Photosensitive resin composition

Abstract

[Problem] To provide a photosensitive resin composition, etc., that can obtain a cured product with excellent developability and suppressed cracking. [Solution] 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 photopolymerizable compound, wherein the content of component (B) is 30 mass% or more when the non-volatile component in the photosensitive resin composition is 100 mass%, the 10% particle diameter (D10) of the particle diameter distribution of component (B) is 0.06 μm or more and 0.6 μm or less, the 50% particle diameter (D50) is 0.11 μm or more and 1.10 μm or less, the 90% particle diameter (D90) is 0.22 μm or more and 2.20 μm or less, and the refractive index of component (E) is 1.45 or more and 1.51 or less.

Description

Technology Field

[0001] The present invention relates to a photosensitive resin composition. Furthermore, the invention relates to a photosensitive film attached to a support, a printed circuit board, and a semiconductor device obtained using the photosensitive resin composition. Background Technology

[0002] In printed circuit boards, a solder resist is provided as a permanent protective film to prevent solder from adhering to areas where solder is unnecessary, while simultaneously preventing corrosion of the circuit board. As for the solder resist, it is common to use a photosensitive resin composition, such as that described in Patent Document 1. Prior art literature

[0003] Japanese Patent Publication No. JP 2014-115672 The problem to be solved

[0004] Photosensitive resin compositions generally require developability during development. Additionally, recently, photosensitive resin compositions are also required to suppress the occurrence of cracks. To suppress the occurrence of cracks, a method of increasing the content of inorganic fillers is considered. However, if the content of inorganic fillers is increased, the adhesion between the layer formed by the photosensitive resin composition and the conductor layer tends to decrease. Furthermore, when via holes are formed in the layer formed by the photosensitive resin composition, light transmission becomes insufficient and the sensitivity of the bottom part of the via hole decreases, causing undercuts, or it becomes impossible to form small-diameter via holes due to light halation, which may result in a decrease in resolution.

[0005] The objective of the present invention is to provide a photosensitive resin composition capable of obtaining a cured product with excellent developability, adhesion between conductor layers, and suppression of crack formation; and a photosensitive film attached to a support, a printed circuit board, and a semiconductor device obtained using the photosensitive resin composition. means of solving the problem

[0006] As a result of careful examination by the inventors, it was discovered that by adjusting the particle diameter distribution of a predetermined amount of inorganic filler and using a combination of a photopolymerizable compound having a predetermined refractive index, a cured product with excellent developability, adhesion between conductor layers, and suppression of crack formation can be obtained, and thus the present invention was completed.

[0007] That is, the present invention includes the following contents.

[0008] [1] (A) A resin containing ethylenically unsaturated groups and carboxyl groups,

[0009] (B) Inorganic filler,

[0010] (C) Photopolymerization initiator,

[0011] (D) Epoxy resin and

[0012] (E) A photosensitive resin composition containing a photopolymerizable compound,

[0013] (B) The content of the component is 30 mass% or more when the non-volatile component in the photosensitive resin composition is 100 mass%, and

[0014] (B) 10% particle diameter in the particle diameter distribution of the component (D 10 ) is 0.06㎛ or more and 0.6㎛ or less, and the 50% particle diameter (D 50 ) is 0.11㎛ or more and 1.10㎛ or less, and the 90% particle diameter (D 90 ) is 0.22㎛ or more and 2.20㎛ or less, and

[0015] (E) A photosensitive resin composition having a refractive index of 1.45 or higher and 1.51 or lower.

[0016] [2] A photosensitive resin composition described in [1], wherein when a via hole with a minimum opening diameter of R (㎛) is formed in a cured product of the photosensitive resin composition, the number of (B) components with a particle diameter of (0.1×R)㎛ or more exposed on the wall of the via hole is 10 or fewer.

[0017] [3] (E) A photosensitive resin composition described in [1] or [2], wherein the component has a divalent cyclic structure.

[0018] [4] A photosensitive resin composition described in [3] having a heterocyclic framework containing a divalent cyclic group.

[0019] [5] A photosensitive resin composition described in any one of [1] to [4], comprising a compound represented by the following chemical formula (E-1) as a component.

[0020] [Chemical Formula (E-1)]

[0021]

[0022] [6] (A) A photosensitive resin composition described in any one of [1] to [5], having a cresol novolak skeleton, a naphthalene skeleton and a naphtholaralkyl skeleton.

[0023] [7] (A) A photosensitive resin composition described in any one of [1] to [6], comprising an acid-modified naphtholarkyl backbone-containing epoxy(meth)acrylate.

[0024] [8] A photosensitive resin composition described in any one of [1] to [7], wherein (D) the components include (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.

[0025] [9] A photosensitive film attached to a support, having a support and a photosensitive resin composition layer comprising a photosensitive resin composition described in any one of [1] to [8] provided on the support.

[0026]

[10] A printed circuit board comprising an insulating layer formed by a cured photosensitive resin composition described in any one of [1] to [8].

[0027]

[11] A printed circuit board described in

[10] , in which the insulating layer is either an interlayer insulating material or a solder resist.

[0028]

[12] A semiconductor device including a printed circuit board as described in

[10] or

[11] . Effects of the invention

[0029] According to the present invention, a photosensitive resin composition is provided that can obtain a cured product having excellent developability, adhesion between conductor layers, and suppression of crack formation; and a photosensitive film attached to a support, a printed circuit board, and a semiconductor device obtained using the photosensitive resin composition. Specific details for implementing the invention

[0030] Hereinafter, the photosensitive resin composition, the photosensitive film attached to a support, the printed circuit board, and the semiconductor device of the present invention will be described in detail.

[0031] [Photosensitive resin composition]

[0032] The photosensitive resin composition of the present invention is 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 photopolymerizable compound, wherein the content of component (B) is 30 mass% or more when the non-volatile component in the photosensitive resin composition is 100 mass%, and the 10% particle diameter (D) in the particle diameter distribution of component (B). 10 ) is 0.06㎛ or more and 0.6㎛ or less, and the 50% particle diameter (D 50 ) is 0.11㎛ or more and 1.10㎛ or less, and the 90% particle diameter (D 90 ) is 0.22㎛ or more and 2.20㎛ or less, and the refractive index of component (E) is 1.45 or more and 1.51 or less.

[0033] In the present invention, by adjusting the particle diameter distribution of a predetermined amount of inorganic filler as component (B), using a photopolymerizable compound having a predetermined refractive index as component (E), and using a combination of components (A), (C) to (D), a photosensitive resin composition can be obtained that has excellent developability, adhesion to a conductor layer, and suppresses the occurrence of cracks. In addition, it is generally possible to obtain a photosensitive resin composition with excellent average linear thermal expansion coefficient (CTE), dielectric constant, dielectric loss tangent, laser via aperture, and surface shape, and it is also generally possible to obtain a photosensitive resin composition with low minimum melt viscosity and to improve the film shape of a photosensitive film attached to a support.

[0034] The photosensitive resin composition may additionally include any components such as (F) a curing accelerator, (G) a solvent, and (H) other additives, as needed. Each component included in the photosensitive resin composition will be described in detail below.

[0035] <(A) Resin containing ethylenically unsaturated groups and carboxyl groups>

[0036] The photosensitive resin composition contains (A) a resin containing an ethylenically unsaturated group and a carboxyl group. By including component (A) in the photosensitive resin composition, developability can be improved.

[0037] The ethylenically unsaturated group has a carbon-carbon double bond and, for example, includes a vinyl group, an allyl group, a propagyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadiimide group, and a (meth)acryloyl group; from the perspective of reactivity for photoradical polymerization, a (meth)acryloyl group is preferred. "(meth)acryloyl group" includes methacryloyl groups, acryloyl groups, and combinations thereof. Since component (A) contains an ethylenically unsaturated group, photoradical polymerization is possible. The number of ethylenically unsaturated groups per molecule of component (A) may be one or two or more. Furthermore, if component (A) contains two or more ethylenically unsaturated groups per molecule, these ethylenically unsaturated groups may be the same or different.

[0038] In addition, since component (A) contains a carboxyl group, the photosensitive resin composition containing component (A) exhibits solubility in an alkaline solution (e.g., an aqueous solution of sodium carbonate at 1 mass% as an alkaline developer). The number of carboxyl groups per molecule of component (A) may be one or two or more.

[0039] (A) The component is not particularly limited to any compound having an ethylenically unsaturated group and a carboxyl group that enables photoradical polymerization and simultaneously enables alkaline phenomena, but a resin having both a carboxyl group and two or more ethylenically unsaturated groups in one molecule is preferred.

[0040] One embodiment of a resin containing ethylenically unsaturated groups and carboxyl groups is an acid-modified unsaturated epoxy ester resin, which is obtained by reacting an epoxy compound with an unsaturated carboxylic acid and further reacting it with an acid anhydride. Specifically, an unsaturated epoxy ester resin can be obtained by reacting an epoxy compound with an unsaturated carboxylic acid, and an acid-modified unsaturated epoxy ester resin can be obtained by reacting the unsaturated epoxy ester resin with an acid anhydride.

[0041] As for the epoxy compound, any compound having an epoxy group within its molecule may be used, for example, bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, hydrogenated bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, and modified bisphenol F-type epoxy resin modified to have three or more functions by reacting bisphenol F-type epoxy resin with epichlorohydrin; biphenol-type epoxy resins such as biphenol-type epoxy resin and tetramethylbiphenol-type epoxy resin; novolak-type epoxy resins such as phenol-novolak-type epoxy resin, cresol-novolak-type epoxy resin, bisphenol A-type novolak-type epoxy resin, and alkylphenol-novolak-type epoxy resin; and fluorine-containing epoxy resins such as bisphenol AF-type epoxy resin and perfluoroalkyl-type epoxy resin. Epoxy resins having a naphthalene backbone, such as naphthalene-type epoxy resin, dihydroxynaphthalene-type epoxy resin, polyhydroxybinaphthalene-type epoxy resin, naphthol-type epoxy resin, naphtholaralkyl-type epoxy resin, binaphthalene-type epoxy resin, naphtylene ether-type epoxy resin, naphthol novolak-type epoxy resin, and naphthalene-type epoxy resin obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes (epoxy resins containing a naphthalene backbone); epoxy resins containing a condensed ring backbone, such as bixylenol-type epoxy resin; dicyclopentadiene-type epoxy resin; trisphenol-type epoxy resin; tert-butyl-catechol-type epoxy resin; and anthracene-type epoxy resin; glycidylamine-type epoxy resin; glycidyl ester-type epoxy resin; biphenyl-type epoxy resin; linear aliphatic epoxy resin; epoxy resin having a butadiene structure; alicyclic epoxy resin; heterocyclic epoxy resin; spiro-ring-containing epoxy resin; Examples include cyclohexanedimethanol-type epoxy resins; trimethylol-type epoxy resins; tetraphenylethane-type epoxy resins; glycidyl group-containing acrylic resins such as polyglycidyl (meth)acrylate and copolymers of glycidyl methacrylate and acrylic acid esters; fluorene-type epoxy resins; and halogenated epoxy resins.

[0042] Regarding epoxy compounds, epoxy resins containing an aromatic backbone are preferred from the perspective of lowering the average linear thermal expansion rate. Here, the term "aromatic backbone" includes polycyclic aromatics and aromatic heterocyclic rings. Among these, naphtholaralkyl type epoxy resins, epoxy resins containing a naphthalene backbone, epoxy resins containing a condensed ring backbone, biphenyl type epoxy resins, bisphenol F type epoxy resins, bisphenol A type epoxy resins, cresol novolak type epoxy resins, and glycidyl ester type epoxy resins are preferred from the perspective that molecular stiffness is increased, thereby suppressing molecular movement and consequently lowering the average linear thermal expansion rate of the cured product of the resin composition. Naphtholaralkyl type epoxy resins, epoxy resins containing a naphthalene backbone, and novolak type epoxy resins are more preferred, and cresol novolak type epoxy resins, epoxy resins containing a naphthalene backbone, and naphtholaralkyl type epoxy resins are even more preferred. As a naphthalene backbone-containing epoxy resin, dihydroxynaphthalene-type epoxy resin, polyhydroxybinaphthalene-type epoxy resin, and naphthalene-type epoxy resin obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes are preferred.

[0043] Examples of dihydroxynaphthalene-type epoxy resins include 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, 2,3-diglycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene.

[0044] Examples of polyhydroxy-bi-naphthalene type epoxy resins include 1,1'-bi-(2-glycidyloxy)naphthyl, 1-(2,7-diglycidyloxy)-1'-(2'-glycidyloxy)binaphthyl, 1,1'-bi-(2,7-diglycidyloxy)naphthyl, etc.

[0045] Examples of naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1'-bis(2,7-diglycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxynaphthyl)-1'-(2'-glycidyloxynaphthyl)methane, and 1,1'-bis(2-glycidyloxynaphthyl)methane.

[0046] Among these, polyhydroxy-binaphthalene type epoxy resins having two or more naphthalene backbones in one molecule, and naphthalene type epoxy resins obtained by a condensation reaction between polyhydroxy-naphthalene and aldehydes are preferred, and in particular, 1,1'-bis(2,7-diglycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxynaphthyl)-1'-(2'-glycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxy)-1'-(2'-glycidyloxy)binaphthyl, and 1,1'-bis-(2,7-diglycidyloxy)naphthyl having three or more epoxy groups in one molecule are preferred in that they have excellent heat resistance in addition to the average linear thermal expansion rate, and 1,1'-bis(2,7-diglycidyloxynaphthyl)methane is more preferred.

[0047] Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, etc., and these may be used individually or in combination of two or more. Among these, acrylic acid and methacrylic acid are preferred from the perspective of improving the photocurability of the photosensitive resin composition. Furthermore, in this specification, the epoxy ester resin, which is the reaction product of the above epoxy compound and (meth)acrylic acid, may be described as "epoxy(meth)acrylate," where the epoxy group of the epoxy compound is substantially eliminated by reaction with (meth)acrylic acid. "(meth)acrylate" refers to methacrylate and acrylate. Acrylic acid and methacrylic acid may be collectively referred to as "(meth)acrylic acid."

[0048] Examples of acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic acid dihydride. Any one of these may be used alone or two or more may be used in combination. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferred for improving the resolution and insulation reliability of the cured product, and tetrahydrophthalic anhydride is more preferred.

[0049] In obtaining an acid-modified unsaturated epoxy ester resin, an unsaturated carboxylic acid may be reacted with an epoxy resin in the presence of a catalyst to obtain an unsaturated epoxy ester resin, and then the unsaturated epoxy ester resin may be reacted with an acid anhydride. Additionally, a solvent and a polymerization inhibitor may be used as needed.

[0050] As an acid-modified unsaturated epoxy ester resin, it is preferable to have one of a cresol novolak backbone, a naphthalene backbone, and a naphtholarkyl backbone. Additionally, as an acid-modified unsaturated epoxy ester resin, an acid-modified epoxy (meth)acrylate is preferred. In the acid-modified unsaturated epoxy ester resin, "epoxy" refers to a structure derived from the above epoxy compound. For example, "acid-modified bisphenol-type epoxy (meth)acrylate" refers to an acid-modified unsaturated epoxy ester resin obtained by using a bisphenol-type epoxy resin as the epoxy compound and (meth)acrylic acid as the unsaturated carboxylic acid. The preferred range of the acid-modified epoxy (meth)acrylate is derived from the preferred range of the epoxy compound. That is, regarding acid-modified unsaturated epoxy ester resins, acid-modified naphthalene-framed epoxy (meth)acrylate, acid-modified cresol novolak-framed epoxy (meth)acrylate, and acid-modified naphtholarkyl-framed epoxy (meth)acrylate are preferred, and acid-modified naphthalene-framed epoxy (meth)acrylate is more preferred. Acid-modified naphthalene-framed epoxy (meth)acrylate is a compound obtained by reacting an acid anhydride, such as succinic anhydride or tetrahydrophthalic anhydride, with a reaction product of a naphthalene-type epoxy resin and a (meth)acrylate. Acid-modified cresol novolak-framed epoxy (meth)acrylate is a compound obtained by reacting a cresol novolak-type epoxy resin and a (meth)acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. Acid-modified naphthoralkyl-framed epoxy (meth)acrylate is a compound obtained by reacting a naphthoralkyl-type epoxy resin and a (meth)acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride.

[0051] Such acid-modified unsaturated epoxy ester resins may be commercially available, and specific examples include "ZAR-2000" (reactant of bisphenol A type epoxy resin, acrylic acid, and succinic anhydride), "ZFR-1491H", and "ZFR-1533H" (reactant of bisphenol F type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride) manufactured by Nippon Kayaku Co., Ltd., "PR-300CP" (reactant of cresol novolak type epoxy resin, acrylic acid, and acid anhydride) manufactured by Showa Denko Co., Ltd., "CCR-1179" (cresol novolak F type epoxy acrylate) and "ZCR-1569H" (acid-modified biphenyl type epoxy acrylate: reactant of biphenyl type epoxy resin, acrylic acid, and acid anhydride) manufactured by Nippon Kayaku Co., Ltd., and "CCR-1171H" (cresol novolak type Examples include epoxy acrylates. These may be used individually or in combination of two or more types.

[0052] (A) As for the weight average molecular weight of the component, from the perspective of film-forming properties, it is preferable that it be 1,000 or more, more preferable that it be 1,500 or more, and even more preferable that it be 2,000 or more. As for the upper limit, from the perspective of developability, it is preferable that it be 10,000 or less, more preferable that it be 8,000 or less, and even more preferable that it be 7,500 or less. The weight average molecular weight is the weight average molecular weight in polystyrene equivalent measured by gel permeation chromatography (GPC).

[0053] (A) Regarding the acid value of component (A), from the perspective of improving the alkali developability of the photosensitive resin composition, it is preferable that the acid value be 0.1 mg KOH / g or higher, more preferable that it be 0.5 mg KOH / g or higher, and even more preferable that it be 1 mg KOH / g or higher. On the other hand, from the perspective of suppressing the leaching of fine patterns of the cured product by development and improving insulation reliability, it is preferable that the acid value be 150 mg KOH / g or lower, more preferable that it be 120 mg KOH / g or lower, and even more preferable that it be 100 mg KOH / g or lower. Here, the acid value refers to the residual acid value of the carboxyl groups present in component (A), and the acid value can be measured by the following method. First, about 1 g of the resin solution to be measured is accurately weighed, and then 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of the indicator phenolphthalein is added to the above solution, and titration is performed using a 0.1N aqueous ethanol solution. Then, the acid value is calculated by the following formula.

[0054] Formula: A = 10×(Vf - BL)×F×56.11 / (Wp×I)

[0055] In addition, among the above formulas, A represents the acid value (mg KOH / g), Vf represents the titration amount of KOH (mL), BL represents the blank, F represents the factor (titer), Wp represents the mass of the resin solution to be measured (g), and I represents the ratio of the non-volatile content of the resin solution to the mass (mass%).

[0056] (A) In the preparation of the component, from the perspective of improving storage stability, it is preferable that the ratio of the number of moles of epoxy groups of the epoxy resin to the number of moles of carboxyl groups of the total of unsaturated carboxylic acid and acid anhydride be in the range of 1:0.8 to 1.3, and more preferable that it be in the range of 1:0.9 to 1.2.

[0057] (A) When the non-volatile component of the photosensitive resin composition is 100 mass%, the content of the component is preferably 5 mass% or more, more preferably 8 mass% or more, and even more preferably 10 mass% or more, from the perspective of improving alkali development properties. The upper limit is preferably 50 mass% or less, more preferably 45 mass% or less, and even more preferably 40 mass% or less, from the perspective of improving heat resistance. In addition, in the present invention, unless otherwise specified, the content of each component in the photosensitive resin composition is the value when the non-volatile component in the photosensitive resin composition is 100 mass%.

[0058] <(B) Inorganic Filler>

[0059] The photosensitive resin composition contains an inorganic filler (B) as component (B). Component (B) is the 10% particle diameter (D) in the particle diameter distribution of component (B). 10 ) is 0.06㎛ or more and 0.6㎛ or less, and the 50% particle diameter (D 50 ) is 0.11㎛ or more and 1.10㎛ or less, and the 90% particle diameter (D 90 The particle diameter is 0.22㎛ or larger and 2.20㎛ or smaller. By including an inorganic filler having such a particle diameter distribution in a photosensitive resin composition, it is possible to suppress developability, adhesion, and cracking even when the content of the inorganic filler is high. In addition, the particle diameter distribution represents the particle diameter distribution of the entire (B) inorganic filler included in the photosensitive resin composition.

[0060] The particle diameter distribution of inorganic fillers can be measured by the laser diffraction scattering method based on Mie scattering theory. Specifically, the particle diameter distribution of inorganic fillers is plotted on a volume basis using a laser diffraction scattering particle diameter distribution measuring device, and the 10% particle diameter (D 10 ), 50% particle diameter (D 50 ) and 90% particle diameter (D90 ) can be measured. Preferably, the measurement sample can be one in which an inorganic filler is dispersed in water or methyl ethyl ketone by ultrasound. As a laser diffraction scattering type particle diameter distribution measuring device, the “LA-500” manufactured by Horiba Sesakusho Co., Ltd., the “SALD-2200” manufactured by Shimadzu Sesakusho Co., Ltd., etc. can be used.

[0061] 10% particle diameter in particle diameter distribution (D 10 ) refers to the particle diameter at which the accumulated volume from the smaller particle diameter side on the particle diameter distribution curve reaches 10% as a result of measuring the particle diameter distribution by the above method. 50% particle diameter (D 50 ) refers to the particle diameter at which the accumulated volume from the smaller particle diameter side on the particle diameter distribution curve reaches 50% as a result of measuring the particle diameter distribution by the above method. In addition, the 90% particle diameter (D 90 ) refers to the particle diameter at which the accumulated volume from the smaller particle diameter side on the particle diameter distribution curve reaches 90% as a result of measuring the particle diameter distribution by the above method. Here, (B) the average particle diameter of the inorganic filler is the 50% particle diameter (D 50 It refers to the particle diameter of ). Below, the 10% particle diameter (D 10 ) to D 10 , 50% particle diameter (D 50 ) to D 50 and 90% particle diameter (D 90 ) to D 90 There are cases where people say that.

[0062] D in particle diameter distribution 10 As such, from the perspective of suppressing scattering of active light and improving resolution, it is 0.06 μm or more, preferably 0.08 μm or more, more preferably 0.10 μm or more. The upper limit is 0.6 μm or less, preferably 0.58 μm or less, more preferably 0.55 μm or less.

[0063] D in particle diameter distribution 50 As such, from the perspective of suppressing scattering of active light and improving resolution, it is 0.11 μm or more, preferably 0.13 μm or more, more preferably 0.15 μm or more. The upper limit is 1.10 μm or less, preferably 1.05 μm or less, more preferably 1.00 μm or less.

[0064] D in particle diameter distribution 90 As such, from the perspective of suppressing scattering of active light and improving resolution, it is 0.22 μm or more, preferably 0.24 μm or more, more preferably 0.25 μm or more. The upper limit is 2.20 μm or less, preferably 2.00 μm or less, more preferably 1.80 μm or less.

[0065] D 50 -D 10 As for the upper limit, from the viewpoint of significantly obtaining the effects of the present invention, it is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more. The upper limit is preferably 1.20 μm or less, more preferably 1.00 μm or less, and even more preferably 0.80 μm or less.

[0066] D 90 -D 10 As for the upper limit, from the viewpoint of significantly obtaining the effects of the present invention, it is preferably 0.05 μm or more, more preferably 0.08 μm or more, and even more preferably 0.10 μm or more. The upper limit is preferably 1.60 μm or less, more preferably 1.40 μm or less, and even more preferably 1.20 μm or less.

[0067] D 90 -D 50As for the upper limit, from the viewpoint of significantly obtaining the effects of the present invention, it is preferably 0.04 μm or more, more preferably 0.06 μm or more, and even more preferably 0.08 μm or more. The upper limit is preferably 2.00 μm or less, more preferably 1.50 μm or less, and even more preferably 1.00 μm or less.

[0068] D 90 / D 50 As for the lower limit, in order to significantly obtain the effects of the present invention, it is preferably 2.4 or less, more preferably 2.2 or less, and even more preferably 1.8 or less. The lower limit is preferably 1.0 or more, more preferably 1.1 or more, and even more preferably 1.2 or more.

[0069] D 90 / D 10 As for the lower limit, in order to significantly obtain the effects of the present invention, it is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. The lower limit is preferably 1.0 or more, more preferably 1.2 or more, and even more preferably 1.5 or more.

[0070] D 50 / D 10 As for the lower limit, in order to significantly obtain the effects of the present invention, it is preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less. The lower limit is preferably 1.0 or more, more preferably 1.1 or more, and even more preferably 1.2 or more.

[0071] (B) The content of inorganic filler is 30 mass% or more, preferably 45 mass% or more, more preferably 50 mass% or more, and 55 mass% or more, when the non-volatile component in the photosensitive resin composition is 100 mass%, in order to suppress the occurrence of cracks and obtain a cured product with high adhesion and low average linear thermal expansion rate. The upper limit is 85 mass% or less, preferably 80 mass% or less, more preferably 70 mass% or less, in order to suppress light reflection.

[0072] The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica, alumina, and barium sulfate are suitable, and silica is particularly suitable. In addition, spherical silica is preferred as silica. The inorganic filler may be used as a single type or in combination of two or more types.

[0073] (B) Commercially available inorganic fillers may be used. (B) Examples of commercially available inorganic fillers include "Adoma Fine" manufactured by Adomatex, "SFP Series" manufactured by Denki Kagaku Kogyo, "SP(H) Series" manufactured by Shin-Nippon Tetsu Sumikin Materials, "Sciqas Series" manufactured by Sakai Kagaku Kogyo, "Shiho Star Series" manufactured by Nippon Shokubai, and "SG-SO Series" manufactured by Sukgyuug. Examples of commercially available alumina include "AZ Series" and "AX Series" manufactured by Shin-Nippon Tetsu Sumikin Materials. Examples of commercially available barium sulfate include "B Series" and "BF Series" manufactured by Sakai Kagaku Kogyo.

[0074] (B) Inorganic filler can be obtained by classifying multiple types of inorganic filler with a classifier or the like to obtain an inorganic filler having a desired average particle diameter.

[0075] The specific surface area of ​​the inorganic filler is 3.0 m² / g or more, preferably 4.0 m² / g or more, and more preferably 5 m² / g or more, in terms of obtaining excellent resolution. The upper limit of the specific surface area is 40 m² / g or less, preferably 30 m² / g or less, more preferably 28 m² / g or less, and even more preferably 25 m² / g or less, in terms of melt viscosity, etc. The specific surface area of ​​the inorganic filler can be obtained by following the BET method, adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mounttec), and calculating the specific surface area using the BET multi-point method.

[0076] In terms of improving moisture resistance and dispersibility, it is preferable that the inorganic filler be treated with one or more surface treatment agents, such as vinylsilane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazanes compounds, and titanate coupling agents. As commercially available surface treatment agents, for example, "KBM1003" (vinyltrimethoxysilane) manufactured by Shin-Etsu Kagaku Kokyo Co., Ltd., "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Kagaku Kokyo Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Kagaku Kokyo Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Kagaku Kokyo Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Kagaku Kokyo Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Kagaku Kokyo Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Kagaku Kokyo Co., Ltd., and "KBM-4803" (long-chain epoxy-type silane) manufactured by Shin-Etsu Kagaku Kokyo Co., Ltd. Examples include coupling agents, etc.

[0077] The degree of surface treatment by a surface treatment agent can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the perspective of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m² or more, more preferably 0.1 mg / m² or more, and even more preferably 0.2 mg / m² or more. Meanwhile, from the perspective of suppressing the increase in melt viscosity of the resin varnish or melt viscosity in sheet form, it is preferably 1 mg / m² or less, more preferably 0.8 mg / m² or less, and even more preferably 0.5 mg / m² or less.

[0078] The carbon content per unit surface area of ​​an inorganic filler can be measured after the inorganic filler is cleaned with a solvent (e.g., methyl ethyl ketone (MEK)) following surface treatment. Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonically cleaned at 25°C for 5 minutes. After removing the supernatant and drying the solids, the carbon content per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, the "EMIA-320V" manufactured by Horiba Sesakusho Co., Ltd. can be used.

[0079] <(C) Photopolymerization Initiator>

[0080] The photosensitive resin composition contains a photopolymerization initiator (C) as component (C). By including component (C), the photosensitive resin composition can be efficiently photocured. One type of component (C) may be used alone, or two or more types may be used in combination.

[0081] (C) The component is not particularly limited, but includes, for example, α-aminoalkylphenone photopolymerization initiators such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-morpholinoyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; oxime ester photopolymerization initiators such as ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime); Examples include benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxantone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphinate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxy-cyclohexyl-phenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc., and also sulfonium salt-based Photopolymerization initiators, etc., may also be used. Any one of these may be used alone or two or more may be used in combination.

[0082] In addition, the photosensitive resin composition may include, in combination with component (C), tertiary amines such as N,N-dimethylaminobenzoate ethyl ester, N,N-dimethylaminobenzoate isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine as photopolymerization initiation aids, or photosensitizers such as pyrazolins, anthracenes, coumarins, xanthones, and thioxantones. Any one of these may be used alone or two or more may be used in combination.

[0083] (C) Specific examples of the component include “Omnirad 907”, “Omnirad 369”, “Omnirad 379”, “Omnirad 819”, “Omnirad TPO” manufactured by IGM, “Irgacure TPO”, “Irgacure OXE-01”, “Irgacure OXE-02” manufactured by BASF, and “N-1919” manufactured by ADEKA.

[0084] (C) The content of the component is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1 mass% or more, in order to sufficiently photocur the photosensitive resin composition to improve insulation reliability, when the non-volatile component of the photosensitive resin composition is 100 mass%. Meanwhile, in order to suppress the decrease in resolution due to excessive sensitivity, the upper limit is preferably 10 mass% or less, more preferably 8 mass% or less, and even more preferably 6 mass% or less.

[0085] <(D) Epoxy Resin>

[0086] The photosensitive resin composition contains (D) epoxy resin as component (D). Insulation reliability can be improved by including component (D). However, the component (D) referred to herein does not include epoxy resin containing ethylenically unsaturated groups and carboxyl groups. One type of component (D) may be used alone or two or more types may be used in combination.

[0087] (D) The epoxy resin may be any epoxy resin other than one containing ethylenically unsaturated groups and carboxyl groups, but in order to improve developability, dielectric constant and dielectric loss tangent, it is preferable to include (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.

[0088] (D-1) The softening point of the component is preferably less than 30°C, more preferably 25°C or lower, and even more preferably 20°C or lower, in order to significantly obtain the effects of the present invention. The lower limit is not particularly limited, but is preferably 0°C or higher, more preferably 5°C or higher, and even more preferably 10°C or higher. The softening point can be measured in accordance with JIS K7234.

[0089] (D-1) As for the component, in order to significantly obtain the effects of the present invention, it is preferable to have one or more epoxy groups in one molecule, more preferable to have two or more epoxy groups in one molecule, and even more preferable to have three or more epoxy groups in one molecule. In order to significantly obtain the desired effects of the present invention, with respect to 100 mass% of the non-volatile component of (D-1), 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, and particularly preferably 70 mass% or more.

[0090] (D-1) The component includes a component that is in a liquid state at a temperature of 20°C and a component that is in a solid state at a temperature of 20°C. As for the (D-1) component, it is preferable that it be in a liquid state to significantly obtain the effects of the present invention.

[0091] (D-1) As for the component, it is preferable to have a cyclic structure from the perspective of significantly obtaining the effects of the present invention. Examples of cyclic structures include aromatic ring structures and alicyclic structures. Examples of aromatic ring structures include benzene rings, naphthalene rings, and anthracene rings. Examples of alicyclic structures include cyclohexane rings, cyclopentane rings, cycloheptane rings, and cyclooctane rings. Among these, as for the cyclic structure, an aromatic ring structure is preferred, a naphthalene ring and a benzene ring are more preferred, and a naphthalene ring is even more preferred.

[0092] In addition, as a component of (D-1), examples include naphthalene-type epoxy resin, glycidylamine-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, glycidyl ester-type epoxy resin, phenol novolak-type epoxy resin, glycidyl cyclohexane-type epoxy resin, isocyanuryl cyclic epoxy resin, and naphthalene ether-type epoxy resin, and naphthalene-type epoxy resin and glycidylamine-type epoxy resin are preferred, and naphthalene-type epoxy resin is more preferred.

[0093] (D-1) Specific examples of the components include “HP4032”, “HP4032D”, and “HP4032SS” (naphthalene-type epoxy resin) manufactured by DIC; “ELM-434L” (glycidylamine-type epoxy resin) manufactured by Sumitomo Chemicals; “630” (glycidylamine-type epoxy resin) manufactured by Mitsubishi Chemicals; “ZX1658GS” (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Shin-Nippon Steel Sumikin Chemicals; “EP-3980S” (difunctional glycidylamine-type epoxy resin) manufactured by ADEKA; “EP-3950L” (trifunctional glycidylamine-type epoxy resin) manufactured by ADEKA; and “TEPIC-VL” (isocyanuryl ring-type epoxy resin) manufactured by Nippon Chemicals. Examples include “ELM-100H” (N-[2-methyl-4-(oxiranylmethoxy)phenyl]-N-(oxiranylmethyl)oxiranmethanamine) manufactured by Sumitomo Chemicals; and “EXA-7311-G4” (naphthylene ether type epoxy resin) manufactured by DIC. These may be used individually or in combination of two or more types.

[0094] (D-1) The epoxy equivalent of the component is preferably 150 g / eq. or less, more preferably 148 g / eq. or less, even more preferably 145 g / eq. or less, and preferably 10 g / eq. or more, more preferably 50 g / eq. or more, and even more preferably 100 g / eq. or more, from the view of significantly obtaining the effects of the present invention. (D) The epoxy equivalent of the component is the mass of an epoxy resin containing 1 equivalent of an epoxy group. Such epoxy equivalent can be measured according to JIS K7236.

[0095] (D-1) The weight average molecular weight (Mw) of the component is preferably 100 or more, more preferably 200 or more, even more preferably 250 or more, preferably 5,000 or less, more preferably 3,000 or less, and even more preferably 1,500 or less, in order to significantly obtain the desired effect of the present invention. The weight average molecular weight of the resin can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC).

[0096] (D-1) The content of the component is preferably 10 mass% or more, more preferably 20 mass% or more, even more preferably 30 mass% or more, when the total of the component (D) is 100 mass%, in terms of the handling properties, melt viscosity, and developability of the resin varnish. It is preferably 90 mass% or less, more preferably 80 mass% or less, even more preferably 70 mass% or less, 60 mass% or less, 50 mass% or less, or 40 mass% or less.

[0097] (D-1) The content of the component is preferably 1 mass% or more, more preferably 1.5 mass% or more, even more preferably 2 mass% or more, and preferably 10 mass% or less, more preferably 8 mass% or less, even more preferably 5 mass% or less, when the non-volatile component in the photosensitive resin composition is 100 mass%, in order to obtain a cured product with excellent insulation, dielectric constant, and dielectric loss tangent in addition to developability.

[0098] (D-2) The softening point of the component is preferably 30°C or higher, more preferably 35°C or higher, and even more preferably 40°C or higher, in order to significantly obtain the effect of the present invention. The upper limit is less than 59°C, preferably 57°C or lower, and more preferably 55°C or lower, in order to significantly obtain the effect of the present invention. The softening point can be measured in the same way as the component (D-1).

[0099] (D-2) As for the component, in order to significantly obtain the effects of the present invention, it is preferable to have one or more epoxy groups in one molecule, more preferable to have two or more epoxy groups in one molecule, and even more preferable to have three or more epoxy groups in one molecule. In order to significantly obtain the desired effects of the present invention, with respect to 100 mass% of the non-volatile component of (D-2), 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, and particularly preferably 70 mass% or more.

[0100] (D-2) It is preferable that the component be in a solid state at a temperature of 20℃.

[0101] (D-2) As a component, an epoxy resin having a softening point of 30°C or higher may be used. For such an epoxy resin, it is preferable to have a cyclic structure in order to significantly obtain the effects of the present invention. Examples of cyclic structures include aromatic ring structures and alicyclic structures. Examples of aromatic ring structures include benzene rings, naphthalene rings, anthracene rings, and biphenyl rings. Examples of alicyclic structures include cyclohexane rings, cyclopentane rings, cycloheptane rings, and cyclooctane rings. Among these, an aromatic ring structure is preferred as the cyclic structure, benzene rings and biphenyl rings are more preferred, and biphenyl rings are even more preferred.

[0102] In addition, as for the (D-2) component, examples include biphenyl-type epoxy resin, dicyclopentadiene-type epoxy resin, naphthylene ether-type epoxy resin, etc., and biphenyl-type epoxy resin is more preferred.

[0103] (D-2) Specific examples of the components include "NC3000L" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "HP-7200L" (dicyclopentadiene-type epoxy resin) and "HP-6000L" (naphthylene ether-type epoxy resin) manufactured by DIC Co., Ltd.; and "NC3000" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used individually or in combination of two or more types.

[0104] (D-2) The epoxy equivalent of the component is preferably 50 g / eq. to 5,000 g / eq., more preferably 50 g / eq. to 3,000 g / eq., even more preferably 80 g / eq. to 2,000 g / eq., and even more preferably 110 g / eq. to 1,000 g / eq. By being within this range, the crosslinking density of the cured layer of the photosensitive resin composition becomes sufficient, so that an insulating layer with low surface roughness can be formed.

[0105] (D-2) The weight average molecular weight (Mw) of the component is preferably 100 or more, more preferably 200 or more, even more preferably 250 or more, preferably 5,000 or less, more preferably 3,000 or less, and even more preferably 1,500 or less, in order to significantly obtain the desired effect of the present invention.

[0106] (D-2) The content of the component is preferably 10 mass% or more, more preferably 20 mass% or more, even more preferably 30 mass% or more, 40 mass% or more, 50 mass% or more, 60 mass% or more, and preferably 90 mass% or less, more preferably 80 mass% or less, even more preferably 70 mass% or less, from the perspective of obtaining adhesion in addition to insulation.

[0107] (D-2) The content of the component is preferably 1 mass% or more, more preferably 1.5 mass% or more, even more preferably 2 mass% or more, and preferably 15 mass% or less, more preferably 12 mass% or less, and even more preferably 10 mass% or less, from the perspective of obtaining adhesion in addition to insulation.

[0108] (D) The content of the component is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more, and preferably 20 mass% or less, more preferably 15 mass% or less, and even more preferably 10 mass% or less, when the non-volatile component in the photosensitive resin composition is 100 mass% in order to obtain the effect of the present invention.

[0109] When the content of the non-volatile component in the photosensitive resin composition of component (D-1) is 100 mass%, let D1 be the content of the non-volatile component in the photosensitive resin composition of component (D-2) is 100 mass%, let D2 be the content of the non-volatile component in the photosensitive resin composition of component (D-2). Then, D2 / D1 is preferably 0.5 or more, more preferably 0.8 or more, even more preferably 1.2 or more, preferably 3.5 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. By having the ratio of component (D-1) and component (D-2) within this range, the desired effect of the present invention can be significantly obtained.

[0110] <(E) Photopolymerizable Compounds>

[0111] The photosensitive resin composition contains a photopolymerizable compound (E) as component (E). However, components corresponding to (A) are excluded. Photoreactivity can be improved by including component (E). One type of component (E) may be used alone, or two or more types may be used in combination.

[0112] The component (E) has a refractive index of 1.45 or higher, preferably 1.46 or higher, and more preferably 1.47 or higher. The upper limit of the refractive index is 1.51 or lower, preferably 1.508 or lower, and more preferably 1.505 or lower. Typically, the refractive index of the inorganic filler (B) is 1.45 or higher and 1.51 or lower. The inventors have discovered that by making the refractive index of component (E) close to the refractive index of the inorganic filler (B), it is possible to suppress the deterioration of the shape of the via hole, thereby making it possible to open a small-diameter via hole. The refractive index can be measured according to the method described in the examples described below.

[0113] (E) As a component, a compound capable of photopolymerization by irradiating with active light may be used. As such a compound, for example, a (meth)acrylate compound that is liquid, solid, or semi-solid at room temperature and has one or more (meth)acryloyl groups per molecule may be used. Room temperature refers to approximately 25°C. “(meth)acryloyl group” refers to an acryloyl group and a methacryloyl group.

[0114] (E) A suitable embodiment of the component is a photosensitive (meth)acrylate compound having a divalent cyclic structure and a refractive index of 1.45 or higher and 1.51 or lower. As the divalent cyclic group, it may be either a cyclic group having an alicyclic structure or a cyclic group having an aromatic ring structure. Among these, it is preferable to have a cyclic group having an alicyclic structure in order to significantly obtain the desired effect of the present invention.

[0115] The divalent ring group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, even more preferably a 5-membered ring or more, and preferably a 20-membered ring or less, more preferably a 15-membered ring or less, and even more preferably a 10-membered ring or less, from the perspective of significantly obtaining the desired effect of the present invention. In addition, the divalent ring group may be a single ring structure or a polycyclic structure.

[0116] In the divalent cyclic group, the ring may have a skeleton composed of heteroatoms other than carbon atoms, and the divalent cyclic group preferably has a heteroatom-containing alicyclic skeleton. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, etc., and oxygen atoms are preferred. The ring may have one heteroatom or two or more heteroatoms.

[0117] Specific examples of a divalent phantom are the following divalent devices (i) to (x). Among them, (x) is preferred as a divalent phantom.

[0118]

[0119] The divalent cyclic group may have a substituent. Examples of such substituents include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfonate group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, an oxo group, etc., and an alkyl group is preferred.

[0120] The (meth)acryloyl group may be directly bonded to a divalent cyclic group or bonded via a divalent linker. Examples of divalent linkers include alkylene groups, alkenylene groups, arylene groups, heteroarylene groups, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc., and groups formed by a combination of these may also be used. As for the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 4 carbon atoms is even more preferred. The alkylene group may be straight-chain, branched, or cyclic. Examples of such alkylene groups include methylene groups, ethylene groups, propylene groups, butylene groups, pentylene groups, hexylene groups, 1,1-dimethylethylene groups, etc., and methylene groups, ethylene groups, and 1,1-dimethylethylene groups are preferred. As for alkenylene groups, alkenylene groups having 2 to 10 carbon atoms are preferred, alkenylene groups having 2 to 6 carbon atoms are more preferred, and alkenylene groups having 2 to 5 carbon atoms are even more preferred. As for arylene groups and heteroarylene groups, arylene groups or heteroarylene groups having 6 to 20 carbon atoms are preferred, and arylene groups or heteroarylene groups having 6 to 10 carbon atoms are more preferred. As for divalent linkers, alkylene groups are preferred, and among them, methylene groups and 1,1-dimethylethylene groups are preferred.

[0121] A photosensitive (meth)acrylate compound having a divalent cyclic structure and a refractive index of 1.45 or higher and 1.51 or lower is preferably represented by the following chemical formula (E).

[0122] [Chemical Formula (E)]

[0123]

[0124] (In chemical formula (E), R 1 and R 4 Each independently represents an acryloyl group or a methacryloyl group, and R 2 and R 3 Each represents a divalent linker independently. Ring A represents a divalent ring.

[0125] R 1 and R 4 Each independently represents an acryloyl group or a methacryloyl group, and an acryloyl group is preferred.

[0126] R 2 and R 3 Each represents a divalent linker independently. As a divalent linker, it is identical to a divalent linker in which a (meth)acryloyl group may be bonded.

[0127] Ring A represents a divalent cyclic group. As Ring A, it is identical to the above divalent cyclic group. Ring A may have a substituent. As a substituent, it is identical to the substituent that the above divalent cyclic group may have.

[0128] Specific examples of photosensitive (meth)acrylate compounds having a divalent cyclic structure and a refractive index of 1.45 or higher and 1.51 or lower include compounds represented by the chemical formula (E-1), but the present invention is not limited thereto.

[0129] [Chemical Formula (E-1)]

[0130]

[0131] Photosensitive (meth)acrylate compounds having a divalent cyclic structure and a refractive index of 1.45 or higher and 1.51 or lower may be commercially available products, such as “A-DOG” (compound represented by chemical formula (E-1) manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.), “NPDGA”, “FM-400”, “R-687”, “THE-330”, “PET-30” manufactured by Nippon Kayaku Co., Ltd.

[0132] (E) Another embodiment of the component is a photosensitive (meth)acrylate compound having a refractive index of 1.45 or higher and 1.51 or lower, which does not have a divalent cyclic structure. Examples of such compounds include, for instance, heterocyclic acrylates such as 4-acryloylmorpholine; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, and neopentyl glycol; acrylamides such as N,N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate; polyhydric alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol, or polyhydric acrylates of their adducts of ethylene oxide, propylene oxide, or ε-caprolactone; Examples include acrylates such as phenols like phenoxyacrylate and phenoxyethylacrylate, or their ethylene oxide or propylene oxide adducts; epoxyacrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether; melamine acrylates and / or methacrylates corresponding to the above acrylates. Among these, alkyl acrylates and heterocyclic acrylates are preferred.

[0133] (E) As a component, it is preferable to include a compound represented by the chemical formula (E-1) in order to significantly obtain the effects of the present invention.

[0134] (E) The content of component (E) is preferably 0.5 mass% or more, more preferably 1 mass% or more, even more preferably 3 mass% or more, and preferably 10 mass% or less, more preferably 9 mass% or less, and even more preferably 8 mass% or less, when the non-volatile component of the photosensitive resin composition is 100 mass%, from the perspective of effectively improving developability and adhesion. In addition, when the amount of component (E) is within the above range, it is possible to promote the photocuring of the photosensitive resin composition or suppress stickiness when the photosensitive resin composition is cured.

[0135] <(F) Curing Accelerator>

[0136] The photosensitive resin composition may contain (F) a curing accelerator as an optional component in addition to the above components. The (F) component may be used as a single type or in combination of two or more types.

[0137] (F) As components, examples include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, etc.

[0138] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., and triphenylphosphine and tetrabutylphosphonium decanate are preferred.

[0139] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

[0140] As imidazole-based curing accelerators, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-Cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, Examples include imidazole compounds such as 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

[0141] As an imidazole-based curing accelerator, commercially available products may be used, for example, “P200-H50” manufactured by Mitsubishi Chemical Co., Ltd.

[0142] As guanidine-based curing accelerators, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, Examples include 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc., and dicyandiamide and 1,5,7-triazabicyclo[4.4.0]deca-5-ene are preferred.

[0143] 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 organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper 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, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0144] (F) The content of the component is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, even more preferably 0.01 mass% or more, and preferably 0.15 mass% or less, more preferably 0.12 mass% or less, and even more preferably 0.1 mass% or less, in order to significantly obtain the desired effect of the present invention.

[0145] <(G) Organic solvents>

[0146] The photosensitive resin composition may additionally contain (G) an organic solvent. By including component (G), the viscosity of the varnish can be adjusted. Examples of organic solvents (G) include ketones such as methyl ethyl ketone (MEK) and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and ethyl diglycol acetate, aliphatic hydrocarbons such as octane and decane, and petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These are used as a single type or in combination of two or more types. When using organic solvents, the content can be appropriately adjusted from the perspective of the coating properties of the photosensitive resin composition.

[0147] <(H) Other Additives>

[0148] The photosensitive resin composition may additionally contain (H) other additives to an extent that does not impede the purpose of the present invention. (G) Other additives may include, for example, thermoplastic resins, organic fillers, fine particles such as melamine and organic bentonite, coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black, polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol, thickeners such as bentonite and montmorillonite, silicone-based, fluorine-based, and vinyl resin-based defoaming agents, brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus-based compounds, flame retardants such as aromatic condensed phosphate esters and halogen-containing condensed phosphate esters, and thermosetting resins such as phenolic curing agents and cyanate ester-based curing agents.

[0149] A photosensitive resin composition can be manufactured as a resin varnish by mixing the above components (A) to (E) as essential components, appropriately mixing the above components (F) to (H) as optional components, and, if necessary, mixing or stirring using a mixing means such as a three-roll mill, ball mill, bead mill, or sand mill, or a stirring means such as a super mixer or planetary mixer.

[0150] <Physical properties and uses of photosensitive resin compositions>

[0151] The lowest melt viscosity of the photosensitive resin composition is preferably 10,000 poise or less, more preferably 8,000 poise or less, and even more preferably 5,000 poise or less. The lower limit is not particularly limited, but can be 10 poise or more. Here, the term "lowest melt viscosity" refers to the lowest melt viscosity at 60°C to 200°C. The lowest melt viscosity can be measured using a dynamic viscoelasticity measuring device. A specific example of a dynamic viscoelasticity measuring device is the "Rheosol-G3000" manufactured by UBM. The lowest melt viscosity can be measured, for example, using a dynamic viscoelasticity measuring device, by using a parallel plate with a diameter of 18 mm for 1 g of sample, increasing the temperature from an initial temperature of 60°C to 200°C at a heating rate of 5°C / min, and measuring under conditions of a measurement temperature interval of 2.5°C, a frequency of 1 Hz, and a strain of 1 deg.

[0152] A cured product obtained by photocuring a photosensitive resin composition and then heat-curing it at 190°C for 90 minutes typically exhibits the characteristic of having a low average coefficient of thermal expansion (CTE). That is, it forms an insulating layer and a solder resist with a low average coefficient of thermal expansion. The average coefficient of thermal expansion is preferably 55 ppm or less, more preferably 50 ppm or less, and even more preferably 45 ppm or less. The lower limit is not particularly limited, but can be 10 ppm or more. The average coefficient of thermal expansion can be measured according to the method described in the examples described below.

[0153] A cured product obtained by photocuring the photosensitive resin composition of the present invention and then heat-curing it at 190°C for 90 minutes typically exhibits the characteristic of having a low dielectric constant. That is, it forms an insulating layer and a solder resist with a low dielectric constant. The dielectric constant is preferably 3.5 or less, more preferably 3.4 or less, and even more preferably 3.3 or less. The lower limit is not particularly limited, but can be 0.1 or more. The dielectric constant can be measured according to the method described in the examples described below.

[0154] A cured product obtained by photocuring the photosensitive resin composition of the present invention and then heat-curing it at 190°C for 90 minutes typically exhibits the characteristic of having a low dielectric loss tangent. That is, it forms an insulating layer and a solder resist with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.03 or less, more preferably 0.020 or less, and even more preferably 0.015 or less. The lower limit is not particularly limited, but can be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in the examples described below.

[0155] The photosensitive resin composition exhibits excellent developability even with a high content of inorganic filler. Specifically, when the photosensitive resin composition is exposed to light and developed, the retention of resin in unexposed areas can be suppressed. The residue in unexposed areas can be evaluated according to the method described in the examples to be described later.

[0156] The photosensitive resin composition exhibits the characteristic of having excellent developability even with a high content of inorganic filler. Specifically, when a via hole is formed by exposing and developing the photosensitive resin composition, the minimum opening diameter (minimum via diameter) of the via hole that can be formed without causing residue or peeling can be reduced. The minimum opening diameter is preferably 60 μm or less, more preferably 45 μm or less, and even more preferably 40 μm or less. The lower limit is not particularly limited, but can be 1 μm or more. The minimum opening diameter can be measured according to the method described in the examples described later.

[0157] The photosensitive resin composition exhibits excellent developability even with a high content of inorganic filler. 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 referred to as "via wall") can be reduced. Specifically, the minimum opening diameter of the via hole is denoted as R (μm). The number of inorganic fillers with a particle diameter of (0.1 × R) or greater exposed from the via wall is counted. In this case, the number of inorganic fillers with a particle diameter of (0.1 × R) or greater exposed from the via wall is less than 10. For example, the number of component (B) with a particle diameter of 1 μm or greater on the wall of a via hole with a minimum opening diameter of 10 μm is preferably 10 or less, more preferably 9 or less, and even more preferably 8 or less. The lower limit is not particularly restricted, but can be 0 or more. The evaluation of via walls can be measured according to the method described in the embodiments below.

[0158] The photosensitive resin composition exhibits the characteristic of having excellent developability even with a high content of inorganic filler. Specifically, when a via hole is formed by exposing and developing the photosensitive resin composition, a tapered via hole can be formed, and preferably, a tapered via hole can be formed in which the difference between the radius of the top and the radius of the bottom is small. Unless otherwise stated, a tapered shape refers to a shape in which the diameter of the top corresponding to the opening of the via hole is larger than the diameter of the bottom corresponding to the bottom of the via hole. Specifically, the radius of the top (μm) and the radius of the bottom (μm) of the cross-section of the via hole are measured by SEM. The difference between the radius of the top and the radius of the bottom (radius of the top - radius of the bottom) is calculated. As a result, it is preferably 5 or less, more preferably 4.5 or less, and even more preferably 4 or less. The evaluation of the taper can be measured according to the method described in the examples described later.

[0159] A cured product obtained by photocuring a photosensitive resin composition and then heat-curing it at 180°C for 30 minutes exhibits the characteristic that via holes can be formed using a conventional laser. In other words, it exhibits the characteristic of having excellent laser via aperture. Specifically, a UV-UAG laser is irradiated onto the cured product under conditions of a power of 0.25 W, a number of shots of 20, and a target top diameter of 30 μm. As a result, via holes can be formed, and there is no delamination when observing the cross-section of the via holes. The evaluation of laser via aperture can be measured according to the method described in the examples to be described later.

[0160] A cured product obtained by photocuring a photosensitive resin composition and then heat-curing it at 180°C for 30 minutes can increase the peel strength (adhesion) between the cured product and the conductor layer formed by plating. Therefore, when an insulating layer is formed with the cured product, an insulating layer with high peel strength between the cured product and the plated conductor layer can be obtained. The peel strength may preferably be 0.20 kgf / cm or higher, and more preferably 0.30 kgf / cm or higher. The upper limit of the peel strength is not particularly limited, but may be, for example, 10.0 kgf / cm or lower. The peel strength can be measured according to the method described in the examples described below.

[0161] The surface of a photosensitive resin composition, after being photocured and further heat-cured at 180°C for 30 minutes, is then treated to be smooth, and the smoothed surface typically exhibits the characteristic of having a low arithmetic mean roughness (Ra). Accordingly, the cured material forms an insulating layer with a low arithmetic mean roughness. The arithmetic mean roughness is preferably 400 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less. In addition, the lower limit of the arithmetic mean roughness can be 1 nm or more. The evaluation of the arithmetic mean roughness (Ra) can be measured according to the method described in the examples described below.

[0162] A cured product obtained by photocuring a photosensitive resin composition exhibits excellent crack resistance. That is, it forms an insulating layer and a solder resist with excellent crack resistance. For example, even when a test is performed in which a thermal cycle treatment including a cooling to -65°C and a cooling to 150°C is repeated 500 times on the cured product, no cracks or delamination are observed. Crack resistance can be evaluated according to the method described in the examples described below.

[0163] The applications of the photosensitive resin composition of the present invention are not particularly limited, but can be widely used in applications requiring a photosensitive resin composition, such as photosensitive films attached to supports, insulating resin sheets such as prepregs, circuit boards (for laminated boards, multilayer printed circuit boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor sealants, hole-filling resins, and component-embedding resins. Among these, it can be suitably used as a photosensitive resin composition for an insulating layer of a printed circuit board (a printed circuit board in which a cured product of the photosensitive resin composition is used as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a printed circuit board in which a cured product of the photosensitive resin composition is used as an interlayer insulating layer (interlayer insulating material)), a photosensitive resin composition for forming a plating (a printed circuit board in which plating is formed on a cured product of the photosensitive resin composition), and a photosensitive resin composition for a solder resist (a printed circuit board in which a cured product of the photosensitive resin composition is used as a solder resist).

[0164] [Photosensitive film attached to a support]

[0165] The photosensitive resin composition of the present invention can be suitably used in the form of a support-attached photosensitive film in which a layer of the photosensitive resin composition is formed on a support. That is, the support-attached photosensitive film comprises a support and a layer of the photosensitive resin composition formed from the photosensitive resin composition of the present invention provided on the support.

[0166] Examples of supports include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, triacetylacetate film, etc., and polyethylene terephthalate film is particularly preferred.

[0167] Examples of commercially available supports include polypropylene films manufactured by Oji Seishi Co., Ltd. (product names “Alpan MA-410”, “E-200C”), Shin-Etsu Film Co., Ltd. (product name “PS-25”), and polyethylene terephthalate films such as the PS series manufactured by Teijin Co., Ltd. (product name “PS-25”), but are not limited to these. To facilitate the removal of the photosensitive resin composition layer, it is preferable for these supports to have a release agent, such as a silicone coating agent, applied to their surface. The thickness of the support is preferably in the range of 5 μm to 50 μm, and more preferably in the range of 10 μm to 25 μm. By making the thickness 5 μm or more, tearing of the support can be suppressed during peeling before development, and by making the thickness 50 μm or less, the resolution can be improved when exposing from the support. Additionally, a support with a low fisheye is preferred. Here, "fish eye" refers to foreign substances, undissolved substances, oxidized deteriorated products, etc., that enter the film when the material is heated, melted, mixed, extruded, biaxially stretched, or cast to manufacture the film.

[0168] In addition, to reduce light scattering during exposure to active light such as ultraviolet rays, it is desirable for the support to have excellent transparency. Specifically, it is desirable for the support to have a haze (standardized as JIS-K6714) which is an indicator of transparency to be 0.1 to 5. In addition, the photosensitive resin composition layer may be protected by a protective film.

[0169] By protecting the photosensitive resin composition layer side of the photosensitive film attached to the support with a protective film, the adhesion of dust or the like, or scratches on the surface of the photosensitive resin composition layer, can be prevented. As the protective film, a film composed of the same material as the support may be used. The thickness of the protective film is not particularly limited, but it is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. By making the thickness 1 μm or more, the handling of the protective film can be improved, and by making it 40 μm or less, there is a tendency for cost-effectiveness to improve. In addition, regarding the adhesion between the photosensitive resin composition layer and the support, it is preferable that the adhesion between the photosensitive resin composition layer and the protective film be smaller.

[0170] A photosensitive film attached to a support can be manufactured, for example, by preparing a resin varnish by dissolving the photosensitive resin composition of the present invention in an organic solvent, applying the resin varnish onto a support, and drying the organic solvent by heating or hot air spraying to form a layer of the photosensitive resin composition. Specifically, a photosensitive film attached to a support can be manufactured by first completely removing bubbles in the photosensitive resin composition using a vacuum degassing method, applying the photosensitive resin composition onto a support, removing the solvent by a hot air furnace or a far-infrared furnace, drying, and then, if necessary, laminating a protective film on the obtained layer of the photosensitive resin composition. Specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of organic solvent in the resin varnish, but for a resin varnish containing 30 mass% to 60 mass% of organic solvent, drying can be performed at 80°C to 120°C for 3 minutes to 13 minutes. In order to prevent the diffusion of organic solvents in the photosensitive resin composition layer, it is preferable to keep the amount of residual organic solvent in the photosensitive resin composition layer at 5 mass% or less, and more preferable to keep it at 2 mass% or less. A person skilled in the art can appropriately set suitable drying conditions through simple experiments. In order to improve handling and also to suppress the decrease in sensitivity and resolution within the photosensitive resin composition layer, the thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm, more preferably in the range of 10 μm to 200 μm, even more preferably in the range of 15 μm to 150 μm, even more preferably in the range of 20 μm to 100 μm, and particularly preferably in the range of 20 μm to 60 μm.

[0171] Examples of coating methods for photosensitive resin compositions include gravure coating, microgravure coating, reverse coating, kiss reverse coating, die coating, slot die coating, lip coating, comma coating, blade coating, roll coating, knife coating, curtain coating, chamber gravure coating, slot orifice coating, spray coating, dip coating, etc.

[0172] The photosensitive resin composition may be applied in multiple layers, in a single layer, or by combining multiple other methods. Among these, a die-coating method is preferred as it offers excellent uniform coating properties. Additionally, to avoid contamination with foreign substances, it is preferable to perform the coating process in an environment with low foreign substance generation, such as a clean room.

[0173] The photosensitive resin composition layer of the photosensitive film attached to the support of the present invention exhibits the characteristic of having excellent flexibility. Therefore, the photosensitive resin composition can suppress the scattering of the resin and the occurrence of cracks even when stress is applied. In addition, it is desirable that no scattering or cracking of the photosensitive resin composition is visible even when the photosensitive resin composition layer is cut with a cutter knife, and it is also desirable that no scattering or cracking of the photosensitive resin composition is visible even when the photosensitive resin composition layer is folded 180°. Flexibility can be measured according to the description of the examples described below.

[0174] The photosensitive resin composition layer of the support-attached photosensitive film of the present invention exhibits excellent adhesive properties. When the support-attached photosensitive film at 25°C is evaluated using a probe tack tester, the appearance of the film is good and no traces remain on the probe. The adhesive properties can be evaluated according to the method described in the examples described below.

[0175] The photosensitive resin composition layer of the support-attached photosensitive film of the present invention exhibits excellent flexibility and adhesion, thereby showing the characteristic that the appearance of the film is good. Accordingly, the occurrence of crawling or stains is suppressed in the photosensitive resin composition layer of the support-attached photosensitive film. The appearance of the film can be measured according to the description of the examples described below.

[0176] [Printed Wiring Board]

[0177] The printed circuit board of the present invention comprises an insulating layer formed by a cured product of the photosensitive resin composition of the present invention. It is preferable to use the insulating layer as a solder resist.

[0178] In detail, the printed circuit board of the present invention can be manufactured using the photosensitive film attached to the support. Below, the case where the insulating layer is a solder resist will be described.

[0179] <Lamination and Drying Process>

[0180] A photosensitive resin composition layer is formed on a circuit board by laminating the photosensitive resin composition layer side of a photosensitive film attached to a support onto a circuit board and drying it.

[0181] Examples of circuit boards include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. Furthermore, the term "circuit board" here refers to a substrate having a patterned conductive layer (circuit) formed on one or both sides of the above-mentioned substrate. In addition, in a multilayer printed circuit board formed by alternately laminating conductive layers and insulating layers, a substrate having one or both sides of the outermost layer of the multilayer printed circuit board formed by a patterned conductive layer (circuit) is also included in the circuit board described here. Furthermore, the surface of the conductive layer may be pre-treated by means of blackening treatment, copper etching, etc.

[0182] As an embodiment of the lamination process, a photosensitive resin composition layer is laminated onto one or both sides of a circuit board using a vacuum laminator. In the lamination process, if the photosensitive film attached to the support has a protective film, the protective film is removed, and if necessary, the photosensitive film attached to the support and the circuit board are preheated, and the photosensitive resin composition layer is pressed onto the circuit board while applying pressure and heating. For the photosensitive film attached to the support, a method of laminating it onto the circuit board under reduced pressure by a vacuum lamination method is suitably used.

[0183] The conditions of the lamination process are not particularly limited, but for example, the pressing temperature (lamination temperature) is preferably set to 70°C to 140°C, and the pressing pressure is preferably set to 1kgf / ㎠ to 11kgf / ㎠ (9.8×10⁻⁶). 4 N / ㎡ to 107.9×10 4 It is preferable to laminate under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less, with a compression time of preferably 5 seconds to 300 seconds (N / m²). In addition, the lamination process may be a batch type or a continuous type using rolls. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nikko Materials, a vacuum pressure type laminator manufactured by Meiki Sesakusho, a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. In this way, a photosensitive film attached to a support is formed on a circuit board.

[0184] Instead of laminating a photosensitive film attached to a support, a layer of the photosensitive resin composition may be formed on the circuit board by directly applying the photosensitive resin composition in the form of a resin varnish and drying it with an organic solvent. As for the application method, full-surface printing by screen printing is generally widely used, but any other application method capable of uniform application may be used. For example, spray coating, hot melt coating, bar coating, applicator coating, blade coating, knife coating, air knife coating, curtain flow cotton coating, roll coating, gravure coating, offset printing, dip coating, brushing, and other conventional application methods may all be used. After application, drying is performed using a hot air oven or a far-infrared oven as needed. The drying conditions are preferably set at 80°C to 120°C for 3 to 13 minutes.

[0185] Photolithography Process

[0186] After a photosensitive resin composition layer is provided on a circuit board by the above process, an exposure process is subsequently performed in which an active light is irradiated onto a predetermined portion of the photosensitive resin composition layer through a mask pattern and the photosensitive resin composition layer in the irradiated portion is photocured. Examples of active light include ultraviolet light, visible light, electron beams, X-rays, etc., and ultraviolet light is particularly preferred. The amount of ultraviolet light irradiated is approximately 10 mJ / cm² to 1,000 mJ / cm². The exposure method may include a contact exposure method in which the mask pattern is pressed against the printed circuit board, and a non-contact exposure method in which parallel light is used for exposure without contact, but either method may be used. In addition, if a support is present on the photosensitive resin composition layer, exposure may be performed from the support, or exposure may be performed after peeling off the support.

[0187] Since the solder resist uses the photosensitive resin composition of the present invention, it has excellent developability (resolution). For this reason, as an exposure pattern in a mask pattern, for example, a pattern in which the ratio (L / S) of the circuit width (line; L) to the width between circuits (space; S) is 100 μm / 100 μm or less (i.e., wiring pitch 200 μm or less), L / S = 80 μm / 80 μm or less (wiring pitch 160 μm or less), L / S = 70 μm / 70 μm or less (wiring pitch 140 μm or less), or L / S = 60 μm / 60 μm or less (wiring pitch 120 μm or less) can be used. In addition, the pitch does not need to be uniform across the entire circuit board.

[0188] <Development Process>

[0189] If a support is present on the photosensitive resin composition layer after the photolithography process, a pattern can be formed by removing the support and then developing the unphotocured portion (unexposed portion) by removing it through wet development or dry development.

[0190] In the case of the above wet phenomenon, a developer that is safe, stable, and easy to operate, such as an alkaline aqueous solution, a water-based developer, or an organic solvent, is used as the developer, and among these, a development process using an alkaline aqueous solution is preferred. In addition, as the development method, known methods such as spraying, shaking immersion, brushing, and scraping are appropriately employed.

[0191] Examples of alkaline aqueous solutions used as developers include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate, alkali metal phosphates such as sodium phosphate and potassium phosphate, alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, or aqueous solutions of organic bases that do not contain metal ions such as tetraalkylammonium hydroxide. An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred in that it does not contain metal ions and does not affect the semiconductor chip.

[0192] In order to enhance the developing effect, surfactants, defoaming agents, etc., may be added to these alkaline aqueous solutions. The pH of the alkaline aqueous solution is preferably in the range of, for example, 8 to 12, and more preferably in the range of 9 to 11. In addition, the base concentration of the alkaline aqueous solution is preferably 0.1 mass% to 10 mass%. The temperature of the alkaline aqueous solution can be appropriately selected to match the development of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

[0193] Organic solvents used as developers are, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

[0194] The concentration of such organic solvents is preferably 2% to 90% by mass relative to the total amount of the developer. In addition, the temperature of such organic solvents can be adjusted according to the developability. Furthermore, such organic solvents may be used alone or in combination of two or more types. Examples of organic solvent-based developers used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methylisobutylketone, and γ-butyrolactone.

[0195] In pattern formation, two or more of the above-mentioned development methods may be used in combination as needed. Development methods include the dip method, paddle method, spray method, high-pressure spray method, brushing, slapping, etc., and the high-pressure spray method is suitable for improving resolution. When using the spray method, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0196] <Thermal Curing (Post-Bake) Process>

[0197] After the above development process is completed, a heat curing (post-baking) process is performed to form a solder resist. Examples of post-baking processes include an ultraviolet irradiation process using a high-pressure mercury lamp or a heating process using a clean oven. When ultraviolet light is irradiated, the amount of irradiation can be adjusted as needed, for example, with an irradiation amount of about 0.05 J / cm² to 10 J / cm². In addition, the heating conditions may be appropriately selected according to the type and content of the resin component in the photosensitive resin composition, but are preferably selected in the range of 20 minutes to 180 minutes at 150°C to 220°C, and more preferably in the range of 30 minutes to 120 minutes at 160°C to 200°C.

[0198] Other Processes

[0199] After forming the solder resist, the printed circuit board may additionally include a perforation process and a desmearing process. These processes may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed circuit boards.

[0200] After forming a solder resist, a drilling process is performed on the solder resist formed on the circuit board to form via holes and through holes as desired. The drilling process can be performed by known methods, such as a drill, laser, or plasma, or by combining these methods as needed, but a drilling process using a laser, such as a carbon dioxide laser or a YAG laser, is preferred.

[0201] The desmearing process is a desmearing process. Generally, resin residue (smear) adheres to the inside of the opening formed during the perforation process. Since this smear causes electrical connection failures, a process to remove the smear (desmearing process) is performed during this process.

[0202] Desmearing treatment may be performed by dry desmearing treatment, wet desmearing treatment, or a combination thereof.

[0203] Examples of dry desmear processing include plasma desmear processing. Plasma desmear processing can be performed using commercially available plasma desmear processing devices. Among commercially available plasma desmear processing devices, examples suitable for manufacturing printed circuit boards include the microwave plasma device manufactured by Nissin Co., Ltd. and the atmospheric pressure plasma etching device manufactured by Sekisui Kagaku Kogyo Co., Ltd.

[0204] As for wet desmear treatment, examples include desmear treatment using an oxidizing agent solution. When desmear treatment using an oxidizing agent solution, it is preferable to perform swelling treatment with a swelling solution, oxidation treatment with an oxidizing agent solution, and neutralization treatment with a neutralizing solution in this order. Examples of swelling solutions include "Swelling Deep Securigans P" and "Swelling Deep Securigans SBU" manufactured by Atotech Japan. Swelling treatment is preferably performed by immersing a substrate with via holes, etc., formed thereon in a swelling solution heated to 60°C to 80°C for 5 to 10 minutes. As for the oxidizing agent solution, an alkaline aqueous permanganate solution is preferred, and examples include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. Oxidation treatment using an oxidizing agent solution is preferably performed by immersing the substrate after swelling treatment in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan. Neutralization treatment using a neutralizing solution is preferably performed by immersing the substrate after oxidation treatment in a neutralizing solution at 30°C to 50°C for 3 to 10 minutes. An acidic aqueous solution is preferred as the neutralizing solution, and examples of commercially available products include "Reduction Solution Securigans P" manufactured by Atotech Japan.

[0205] When performing a combination of dry desmear treatment and wet desmear treatment, the dry desmear treatment may be performed first, or the wet desmear treatment may be performed first.

[0206] Even when the insulating layer is used as an interlayer insulating layer, it can be done in the same way as in the case of solder resist, and after the heat curing process, a perforation process, a desmearing process, and a plating process may be performed.

[0207] The plating process is a process of forming a conductive layer on an insulating layer. The conductive layer may be formed by combining electroless plating and electrolytic plating, or a plating resist with an inverse pattern to the conductive layer may be formed and the conductive layer formed solely by electroless plating. As a method for forming the pattern thereafter, for example, the subtractive method, the semi-additive method, etc., known to those skilled in the art, may be used.

[0208] [Semiconductor device]

[0209] 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.

[0210] Examples of semiconductor devices include various semiconductor devices provided for electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trams, ships, and aircraft).

[0211] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at a conductive location on a printed circuit board. A "conductive location" is a "location that transmits an electrical signal on a printed circuit board," and the location may be either a surface location or an embedded location. Furthermore, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of semiconductor material.

[0212] The method of mounting a semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, examples include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bump-free build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), etc. Here, "mounting method using a bump-free build-up layer (BBUL)" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed circuit board to connect the semiconductor chip with the wiring on the printed circuit board."

[0213] [Example]

[0214] The present invention will be described in detail below by way of examples, but the present invention is not limited to these examples. Furthermore, in the following description, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass," respectively, unless otherwise specified.

[0215] (Preparation of weapon fillers)

[0216] Inorganic fillers B-1 to B-7 were obtained by using the “SFP series” manufactured by Denki Kagaku Kogyo Co., Ltd., the “SP(H) series” manufactured by Shin-Nippon Tetsu Sumikin Materials Co., Ltd., the “Sciqas series” manufactured by Sakai Kagaku Kogyo Co., Ltd., the “Shiho Star series” manufactured by Nippon Shokubai Co., Ltd., and the “SG-SO series” manufactured by Sukyuug Co., Ltd., either alone or in combination, performing surface treatment with a vinylsilane-based coupling agent (manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd., KBM1003), and then filtering and classifying. The particle diameter distribution of inorganic fillers B-1 to B-7 was measured by the following method.

[0217] 50 mg of powdered inorganic filler B-1, 2 g of non-ionic dispersant ("T208.5" manufactured by Nippon Yoshida), and 40 g of pure water were weighed and placed in a vial, and dispersed using ultrasound for 20 minutes. The particle diameter distribution was measured using a laser diffraction particle diameter distribution measuring device (LA-950 manufactured by Horiba Sesakusho) in a batch cell manner, and D 10 , D 50 , D 90 The average particle diameter was calculated for inorganic fillers B-2 to B-6 in the same manner. For B-7, the particle diameter distribution was measured using the same method, except that the pure water was replaced with MEK.

[0218] The specific surface area of ​​inorganic fillers B-1 to B-7 was measured using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mounttec).

[0219] D of each weapon filler 10 , D 50 , D 90 and specific surface area are shown in the table below.

[0220]

[0221] (Measurement of refractive index)

[0222] (E) The refractive index of the component was measured at 589 nm using an Abbe refractive index meter (manufactured by Atago, DR-M2) while maintaining the temperature at 25°C.

[0223] (Synthesization Example: Synthesis of Component A-1)

[0224] 325 parts of an epoxy resin having a naphtholarkyl backbone with an epoxy equivalent of 325 g / eq. ("ESN-475V", manufactured by Nittetsu Chemicals Co., Ltd.) were placed in a flask equipped with a gas inlet tube, a stirring device, a cooling tube, and a thermometer; 340 parts of carbitol acetate were added and heated to dissolve; then 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. This mixture was heated to 95 to 105°C, 72 parts of acrylic acid were slowly added dropwise, and the reaction was carried out for 16 hours. The reaction product was cooled to 80 to 90°C, 80 parts of tetrahydrophthalic anhydride were added, and the reaction was carried out for 8 hours, followed by cooling. The amount of solvent was adjusted to obtain a resin solution (non-volatile content 70%, hereinafter abbreviated as "A-1") having a solid acid value of 60 mg KOH / g.

[0225] <Examples 1 to 7, Comparative Examples 1 to 9>

[0226] Each component was mixed according to the mixing ratios shown in the table below, and a resin varnish was prepared using a high-speed rotary mixer. Next, a PET film (manufactured by Tore, “Lumira T6AM”, thickness 38 μm, softening point 130°C, “Release PET”) was prepared as a support by being released with an alkyd resin-based release agent (manufactured by Lintec, “AL-5”). The prepared resin varnish was uniformly applied to this release PET using a die coater so that the thickness of the photosensitive resin composition layer after drying was 20 μm, and by drying at 80°C to 110°C for 7 minutes, a support-attached photosensitive film having a photosensitive resin composition layer on the release PET was obtained.

[0227] <Evaluation of Film Appearance, Flexibility, and Adhesion>

[0228] The appearance of the photosensitive resin composition layer of the support-attached photosensitive film prepared in the examples and comparative examples was visually inspected. In addition, the scattering of resin and the occurrence of cracks when the photosensitive resin composition layer was cut with a cutter knife were visually inspected. Furthermore, the occurrence of cracks when the support-attached photosensitive film was folded 180° was visually inspected. In addition, the adhesion of the support-attached photosensitive film was evaluated using a probe tack tester (TE-6002) in a constant temperature chamber at 25°C. The measurement conditions were set as a probe with a diameter of 5 mm, a load of 1 kgf / ㎠, a contact time of 10 seconds, and a peeling speed of 0.1 mm / sec. The appearance, flexibility, and adhesion of the film were evaluated as follows.

[0229] ○: There is no crawling or staining, and no resin scattering or cracking is visible. Additionally, the film's appearance is good after the adhesion evaluation, and the resin does not adhere to the probe due to excessive adhesion.

[0230] ×: After crawling, staining, resin scattering, cracking, or adhesion evaluation, resin remains on the frog due to excessive adhesion, causing the film to tear.

[0231] <Measurement of Minimum Melt Viscosity>

[0232] A measurement pellet (diameter 18 mm, 1.2 to 1.3 g) was produced by peeling off only the photosensitive resin composition layer from the release PET of the photosensitive film attached to the support and compressing it with a mold. Using the measurement pellet and a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM), for 1 g of the photosensitive resin composition layer of the sample, using a parallel plate with a diameter of 18 mm, the temperature was raised from an initial temperature of 60°C to 200°C at a heating rate of 5°C / min, and the dynamic viscoelasticity was measured under measurement conditions of a measurement temperature interval of 2.5°C, a frequency of 1 Hz, and a strain of 1 deg, and the lowest melt viscosity (poise) was calculated.

[0233] Average linear thermal expansion rate, measurement of dielectric properties

[0234] (Formation of cured material for evaluation)

[0235] The photosensitive resin composition layer of the support-attached photosensitive film obtained in the examples and comparative examples was photocured by exposing it to ultraviolet light at 100 mJ / cm². Subsequently, a 1 mass% aqueous sodium carbonate solution at 30°C was spray-developed on the entire surface of the photosensitive resin composition layer at a spray pressure of 0.2 MPa for 2 minutes as a developer. After spray development, ultraviolet irradiation at 1 J / cm² was performed, followed by heat treatment at 190°C for 90 minutes to obtain a cured product. Afterward, the support was peeled off to obtain a cured product for evaluation.

[0236] (Measurement of average linear thermal expansion rate)

[0237] The hardened material for evaluation was cut into a test specimen with a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed using the tensile weighting method with a thermomechanical analysis device (manufactured by Rigaku Co., Thermo Plus, TMA8310). After mounting the test specimen on the device, two consecutive measurements were taken under measurement conditions of a load of 1 g and a heating rate of 5°C / min. The average linear thermal expansion rate (ppm) from 25°C to 150°C was calculated during the second measurement.

[0238] (Measurement of genetic properties (permittivity, dielectric loss tangent))

[0239] The evaluation cured material was cut into a test specimen with a width of 2 mm and a length of 80 mm to obtain evaluation cured material B. For each evaluation cured material B, the dielectric constant (Dk value) and dielectric loss tangent (Df value) were measured using the cavity resonance perturbation method with a “HP8362B” manufactured by Agilent Technologies at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Measurements were performed on three test specimens (N=3), and the average was calculated.

[0240] Evaluation of Phenomenality

[0241] (Formation of evaluation laminate A)

[0242] A copper layer of a glass epoxy substrate (copper-clad laminate) having a patterned circuit formed on a copper layer with a thickness of 18 μm was treated with a surface treatment agent containing an organic acid (CZ8100, manufactured by Mack Co., Ltd.). Next, a photosensitive resin composition layer of a support-attached photosensitive film obtained in the example and comparative example was placed in contact with the surface of the copper circuit, and laminated using a vacuum laminator (manufactured by Nikko Materials Co., Ltd., VP160) to form a laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order. The compression conditions were a vacuum treatment time of 30 seconds, a compression temperature of 80°C, a compression pressure of 0.7 MPa, and a pressurization time of 30 seconds. The laminate was left standing at room temperature for at least 30 minutes, and via holes were formed by exposing the laminate to ultraviolet light using a pattern forming device with a round hole pattern from the support. For the exposure pattern, a quartz glass mask was used to draw a square of 1cm × 2cm with a round hole aperture of 20㎛ / 25㎛ / 30㎛ / 40㎛ / 50㎛ / 60㎛ / 70㎛ / 80㎛ / 90㎛ / 100㎛, line and space L / S (line / space) of 20㎛ / 20㎛, 25㎛ / 25㎛, 30㎛ / 30㎛, 40㎛ / 40㎛, 50㎛ / 50㎛, 60㎛ / 60㎛, 70㎛ / 70㎛, 80㎛ / 80㎛, 90㎛ / 90㎛, and 100㎛ / 100㎛. After standing at room temperature for 30 minutes, the support was peeled off from the laminate. Next, a 1 mass% aqueous sodium carbonate solution at 30°C was spray-developed on the front surface of the photosensitive resin composition layer at a spray pressure of 0.2 MPa. This substrate was designated as evaluation laminate A.

[0243] (Remnants of the Mino miner)

[0244] A 1cm × 2cm portion of the unexposed area of ​​the evaluation laminate A was visually observed and evaluated according to the following criteria.

[0245] ○: No resin remains in the unexposed area.

[0246] ×: The resin can be visually confirmed or there is a reduction in the membrane.

[0247] (Evaluation of minimum opening diameter)

[0248] The formed via holes were observed with an SEM (magnification 1,000x), and the minimum via hole diameter without residue or peeling was measured.

[0249] (Assessment of the non-wall)

[0250] In addition, the evaluation of the inner wall (via wall) of the via hole was performed by counting the number of inorganic fillers exposed from the via wall with a particle diameter of 0.1 × R, where R is the minimum opening diameter, and evaluating according to the following criteria.

[0251] ○: Fewer than 10 inorganic fillers with a particle diameter of (0.1×R) or greater are exposed from the via wall.

[0252] ×: The number of inorganic fillers with a particle diameter of (0.1×R) or greater exposed from the via wall is 10 or more.

[0253] (Evaluation of Taper)

[0254] For a via hole having the obtained minimum opening diameter, cross-sectional observation was performed using SEM, the radius of the top part (μm) and the radius of the bottom part (μm) of the cross-section were measured, and the difference (radius of the top part - radius of the bottom part) was calculated. A positive value was considered a taper shape, and a negative value was considered an undercut shape.

[0255] Laser via aperture, copper plating adhesion

[0256] (Fabrication of evaluation laminate B)

[0257] A copper layer of a glass epoxy substrate (copper-clad laminate) having a patterned circuit formed on a copper layer with a thickness of 18 μm was treated with a surface treatment agent containing an organic acid (CZ8100, manufactured by Mack). Next, the photosensitive resin composition layer of the support-attached photosensitive film obtained in the example and comparative example was placed in contact with the surface of the copper circuit, and laminated using a vacuum laminator (VP160, manufactured by Nikko Materials), thereby forming a laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order. The compression conditions were a vacuum treatment time of 30 seconds, a compression temperature of 80°C, a compression pressure of 0.7 MPa, and a pressing time of 30 seconds. The laminate was left standing at room temperature for at least 30 minutes, and then exposed to ultraviolet light through a quartz glass. After leaving it standing at room temperature for 30 minutes, the support was peeled off from the laminate. On the front surface of the photosensitive resin composition layer on the laminate plate from which the support had been removed, a 1 mass% aqueous sodium carbonate solution at 30°C was spray-developed as a developer at a spray pressure of 0.2 MPa. Afterwards, exposure was performed using a metal halide lamp, and heat curing was carried out at 180°C for 30 minutes to obtain an evaluation laminate B.

[0258] (Laser via aperture configuration)

[0259] Via holes were formed in the insulating layer of evaluation laminate B using a UV-YAG laser processor (Via Mechanics "LU-2L212 / M50L") under the following conditions, and evaluated according to the following criteria. Conditions: Power 0.25W, number of shots 20, target top diameter 30㎛.

[0260] ○: An opening of the via hole is created, and there is no delamination when observing the cross-section.

[0261] ×: No opening of the via hole or delamination upon cross-section.

[0262] (Evaluation of copper plating adhesion)

[0263] Evaluation laminate B was immersed in a swelling dip securigant P containing diethylene glycol monobutyl ether manufactured by Atotech Japan, which was a swelling solution, at 60°C for 5 minutes; then, as a harmonizing solution, it was immersed in a concentrate compact P (aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L) manufactured by Atotech Japan, at 80°C for 20 minutes; and finally, as a neutralizing solution, it was immersed in a reduction solucine securigant P manufactured by Atotech Japan, at 40°C for 5 minutes. Evaluation laminate B after the harmonizing treatment is referred to as evaluation laminate C.

[0264] Next, the above-mentioned evaluation laminate C was immersed in an electroless plating solution containing PdCl2, and then immersed in an electroless copper plating solution. After performing an annealing treatment by heating at 150°C for 30 minutes, an etching resist was formed, and after forming a pattern by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 20±5㎛. Next, an annealing treatment was performed at 180°C for 60 minutes. A cut with a width of 10mm and a length of 100mm was made in this plated conductor layer using a cutter, and one end of it was peeled off and picked up with a collecting device (manufactured by TSE, Autocom type tester AC-50C-SL). The load was measured when peeling 35mm vertically at a speed of 50mm / min at room temperature, and evaluated according to the following criteria.

[0265] ◎: Load of 0.30 kgf / cm or more

[0266] ○: Load less than 0.30 kgf / cm², 0.20 kgf / cm² or greater

[0267] ×: Load less than 0.20 kgf / cm²

[0268] (Measurement of surface shape (arithmetic mean roughness Ra))

[0269] The average value of the arithmetic mean roughness Ra of 10 randomly selected points on the surface of the evaluation laminate C was measured as the arithmetic mean roughness Ra of the evaluation laminate C. The measurement of the arithmetic mean roughness Ra at each point was evaluated using a non-contact surface roughness meter (WYKO NT3300 manufactured by Veecor Instruments, Inc.), with VSI contact mode and a 50x lens, with a measurement range of 121㎛×92㎛, according to the following criteria.

[0270] ◎: Ra is 200nm or less

[0271] ○: Ra is greater than 200nm and less than or equal to 400nm

[0272] ×: Ra exceeds 400nm

[0273] Crack's Evaluation

[0274] A copper layer of a glass epoxy substrate (copper laminate) having a circuit formed by patterning copper pads with a thickness of 18 μm and φ100 μm was treated with a surface treatment agent containing an organic acid (CZ8100, manufactured by Mack). Except for this, evaluation laminate D was fabricated using the same process as evaluation laminate A. A test was performed by repeating a thermal cycle treatment 500 times, in which the substrate was exposed to an atmosphere of -65°C for 15 minutes, then heated at a heating rate of 180°C / minute, followed by exposure to an atmosphere of 150°C for 15 minutes, and then heated at a cooling rate of 180°C / minute. After the test, the degree of cracking and delamination of the evaluation substrate was observed using an optical microscope (manufactured by Nikon, "ECLIPSE LV100ND") and evaluated according to the following criteria.

[0275] ○: No cracks or peeling are observed.

[0276] ×: Cracks and peeling are confirmed.

[0277]

[0278]

[0279] Abbreviations, etc. in the table are as follows.

[0280] · (ACA)Z-251: Acrylic polymer, cyclomer P (Manufactured by Daicel Ornex, acid value 66 mg KOH / g, solids concentration approx. 46%)

[0281] · CCR-1171H: Cresol novolak type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mg KOH / g, solid content approx. 60%)

[0282] · A-1: ​​Component A-1 synthesized in Synthesis Example 1 (non-volatile content 70%)

[0283] · B-1: Weapon Filler B-1

[0284] · B-2: Weapon Filler B-2

[0285] · B-3: Weapon Filler B-3

[0286] · B-4: Weapon Filler B-4

[0287] · B-5: Weapon Filler B-5

[0288] · B-6: Weapon Filler B-6

[0289] · B-7: Weapon filler B-7

[0290] · Irgacure TPO: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, manufactured by BASF

[0291] · HP4032: Naphthalene-type epoxy resin (manufactured by DIC, epoxy equivalent 144 g / eq., softening point less than 30℃)

[0292] · NC3000L: Biphenyl-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 271 g / eq., softening point 53℃)

[0293] · NPGDA: Neopentyl glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd., refractive index 1.452)

[0294] · A-DOG: Dioxane glycol diacrylate (manufactured by Shinnakamura Kagaku Kogyo Co., Ltd., refractive index 1.472)

[0295] · ACMO: 4-Acryloylmorpholine (Manufactured by KJ Chemical, Refractive index 1.508)

[0296] · NOAA: Normal octyl acrylate (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd., refractive index 1.433)

[0297] · R-551: Bisphenol A tetraethoxydiaacrylate (manufactured by Nippon Kayaku Co., Ltd., refractive index 1.538)

[0298] · 1B2PZ: 2-phenyl-1-benzyl-1H-imidazole, manufactured by Shikoku Kasei Co., Ltd.

[0299] · EDGAc: Ethyl diglycol acetate

[0300] · MEK: Methyl ethyl ketone

[0301] From the results of the table above, it was found that in Examples 1 to 7, the resin compositions were excellent in terms of film appearance, resin viscosity, average linear thermal expansion coefficient, electrical properties, and crack resistance, and were capable of forming via holes with fine openings.

[0302] Meanwhile, Comparative Examples 1 and 2, in which the refractive index of the resin of component (E) was outside the specified range, allowed for the formation of via holes, but compared to Examples 1 to 7, the shape of the via holes deteriorated or the plating adhesion decreased. Comparative Examples 3 to 7, in which the particle diameter distribution of the inorganic filler deviated, showed significantly deteriorated resolution. In addition, Comparative Example 8, in which the content of the inorganic filler was less than 30 mass%, had a high average linear thermal expansion coefficient and deteriorated crack resistance. Comparative Example 8, in which an acrylic polymer was used instead of component (A), showed deterioration in via hole shape, laser aperture, copper plating adhesion, surface shape, crack resistance, etc., and could not be used as a photosensitive resin composition.

[0303] In each embodiment, it is confirmed that even if component (F) is not included, the same result as the above embodiment is obtained, although there are differences in degree.

Claims

Claim 1 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 photopolymerizable compound, wherein the content of component (B) is 30 mass% or more when the non-volatile component in the photosensitive resin composition is 100 mass%, and (B) the 10% particle diameter (D) in the particle diameter distribution of component B. 10 ) is 0.06㎛ or more and 0.6㎛ or less, and the 50% particle diameter (D 50 ) is 0.11㎛ or more and 1.10㎛ or less, and the 90% particle diameter (D 90 A photosensitive resin composition having a refractive index of 0.22㎛ or more and 2.20㎛ or less, and a refractive index of (E) component of 1.45 or more and 1.51 or less. Claim 2 A photosensitive resin composition according to claim 1, wherein when a via hole with a minimum opening diameter of R (㎛) is formed in a cured product of the photosensitive resin composition, the number of (B) components having a particle diameter of (0.1×R)㎛ or more exposed on the wall of the via hole is 10 or fewer. Claim 3 A photosensitive resin composition according to claim 1, wherein (E) a component has a divalent cyclic structure. Claim 4 A photosensitive resin composition according to paragraph 3, wherein a divalent cyclic group has a heteroatom-containing alicyclic framework. Claim 5 A photosensitive resin composition according to claim 1, wherein component (E) comprises a compound represented by the following chemical formula (E-1). [Chemical formula (E-1)] Claim 6 A photosensitive resin composition according to claim 1, wherein (A) a component has any one of a cresol novolak skeleton, a naphthalene skeleton, and a naphtholaralkyl skeleton. Claim 7 A photosensitive resin composition according to claim 1, wherein (A) a component comprises an acid-modified naphtholarkyl backbone-containing epoxy(meth)acrylate. Claim 8 A photosensitive resin composition according to claim 1, wherein (D) the component comprises (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. Claim 9 A photosensitive film attached to a support, having a support and a photosensitive resin composition layer provided on the support, the photosensitive resin composition layer comprising the photosensitive resin composition described in any one of claims 1 to 8. Claim 10 A printed circuit board comprising an insulating layer formed by a cured product of a photosensitive resin composition described in any one of claims 1 to 8. Claim 11 A printed circuit board in which, in paragraph 10, the insulating layer is either an interlayer insulating material or a solder resist. Claim 12 A semiconductor device comprising a printed circuit board as described in paragraph 10.

Images