JP2016109779A - Resin composition for interlayer insulation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for interlayer insulation, which exhibits good developing property upon forming a small diameter via hole and gives a small diameter via hole excellent in connection reliability.SOLUTION: The resin composition for interlayer insulation comprises (A) a resin described below, (B) an epoxy resin, and (C) a photopolymerization initiator. The (A) resin is a (meth)acrylate-modified phenolic resin having such a property that when a resin film having a thickness of 5 μm, obtained by applying a carbitol acetate solution of the above resin and having 30 wt.% of a nonvolatile component on a silicon wafer and dried at 120°C for 3 minutes, is immersed in an aqueous solution of 2.38 mass% tetramethyl ammonium hydroxide at 23°C, a dissolution rate of the resin film is 2 to 14 μm/min.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for interlayer insulation. Furthermore, it is related with the manufacturing method of a photosensitive film, a printed wiring board, a semiconductor device, and a printed wiring board.

  In recent years, miniaturization and high performance of electronic devices have progressed, and in printed wiring boards, wiring density has been increased by miniaturization of wiring and multilayering of build-up layers. Therefore, a smaller diameter is required also in the via hole provided for the conduction of the interlayer insulating layer.

  In general, in a printed wiring board, a thermosetting resin composition is used for an interlayer insulating layer, and a photosensitive resin composition is used for a solder resist layer. For example, Patent Document 1 describes that a specific alkali-soluble resin is used to provide a resin composition that is excellent in various properties as a solder resist and has sufficient resistance to plating under alkaline conditions. Yes.

JP 7-56336 A

  The photosensitive resin composition has advantages such as being inexpensive and contributing to simplification of the production process. The inventors of the present invention formed an interlayer insulating layer using a photosensitive resin composition and attempted conduction between layers through a small-diameter via hole (also simply referred to as “small-diameter via”). It has been found that there are cases in which there are problems such as failure of the device and a reduction in the diameter of the via having poor connection reliability.

  An object of the present invention is to provide a photosensitive resin composition for interlayer insulation that provides a small-diameter via having good developability when forming a small-diameter via and having excellent connection reliability.

  As a result of intensive studies on the above problems, the present inventors have solved the above problems by using a combination of a (meth) acrylate-modified phenol resin exhibiting a specific alkali dissolution rate, an epoxy resin, and a photopolymerization initiator. The inventors have found that this can be solved, and have completed the present invention.

That is, the present invention includes the following contents.
[1] (A) (Meth) acrylate-modified phenolic resin having a thickness of 5 μm obtained by applying a non-volatile component 30 wt% carbitol acetate solution of the resin onto a silicon wafer and drying at 120 ° C. for 3 minutes. A resin having a dissolution rate of 2 to 14 μm / min when the resin film is immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C.,
(B) An epoxy resin, and (C) a resin composition for interlayer insulation containing a photopolymerization initiator.
[2] The resin composition according to [1], wherein the proportion of the (meth) acrylate group of the component (A) is 35 to 80%.
[3] The resin composition according to [1] or [2], further comprising (D) a reactive diluent.
[4] The resin composition according to any one of [1] to [3], wherein the content of the component (A) is 10 to 85% by mass when the nonvolatile component in the resin composition is 100% by mass. .
[5] The resin composition according to any one of [1] to [4], wherein the content of the component (B) is 5 to 60% by mass when the nonvolatile component in the resin composition is 100% by mass. .
[6] The resin according to any one of [1] to [5], wherein the content of the component (C) is 0.1 to 3% by mass when the nonvolatile component in the resin composition is 100% by mass. Composition.
[7] The resin according to any one of [3] to [6], wherein the content of the component (D) is 0.5 to 30% by mass when the nonvolatile component in the resin composition is 100% by mass. Composition.
[8] The resin composition according to any one of [1] to [7], further comprising (E) a curing accelerator.
[9] The resin composition according to any one of [1] to [8], wherein the component (C) includes an oxime ester photopolymerization initiator.
[10] A photosensitive film with a support, comprising a support and a layer of the resin composition according to any one of [1] to [9] provided on the support.
[11] A printed wiring board including a cured product layer of the resin composition according to any one of [1] to [9].
[12] A semiconductor device including the printed wiring board according to [11].
[13] (A) (meth) acrylate-modified phenolic resin having a thickness of 5 μm obtained by applying a 30 wt% carbitol acetate solution of the nonvolatile component of the resin on a silicon wafer and drying at 120 ° C. for 3 minutes. When the resin film is immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C., a resin whose dissolution rate is 2 to 14 μm / min, (B) an epoxy resin, and (C) Providing a resin composition layer containing a photopolymerization initiator on the inner layer substrate;
An exposure step of irradiating the surface of the resin composition layer with an actinic ray through a mask pattern and photocuring the resin composition layer of the irradiated portion;
Developing the resin composition layer and removing the unexposed areas to form vias; and
A post-baking step of post-baking the resin composition layer to form an insulating layer.
[14] The method according to [13], wherein a top diameter of the via is 50 μm or less.
[15] The method according to [13] or [14], wherein an opening ratio of the via is 70% or more.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition for interlayer insulation which brings about the small diameter via which is excellent in the developability at the time of small diameter via formation, and is excellent in connection reliability can be provided.

FIG. 1 is a schematic diagram of a laminated body for connection reliability evaluation.

  Hereinafter, the present invention will be described in detail.

[Resin composition for interlayer insulation]
The resin composition for interlayer insulation of the present invention is (A) (meth) acrylate-modified phenol resin, and a 30% by weight non-volatile component carbitol acetate solution of the resin is applied onto a silicon wafer and dried at 120 ° C. for 3 minutes. A resin film having a dissolution rate of 2 to 14 μm / min when the resin film having a thickness of 5 μm is immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. (B ) An epoxy resin, and (C) a photopolymerization initiator.

<(A) (Meth) acrylate modified phenolic resin>
The resin composition for interlayer insulation of this invention contains (meth) acrylate modified phenol resin as (A) component. The (meth) acrylate-modified phenol resin exhibits a function as a curing agent for the (B) epoxy resin, and can impart photocurability to the resin composition for interlayer insulation. “(Meth) acrylate” refers to methacrylate and acrylate.

  In the resin composition for interlayer insulation of the present invention, the (meth) acrylate-modified phenolic resin exhibits a specific alkali dissolution rate. Specifically, a resin film having a thickness of 5 μm obtained by applying a 30 wt% carbitol acetate solution of the (meth) acrylate-modified phenol resin on a silicon wafer and drying at 120 ° C. for 3 minutes, When immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution, the dissolution rate (Rs) of the resin film is 2 to 14 μm / min. By using such a (meth) acrylate-modified phenol resin exhibiting such a specific alkali dissolution rate in combination with (B) an epoxy resin and (C) a photopolymerization initiator, which will be described later, a small diameter via is formed. The present invention has led to the realization of a resin composition for interlayer insulation that provides a small-diameter via with good developability and excellent connection reliability.

  From the viewpoint of obtaining a resin composition for interlayer insulation that provides better developability and connection reliability, the lower limit of the dissolution rate Rs is preferably 2.2 μm / min or more, more preferably 2.4 μm / min or more, and further Preferably, it is 2.6 μm / min or more, 2.8 μm / min or more, or 3 μm / min or more. The upper limit of the dissolution rate Rs is preferably 13.8 μm / min or less, more preferably 13.6 μm / min or less, further preferably 13.4 μm / min or less, 13.2 μm / min or less, 13 μm / min or less, 12 μm. / Min or less, 11 μm / min or less, or 10 μm / min or less. The dissolution rate Rs can be measured in accordance with the description of <Measurement of alkali dissolution rate> described later.

  The (meth) acrylate-modified phenol resin is not particularly limited as long as part of the phenolic hydroxyl group is a phenol resin in which a (meth) acrylate group ((meth) acryloyl group) is modified. From the viewpoint of obtaining an insulating layer having excellent mechanical strength, the (meth) acrylate-modified phenol resin preferably has two or more (meth) acrylate groups in one molecule.

  The (meth) acrylate-modified phenol resin can be synthesized, for example, by reacting a phenol resin with a compound containing a functional group capable of reacting with a phenolic hydroxyl group and a (meth) acrylate group.

  Examples of the phenol resin include phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, and naphthol novolak resin. From the viewpoint of obtaining good developability and connection reliability, phenol novolak resin and cresol novolak resin are preferable. A phenol novolac resin is more preferable. A phenol resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  As a functional group which can react with a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a carboxy group are mentioned, for example, An epoxy group and an isocyanate group are preferable.

  As a compound containing an epoxy group and a (meth) acrylate group, for example, glycidyl (meth) acrylate; glycidyl alkyl (meth) acrylate (wherein the number of carbon atoms in the alkyl portion is preferably 1 to 10, more preferably 1) ~ 6 or 1-4); and a reaction product obtained by partial addition reaction of a polyglycidyl compound and a (meth) acrylate compound having a functional group (for example, a hydroxyl group) capable of reacting with a glycidyl group. Can be mentioned. These may be used alone or in combination of two or more. Here, as the polyglycidyl compound, for example, glycerol diglycidyl ether, glycerol triglycidyl ether, arylene glycidyl ether (wherein the number of carbon atoms in the arylene part is preferably 6-20, more preferably 6-10), Examples include alkylene diglycidyl ether (wherein the number of carbon atoms in the alkylene portion is preferably 1 to 10, more preferably 1 to 6 or 1 to 4), trimethylolpropane triglycidyl ether, and the like, and can react with a glycidyl group. Examples of the (meth) acrylate compound having a functional group include pentaerythritol tri (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-methylolacrylamide, glycerol di (meth) acrylate, and dipentaerythritol pen. Data (meth) acrylate.

  Examples of the compound containing an isocyanate group and a (meth) acrylate group include (meth) acryloyl isocyanate; isocyanate ethyl (meth) acrylate; and a polyisocyanate compound and a functional group (for example, a hydroxyl group) capable of reacting with the isocyanate group. Examples thereof include a reaction product obtained by partially subjecting a (meth) acrylate compound to a reaction. These may be used alone or in combination of two or more. Here, examples of the polyisocyanate compound include 3-isocyanate-3,5,5-trimethylcyclohexyl isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methylene bisphenyl isocyanate, polymethylene polyphenyl polyisocyanate, and the like. Examples of the (meth) acrylate compound having a functional group capable of reacting with an isocyanate group include pentaerythritol tri (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-methylolacrylamide, and glycerol di (meth) acrylate. And dipentaerythritol penta (meth) acrylate.

  The (meth) acrylate-modified phenol resin can be obtained by reacting a phenol resin with a compound containing a functional group capable of reacting with a phenolic hydroxyl group and a (meth) acrylate group in the presence of a catalyst. Such a reaction is well known, and reaction conditions such as reaction temperature, reaction time, type of catalyst and amount used may be appropriately determined by those skilled in the art. Examples of the (meth) acrylate-modified phenol resin include compounds included in alkali-soluble resins described in JP-A-7-56336.

  From the viewpoint of obtaining a resin composition for interlayer insulation that provides a small diameter via having good developability at the time of forming a small diameter via and excellent in connection reliability, the ratio of the (meth) acrylate group of the (meth) acrylate-modified phenol resin is 35 to 35. 80% is preferable. Here, the ratio of the (meth) acrylate group of the (meth) acrylate-modified phenol resin means that the total number of phenolic hydroxyl groups and (meth) acrylate groups of the (meth) acrylate-modified phenol resin is 100% ( It is the ratio of the number of (meth) acrylate groups. From the viewpoint of obtaining a resin composition for interlayer insulation that provides better developability and connection reliability, the lower limit of the ratio of the (meth) acrylate group is preferably 40% or more, more preferably 45% or more, and still more preferably. 50% or more. The upper limit of the ratio of the (meth) acrylate group is preferably 75% or less, more preferably 70% or less, and still more preferably 65% or less.

  The weight average molecular weight (Mw) of the (meth) acrylate-modified phenol resin is preferably 10,000 or less, more preferably 8000 or less, and even more preferably 6000 or less from the viewpoint of obtaining good developability when forming a small-diameter via. Further, the Mw of the (meth) acrylate-modified phenol resin is preferably 1000 or more, more preferably 2000 or more, and still more preferably 3000 or more, from the viewpoint of obtaining good resolution.

  The weight average molecular weight is measured by gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K- manufactured by Showa Denko KK as a column. 804 L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  The hydroxyl equivalent of the (meth) acrylate-modified phenol resin is preferably 100 to 500 and more preferably 150 to 400 in order to appropriately form a crosslinking density by thermosetting.

  Viewpoint of obtaining a resin composition for interlayer insulation that provides a small-diameter via having good developability at the time of forming a small-diameter via and excellent in connection reliability in the combination of (B) epoxy resin and (C) photopolymerization initiator described later Therefore, the content of the (meth) acrylate-modified phenol resin is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass, when the nonvolatile component in the resin composition is 100% by mass. These are 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more. The upper limit of the content of the (meth) acrylate-modified phenol resin is preferably 85% by mass or less, more preferably 75% by mass or less, and further preferably 65% by mass or less or 60% by mass or less.

<(B) Epoxy resin>
Although it does not specifically limit as an epoxy resin, For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol Novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type Epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy Butter, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass is preferably an epoxy resin having two or more epoxy groups in one molecule.

  The epoxy resin may be a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C., or a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. It may be. The resin composition for interlayer insulation of the present invention preferably contains a solid epoxy resin alone or in combination of a solid epoxy resin and a liquid epoxy resin. When a liquid epoxy resin and a solid epoxy resin are used in combination, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 1: 5, and 1: A range of 0.3 to 1: 4 is more preferable.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, and naphthalene type epoxy resin are preferable, and bisphenol AF type epoxy resin and naphthalene type epoxy resin are preferable. More preferred. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, and “jER828EL” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. , “JER807” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), “YL7223”, “YL7660”, “YL7723” (bisphenol AF type epoxy resin), and the like. A liquid epoxy resin may be used individually by 1 type, or may use 2 or more types together.

  Solid epoxy resins include tetrafunctional naphthalene type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, biphenyl type epoxy resins, and naphthylene ether type epoxies. Resin is preferable, tetrafunctional naphthalene type epoxy resin, biphenyl type epoxy resin, and naphthylene ether type epoxy resin are more preferable, and biphenyl type epoxy resin is more preferable. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710” (tetrafunctional naphthalene type epoxy resin), “HP7200”, “HP7200H”, “HP7200K” (dicyclo) manufactured by DIC Corporation. Pentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA-7311G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" (Trisphenol) manufactured by Nippon Kayaku Co., Ltd. Epoxy resin), “NC7000L” (naphthol novolac epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475”, “ESN485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "(Naphthol novolak type Epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin) and the like. A solid epoxy resin may be used individually by 1 type, or may use 2 or more types together.

  From the viewpoint of obtaining good developability when forming a small diameter via, the epoxy resin preferably contains an epoxy resin having a number average molecular weight (Mn) of 1000 or less, more preferably 950 or less, and even more preferably 900 or less. When Mn of the epoxy resin exceeds 1000, when the resin composition is exposed and developed, the unexposed portion of the resin composition adheres to the surface of the surrounding resin composition as a development residue. There is a risk of problems occurring in the process. On the other hand, from the viewpoint of improving the crosslink density of the insulating layer and obtaining an insulating layer having good mechanical strength, the lower limit of Mn of the epoxy resin is preferably 100 or more, more preferably 300 or more, and even more preferably 500 or more.

  When the nonvolatile component of the epoxy resin is 100% by mass, the content of the epoxy resin having Mn of 1000 or less is preferably 50% by mass to 100% by mass, more preferably 80% by mass from the viewpoint of obtaining good developability. It is -100 mass%, More preferably, it is 90 mass%-100 mass%.

  The content of the epoxy resin is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more when the nonvolatile component in the resin composition is 100% by mass. The upper limit of the content of the epoxy resin is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 45% by mass or less or 40% by mass or less. By setting it within this range, the developability at the time of forming a small diameter via can be improved.

  The epoxy equivalent of the epoxy resin is preferably 50 to 3000, more preferably 80 to 2000, and still more preferably 110 to 1000. By being in this range, the obtained insulating layer has a sufficient crosslinking density, and an insulating layer having excellent heat resistance can be obtained. In addition, an epoxy equivalent can be measured according to JISK7236, for example, and is the mass of resin containing 1 equivalent of epoxy groups.

<(C) Photopolymerization initiator>
The photopolymerization initiator is not particularly limited, and examples thereof include alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, oxime ester photopolymerization initiators, and sulfonium salt photopolymerization initiators. It is done. Examples of the alkylphenone photopolymerization initiator include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone and 2- (dimethylamino) -2-[(4-methylphenyl). Methyl]-[4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzophenone, methylbenzophenone, o-benzoyl Benzoic acid, benzoyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenyl Phosphinate, 4,4′-bis (diethylamino) benzophenone, 1-H Droxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane -1-one etc. are mentioned. Examples of the acylphosphine oxide photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Examples of the oxime ester photopolymerization initiator include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  As a commercially available photopolymerization initiator, for example, “OXE-02” (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) manufactured by BASF Japan Ltd. ]-, 1- (O-acetyloxime)), "OXE-01" (1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]).

  Especially, since it is highly sensitive, it is preferable that a photoinitiator contains an oxime ester system photoinitiator. A photoinitiator may be used individually by 1 type and may use 2 or more types together.

  The content of the photopolymerization initiator is preferably 0.1% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining an interlayer insulating resin composition that can be efficiently photocured. More preferably, it is 0.3 mass% or more, More preferably, it is 0.5 mass% or more. On the other hand, the upper limit of the content of the photopolymerization initiator is preferably 3% by mass or less when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of suppressing a decrease in resolution due to excessive sensitivity. Preferably it is 2.5 mass% or less, More preferably, it is 2 mass% or less.

<(D) Reactive diluent>
The interlayer insulating resin composition of the present invention may further contain a reactive diluent as the component (D). By using a reactive diluent, the reactivity during exposure can be improved.

  Examples of the reactive diluent include a photosensitive (meth) acrylate compound which has one or more (meth) acryloyl groups in one molecule and is liquid, solid or semisolid at room temperature.

  Examples of the photosensitive (meth) acrylate compound that can be suitably used as the component (D) include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol Mono- or diacrylates of glycols such as propylene glycol; acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate; trimethylolpropane and pentaerythritol Polyhydric alcohols such as dipentaerythritol or adducts of these ethylene oxide, propylene oxide or ε-caprolactone Acrylates; phenols such as phenoxy acrylate and phenoxyethyl acrylate; or acrylates such as ethylene oxide or propylene oxide adducts thereof; epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether; melamine acrylates And / or methacrylates corresponding to the above acrylates. Among them, polyvalent acrylates or polyvalent methacrylates are preferable. For example, as trivalent acrylates or methacrylates, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane EO addition tri (Meth) acrylate, glycerin PO-added tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetrafurfuryl alcohol oligo (meth) acrylate, ethyl carbitol oligo (meth) acrylate, 1,4-butanediol oligo (meta ) Acrylate, 1,6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, And (meth) acrylic acid esters of N, N, N ′, N′-tetrakis (β-hydroxyethyl) ethyldiamine and the like, such as tramethylol methane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 3 As acrylates or methacrylates having a valence higher than tri (2- (meth) acryloyloxyethyl) phosphate, tri (2- (meth) acryloyloxypropyl) phosphate, tri (3- (meth) acryloyloxypropyl) phosphate, Tri (3- (meth) acryloyl-2-hydroxyloxypropyl) phosphate, di (3- (meth) acryloyl-2-hydroxyloxypropyl) (2- (meth) acryloyloxyethyl) phosphate, (3- (meth) Acryloyl-2 Can be exemplified hydroxyl propyl) di (2- (meth) acryloyloxyethyl) phosphate triester (meth) acrylates such as phosphates. These photosensitive (meth) acrylate compounds may be used alone or in combination of two or more.

  Commercially available reactive diluents include “M-306” (liquid trifunctional acrylate) manufactured by Toagosei Co., Ltd., “DPHA” (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd., Kyoeisha Chemical Industries "DCPA" (tricyclodecane dimethanol diacrylate) manufactured by Co., Ltd. may be mentioned.

  When using a reactive diluent, the content of the reactive diluent promotes photocuring and, from the viewpoint of obtaining a non-sticky insulating layer, when the nonvolatile component of the resin composition is 100% by mass, 0.5 mass%-30 mass% are preferable, and 3 mass%-15 mass% are more preferable.

<(E) Curing accelerator>
The resin composition for interlayer insulation of this invention may further contain a hardening accelerator as (E) component. By using a curing accelerator, better thermosetting can be obtained.

  Although it does not specifically limit as a hardening accelerator, For example, an amine type hardening accelerator, a guanidine type hardening accelerator, an imidazole type hardening accelerator, a phosphonium type hardening accelerator, a metal type hardening accelerator etc. are mentioned. A hardening accelerator may be used individually by 1 type, and may use 2 or more types together.

  The amine curing accelerator is not particularly limited, and examples thereof include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, And amine compounds such as 1,8-diazabicyclo (5,4,0) -undecene (DBU). These may be used alone or in combination of two or more.

  Although it does not specifically limit as a guanidine type hardening accelerator, For example, a dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine, diphenyl Guanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4 4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1 -Cyclohexyl biguanide, 1-allyl biguanide, 1-pheny Biguanides, 1-(o-tolyl) biguanide, and the like. These may be used alone or in combination of two or more.

  Although it does not specifically limit as an imidazole series hardening accelerator, For example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 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, 2 , 3-Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2- Tyrimidazoline, 2-phenylimidazoline, 2- (benzoimidazol-1-yl) ethyl methacrylate, imidazole compounds such as methyl methacrylate (5-methyl-3H-imidazol-4-yl) methyl, and imidazole compounds and epoxy resins Adduct body is mentioned. These may be used alone or in combination of two or more. In addition, since an imidazole series hardening accelerator has the function as (F) adhesiveness improvement agent mentioned later later, it is suitable.

  Although it does not specifically limit as a phosphonium type hardening accelerator, For example, a triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) ) Triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like. These may be used alone or in combination of two or more.

  Examples of commercially available curing accelerators include “2P4MZ” (2-phenyl-4-methylimidazole), “2E4MZ” (2-ethyl-4-methylimidazole), and “1HBZM” (manufactured by Shikoku Kasei Co., Ltd.). 2- (benzimidazol-1-yl) ethyl methacrylate), “4M5HZM” (methacrylic acid (5-methyl-3H-imidazol-4-yl) methyl).

  When a curing accelerator is used, the content of the curing accelerator is preferably in the range of 0.005 to 1% by mass when the nonvolatile component in the resin composition is 100% by mass, 0.01 to A range of 0.5% by mass is more preferable. If it is less than 0.005% by mass, curing tends to be slow and a long curing time is required, and if it exceeds 1% by mass, the storage stability of the resin composition tends to decrease.

<(F) Adhesion improver>
The interlayer insulating resin composition of the present invention may further contain an adhesion improver as the component (F). By using the adhesion improver, the adhesion between the insulating layer and the conductor circuit such as copper can be improved, which contributes to further improvement in the connection reliability of the small diameter via.

  It does not specifically limit as an adhesive improvement agent, You may use the well-known adhesive improvement agent used for the insulating layer of a printed wiring board. Examples of the adhesion improver include silane coupling agents and nitrogen-containing compounds.

  As the silane coupling agent, a silane coupling agent having a reactive substituent such as an epoxy group, an amino group, a carboxy group, a (meth) acrylate group, a mercapto group, or an isocyanate group is preferable. Xylpropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane trimethoxysilylbenzoic acid, 3-methacryloxy Examples include propyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. These may be used alone or in combination of two or more. Examples of commercially available silane coupling agents suitable as the component (F) include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM803” manufactured by Shin-Etsu Chemical Co., Ltd. (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. “KBE903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. “KBM573” (N-phenyl-3-aminopropyl) Trimethoxysilane).

As the nitrogen-containing compound, a compound having a nitrogen-containing functional group such as an azole group, amino group, amide group, imino group or imide group is suitable. For example, imidazole, pyrazole, benzimidazole, benzotriazole, C _1-10 Alkylamine, piperidine, piperazine, morpholine, aniline, ethylenediamine, catecholamine, ethylenediaminetetraacetic acid, bipyridine, terpyridine, phenanthroline, melamine, acetoguanamine, benzoguanamine, melamine-phenol-formalin resin, ethyldiamino-S-triazine, 2,4- Examples include diamino-S-triazine and 2,4-diamino-6-xylyl-S-triazine. These nitrogen-containing compounds may further have a reactive substituent such as an epoxy group, a carboxy group, a (meth) acrylate group, a mercapto group, etc. Among them, a (meth) acrylate group as a reactive substituent. It is suitable to have. These may be used alone or in combination of two or more. Examples of commercially available nitrogen-containing compounds suitable as the component (F) include “2MZ-AZINE”, “2E4MZ-AZINE”, “C11Z-AZINE”, “2MA-OK”, “1HBZM” manufactured by Shikoku Kasei Kogyo Co., Ltd. , “4M5HZM” and the like.

  When using an adhesion improver, the content of the adhesion improver is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, it is in the range of 0.1 to 10% by mass. Is preferable, and the range of 0.5 to 5% by mass is more preferable.

<(G) Photosensitizer>
The interlayer insulating resin composition of the present invention may further contain a photosensitizer as the component (G). By using a photosensitizer, better photocurability can be obtained.

  The photosensitizer is not particularly limited, and a known photosensitizer may be used. For example, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl Tert-amines such as -4-dimethylaminobenzoate, triethylamine, triethanolamine; pyrarizones; anthracenes; coumarins; xanthones; thioxanthones. Among them, as the photosensitizer, thioxanthones are preferable, and 2,4-diethylthioxanthone is more preferable. Examples of commercially available photosensitizers include “DETX-S” (2,4-diethylthioxanthone) manufactured by Nippon Kayaku Co., Ltd. A photosensitizer may be used individually by 1 type and may use 2 or more types together.

  When using a photosensitizer, the content of the photosensitizer is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is in the range of 0.01 to 3% by mass. Is preferable, and the range of 0.05 to 1% by mass is more preferable.

<(H) Inorganic filler>
The interlayer insulating resin composition of the present invention may further contain an inorganic filler as the component (H). By using an inorganic filler, it contributes to the improvement of the resolution, the low thermal expansion coefficient of the insulating layer, and the low dielectric constant.

  The inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate , Magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, phosphoric acid Zirconium, zirconium tungstate phosphate, etc. are mentioned. Among these, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferable as the inorganic filler. From the viewpoint of reducing the thermal expansion coefficient of the insulating layer, fused silica and spherical Silica is more preferable, and spherical fused silica is more preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of commercially available spherical fused silica include “SO-C2”, “SO-C1”, “SC2050” manufactured by Admatechs Co., Ltd., “UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd., Asahi Glass Co., Ltd. ) “AZ filler” and the like.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 3 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less from the viewpoint of improving the light transmittance of the resin composition and obtaining good developability. Even more preferably, it is 0.6 μm or less, particularly preferably 0.4 μm or less or 0.2 μm or less. On the other hand, when the resin composition is a resin varnish, the average particle size of the inorganic filler from the viewpoint of suppressing the viscosity of the resin varnish from increasing and handling performance from decreasing, and the resolution from decreasing. Is preferably 0.01 μm or more, more preferably 0.03 μm or more, and still more preferably 0.05 μm or more. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring apparatus, “LA-500”, “LA-950” manufactured by Horiba, Ltd., and the like can be used.

  The inorganic filler is preferably surface-treated with a surface treatment agent. Specifically, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a styrylsilane coupling agent, One or more selected from acrylate silane coupling agents, isocyanate silane coupling agents, sulfide silane coupling agents, vinyl silane coupling agents, silane coupling agents, organosilazane compounds and titanate coupling agents. More preferably, the surface is treated with a surface treatment agent. Thereby, the dispersibility and moisture resistance of an inorganic filler can be improved. The amount of the surface treatment agent used for the surface treatment is preferably 0.1 to 6% by mass, more preferably 0.2 to 4% by mass, and further preferably 0.3 to 3% with respect to 100% by mass of the inorganic filler. % By mass.

  When an inorganic filler is used, the content of the inorganic filler is not particularly limited, but from the viewpoints of improving resolution, lowering the thermal expansion coefficient of the insulating layer, and lowering the dielectric constant, nonvolatile components in the resin composition Is 100% by mass, preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and still more preferably 10 to 60% by mass.

<(I) Organic filler>
The resin composition for interlayer insulation of the present invention may further contain an organic filler as the component (I). By using the organic filler, the stress applied to the insulating layer can be relaxed, and the connection reliability of the small diameter via can be further enhanced. As the organic filler, any organic filler that can be used for forming an insulating layer of a printed wiring board may be used. Examples thereof include rubber particles, polyamide fine particles, and silicone particles, and rubber particles are preferable. The content of the organic filler is preferably 0.1 to 6% by mass and more preferably 1 to 3% by mass when the nonvolatile component in the resin composition is 100% by mass.

<(J) Organic solvent>
The resin composition for interlayer insulation of the present invention may further contain an organic solvent as the component (J). By using an organic solvent, the viscosity of the resin composition (resin varnish) can be adjusted. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. An organic solvent may be used individually by 1 type and may use 2 or more types together. In the case of using an organic solvent, the content of the organic solvent may be appropriately determined from the viewpoint of applicability of the interlayer insulating resin composition.

<(K) Other additives>
The interlayer insulating resin composition of the present invention may further contain other additives as the component (K) to the extent that the object of the present invention is not impaired. Other additives include, for example, fine particles such as organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and other colorants, hydroquinone, phenothiazine, methyl hydroquinone. Polymerization inhibitors such as hydroquinone monomethyl ether, catechol and pyrogallol, thickeners such as benton and montmorillonite, silicone antifoaming agents, fluorine antifoaming agents, vinyl resin antifoaming agents, brominated epoxy compounds, acid-modified bromine Epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphate esters, halogen-containing condensed phosphate esters and other flame retardants, phenolic curing agents, cyanate ester curing agents, amino resins, alkyls Thermosetting resins such as compounds having two or more etherified amino groups, oxetane ring-containing compounds, isocyanate group-containing compounds (including blocked ones), aldehyde group-containing phenol compounds, methylol group-containing phenol compounds, Etc.

  The resin composition for interlayer insulation of the present invention is prepared by appropriately mixing the above-mentioned blending components, and kneading means (three rolls, ball mill, bead mill, sand mill, etc.) or stirring means (super mixer, planetary mixer, etc.) as necessary. Can be prepared by kneading or stirring.

  The resin composition for interlayer insulation of the present invention can provide a small-diameter via having excellent developability when forming a small-diameter via and excellent connection reliability when producing a printed wiring board. In particular, it can be suitably used as a resin composition for forming an interlayer insulating layer of a multilayer printed wiring board in which a conductor layer is formed by plating (an interlayer insulating resin composition for forming a conductor layer by plating).

[Photosensitive film]
The photosensitive film of the present invention comprises a layer of the resin composition for interlayer insulation of the present invention (hereinafter also simply referred to as “resin composition layer”).

  For example, in the production of a printed wiring board, the interlayer insulating resin composition of the present invention can be applied to the inner layer substrate as a resin varnish and dried to form a layer of the interlayer insulating resin composition of the present invention. it can. In the present embodiment, the photosensitive film of the present invention is formed on the inner layer substrate. Details of the inner layer substrate will be described later.

  Alternatively, prior to the production of the printed wiring board, the interlayer insulating resin composition of the present invention is applied as a resin varnish on the support and dried to form the photosensitive film of the present invention on the support. Also good. In manufacturing a printed wiring board, such a photosensitive film may be laminated on the inner layer substrate. Details of the support will be described later.

  In the photosensitive film of the present invention, the content of the organic solvent in the resin composition layer is preferably when the total mass of the resin composition layer is 100% by mass from the viewpoint of suppressing swelling during thermosetting. It is 10 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less.

[Photosensitive film with support]
The photosensitive film with a support of the present invention comprises a support and a layer of the resin composition for interlayer insulation of the present invention (photosensitive film of the present invention) provided on the support.

  As the support, a film made of a plastic material is suitable. Examples of plastic materials include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate and polymethyl methacrylate, cyclic polyolefins, triacetyl cellulose, triacetyl acetate, polyether sulfide, and polyether ketone. And polyimide. Among these, PET and PEN are preferable, and PET is particularly preferable. Examples of commercially available supports include “FB40” manufactured by Toray Industries, Inc., “Alphan MA-410” manufactured by Oji Paper Co., Ltd., “E-200C”, and “PS-25” manufactured by Teijin Limited. PS series such as “Shin-Etsu Film Co., Ltd.” and the like.

  The support may be subjected to mat treatment or corona treatment on the surface to be bonded to the photosensitive film. Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface of the side joined with a photosensitive film. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. . Examples of commercially available release agents include “SK-1”, “AL-5”, and “AL-7” manufactured by Lintec Corporation, which are alkyd resin release agents.

  The thickness of the support is preferably 5 to 50 μm, more preferably 10 to 25 μm, from the viewpoint of obtaining good support strength and obtaining good resolution when exposing from above the support. In addition, when a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  Further, from the viewpoint of reducing light scattering during exposure, the support is preferably a support having excellent transparency. Specifically, a support having a turbidity (haze standardized by JIS-K6714) as an index of transparency in the range of 0.1 to 5 is preferable.

  The photosensitive film with a support of the present invention is a method known to those skilled in the art, for example, the resin composition for interlayer insulation of the present invention is applied as a resin varnish on a support and further dried to form a resin composition layer. Can be manufactured. It is preferable that the resin composition for interlayer insulation completely removes bubbles in the resin composition by vacuum defoaming or the like prior to coating.

  The application method of the resin composition for interlayer insulation is not particularly limited. For example, gravure coating method, micro gravure coating method, reverse coating method, kiss reverse coating method, die coating method, slot die method, lip coating method, comma coating Method, blade coating method, roll coating method, knife coating method, curtain coating method, chamber gravure coating method, slot orifice method, spray coating method, dip coating method and the like. The resin composition for interlayer insulation may be applied once, or may be applied in several times. When applying in several times, you may apply combining several different application methods. Especially, since the uniformity of the apply | coated layer is favorable, as a coating method, the die-coating method is preferable. The application of the resin composition for interlayer insulation is preferably performed in an environment with few foreign matters such as a clean room in order to prevent foreign matters from being mixed.

  Drying may be performed by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 80 ° C. to 120 ° C. for 3 minutes to 13 minutes. A physical layer can be formed. Those skilled in the art can appropriately set suitable drying conditions by simple experiments.

  In the photosensitive film with a support, the thickness of the resin composition layer (photosensitive film) is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 60 μm, from the viewpoint of obtaining good developability when forming a small-diameter via. Hereinafter, it is still more preferably 50 μm or less, 40 μm or less, or 30 μm or less. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, 1 micrometer or more, 5 micrometers or more, 10 micrometers or more etc. can be used.

  In the photosensitive film with a support, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). . Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The protective film preferably has a smaller adhesive force between the resin composition layer and the protective film than the adhesive force between the resin composition layer and the support. The photosensitive film with a support can be stored in a roll. When the photosensitive film with a support has a protective film, it can be used by removing the protective film.

[Printed wiring board and manufacturing method thereof]
The printed wiring board of this invention contains the hardened | cured material layer of the resin composition for interlayer insulations of this invention. In detail, the printed wiring board of this invention contains this hardened | cured material layer as an interlayer insulation layer.

In one embodiment, the printed wiring board of the present invention is
(A) A (meth) acrylate-modified phenolic resin, a resin film having a thickness of 5 μm obtained by applying a 30 wt% carbitol acetate solution of a nonvolatile component of the resin on a silicon wafer and drying at 120 ° C. for 3 minutes. A resin whose dissolution rate is 2 to 14 μm / min when immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C., (B) an epoxy resin, and (C) photopolymerization initiation Providing a resin composition layer containing an agent on the inner layer substrate;
An exposure step of irradiating the surface of the resin composition layer with an actinic ray through a mask pattern and photocuring the resin composition layer of the irradiated portion;
Developing the resin composition layer and removing the unexposed areas to form vias; and
The resin composition layer can be manufactured by a method including a post-baking step of post-baking the resin composition layer to form an insulating layer.

<Process of providing a resin composition layer on an inner layer substrate>
In this step, a layer (resin composition layer) of the resin composition for interlayer insulation of the present invention is provided on the inner layer substrate. The resin composition layer may be provided on one side of the inner layer substrate or on both sides.

  The “inner layer substrate” used in this step is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or a pattern process on one or both sides of the substrate. A circuit board on which a conductive layer (circuit) is formed. Further, when the printed wiring board is manufactured, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is further formed is also included in the “inner layer board” in the present invention. When the printed wiring board is a component built-in circuit board, an inner layer board with built-in components may be used. When an inner layer substrate having a surface circuit is used, the surface circuit may be roughened in advance by blackening, etching, or the like.

  The resin composition layer is preferably provided on the inner layer substrate by (1) coating method or (2) laminating method. Hereinafter, these methods will be described.

(1) Coating method In the coating method, the resin composition layer is provided on the inner layer substrate by applying the resin composition for interlayer insulation of the present invention onto the inner layer substrate as a resin varnish and drying it.

  As a resin varnish coating method, full-screen printing by a screen printing method is generally used, but any other means may be used as long as the resin varnish can be uniformly applied. For example, spray coating method, hot melt coating method, bar coating method, applicator method, blade coating method, knife coating method, air knife coating method, curtain flow coating method, roll coating method, gravure coating method, offset printing method, dip coating method A known coating method such as brush coating may be used.

  After application of the resin varnish, drying is performed in a hot air furnace or a far infrared furnace as necessary. The drying conditions are preferably 80 ° C. to 120 ° C. for 3 minutes to 13 minutes. Thus, the resin composition layer is provided on the inner layer substrate.

(2) Laminating method In the laminating method, the resin composition layer is provided on the inner layer substrate using the above-mentioned photosensitive film with a support. When the photosensitive film with a support has a protective film, it may be used after the protective film is removed.

  In the laminating method, the photosensitive film with a support is laminated on the inner layer substrate so that the resin composition layer of the film is bonded to the inner layer substrate. Prior to lamination, the photosensitive film with support and the inner layer substrate may be preheated as necessary.

  Lamination | stacking with the photosensitive film with a support body and an inner layer board | substrate can be performed by heat-pressing a resin composition layer to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the resin composition layer to the inner layer substrate (hereinafter, also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll). . The thermocompression bonding member is preferably not pressed directly on the adhesive film, but is pressed through an elastic material such as heat-resistant rubber so that the resin composition layer sufficiently follows the surface irregularities of the inner substrate.

  The lamination of the photosensitive film with a support and the inner layer substrate is preferably carried out by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 5 seconds to 400 seconds, more preferably in the range of 20 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less. The lamination method may be a batch method or a continuous method.

  Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nichigo Morton, a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC. For example, a vacuum laminator manufactured by KK Thus, a resin composition layer is formed on the inner layer substrate.

  The support may be peeled off before the development step described below, and may be peeled off between the step of forming the resin composition layer on the inner layer substrate and the exposure step, or between the exposure step and the development step.

<Exposure process>
In the exposure step, the surface of the resin composition layer is irradiated with actinic rays through a mask pattern, and the resin composition layer in the irradiated portion is photocured.

  An exposure process may be implemented in the state in which the support body was attached to the resin composition layer, and may be implemented after peeling a support body.

Examples of the actinic rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The dose of the ultraviolet rays is ^{usually, 10mJ / cm 2 ~1000mJ / cm} 2. The exposure method includes a contact exposure method in which the mask pattern is exposed to a resin composition layer (support when a support is present) and exposure, and the mask pattern is supported by a resin composition layer (support is present when a support is present). Any of the non-contact exposure methods in which exposure is performed using parallel light rays without being in close contact with the body may be used.

<Development process>
In the development step, the resin composition layer is developed, and unexposed portions (portions not photocured) are removed to form vias.

  The development is preferably wet development. As a developer used for wet development, as long as it is a safe and stable developer with good operability, any aqueous or organic solvent-based developer may be used, but an aqueous developer is preferred, An alkaline aqueous solution is more preferable.

  Examples of the alkaline aqueous solution that can be suitably used as a developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate, phosphorus Examples include alkali metal phosphates such as sodium phosphate and potassium phosphate, aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and aqueous solutions of organic bases that do not contain metal ions such as tetraalkylammonium hydroxide. . An aqueous solution of tetraalkylammonium hydroxide (wherein the number of carbon atoms in the alkyl moiety is preferably 1 to 4) is preferred in that it does not contain metal ions and does not affect the semiconductor chip, and tetramethylammonium hydroxide ( A TMAH) aqueous solution is more preferred.

  From the viewpoint of obtaining good developability, a surfactant, an antifoaming agent, or the like may be added to the alkaline aqueous solution used as the developer. The pH of the alkaline aqueous solution is preferably 8 to 14, more preferably 12 to 14. Moreover, it is preferable that the base concentration of alkaline aqueous solution is 0.1-10 mass%. Although the temperature of alkaline aqueous solution can be suitably selected according to the developability of a resin composition layer, it is preferable to set it as 20-50 degreeC.

  Examples of the developing method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and the paddle method is preferable from the viewpoint of resolution. When the paddle method is adopted, the spray pressure when dropping the developer is preferably 0.05 MPa to 0.3 MPa.

  The top diameter of the via (the diameter of the opening on the surface of the resin composition layer) is preferably 50 μm or less, more preferably 45 μm or less, even more preferably 40 μm or less, 35 μm or less, 30 μm, from the viewpoint of finer wiring and higher density. Hereinafter, it is 25 μm or less, or 20 μm or less. The lower limit of the top diameter of the via is only required to ensure electrical connection between insulating layers by introducing a conductive material into the via by plating, preferably 5 μm or more, more preferably 10 μm or more, and further preferably 15 μm or more. . In the present invention using the interlayer insulating resin composition containing a combination of the specific components (A) to (C), good developability can be achieved even when such a small-diameter via is formed.

  The via opening ratio [(via bottom diameter) / (via top diameter) × 100] (%) is preferably 70% or more, more preferably 75% or more, and further preferably 80% or more or 85% or more. is there. The upper limit of the via opening ratio is preferably as high as possible, and may be 100%, but is usually 99% or less, 98% or less, and the like. In the present invention using the interlayer insulating resin composition containing a combination of the specific components (A) to (C), it is possible to advantageously form a via having such a high aperture ratio.

<Post-bake process>
In the post-baking step, the resin composition layer is post-baked to form an insulating layer (cured material layer of the resin composition). Thereby, an insulating layer having excellent mechanical strength can be obtained.

  The post-baking of the resin composition layer is performed by, for example, i) an ultraviolet irradiation treatment for irradiating the resin composition layer with ultraviolet rays, ii) a heat treatment for heating the resin composition layer, or iii) a combination of the ultraviolet treatment and the heat treatment. You can do it.

In the ultraviolet irradiation treatment, the ultraviolet light source may be a high-pressure mercury lamp. The irradiation amount of ultraviolet rays may be determined as appropriate, and may be in the range of, for example, 0.05 J / cm ^{2 to} 10 J / cm ² .

  In the heat treatment, the heating temperature varies depending on the composition of the resin composition layer and the like, but is not particularly limited as long as an appropriate insulating layer can be finally formed, and a range of 140 ° C to 240 ° C is preferable. The range of 150 to 210 ° C is more preferable, and the range of 160 to 190 ° C is more preferable. The heating time varies depending on the composition of the resin composition layer and the thermosetting temperature, but is not particularly limited as long as an appropriate insulating layer is finally formed. For example, the heating time is 20 minutes to 150 minutes, preferably 30 minutes to 120. Can be minutes.

<Plating process>
The printed wiring board manufacturing method of the present invention may further include a plating step of forming a conductor layer on the insulating layer by plating after the post-baking step.

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Above all, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloy, copper An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

  The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel / chromium alloy.

  The thickness of the conductor layer depends on the desired printed wiring board design, but is usually 35 μm or less, preferably 30 μm or less, more preferably 25 μm or less. Although the minimum of the thickness of a conductor layer is not specifically limited, Usually, 3 micrometers or more, Preferably it is 5 micrometers or more.

  In the plating step, the conductor layer may be formed by dry plating, wet plating, or a combination thereof.

  Examples of dry plating include physical vapor deposition (PVD) methods such as vapor deposition, sputtering, ion plating, and laser ablation, and chemical vapor deposition (CVD) methods such as thermal CVD and plasma CVD. Sputtering is preferred. In vapor deposition (vacuum vapor deposition), for example, a conductor layer can be formed on an insulating layer by placing a substrate in a vacuum vessel and heating and evaporating a metal. In sputtering, for example, the substrate is placed in a vacuum vessel, an inert gas such as argon is introduced, a direct current voltage is applied, the ionized inert gas collides with the target metal, and the insulating layer is formed by the struck metal. A conductor layer can be formed thereon. When the conductor layer is formed only by dry plating, the conductor layer (circuit) may be formed by a known method such as a full additive method or a subtractive method.

  When the conductive layer is formed by wet plating, the conductive layer may be formed by a combination of electroless plating and electrolytic plating by a semi-additive method or a subtractive method, and a plating resist having a pattern opposite to the conductive layer is formed. The conductor layer may be formed by a fully additive method using only electroless plating.

  When the conductor layer is formed by wet plating, an uneven anchor is formed on the surface of the insulating layer by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order prior to wet plating. Is preferably formed. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. The roughening treatment with an oxidizing agent is preferably performed by immersing the insulating layer in an oxidizing agent heated to 60 to 80 ° C. for 10 to 30 minutes. The oxidizing agent is not particularly limited. For example, an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid. Etc. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. Neutralization treatment with a neutralizing solution can be performed by immersing the treated surface, which has been roughened with an oxidizing agent, in a neutralizing solution at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, “Reduction Solution Securigans P” manufactured by Atotech Japan Co., Ltd. can be mentioned.

  The conductor layer may be formed by combining dry plating and wet plating. For example, a metal layer formed by dry plating can be used as a plating seed layer, and a conductor layer can be formed by a semi-additive method using electrolytic plating or electroless plating.

  In the present invention using the interlayer insulating resin composition containing a combination of the specific components (A) to (C), a printed wiring board having a small-diameter via excellent in connection reliability can be advantageously realized. .

[Semiconductor device]
A semiconductor device can be manufactured using the printed wiring board of the present invention.

  Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

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

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. “Part” means part by mass.

[Measurement and evaluation methods]
Various measurement methods and evaluation methods will be described.

<Preparation of laminate for evaluation of developability>
The circuit copper layer of the glass epoxy substrate (inner layer substrate) on which the circuit copper layer is formed is etched with “HE-7000Y” (sulfuric acid-hydrogen peroxide etching solution) manufactured by MEC, and the thickness of the circuit copper layer is reduced. It was 18 μm. Next, the photosensitive film with a support produced in Examples and Comparative Examples was applied to the inner layer substrate using a vacuum laminator (“CVP700” manufactured by Nichigo Morton Co., Ltd.) so that the resin composition layer was bonded to the circuit copper layer. Lamination was performed to obtain a laminate having a layer configuration of inner layer substrate \ resin composition layer \ support. The lamination conditions were a vacuuming time of 30 seconds, a pressure bonding temperature of 80 ° C., a pressure bonding pressure of 0.5 MPa, and a pressure bonding time of 30 seconds.

The obtained laminate was allowed to stand at room temperature for 1 hour or longer. Thereafter, a round hole pattern (round hole diameter: 20 μm) was placed on the support of the laminate, and ultraviolet rays of 200 mJ / cm ² were irradiated using a pattern forming apparatus. After standing at room temperature for 30 minutes, the support was peeled from the laminate. On the entire surface of the exposed resin composition layer, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide (TMAH) at 23 ° C. as a developer is developed at a spray pressure of 0.1 MPa for a minimum development time (the unexposed portion is developed Spray development was performed in 1.5 times the minimum time. After spray development, the resin composition layer is irradiated with ultraviolet rays of 1 J / cm ² , further subjected to heat treatment at 130 ° C. for 30 minutes and 180 ° C. for 30 minutes, and an opening having a diameter (top diameter) of 20 μm. An insulating layer having was formed. The obtained laminate is referred to as “development evaluation laminate”.

<Preparation of laminate for connection reliability evaluation>
The laminated body used for evaluation of the connection reliability of the small diameter via was prepared according to the following procedure.
(I) A first copper land (thickness 3 μm, land diameter 50 μm, pitch 100 μm) was formed on a glass epoxy substrate (inner layer substrate).
(Ii) A vacuum laminator (“CVP700” manufactured by Nichigo Morton Co., Ltd.) is used to bond the photosensitive film with a support prepared in Examples and Comparative Examples to the substrate so that the resin composition layer is bonded to the first copper land. ]). Lamination was performed under the same conditions as the laminate for developing evaluation.
(Iii) Ultraviolet irradiation, development, and thermosetting are performed under the same conditions as in the development evaluation laminate so that the center of the first copper land coincides with the center of the via hole after development. A first insulating layer having a via hole with a top diameter of 20 μm was formed.
(Iv) A copper layer was formed on the surface of the obtained first insulating layer using a sputtering apparatus (“E-400S” manufactured by Canon Anelva Co., Ltd.). Then, after forming a pattern using a dry film resist (DFR) so that a second copper land (thickness 3 μm, land diameter 50 μm, pitch 100 μm) is formed at the via hole position, via filling is performed by electroplating. A filled via was formed. Thereafter, the DFR was peeled off, and unnecessary copper layers were etched to form a pattern.

  In the same manner as (ii) and (iii) above, a second insulating layer having a via hole with a diameter (top diameter) of 20 μm is formed so that the center of the second copper land and the center of the via hole after development are aligned. Formed. Thereafter, a third copper land (thickness 3 μm, land diameter 50 μm, pitch 100 μm) was formed at the via hole position in the same manner as (iv) above. The obtained laminated body is referred to as a “connection reliability evaluation laminated body”. In FIG. 1, the schematic diagram of this laminated body for connection reliability evaluation is shown.

<Measurement of alkali dissolution rate>
Modified phenol resins A, B, and C synthesized in Synthesis Examples 1, 2, and 3, respectively, were dissolved in carbitol acetate to prepare a solution containing 30% by weight of nonvolatile components. The solution was applied onto a silicon wafer and dried at 120 ° C. for 3 minutes to form a resin film having a thickness of 5 μm. Next, the resin film was immersed in a 2.38 wt% TMAH aqueous solution at 23 ° C. Then, the dissolution rate was calculated based on the time until the resin film disappeared due to dissolution of the modified phenolic resin.

<Development evaluation>
About the laminated body for developability evaluation, the bottom of the round hole was observed with a scanning electron microscope (SEM) (magnification 4500 times). The developability was evaluated according to the following criteria.
Evaluation criteria:
○: There is no development residue at the bottom of a round hole with a diameter of 20 μm, and the developability is excellent. ×: There is a development residue at the bottom of a round hole with a diameter of 20 μm, and the developability is poor.

<Evaluation of connection reliability>
About the laminated body for connection reliability evaluation, the thermal cycle test which made 1 cycle at -55 degreeC for 10 minutes and 125 degreeC for 10 minutes was implemented (cycle number: 1000). The cross section of the laminate after the thermal cycle test was observed with an SEM (magnification 4500 times). Connection reliability was evaluated according to the following criteria.
Evaluation criteria:
○: No crack or peeling observed in the via connection portion ×: Crack or peeling observed in the via connection portion

<Synthesis Example 1> Synthesis of Modified Phenolic Resin A In a 1000 mL separable flask, 176 g of cyclohexanone and 176 g (1.68 mol) of phenol novolac resin (DIC Co., Ltd. “TD-2090”) were weighed and dissolved completely. Stir at 90 ° C. While heating at the same temperature, 118 g (0.84 mol) of glycidyl methacrylate (manufactured by NOF Corporation, chlorine-free type), 142 g of cyclohexanone, 1 g of triethylamine and 0.1 g of hydroquinone monomethyl ether were added dropwise. Then, the mixture was stirred and reacted for 24 hours to obtain 613.1 g of a modified phenol resin A (methacrylate-modified phenol resin).

(Properties of modified phenolic resin A)
-Solvent-dissolved product with a solid content of 50 mass%-Methacrylate group ratio: 50%
Weight average molecular weight: 4870
-Hydroxyl equivalent: 352
Alkali dissolution rate: 6.86 μm / min

<Synthesis Example 2> Synthesis of Modified Phenolic Resin B In a 1000 mL separable flask, 176 g of cyclohexanone and 176 g (1.68 mol) of phenol novolac resin (DIC Co., Ltd. “TD-2090”) were weighed and dissolved completely. Stir at 90 ° C. While heating at the same temperature, 47.8 g (0.34 mol) of glycidyl methacrylate (manufactured by NOF Corporation, “Blenmer GS”, chlorine-free type), 47.8 g of cyclohexanone, 1 g of triethylamine and 0.1 g of hydroquinone monomethyl ether The mixed solution was added dropwise, and the mixture was stirred and reacted for 8 hours to obtain 448.7 g of a modified phenol resin B (methacrylate-modified phenol resin).

(Properties of modified phenolic resin B)
-Solvent dissolved product with a solid content of 50% by weight-Ratio of methacrylate group: 20%
Weight average molecular weight: 2240
Hydroxyl equivalent: 167
Alkali dissolution rate: 15.4 μm / min

<Synthesis Example 3> Synthesis of Modified Phenol Resin C In a 2000 mL separable flask, 176 g of cyclohexanone and 176 g (1.68 mol) of phenol novolac resin (DIC Co., Ltd. “TD-2090”) were weighed and dissolved completely. Stir at 90 ° C. While heating at the same temperature, 214.6 g (1.51 mol) of glycidyl methacrylate (“Blenmer GS” manufactured by NOF Corporation, chlorine-free type), 214.6 g of cyclohexanone, 1 g of triethylamine and 0.1 g of hydroquinone monomethyl ether The mixed solution was added dropwise, and the mixture was stirred and reacted for 48 hours to obtain 782.3 g of a modified phenol resin C (methacrylate-modified phenol resin).

(Properties of modified phenolic resin C)
-Solvent dissolved product with a solid content of 50% by weight-Ratio of methacrylate group: 90%
-Weight average molecular weight: 4200
・ Hydroxyl equivalent: 1290
Alkali dissolution rate: 0.20 μm / min

<Example 1>
(1) Preparation of resin varnish 58 parts of modified phenolic resin A, bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation), epoxy equivalent 185, number average molecular weight 800, non-volatile component 40% by mass of MEK and cyclohexanone 1: 1 solution) 40 parts, reactive diluent (“M-306” manufactured by Toagosei Co., Ltd., liquid trifunctional acrylate), photopolymerization initiator (“OXE-02” manufactured by BASF Japan Ltd.), Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), MEK solution containing 10% by mass of nonvolatile components), 6 parts, cured Accelerator (“1HBZM” manufactured by Shikoku Kasei Co., Ltd., 2- (benzimidazol-1-yl) ethyl methacrylate, 10% by mass of non-volatile component 1-methoxy-2propaprop 5 parts of a diol solution, 2 parts of a silane coupling agent (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane) and a stirrer A resin varnish was prepared by kneading using "Nentaro").

(2) Production of Photosensitive Film with Support As a support, a PET film (“FB40” manufactured by Toray Industries, Inc., thickness 16 μm) was prepared. The resin varnish obtained in (1) above is uniformly coated on the support with a die coater and dried at 75 to 120 ° C. (average 105 ° C.) for 10 minutes using a hot air convection dryer, A photosensitive film with a support having a composition layer thickness of 10 μm was obtained.

<Example 2>
(1) Preparation of resin varnish 58 parts of phenolic resin A, bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation), epoxy equivalent 185, number average molecular weight 800, non-volatile component 40% by mass of MEK and cyclohexanone 1 : 1 solution) 20 parts, bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent 233, number average molecular weight 880) 10 parts, reactive diluent (Toa Gosei Co., Ltd. "M-306"", 3 parts of liquid trifunctional acrylate), photopolymerization initiator (" OXE-02 "manufactured by BASF Japan Ltd.), Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Yl]-, 1- (0-acetyloxime), MEK solution containing 10% by mass of nonvolatile components), 4 parts of photopolymerization initiator (BASF Japan ( "OXE-01", 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]), MEK solution containing 10% by mass of nonvolatile components), 4 parts, cured Accelerator (“1HBZM” manufactured by Shikoku Kasei Co., Ltd., 2- (benzoimidazol-1-yl) ethyl methacrylate, 1-methoxy-2-propanol solution containing 10% by mass of non-volatile components), silane coupling agent (Shin-Etsu) 2 parts of “KBM-403” manufactured by Chemical Industry Co., Ltd. and 3-glycidoxypropyltrimethoxysilane) are blended and kneaded using a stirrer (“Netaro Awatori” manufactured by Shinkey Co., Ltd.) A varnish was prepared.

(2) Production of photosensitive film with support A photosensitive film with a support having a thickness of 10 μm was obtained in the same manner as in Example 1 except that the resin varnish prepared in (1) above was used. It was.

<Example 3>
(1) Preparation of resin varnish 58 parts of phenolic resin A, bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation), epoxy equivalent 185, number average molecular weight 800, non-volatile component 40% by mass of MEK and cyclohexanone 1 : 1 solution) 25 parts, bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 233, number average molecular weight 880), 8 parts reactive diluent (“DPHA” manufactured by Nippon Kayaku Co., Ltd.) , Liquid hexafunctional acrylate), 3 parts, photopolymerization initiator (“OXE-02” manufactured by BASF Japan Ltd., Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Yl]-, 1- (0-acetyloxime), 3 parts of MEK solution containing 10% by mass of nonvolatile components), photopolymerization initiator (BASF Japan K.K.) "OXE-01", 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]), MEK solution containing 10% by mass of nonvolatile components), 8 parts, curing accelerator (“1HBZM” manufactured by Shikoku Kasei Co., Ltd., 2- (benzimidazol-1-yl) ethyl methacrylate, 1-methoxy-2-propanol solution containing 10% by mass of nonvolatile components), 5 parts photosensitizer (Nippon Kayaku) “DETX-S” manufactured by Co., Ltd., 2 parts of 2,4-diethylthioxanthone, MEK solution containing 10% by mass of nonvolatile components, silane coupling agent (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycol 2 parts (sidoxypropyltrimethoxysilane) were blended and kneaded using a stirrer (“Shintaro Awatori” manufactured by Shinkey Co., Ltd.) to prepare a resin varnish.

(2) Production of photosensitive film with support A photosensitive film with a support having a thickness of 10 μm was obtained in the same manner as in Example 1 except that the resin varnish prepared in (1) above was used. It was.

<Example 4>
(1) Preparation of resin varnish 58 parts of phenolic resin A, bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation), epoxy equivalent 185, number average molecular weight 800, non-volatile component 40% by mass of MEK and cyclohexanone 1 : 1 solution) 30 parts, bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent 233, number average molecular weight 880) 5 parts, reactive diluent (Nippon Kayaku Co., Ltd. "DPHA" , Liquid hexafunctional acrylate), 3 parts, photopolymerization initiator (“OXE-02” manufactured by BASF Japan Ltd., Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Yl]-, 1- (0-acetyloxime), MEK solution containing 10% by mass of nonvolatile components), photopolymerization initiator (BASF Japan K.K.) “OXE-01”, 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]), MEK solution containing 10% by mass of nonvolatile components), 3 parts, curing accelerator (“4M5HZM” manufactured by Shikoku Kasei Co., Ltd., 8 parts of methacrylic acid (5-methyl-3H-imidazol-4-yl) methyl, methanol solution of 10% by mass of non-volatile components), photosensitizer (Nippon Kayaku Co., Ltd. ) "DETX-S", 2,4-diethylthioxanthone, MEK solution with 10% by mass of non-volatile components, 1 part of silane coupling agent ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxy 2 parts of propyltrimethoxysilane) was blended and kneaded using a stirrer (“Shintaro Awatori” manufactured by Sinky Corporation) to prepare a resin varnish.

(2) Production of photosensitive film with support A photosensitive film with a support having a thickness of 10 μm was obtained in the same manner as in Example 1 except that the resin varnish prepared in (1) above was used. It was.

<Comparative Example 1>
(1) Preparation of resin varnish 29 parts of phenol resin B, bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation), epoxy equivalent 185, number average molecular weight 800, non-volatile component 40% by mass of MEK and cyclohexanone 1 : 1 solution) 40 parts, reactive diluent (“M-306” manufactured by Toa Gosei Co., Ltd., liquid trifunctional acrylate) 3 parts, photopolymerization initiator (“OXE-02” manufactured by BASF Japan Ltd.), Ethanon , 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), MEK solution with 10% by mass of nonvolatile components), 5 parts, photopolymerization Initiator (“OXE-01” manufactured by BASF Japan Ltd., 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]), 2 parts of a 10% by mass volatile component MEK solution, a curing accelerator ("1HBZM" manufactured by Shikoku Kasei Co., Ltd.), 2- (benzimidazol-1-yl) ethyl methacrylate, 10% by mass of 1-methoxy-volatile component 9 parts of 2 propanol solution), 3 parts of photosensitizer (“DETX-S” manufactured by Nippon Kayaku Co., Ltd., 2,4-diethylthioxanthone, MEK solution containing 10% by mass of nonvolatile components), silane coupling agent (Shin-Etsu) 2 parts of “KBM-403” manufactured by Chemical Industry Co., Ltd. and 3-glycidoxypropyltrimethoxysilane) are blended and kneaded using a stirrer (“Netaro Awatori” manufactured by Shinkey Co., Ltd.) A varnish was prepared.

(2) Production of photosensitive film with support A photosensitive film with a support having a thickness of 10 μm was obtained in the same manner as in Example 1 except that the resin varnish prepared in (1) above was used. It was.

<Comparative Example 2>
(1) Preparation of resin varnish 225 parts of phenol resin C, bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation), epoxy equivalent 185, number average molecular weight 800, non-volatile component 40% by mass of MEK and cyclohexanone 1 : 1 solution) 40 parts, reactive diluent (“M-306” manufactured by Toa Gosei Co., Ltd., liquid trifunctional acrylate) 3 parts, photopolymerization initiator (“OXE-02” manufactured by BASF Japan Ltd.), Ethanon , 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), MEK solution with 10% by mass of nonvolatile components), 5 parts, photopolymerization Initiator ("SF-01" manufactured by BASF Japan Ltd., 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]), 1 part of MEK solution with 10% by mass of nonvolatile components, curing accelerator (“1HBZM” manufactured by Shikoku Kasei Co., Ltd.), 2- (benzimidazol-1-yl) ethyl methacrylate, 1-methoxy- with 10% by mass of nonvolatile components 10 parts of 2 propanol solution), 2 parts of photosensitizer (“DETX-S” manufactured by Nippon Kayaku Co., Ltd., 2,4-diethylthioxanthone, MEK solution of 10% by mass of nonvolatile components), silane coupling agent (Shin-Etsu) 2 parts of “KBM-403” manufactured by Chemical Industry Co., Ltd. and 3-glycidoxypropyltrimethoxysilane) are blended and kneaded using a stirrer (“Netaro Awatori” manufactured by Shinkey Co., Ltd.) A varnish was prepared.

(2) Production of photosensitive film with support A photosensitive film with a support having a thickness of 10 μm was obtained in the same manner as in Example 1 except that the resin varnish prepared in (1) above was used. It was.

  The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 Inner layer board | substrate 2 1st copper land 10 1st insulating layer 11 Filled via | veer 12 2nd copper land 20 2nd insulating layer 21 Filled via 22 3rd copper land 100 Laminated body for connection reliability evaluation

Claims (15)

(A) A (meth) acrylate-modified phenolic resin, a resin film having a thickness of 5 μm obtained by applying a 30 wt% carbitol acetate solution of a nonvolatile component of the resin on a silicon wafer and drying at 120 ° C. for 3 minutes. A resin having a dissolution rate of 2 to 14 μm / min when immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C.,
(B) An epoxy resin, and (C) a resin composition for interlayer insulation containing a photopolymerization initiator.   (A) The resin composition of Claim 1 whose ratio of the (meth) acrylate group of a component is 35 to 80%.   The resin composition according to claim 1 or 2, further comprising (D) a reactive diluent.   The resin composition of any one of Claims 1-3 whose content of (A) component is 10-85 mass% when the non-volatile component in a resin composition is 100 mass%.   The resin composition of any one of Claims 1-4 whose content of (B) component is 5-60 mass% when the non-volatile component in a resin composition is 100 mass%.   The resin composition of any one of Claims 1-5 whose content of (C) component is 0.1-3 mass% when the non-volatile component in a resin composition is 100 mass%.   The resin composition of any one of Claims 3-6 whose content of (D) component is 0.5-30 mass% when the non-volatile component in a resin composition is 100 mass%.   Furthermore, the resin composition of any one of Claims 1-7 containing (E) hardening accelerator.   (C) The resin composition of any one of Claims 1-8 in which a component contains an oxime ester type photoinitiator.   The photosensitive film with a support containing the support body and the layer of the resin composition of any one of Claims 1-9 provided on this support body.   The printed wiring board containing the hardened | cured material layer of the resin composition of any one of Claims 1-9.   A semiconductor device comprising the printed wiring board according to claim 11. (A) A (meth) acrylate-modified phenolic resin, a resin film having a thickness of 5 μm obtained by applying a 30 wt% carbitol acetate solution of a nonvolatile component of the resin on a silicon wafer and drying at 120 ° C. for 3 minutes. A resin whose dissolution rate is 2 to 14 μm / min when immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C., (B) an epoxy resin, and (C) photopolymerization initiation Providing a resin composition layer containing an agent on the inner layer substrate;
An exposure step of irradiating the surface of the resin composition layer with an actinic ray through a mask pattern and photocuring the resin composition layer of the irradiated portion;
Developing the resin composition layer and removing the unexposed areas to form vias; and
A post-baking step of post-baking the resin composition layer to form an insulating layer.   The method of claim 13, wherein a top diameter of the via is 50 μm or less.   The method according to claim 13 or 14, wherein an opening ratio of the via is 70% or more.

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