellothane acetate, carbitol acetate, ethyl diglycol acetate, etc., aliphatic hydrocarbons such as octane and decane Petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, mineral spirits, etc. These can be used individually by 1 type or in combination of 2 or more types. The content in the case of using an organic solvent can be appropriately adjusted from the viewpoint of coatability of the photosensitive resin composition.

＜(H)Other additives＞ The photosensitive resin composition may further contain (H) other additives to an extent that does not interfere with the object of the present invention. As (G) other additives, for example, fine particles such as thermoplastic resin, organic filler, melamine, organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, Coloring agents such as naphthalene black, polymerization inhibitors such as hydroquinone, phenanthrene, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogalchol, etc., benton, montmorillonite, etc. Tackifiers, silicone-based, fluorine-based, vinyl resin-based defoamers, brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus-based compounds, aromatic condensed phosphates, halogen-containing condensation Various additives such as flame retardants such as phosphate esters, phenolic hardeners, cyanate hardeners, etc. thermosetting resins.

The photosensitive resin composition is mixed with the above-mentioned (A)-(E) components as essential components, suitably mixed with the above-mentioned (F)-(H) components as optional components, and can be mixed with a three-roll mill, a ball mill, or a bead mill if necessary. Mixing means such as machine, sand mill, etc., or mixing means such as super mixer, planetary mixer, etc., are kneaded or stirred, and manufactured as resin varnish.

<Physical properties and uses of photosensitive resin composition> The minimum melt viscosity of the photosensitive resin composition is preferably less than 10000 poise, more preferably less than 8000 poise, and most preferably less than 5000 poise. The lower limit is not particularly limited, but may be 10 poise or more. Here, the term "minimum melt viscosity" refers to the minimum melt viscosity at 60°C to 200°C. The minimum melt viscosity can be measured using a dynamic viscoelasticity measuring device. As a specific example of the dynamic viscoelasticity measurement device, "Rheosol-G3000" manufactured by UBM Corporation is mentioned. For the lowest melt viscosity, for example, a dynamic viscoelasticity measuring device can be used. For 1 g of the sample, a parallel plate with a diameter of 18 mm is used, and the temperature is raised from the starting temperature of 60°C at a rate of 5°C/min to 200°C. The measured temperature interval is 2.5°C, The measurement was carried out under the conditions of vibration frequency 1Hz and strain 1deg.

After photocuring the photosensitive resin composition, the cured product that is thermally cured at 190° C. for 90 minutes usually exhibits low average coefficient of thermal expansion (CTE). That is, an insulating layer and a solder resist that result in a low average linear thermal expansion rate. The average linear thermal expansion rate is preferably at most 55 ppm, more preferably at most 50 ppm, and most preferably at most 45 ppm. The lower limit is not particularly limited, but may be set to 10 ppm or more. The measurement of the average linear thermal expansion coefficient can be measured according to the method described in the Example mentioned later.

After photocuring the photosensitive resin composition of the present invention, the cured product that is thermally cured at 190° C. for 90 minutes usually exhibits low dielectric constant. That is, an insulating layer and a solder resist having a low dielectric constant are created. The dielectric constant is preferably at most 3.5, more preferably at most 3.4, most preferably at most 3.3. The lower limit is not particularly limited, but may be 0.1 or more. The measurement of the dielectric constant can be carried out according to the method described in the examples described later.

After photocuring the photosensitive resin composition of the present invention, the cured product that is thermally cured at 190° C. for 90 minutes usually exhibits low dielectric tangent characteristics. That is, insulating layers and solder resists that result in low dielectric tangent. The dielectric tangent is preferably at most 0.03, more preferably at most 0.020, and most preferably at most 0.015. The lower limit is not particularly limited, but may be 0.0001 or more. The dielectric tangent can be measured according to the method described in the examples described later.

The photosensitive resin composition exhibits excellent image development properties even when the content of the inorganic filler is increased. Specifically, when exposing and developing the photosensitive resin composition, it is possible to suppress the resin from remaining in the unexposed portion. The evaluation of the residue in the unexposed part can be measured according to the method described in the Example mentioned later.

The photosensitive resin composition exhibits excellent image development properties even when the content of the inorganic filler is increased. Specifically, when a via hole is formed by exposing and developing a photosensitive resin composition, the minimum opening diameter (minimum via hole diameter) of a via hole that can be formed without residue and peeling can be reduced. The minimum opening diameter is preferably at most 60 μm, more preferably at most 45 μm, and most preferably at most 40 μm. The lower limit is not particularly limited, but may be 1 μm or more. The minimum opening diameter can be measured in accordance with the method described in the examples described later.

The photosensitive resin composition exhibits excellent image development properties even when the content of the inorganic filler is increased. Specifically, when a via hole is formed by exposing and developing the photosensitive resin composition, the number of inorganic fillers exposed from the wall of the via hole (hereinafter also referred to as "via hole wall") can be reduced. Specifically, the minimum opening diameter of the through-hole was regarded as R (μm), and the number of inorganic fillers having a particle size of (0.1×R) or more exposed from the through-hole wall was counted. At this time, the number of inorganic fillers having a particle diameter of (0.1×R) or more exposed from the through-hole walls was less than 10. For example, the number of components (B) having a particle size of 1 μm or more is preferably 10 or less, more preferably 9 or less, and most preferably 8 or less on the wall of a through hole with a minimum opening diameter of 10 μm. The lower limit is not particularly limited, but may be 0 or more. The evaluation of the through-hole wall can be measured according to the method described in the examples described later.

The photosensitive resin composition exhibits excellent image development properties even when the content of the inorganic filler is increased. Specifically, when the photosensitive resin composition is exposed and developed to form a through hole, a tapered through hole can be formed, preferably a tapered shape with a small difference between the radius of the uppermost part and the radius of the bottom. The through hole. The term "tapered shape" refers to a shape in which the diameter of the uppermost portion corresponding to the opening of the through-hole is larger than the diameter of the bottom portion corresponding to the bottom of the through-hole, unless otherwise specified. Specifically, the radius (μm) of the uppermost part and the radius (μm) of the bottom of the cross-section of the through-hole were measured by SEM. Find the difference between the uppermost radius and the bottom radius (uppermost radius - bottom radius). The result is preferably 5 or less, more preferably 4.5 or less, and especially preferably 4 or less. The evaluation of the cone shape can be measured according to the method described in the examples described later.

After photocuring the photosensitive resin composition, the cured product that is thermally cured at 180° C. for 30 minutes usually exhibits the property that via holes can be formed by laser. That is, it exhibits the characteristic of being excellent in opening property of a laser via hole. Specifically, the cured product was irradiated with UV-YAG laser under the conditions of power 0.25W, number of shots 20, and target top diameter 30 μm. As a result, through-holes were formed, and the cross-section of the through-holes was observed without peeling. The evaluation of the openness of the laser via hole can be measured according to the method described in the examples described later.

After photocuring the photosensitive resin composition, the cured product is thermally cured at 180° C. for 30 minutes to improve the peel strength (adhesion) with the conductor layer formed by plating. Therefore, when the insulating layer is formed from the cured product, an insulating layer having high peel strength from the plated conductor layer can be obtained. The peel strength is preferably at least 0.20 kgf/cm, more preferably at least 0.30 kgf/cm. The upper limit of the peel strength is not particularly limited, but may be, for example, 10.0 kgf/cm or less. The peel strength can be measured according to the method described in the Examples described later.

The photosensitive resin composition is light-cured, and further heat-cured at 180° C. for 30 minutes, and the surface of the obtained cured product is roughened, and the roughened surface generally exhibits low arithmetic average roughness (Ra). Therefore, the aforementioned hardening system results in an insulating layer having a low arithmetic mean roughness. The arithmetic mean roughness is preferably at most 400 nm, more preferably at most 300 nm, and most preferably at most 200 nm. On the other hand, the lower limit of the arithmetic mean roughness may be set to 1 nm or more. The evaluation of arithmetic mean roughness (Ra) can be measured according to the method described in the Example mentioned later.

The cured product obtained by photocuring the photosensitive resin composition exhibits excellent crack resistance. That is, an insulating layer and a solder resist excellent in crack resistance are produced. For example, no cracks or peeling were observed even when the heat cycle treatment including temperature drop to -65°C and temperature rise to 150°C was repeated 500 times on the cured product. The evaluation of crack resistance can be measured according to the method described in the Example mentioned later.

The application of the photosensitive resin composition of the present invention is not particularly limited, but it can be used for photosensitive films with supports, insulating resin sheets such as prepregs, circuit boards (laminated boards, multilayer printed circuit boards) etc.), solder resist, underfill material, crystal bonding material, semiconductor sealing material, buried hole resin, part embedding resin, etc., which require a wide range of uses for photosensitive resin compositions. Among them, photosensitive resin compositions for insulating layers of printed circuit boards (printed circuit boards using cured products of photosensitive resin compositions as insulating layers), photosensitive resin compositions for interlayer insulating layers (based on photosensitive resin compositions) The hardened product of the permanent resin composition is used as an interlayer insulating layer (interlayer insulating material) for printed circuit boards), the photosensitive resin composition for plating formation (the printed circuit board with plating formed on the cured product of the photosensitive resin composition ) and photosensitive resin composition for solder resist (printed circuit board using the cured product of photosensitive resin composition as solder resist).

[Photosensitive film with support] The photosensitive resin composition of the present invention can be suitably used in the form of a photosensitive film with a support in which a photosensitive resin composition layer is formed on a support. That is, the photosensitive film with a support 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, triacetal acetate film, etc. Particularly preferred is a polyethylene terephthalate film.

Examples of commercially available supports include product names "Arufun MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and product names "PS-200C" manufactured by Teijin Corporation. 25", PS series and other polyethylene terephthalate films, etc., but not limited thereto. In order to easily remove the photosensitive resin composition layer of these support systems, a release agent such as polysiloxane coating can be coated 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, the support can be suppressed from being damaged when the support is peeled off before development, and by setting the thickness to 50 μm or less, the resolution at the time of exposure from the support can be improved. Also, a low fisheye support is preferable. The so-called fisheye here refers to the foreign matter, undissolved matter, oxidative degradation product, etc. of the material entering the film when the material is thermally melted to produce a film by kneading, extrusion, biaxial stretching, casting, etc.

Moreover, in order to reduce the light scattering at the time of exposure by active light rays, such as an ultraviolet-ray, it is preferable that a support body is excellent in transparency. It is preferable that the turbidity (the standard standardized by JIS-K6714) which is an index of transparency of a support body is 0.1-5 specifically. Furthermore, the photosensitive resin composition layer can be protected by a protective film.

By protecting the photosensitive resin composition layer side of the photosensitive film with the support with the protective film, adhesion of dust or the like to the surface of the photosensitive resin composition layer or scratches can be prevented. As the protective film, a thin film made of the same material as the above-mentioned support can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and most preferably in the range of 10 μm to 30 μm. When the thickness is set to be 1 μm or more, the handleability of the protective film can be improved, and when the thickness is set to be 40 μm or less, there is a tendency that the cheapness becomes good. Furthermore, the protective film is preferably one in which the adhesive force between the photosensitive resin composition layer and the protective film is small compared to the adhesive force between the photosensitive resin composition layer and the support.

A photosensitive film with a support can be prepared by dissolving the photosensitive resin composition of the present invention in an organic solvent to prepare a resin varnish, coating the resin varnish on the support, and heating or spraying hot air to make the film varnish. The organic solvent is dried to form a photosensitive resin composition layer and manufactured. Specifically, firstly, after completely removing air bubbles in the photosensitive resin composition by vacuum defoaming method, etc., the photosensitive resin composition is coated on the support, and the solvent is removed by a hot air furnace or a far-infrared furnace to make it After drying, a photosensitive film with a support can be produced by laminating a protective film on the obtained photosensitive resin composition layer if necessary. The specific drying conditions also vary with the curability of the photosensitive resin composition or the amount of organic solvent in the resin varnish, but in a resin varnish containing 30% by mass to 60% by mass of organic solvent, it can be dried at 80°C to 120°C. It is dried at ℃ for 3 minutes 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 the diffusion of the organic solvent in the subsequent step Preferably, it is 2 mass % or less. Those skilled in the art can properly set the appropriate drying conditions through simple experiments. The thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm, more preferably 10 μm, from the viewpoint of improving operability and suppressing reduction in sensitivity and resolution inside the photosensitive resin composition layer. The range of ~200 μm is more preferably in the range of 15 μm to 150 μm, still more preferably in the range of 20 μm to 100 μm, and particularly preferably in the range of 20 μm to 60 μm.

As the coating method of the photosensitive resin composition, for example, gravure coating method, micro gravure coating method, reverse coating method, contact reverse coating method, die coating method, slit die method, lip coating method, etc. Coating method, chipping wheel coating method, blade coating method, roller coating method, knife coating method, curtain coating method, chamber gravure coating method, slot die method, spray coating method, dip coating way etc.

The photosensitive resin composition may be applied several times, may be applied once, and may be applied in combination of a plurality of different methods. Among them, the die coating method excellent in uniform coating property is preferable. In addition, in order to avoid contamination of foreign matter, etc., it is preferable to carry out the coating step in an environment such as a clean room where foreign matter is rarely generated.

The photosensitive resin composition layer of the photosensitive film with a support of the present invention exhibits a characteristic of excellent flexibility. Therefore, even when stress is applied to the photosensitive resin composition, scattering of resin and generation of cracks can be suppressed. Also, it is preferable that even if the photosensitive resin composition layer is cut out with a knife, no scattering or cracks of the photosensitive resin composition can be seen, and it is also preferable that even if the photosensitive resin composition layer is bent by 180°, the No scattering or cracks of the photosensitive resin composition were observed. The softness can be measured according to the description of the examples described later.

The photosensitive resin composition layer of the photosensitive film with a support of the present invention exhibits excellent adhesive properties. If the photosensitive film with a support at 25°C is evaluated by a probe stickiness tester, the appearance of the film is good, and no trace remains on the probe. The evaluation of adhesiveness can be measured according to the method described in the Example mentioned later.

The photosensitive resin composition layer of the photosensitive film with a support of the present invention exhibits the characteristic of good appearance of the film due to its excellent flexibility and adhesiveness. Therefore, the photosensitive resin composition layer of the photosensitive film with a support suppresses the occurrence of shrinkage spots or unevenness. The appearance of the film can be measured in accordance with the description in the Examples described later.

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

In detail, the printed circuit board of this invention can be manufactured using the above-mentioned photosensitive film with a support. Hereinafter, the case where the insulating layer is a solder resist will be described.

＜Lamination and drying process＞ The photosensitive resin composition layer is formed on the circuit board by laminating the photosensitive resin composition layer side of the photosensitive film with the support on the circuit board and drying it.

Examples of circuit boards include glass epoxy boards, metal boards, polyester boards, polyimide boards, BT resin boards, and thermosetting polyphenylene ether boards. Furthermore, the term "circuit substrate" here refers to a substrate on which a patterned conductor layer (circuit) is formed on one or both surfaces of the support substrate as described above. In addition, in a multilayer printed circuit board formed by laminating conductor layers and insulating layers alternately, one or both sides of the outermost layer of the multilayer printed circuit board become patterned conductor layers (circuits), which are also included here The circuit substrate in the place. Furthermore, the surface of the conductor layer may also be pre-roughened by blackening treatment, copper etching, or the like.

As one embodiment of the lamination process, a vacuum laminator is used to laminate the photosensitive resin composition layer side on one or both surfaces of the circuit board. In the lamination step, if the photosensitive film with the support has a protective film, after removing the protective film, preheat the photosensitive film with the support and the circuit board if necessary, pressurize and heat the photosensitive resin composition layer, one side is crimped to the circuit board. For the photosensitive film with a support, it is preferable to adopt the method of laminating on the circuit board under reduced pressure by vacuum lamination.

The conditions of the lamination step are not particularly limited. For example, the crimping temperature (lamination temperature) is preferably 70°C to 140°C, and the crimping pressure is preferably 1kgf/cm ² to 11kgf/cm ² (9.8×10 ⁴ N /m ² to 107.9×10 ⁴ N/m ² ), the crimping time is preferably 5 seconds to 300 seconds, and the lamination is preferably performed under a reduced air pressure of 20 mmHg (26.7 hPa). In addition, the lamination step may be a batch method or a continuous method using a roll. The vacuum lamination method can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum applicator made by Nikko-Materials Co., Ltd., a vacuum pressurized laminator made by Meiji Seisakusho Co., Ltd., a roll-type dry coater made by Hitachi Industries, Ltd., a vacuum laminator made by Hitachi AIC Laminators etc. In this way, the photosensitive film with the support was formed on the circuit board.

Instead of laminating a photosensitive film with a support, the photosensitive resin composition can also be formed on the circuit board by directly coating the photosensitive resin composition on the circuit board in the state of resin varnish and drying the organic solvent Floor. As a coating method, generally, full-surface printing by a screen printing method is often used, but any method can be used as long as it is a coating method that enables uniform coating. 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 coating method, roll coating method, gravure coating method method, lithography method, dip coating method, brush coating, and other common coating methods can be used. After application|coating, it dries in a hot-air oven, a far-infrared oven, etc. as needed. The drying conditions are preferably at 80° C. to 120° C. for 3 minutes to 13 minutes.

<Exposure step> Through the above steps, after the photosensitive resin composition layer is provided on the circuit board, then through the mask pattern, the active light is irradiated to the specific part of the photosensitive resin composition layer to make the irradiated part photosensitive. Exposure step for photohardening of the permanent resin composition layer. Examples of actinic rays include ultraviolet rays, visible rays, electron beams, X-rays, and the like, particularly preferably ultraviolet rays. The irradiation dose of ultraviolet light is about 10mJ/cm ² -1000mJ/cm ² . In the exposure method, there are a contact exposure method in which a mask pattern is placed in close contact with a printed circuit board, and a non-contact exposure method in which exposure is performed using parallel light rays without close contact, and either one can be used. Moreover, when a support exists on a photosensitive resin composition layer, exposure may be performed from a support, or may expose a support after peeling.

Solder resist is excellent in developability (resolution) by using the photosensitive resin composition of this invention. Therefore, as the exposure pattern in the mask pattern, for example, a ratio (L/S) of 100 μm/100 μm or less (that is, circuit pitch 200μm or less), L/S=80μm/80μm or less (circuit spacing 160μm or less), L/S=70μm/70μm or less (circuit spacing 140μm or less), L/S=60μm/60μm or less (circuit spacing 120μm or less) graphics. Also, the pitch does not have to be the same over the entire circuit board.

＜Development procedure＞ After the exposure step, when a support exists on the photosensitive resin composition layer, after removing the support, by wet or dry development, by removing the part that is not photohardened (unexposed part) Visualization can form graphics.

In the above-mentioned wet development, as the developing solution, safe and stable developing solutions such as alkaline aqueous solution, water-based developing solution, and organic solvent are used, and among them, the developing solution by alkaline aqueous solution is preferred. like steps. Moreover, well-known methods, such as spraying, shaking dipping, scrubbing, scrubbing, etc., can be suitably used as a developing method.

Alkaline aqueous solutions used as developing solutions include, for example, 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. , potassium phosphate and other alkali metal phosphates, aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, aqueous solutions of metal ion-free organic bases such as tetraalkylammonium hydroxide, etc. , In terms of not affecting the semiconductor wafer, it is preferably an aqueous solution of tetramethylammonium hydroxide (TMAH).

In these alkaline aqueous solutions, in order to improve the imaging effect, surfactants, defoamers, etc. can be added to the imaging solution. The pH of the above-mentioned alkaline aqueous solution is, for example, preferably in the range of 8-12, more preferably in the range of 9-11. Moreover, it is preferable that the alkali concentration of the said alkaline aqueous solution is 0.1 mass % - 10 mass %. The temperature of the above-mentioned alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, but it is preferably set at 20°C to 50°C.

Examples of organic solvents used in the developer include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether.

The concentration of such an organic solvent is preferably 2% by mass to 90% by mass relative to the total amount of the developer. Also, the temperature of such an organic solvent can be adjusted according to the developability. In addition, such an organic solvent can be used individually or in combination of 2 or more types. Examples of organic solvent-based developers used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, formaldehyde Base isobutyl ketone, γ-butyrolactone.

In pattern formation, if necessary, two or more types of image development methods described above may be used in combination. There are immersion methods, liquid covering methods, spray methods, high-pressure spray methods, brushing, scrubbing, etc. in the imaging methods. In order to improve the resolution, the high-pressure spray method is suitable. The spray pressure should be 0.05MPa ~ 0.3MPa when spraying is used.

<Thermal hardening (post-baking) process> After completion|finish of the said image development process, a thermal hardening (post-baking) process is performed as needed, and a solder resist is formed. As a post-baking process, the ultraviolet-ray irradiation process by a high-pressure mercury lamp, the heating process using a clean oven, etc. are mentioned, for example. When irradiating ultraviolet rays, the irradiation dose can be adjusted as necessary, for example, the irradiation dose can be about 0.05 J/cm ² to 10 J/cm ² . Also, the heating conditions may be appropriately selected according to the type and content of the resin components in the photosensitive resin composition, but it is preferably selected within the range of 20 minutes to 180 minutes at 150° C. to 220° C., more preferably at 150° C. to 220° C. Select from the range of 30 minutes to 120 minutes at 160°C to 200°C.

＜Other steps＞ After the solder resist is formed on the printed circuit board, it may further include the steps of opening holes and removing smear. These steps can be carried out according to various methods well known in the art for the manufacture of printed circuit boards.

After forming the solder resist, a hole-opening step is performed in the solder resist formed on the circuit board as desired to form through holes and through holes. The hole opening step can be performed by well-known methods such as drilling, laser, plasma, etc., and a combination of these methods as needed, but the hole opening of carbon dioxide laser, YAG laser, etc. is preferred. step.

The desmearing step is a step of desmearing treatment. In general, resin residue (smear) adheres to the inside of the opening formed in the drilling step. Since such smears cause poor electrical connection, a process of removing smears (smear removal process) is performed in this step.

The desmearing treatment can be implemented by dry desmearing treatment, wet desmearing treatment or a combination thereof.

As a dry type desmear process, the desmear process etc. which use plasma are mentioned, for example. The desmear treatment using plasma can be implemented using a commercially available plasma desmear treatment device. Among the commercially available plasma desmear processing equipment, as examples suitable for the production of printed circuit boards, there are microwave plasma equipment manufactured by NISSIN Co., Ltd., and atmospheric pressure plasma etching equipment manufactured by Sekisui Chemical Co., Ltd., etc. .

As a wet desmear process, the desmear process etc. which use an oxidizing agent solution are mentioned, for example. When desmearing treatment is performed using an oxidant solution, it is preferable to sequentially perform swelling treatment with a swelling solution, oxidation treatment with an oxidant solution, and neutralization treatment with a neutralization solution. As a swelling liquid, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd., etc. are mentioned, for example. The swelling treatment is preferably carried out by immersing the substrate on which the through holes and the like are formed in a swelling liquid heated to 60° C. to 80° C. for 5 minutes to 10 minutes. The oxidizing agent solution is preferably an aqueous alkaline permanganic acid solution, for example, a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment by 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. As a commercial item of alkaline permanganic acid aqueous solution, "Concentrate Compact CP" and "Dosing Solution Securiganth P" by Atotech Japan Co., Ltd. are mentioned, for example. The neutralization treatment by the neutralizing solution is preferably carried out by immersing the oxidized substrate in a neutralizing solution at 30° C. to 50° C. for 3 minutes to 10 minutes. As a neutralization liquid, an acidic aqueous solution is preferable, and "Reduction Solution Securigand P" manufactured by Atotech Japan Co., Ltd. is mentioned as a commercial item, for example.

When combining the dry desmear treatment and the wet desmear treatment, the dry desmear treatment may be implemented first, or the wet desmear treatment may be implemented first.

When an insulating layer is used as an interlayer insulating layer, it can also be performed in the same manner as in the case of a solder resist, and a hole opening step, a desmearing step, and a plating step can be performed after the thermosetting step.

The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer can be formed by combining electroless plating and electrolytic plating. In addition, it is also possible to form a plating resist with a pattern reversed to that of the conductor layer, and form the conductor layer only by electroless plating. As the subsequent pattern forming method, for example, a subtractive method, a semi-additive method, etc. well known to those skilled in the art can be used.

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

Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as locomotives, automobiles, trains, ships, and aircraft).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conducting portion of a printed circuit board. The so-called "conduction part" is "the part of the printed circuit board that transmits electrical signals", which can be the surface or the buried part, regardless. Also, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element made of a semiconductor.

The mounting method of the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip can effectively function, but specific examples include a wire bonding mounting method, a flip chip mounting method, and a bumpless mounting method. The mounting method by build-up layer (BBUL), the mounting method by anisotropic conductive film (ACF), the mounting method by non-conductive film (NCF), etc. Here, the so-called "mounting method by build-up layer (BBUL) without bumps" means "embedding the semiconductor chip directly into the recess of the printed circuit board, and connecting the semiconductor chip to the circuit on the printed circuit board. method". [Example]

Hereinafter, the present invention will be specifically described by means of examples, but the present invention is not limited by these examples. In addition, in the description below, "parts" and "%" indicating 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., Japan The "Seahostar series" produced by Catalyst Co., Ltd. and the "SG-SO series" produced by Sukgyuug Co., Ltd. were obtained by surface treatment with a vinyl silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM1003), filtered and classified. The particle size distribution of inorganic fillers B-1 to B-7 was measured by the following method.

50 mg of powder of inorganic filler B-1, 2 g of nonionic dispersant (manufactured by NOF Corporation "T208.5"), and 40 g of pure water were weighed into a vial, and dispersed by ultrasonic waves for 20 minutes. D ₁₀ , D ₅₀ , and D ₉₀ were calculated by measuring the particle size distribution in a batch cell system using a laser diffraction particle size distribution measuring device (LA-950, manufactured by Horiba, Ltd.). Also about the inorganic fillers B-2 to B-6, the average particle diameter was calculated similarly. The particle size distribution was measured in the same manner except that pure water was changed to MEK regarding B-7.

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

D ₁₀ , D ₅₀ , D ₉₀ and specific surface area of each inorganic filler are shown in the following table.

(Measurement of Refractive Index) (E) The refractive index of the component was measured at 589 nm while keeping the temperature at 25° C. using an Abbe refractometer (manufactured by ATAGO, DR-M2).

(Synthesis Example 1: Synthesis of Component A-1) Put 325 parts of an epoxy resin having a naphthol aralkyl skeleton ("ESN-475V", manufactured by Nippon Steel Chemical Co., Ltd.) with an epoxy equivalent of 325g/eq. Into the flask, 340 parts of carbitol acetate were added, heated and dissolved, and 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. This mixture was heated to 95-105° C., 72 parts of acrylic acid was slowly dropped, and reacted for 16 hours. This reaction product was cooled to 80-90 degreeC, 80 parts of tetrahydrophthalic anhydrides were added, it was made to react for 8 hours, and it was made to cool. Adjust the amount of solvent to obtain a resin solution (70% non-volatile matter, hereinafter referred to as "A-1") with an acid value of solid matter of 60 mgKOH/g.

<Examples 1-7, Comparative Examples 1-9> Each component was blended in the blending ratio shown in the following table, and the resin varnish was prepared using the high-speed rotary mixer. Next, a PET film ("Lumirror T6AM" manufactured by Toray Co., Ltd., thickness 38 μm, softening point 130°C, "Release Mold PET") as a support. The prepared resin varnish was uniformly coated on the release PET with a die coater so that the thickness of the dried photosensitive resin composition layer was 20 μm, and dried at 80° C. to 110° C. for 7 minutes to obtain A photosensitive film with a support attached to a photosensitive resin composition layer on a molded PET.

<Evaluation of Appearance, Flexibility, and Adhesiveness of Film> The appearance of the photosensitive resin composition layer of the photosensitive film with a support produced in Examples and Comparative Examples was visually observed. Moreover, when the photosensitive resin composition layer was cut out with a cutter, the scattering of resin and the generation|occurrence|production of a crack were visually observed. Furthermore, the state of occurrence of cracks when the photosensitive film with a support was bent by 180° was visually observed. In addition, the adhesiveness of the photosensitive film with the support attached was evaluated in a thermostatic chamber at 25°C with a probe adhesion 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. The appearance, flexibility and adhesiveness of the film were evaluated as follows. ◯: There is no shrinkage spot or unevenness, and no scattering or cracking of the resin is observed. Also, after the adhesiveness evaluation, the appearance of the film was good, and the resin did not adhere to the probe due to excess adhesiveness. ×: Shrinkage spots or unevenness, resin scattering, cracks, or after adhesive evaluation, resin remained on the probe due to excess adhesiveness, and the film was damaged.

＜Determination of minimum melt viscosity＞ Only the photosensitive resin composition layer was peeled off from the release PET of the photosensitive film with a support, and compressed by a mold to produce pellets for measurement (18 mm in diameter, 1.2 to 1.3 g). Using the particles for measurement, using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM Co., Ltd.), for 1 g of the photosensitive resin composition layer of the sample, using a parallel plate with a diameter of 18 mm, starting from the starting temperature of 60 ° C at 5 ° C / The heating rate of 1 minute is raised to 200°C, and the dynamic viscoelasticity is measured under the measurement conditions of the measurement temperature interval of 2.5°C, the vibration frequency of 1Hz, and the strain of 1deg, and the minimum melt viscosity (poise) is calculated.

<Measurement of Average Linear Thermal Expansion Coefficient and Dielectric Properties> (Formation of Cured Product for Evaluation) For the photosensitive resin composition layer of the photosensitive film with support obtained in Examples and Comparative Examples, 100 mJ/cm ² It is photohardened by exposure to ultraviolet light. Then, the entire surface of the photosensitive resin composition layer was subjected to spray development for 2 minutes with a 30° C. 1% by mass sodium carbonate aqueous solution as a developing solution at a spray pressure of 0.2 MPa. After the spray image development, 1 J/cm ² of ultraviolet rays was irradiated, and heat treatment was further performed at 190° C. for 90 minutes to obtain a cured product. Then, the support was peeled off to obtain a hardened product for evaluation.

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

(Measurement of dielectric properties (permittivity, dielectric tangent)) The cured product for evaluation was cut into test pieces 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, Inc., the value of dielectric constant (Dk value) and The value of dielectric tangent (Df value). The measurement was implemented with 3 test pieces (N=3), and the average was calculated.

＜Evaluation of Visibility＞ (Formation of laminate A for evaluation) Roughen the copper layer of the glass epoxy substrate (copper-clad laminate) on which the patterned circuit of the copper layer with a thickness of 18 μm is formed with a surface treatment agent containing an organic acid (CZ8100, manufactured by MEC Co., Ltd.) . Next, the photosensitive resin composition layer of the photosensitive film with support obtained in Examples and Comparative Examples was placed in contact with the surface of the copper circuit, using a vacuum laminator (manufactured by Nikko-Materials, VP160). Lamination, forming a laminate in which the aforementioned copper-clad laminate, the aforementioned photosensitive resin composition layer, and the aforementioned support are sequentially stacked. As for the crimping conditions, the vacuum suction time was 30 seconds, the crimping temperature was 80° C., the crimping pressure was 0.7 MPa, and the pressing time was 30 seconds. The laminate was allowed to stand at room temperature for at least 30 minutes, and a hole pattern was used on the support of the laminate to expose it to ultraviolet light using a pattern forming device to form through holes. Exposure patterns use openings: 20μm/25μm/30μm/40μm/50μm/60μm/70μm/80μm/90μm/100μm circular holes, L/S (line/space): 20μm/20μm, 25μm/25μm, 30μm/30μm , 40μm/40μm, 50μm/50μm, 60μm/60μm, 70μm/70μm, 80μm/80μm, 90μm/90μm, 100μm/100μm lines and spaces, and a quartz glass mask that draws a square of 1cm×2cm. After leaving still at room temperature for 30 minutes, the support body was peeled off from the said laminated body. Then, the entire surface of the photosensitive resin composition layer was spray-developed with a 30° C. 1% by mass sodium carbonate aqueous solution as a developing solution at a spray pressure of 0.2 MPa. This board|substrate was made into the laminated body A for evaluation.

(residue of unexposed part) The non-exposed part of the 1 cm x 2 cm part of the laminated body A for evaluation was visually observed, and it evaluated by the following reference|standard. ◯: Resin does not remain on the unexposed portion. ×: Resin was visually confirmed, or film damage occurred.

(evaluation of minimum opening diameter) The formed via hole was observed by SEM (magnification: 1000 times), and the minimum via hole diameter without residue and peeling was measured.

(Evaluation of through-hole wall) In addition, the inner wall of the through hole (through hole wall) was evaluated by the number of inorganic fillers with a count particle diameter of 0.1×R exposed from the through hole wall when the minimum opening diameter was taken as R, and the following criteria were used for evaluation. ◯: The number of inorganic fillers having a particle size of (0.1×R) or more exposed from the through-hole wall is less than 10. ×: The number of inorganic fillers having a particle size of (0.1×R) or more exposed from the through-hole wall is 10 or more.

(Evaluation of the cone) In the obtained through-hole with the smallest opening diameter, conduct SEM cross-sectional observation, measure the radius (μm) at the top of the cross-section and the radius (μm) at the bottom, and calculate the difference (radius at the top-radius at the bottom). A positive value is a tapered shape, and a negative value is an undercut shape.

＜Laser via hole opening, copper plating adhesion＞ (Preparation of laminate B for evaluation) Roughen the copper layer of the glass epoxy substrate (copper-clad laminate) on which the patterned circuit of the copper layer with a thickness of 18 μm is formed with a surface treatment agent containing an organic acid (CZ8100, manufactured by MEC Co., Ltd.) . Next, the photosensitive resin composition layer of the photosensitive film with support obtained in Examples and Comparative Examples was placed in contact with the surface of the copper circuit, using a vacuum laminator (manufactured by Nikko-Materials, VP160). Lamination, forming a laminate in which the aforementioned copper-clad laminate, the aforementioned photosensitive resin composition layer, and the aforementioned support are sequentially stacked. As for the crimping conditions, the vacuum suction time was 30 seconds, the crimping temperature was 80° C., the crimping pressure was 0.7 MPa, and the pressing time was 30 seconds. This laminate was left to stand at room temperature for 30 minutes or more, and then exposed to ultraviolet rays through quartz glass. After leaving still at room temperature for 30 minutes, the support body was peeled off from the said laminated body. The whole surface of the photosensitive resin composition layer on the laminated board after peeling off the support was sprayed and developed with a 30° C. 1% by mass sodium carbonate aqueous solution as a developing solution at a spray pressure of 0.2 MPa. Then, exposure was performed with a metal halide lamp, thermal curing was performed at 180° C. for 30 minutes, and a laminate B for evaluation was obtained.

(Laser via opening) In the evaluation laminate B, via holes were formed in the insulating layer under the following conditions using a UV-YAG laser processing machine ("LU-2L212/M50L" manufactured by VIA MECHANICS Co., Ltd.), and the following criteria were used for evaluation. Conditions: power 0.25W, number of shots 20, target top diameter 30μm. ◯: The opening of the through-hole was formed, and there was no peeling even when the cross-section was observed. ×: The opening of the through-hole was not formed, or peeling occurred when the cross-section was observed.

(Evaluation of Copper Plating Adhesion) The laminate B for evaluation was immersed in Swelling Dip Securiganth P made by ATOTECH Japan Co., Ltd. as a swelling solution containing diethylene glycol monobutyl ether at 60°C for 5 minutes, and then In Concentrate Compact CP P (KMnO ₄ : 60g/L, NaOH: 40g/L aqueous solution) manufactured by ATOTECH Japan Co., Ltd. Immerse in Reduction Solution Securigant P prepared by the manufacturer at 40°C for 5 minutes. The laminate B for evaluation after the roughening treatment is referred to as laminate C for evaluation.

Next, this evaluation laminate C was immersed in a solution for electroless plating containing PdCl ₂ , and then immersed in an electroless copper plating solution. After annealing by heating at 150°C for 30 minutes, an etch resist was formed, and after patterning by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 20±5 μm. Next, annealing treatment was performed at 180° C. for 60 minutes. A slit with a width of 10mm and a length of 100mm is introduced into the plated conductor layer with a knife, and one end is peeled off, and grasped with a jig (manufactured by TSE Corporation, Autocom type testing machine AC-50C-SL), and measured at room temperature at 50mm The load when tearing off 35 mm in the vertical direction at a speed per minute was evaluated using the following criteria. ◎: The load is 0.30kgf/cm or more ○: The load is less than 0.30kgf/cm and 0.20kgf/cm or more ×: The load is less than 0.20kgf/cm

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

＜Evaluation of Cracks＞ For the copper layer of the glass epoxy substrate (copper-clad laminate) on which the patterned circuit of the copper pad with a thickness of 18 μm and ϕ100 μm is formed, the surface treatment agent (CZ8100, manufactured by MEC Co., Ltd.) containing an organic acid is treated. to coarsen. Other than that, the laminated body D for evaluation was produced in the same procedure as the laminated body A for evaluation. After exposing the substrate to the atmosphere at -65°C for 15 minutes, the temperature was raised at a rate of 180°C/min, and after being exposed to the atmosphere at 150°C for 15 minutes, the temperature was lowered at a rate of 180°C/min. This heat cycle treatment was repeated 500 times. After the test, the degree of cracking and peeling of the substrate for evaluation was observed with an optical microscope ("ECLIPSE LV100ND" manufactured by NIKON Corporation), and the following criteria were used for evaluation. ◯: No crack or peeling was observed. ×: Cracks and peeling were observed.

The abbreviated symbols and the like in the table are as follows. ・(ACA)Z-251: Acrylic polymer, Cyclomer P (manufactured by DAICEL-ALLNEX, acid value 66mgKOH/g, solid content concentration about 46%) ・CCR-1171H: Cresol novolak type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH/g, solid content concentration about 60%) ・A-1: Component A-1 synthesized in Synthesis Example 1 (70% non-volatile content) ・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 Corporation ・HP4032: Naphthalene-type epoxy resin (manufactured by DIC Corporation, epoxy equivalent 144g/eq., softening point less than 30°C) ・NC3000L: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 271g/eq., softening point 53°C) ・NPGDA: Neopentyl glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd., refractive index 1.452) ・A-DOG: Dioxanediol diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., refractive index 1.472) ・ACMO: 4-acryloylmorpholine (manufactured by KJ Chemical Co., Ltd., refractive index 1.508) ・NOAA: n-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 Chemicals Co., Ltd. ・EDGAc: Ethyl diglycol acetate ・MEK: methyl ethyl ketone

From the results in the above table, it can be seen that the appearance, resin viscosity, average linear thermal expansion coefficient, electrical characteristics, and crack resistance of the films in Examples 1 to 7 are excellent, and they are resin compositions that can form through-holes with fine openings.

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

In each Example, when (F) component etc. were not contained, although there were differences in degree, it confirmed that it belonged to the result similar to the said Example.

Claims (12)

A photosensitive resin composition comprising (A) a resin containing ethylenically unsaturated groups and carboxyl groups, (B) an inorganic filler, (C) a photopolymerization initiator, (D) an epoxy resin, and (E) A photosensitive resin composition of a photopolymerizable compound, when the non-volatile components in the photosensitive resin composition are taken as 100% by mass, the content of (B) component is 30% by mass or more, and the particle size distribution of (B) component is 10% particle size (D ₁₀ ) of 0.06 μm to 0.6 μm, 50% particle size (D ₅₀ ) of 0.11 μm to 1.10 μm, 90% particle size (D ₉₀ ) of 0.22 μm to 2.20 μm Hereinafter, the refractive index of (E) component is 1.45-1.51. Such as the photosensitive resin composition of claim 1, wherein in the cured product of the photosensitive resin composition, when forming a through hole with a minimum opening diameter of R (μm), the particle diameter exposed on the wall surface of the through hole is (0.1 The number of objects of the (B) component having xR) μm or more is 10 or less. The photosensitive resin composition according to claim 1, wherein component (E) has a divalent ring structure. The photosensitive resin composition according to claim 3, wherein the divalent cyclic group has an alicyclic skeleton containing heteroatoms. The photosensitive resin composition according to claim 1, wherein component (E) includes a compound represented by the following formula (E-1);

. The photosensitive resin composition according to claim 1, wherein the component (A) has any one of a cresol novolak skeleton, a naphthalene skeleton, and a naphthol aralkyl skeleton. The photosensitive resin composition according to claim 1, wherein component (A) comprises acid-modified epoxy (meth)acrylate containing naphthol aralkyl skeleton. The photosensitive resin composition according to claim 1, wherein the component (D) includes (D-1) 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. A photosensitive film with a support, which has a support and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of Claims 1-8 provided on the support. A printed circuit board comprising an insulating layer formed of a cured product of the photosensitive resin composition according to any one of claims 1-8. The printed circuit board according to claim 10, wherein the insulating layer is any one of an interlayer insulating material and a solder resist. A semiconductor device comprising the printed circuit board according to claim 10 or 11.