TW201641276A - Dry film, cured product, laminate, and method for forming resist pattern - Google Patents

Abstract

Provided is a dry film comprising a photosensitive layer and a non-photosensitive layer, said non-photosensitive layer containing a thermosetting resin.

Description

Method for forming dry film, cured product, laminated body and resist pattern

The present invention relates to a method of forming a dry film, a cured product thereof, a laminate, and a resist pattern.

In recent years, with the increase in the performance of electronic devices (small size, light weight, and multi-function), high-level semiconductor components such as large-scale integrated circuits (LSI) and chips have been promoted. The form of the semiconductor component is rapidly changing in pinning and miniaturization. In addition, mounting forms such as a package on package in which a semiconductor device is stacked on a semiconductor device are also prevailing, and it is expected that the mounting density of the semiconductor device will become higher later.

The printed wiring board is formed by forming a plurality of wiring layers on a core substrate, and includes a core substrate, an interlayer insulating film provided between the wiring layers (also referred to as a conductor pattern layer), and a solder resist provided on the outermost surface ( Surface protective film).

In the interlayer insulating film of the printed wiring board, a via (via) for electrically connecting the upper and lower wiring layers must be provided. If the number of pins of a flip chip mounted on a printed wiring board is increased, it is necessary to provide a number of channels corresponding to the number of the pins. However, the conventional printed wiring board has a low mounting density. The number of pins of the mounted semiconductor component also becomes a design of several thousand pins to about 10,000 pins, so there is no need to provide a small-diameter and narrow-pitch channel. However, with the development of the miniaturization of the semiconductor element, and the number of pins is increased from tens of thousands of pins to hundreds of thousands of pins, the channel formed in the interlayer insulating film of the printed wiring substrate is also connected to the semiconductor element. The need to narrow the number of feet is increasing.

Regarding a method of forming a via and a wiring layer for an interlayer insulating film, for example, a method is known in which an insulating layer is formed on an inner layer circuit board (a substrate having a first conductor pattern) using a thermosetting resin material, and A channel is formed by laser processing, and then the insulating layer is subjected to electroless copper plating treatment, whereby a second conductor pattern is formed (for example, refer to Patent Document 1). [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-3705

[Problems to be Solved by the Invention] However, in the conventional method, that is, a method of providing a channel by using a laser, there is a problem in that each channel must be formed one by one, and it takes time to set a plurality of channels, and it is necessary to The laser used for the use is distinguished according to the diameter of the channel, and it is difficult to set a fine channel or the like.

Further, in the case where a conductor pattern is formed on the insulating layer by electroless copper plating, the adhesion between the insulating layer and the copper plating is not sufficient, and the conductor pattern may be peeled off.

An object of the present invention is to provide a dry film which can form a resist pattern which is excellent in adhesion to copper plating and excellent in resolvability, a cured product thereof, a laminate, and a resist using the same. A method of forming a pattern. [Means for solving the problem]

The inventors of the present invention have diligently studied in order to solve the above problems, and as a result, have found a dry film having excellent characteristics. That is, the dry film of the present invention includes a photosensitive layer and a non-photosensitive layer, and the non-photosensitive layer contains a thermosetting resin.

Here, the non-photosensitive layer is, for example, a layer used as an insulating layer when manufacturing a multilayer wiring board, and a conductor pattern (wiring layer) can be formed by plating on the surface thereof. The non-photosensitive layer of the dry film of the present invention can improve the adhesion of the insulating layer formed of the non-photosensitive layer and the conductor pattern formed by plating on the insulating layer, thereby improving the electrical reliability of the formed circuit. . Furthermore, the non-photosensitive layer may also be referred to as an auxiliary layer. It has been found that the non-photosensitive layer of the present invention has low solubility in a chemical liquid such as a developer, and therefore the surface roughness after the roughening treatment is small. Further, the inventors of the present invention have found that the non-photosensitive layer of the dry film of the present invention can ensure good adhesion to copper plating as compared with the insulating layer of one layer in which the non-photosensitive layer of the present invention and the photosensitive layer are mixed. .

Further, by using the dry film of the present invention, not only a channel can be formed without using a laser, but also a finer channel pattern can be formed as compared with the case of using a laser. That is, it was found that by using the dry film, the non-photosensitive layer and the photosensitive layer can be combined to form a fine channel. Further, by forming the insulating layer using the dry film of the present invention, generation of residue of the channel can be suppressed, and insulation reliability between the layers can be improved.

The non-photosensitive layer preferably contains the component (A): an epoxy resin, a component (B-1): an epoxy resin curing agent, and (C) a component: a resin having a mercaptoamine group or a quinone imine group.

The non-photosensitive layer preferably further contains the component (E): an ester group-containing compound.

The non-photosensitive layer preferably contains the component (A): an epoxy resin, a component (B-2): an epoxy resin hardening accelerator, and (E) a component: an ester group-containing compound. The surface roughness of the non-photosensitive layer after the ultraviolet irradiation treatment is also small, and good adhesion to copper plating can be ensured.

The non-photosensitive layer preferably further contains a component (D): an inorganic filler.

The thickness of the photosensitive layer is preferably from 1 μm to 50 μm.

The thickness of the non-photosensitive layer is preferably 10 μm or less.

The photosensitive layer preferably contains (F) a component: a resin having a phenolic hydroxyl group; and (G) component: at least one selected from the group consisting of an aromatic ring, a heterocyclic ring, and an alicyclic ring, and has a hydroxyl group. a compound of a group or alkoxyalkyl group; (H) component: an aliphatic group having two or more functional groups selected from the group consisting of an acryloxy group, a methacryloxy group, a glycidoxy group, and a hydroxyl group a compound; and (I) a component: a photo-sensitive acid generator.

The dry film according to claim 8, wherein the (H) component is contained in an amount of 20 parts by mass to 70 parts by mass based on 100 parts by mass of the component (F).

The photosensitive layer preferably further contains a (D') component: an inorganic filler.

The (D') component is preferably an inorganic filler having an average primary particle diameter of 100 nm or less.

The (D') component is preferably cerium oxide.

The dry film can be used to form an interlayer insulating layer.

Further, the present invention also provides a cured product obtained by using the dry film.

The method for forming a resist pattern of the present invention comprises the steps of: sequentially forming a photosensitive layer and a non-photosensitive layer on a substrate using the dry film; exposing the photosensitive layer to a predetermined pattern; and exposing The photosensitive layer is developed and subjected to a heat treatment step.

The method of forming the resist pattern preferably further includes the step of performing heat treatment before developing the exposed photosensitive layer.

Furthermore, the present invention provides a dry film comprising a photosensitive layer and a non-photosensitive layer, and the dry film sequentially forms a photosensitive layer and a non-photosensitive layer on the substrate, exposing the photosensitive layer, and performing the dry film Development is performed to dissolve the unexposed portion of the photosensitive layer to rupture the non-photosensitive layer on the unexposed portion, and a channel can be formed at a portion where the non-photosensitive layer is broken by heat treatment after development. According to such a dry film, a channel can be formed without using a laser, and a plurality of channels can be easily formed at one time.

The present invention provides a laminate in which a substrate, a photosensitive layer, and a non-photosensitive layer containing a thermosetting resin are sequentially laminated.

The method for forming a resist pattern of the present invention includes the steps of: applying a photosensitive composition onto a substrate to form a photosensitive layer; and coating a resin composition containing a thermosetting resin on the photosensitive layer to form a step of non-photosensitive layer; a step of exposing the photosensitive layer in a predetermined pattern; and a step of developing the exposed photosensitive layer and performing a heat treatment. [Effects of the Invention]

According to the present invention, it is possible to provide a dry film which can form a resist pattern which is excellent in adhesion to copper plating and excellent in resolution. Further, according to the present invention, it is possible to provide a cured product of the dry film, a laminate, and a method of forming a resist pattern using the dry film.

(First embodiment) Hereinafter, a first embodiment of the present invention will be specifically described, but the present invention is not limited thereto. In the present specification, the term "(meth)acrylate" means at least one of an acrylate and a corresponding methacrylate. In addition, other similar expressions such as (meth)acrylic compounds are also the same.

In this specification, the term "step" refers not only to an independent step, but also to the intended use of the step, as long as the intended effect of the step can be achieved. In the present specification, the term "layer" is used in the form of a plan view, and includes a structure partially formed in addition to the structure formed on the entire surface. Further, in the present specification, the numerical range indicated by "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. Further, in the numerical range described step by step in the present specification, the upper limit value or the lower limit value of the numerical range of a certain stage may be replaced with the upper limit value or the lower limit value of the numerical range of the other stage. In addition, in the numerical range described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment.

[Dry Film] The dry film of the present embodiment will be described with reference to Fig. 1 . Fig. 1 is a schematic cross-sectional view showing a dry film 10 of the present embodiment.

The dry film 10 of the present embodiment includes a non-photosensitive layer 3 and a photosensitive layer 5. The non-photosensitive layer 3 is a layer formed using a resin composition described later, and the photosensitive layer 5 is a layer formed using a photosensitive composition described later. Further, the dry film 10 can also be formed on the support 1 such that the non-photosensitive layer 3 is in contact with the support 1. That is, the dry film 10 of the present embodiment may be provided with the support 1, the non-photosensitive layer 3, and the photosensitive layer 5 in this order. Further, a protective layer 7 covering the photosensitive layer 5 may be further provided on the photosensitive layer 5.

As the support 1, for example, a polymer film having heat resistance and solvent resistance can be used. Examples of the support 1 (polymer film) include polyolefins such as polypropylene and polyethylene, and polyesters such as polyethylene terephthalate. The thickness of the support 1 (polymer film) is preferably set to 5 μm to 25 μm. Further, one piece of the polymer film may be used as the support 1 and the other piece of the polymer film may be used as the protective layer 7. Further, the support 1 may be a person who exhibits light blocking properties (such as copper foil).

As the protective layer 7, for example, a polymer film having heat resistance and solvent resistance can be used. Examples of the protective layer 7 (polymer film) include polyolefins such as polypropylene and polyethylene, and polyesters such as polyethylene terephthalate. Further, as the protective layer 7, a person who exhibits light blocking properties (such as copper foil) can also be used.

The non-photosensitive layer 3 and the photosensitive layer 5 can be formed by applying a resin composition and a photosensitive composition to a support or a protective layer, respectively. Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, and a spin coating method. Specifically, for example, the dry film of the present embodiment can be obtained by the method described below. First, the non-photosensitive layer 3 is formed by applying and drying the resin composition onto a polymer film or a copper foil to be a support. Then, the photosensitive composition is applied onto the non-photosensitive layer 3 and dried to form the photosensitive layer 5, whereby the dry film of the present embodiment is obtained. Further, a non-photosensitive layer 3 may be formed on the support 1 and a photosensitive layer 5 may be formed on the protective layer 7, and the dry film of the present embodiment may be obtained.

The non-photosensitive layer 3 may have a thickness of 10 μm or less, 0.1 μm to 10 μm, 0.1 μm to 5 μm, 0.2 μm to 1.5 μm, or 0.3 μm to 1 μm. By setting the thickness of the non-photosensitive layer 3 to 10 μm or less, the developability in the alkaline aqueous solution is improved, or the sensitivity of the photosensitive layer 5 due to absorption of actinic rays by the non-photosensitive layer 3 can be suppressed, so the resolution is improved. improve. When the thickness of the non-photosensitive layer 3 is 0.1 μm or more, the workability is improved.

The transmittance of the non-photosensitive layer 3 may be 80% or more, may be 85% or more, or may be 90% or more. When the transmittance of the non-photosensitive layer 3 is 80% or more, the sensitivity of the photosensitive layer 5 can be sufficiently suppressed to be lowered, so that the resolution is improved. The upper limit is not particularly limited and may be less than 100%. The transmittance can be measured by a known method.

The thickness of the photosensitive layer 5 varies depending on the application, and the thickness of the photosensitive layer 5 is preferably from 1 μm to 50 μm, more preferably from 5 μm to 40 μm, even more preferably from 10 μm to 30 μm. When the thickness of the photosensitive layer 5 is in the above range, the resolution tends to be more excellent.

[Resin Composition for Forming Non-Photosensitive Layer] The resin composition of the present embodiment is not photosensitive and can be used to form a non-photosensitive layer. The resin composition of the present embodiment contains a thermosetting resin. The thermosetting resin is not particularly limited as long as it is a component containing a reactive compound which causes a crosslinking reaction by heat, and examples thereof include an epoxy resin, a cyanate resin, a maleimide resin, and an acryl. A ruthenium imine resin, a phenol resin, a urea resin, a melamine resin, an alkyd resin, an acrylic resin, an unsaturated polyester resin, a diallyl phthalate resin, an anthrone resin, and a resorcinol formaldehyde. Resin, xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, resin containing tris(2-hydroxyethyl) isocyanurate, A resin containing triallyl trimellitate, a thermosetting resin synthesized from cyclopentadiene, a thermosetting resin obtained by trimerization of aromatic dicyandiamide, or the like. The resin composition may also contain a hardener of a thermosetting resin.

The resin composition of the present embodiment may contain (A) component: epoxy resin, (B-1) component: epoxy resin hardener, and (C) component: resin having a mercaptoamine group or a quinone imine group. Further, the resin composition for forming the resin layer of the present embodiment may contain (A) component: epoxy resin, (B-2) component: epoxy resin hardening accelerator, and (E) component: ester group-containing Compound. In the present specification, the components may be simply referred to as (A) component, (B-1) component, (B-2) component, (C) component, (E) component, and the like. Further, the resin layer of the present embodiment can be preferably used in a method of forming a plating step.

<(A) Component> The epoxy resin is preferably a compound which varies depending on the use, and is preferably a polyfunctional epoxy resin. Specific examples of preferred epoxy resins include cresol novolak type epoxy resin, phenol novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type. Epoxy resin, bisphenol T epoxy resin, bisphenol Z epoxy resin, tetrabromobisphenol A epoxy resin, biphenyl epoxy resin, biphenyl aralkyl epoxy resin, tetramethyl Biphenyl type epoxy resin, triphenyl type epoxy resin, tetraphenyl type epoxy resin, naphthol aralkyl type epoxy resin, naphthalene diphenol aralkyl type epoxy resin, fluorene type epoxy resin, An epoxy resin having a dicyclopentadiene skeleton, an epoxy resin having a skeleton derived from butylene glycol, an epoxy resin having a skeleton derived from pentanediol, and an epoxy resin having a skeleton derived from hexanediol An epoxy resin having a skeleton derived from heptanediol, an epoxy resin having a skeleton derived from octylene glycol, an alicyclic epoxy resin, or the like. Among them, a biphenyl aralkyl type epoxy resin or an epoxy resin having a skeleton derived from hexanediol is more preferable. The commercially available epoxy resin is, for example, a biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000). From the viewpoint of further improving the insulation reliability and heat resistance, these epoxy resins may be used in combination of two or more kinds.

The content of the component (A) is preferably from 20 parts by mass to 90 parts by mass, more preferably from 30 parts by mass to 80 parts by mass, per 100 parts by mass of the total of the solid content of the resin composition for forming the non-photosensitive layer. In addition, the solid content in the present specification means a component in a composition other than a volatile substance such as water or a solvent to be described later. That is, the solid component also includes a liquid, saccharide, and waxy component at room temperature around 25 ° C, and does not necessarily mean a solid.

<Component (B-1)> The epoxy resin curing agent is preferably a compound which varies depending on the use, and examples thereof include a phenol resin, an acid anhydride, an amine, and a hydrazide. As the phenol resin, a novolac type phenol resin such as a cresol novolac type phenol resin, a resol type phenol resin or the like can be used. As the acid anhydride, phthalic anhydride, benzophenonetetracarboxylic dianhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (methylhimic anhydride) or the like can be used. As the amine, dicyandiamide, diaminodiphenylmethane, guanylurea or the like can be used.

The content of the component (B-1) is preferably from 0.5 equivalent to 1.5 equivalents based on the epoxy group of the component (A). When the content of the epoxy resin hardener is from 0.5 equivalent to 1.5 equivalents based on the epoxy group of the component (A), the Tg (glass transition temperature) and the decrease in insulation properties can be suppressed.

<Component (B-2)> The component (B-2) which can be used in the resin composition of the present embodiment: an epoxy resin hardening accelerator, preferably a compound varies depending on the use, and the hardening of the component (A) can be used. The usual hardening accelerator used. Specific examples of the epoxy resin hardening accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, and 2- An imidazole compound such as undecylimidazole or 1-cyanoethyl-2-phenylimidazolium trimellitate; an organophosphine compound such as triphenylphosphine or tributylphosphine; trimethyl phosphite; An organic phosphite compound such as triethyl phosphite; an sulfonium salt compound such as ethyltriphenylphosphonium bromide or tetraphenylphosphonium tetraphenylborate; or a trialkylamine such as triethylamine or tributylamine. ; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo (5.4.0)-ten An amine compound such as 1,8-diazobicyclo(5.4.0)-undecene-7 (hereinafter abbreviated as "DBU"), and DBU and terephthalic acid or 2,6-naphthalenedicarboxylic acid Salt; tetra-ammonium salt compound such as tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrahexylammonium bromide, benzyltrimethylammonium chloride Wait. These compounds may be used alone or in combination of two or more.

In addition, the content of the component (B-2) is preferably 0.02 parts by mass to 1.5 parts by mass, more preferably 0.8 parts by mass to 1.3 parts by mass, per 100 parts by mass of the component (A). When the amount is 0.02 parts by mass or more, the curing of the component (A) is sufficient, and the heat resistance tends to be maintained. On the other hand, when the amount is 1.5 parts by mass or less, the storage stability of the resin composition is B-staged. The handleability of the resin composition became good.

<(C) Component> Examples of the resin having a mercaptoamine group or a quinone imine group include polyamine, polyamidimide, polyimine, and the like. Examples of the diamine which can be used for the production of these resins include aromatic diamines and aliphatic diamines. The component (C) may also be referred to as a heat resistant resin.

Specific examples of the aromatic diamine include diaminobenzene, diaminotoluene, diaminophenol, diaminodimethylbenzene, diamine mesitylene, diaminonitrobenzene, and diamine. Diazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether, diaminodimethyldiphenyl ether, methylene diamine, Methylene bis(dimethylaniline), methylene bis(methoxyaniline), methylene bis(dimethoxyaniline), methylene bis(ethylaniline), methylene bis (two Ethyl aniline), methylene bis(ethoxyaniline), methylene bis(diethoxyaniline), isopropylidene diphenylamine, diaminobenzophenone, diaminodimethyl dimethyl Benzophenone, diaminoguanidine, diaminodiphenyl sulfide, diaminodimethyldiphenyl sulfide, diaminodiphenylphosphonium, diaminodiphenylarylene, diamine Basics and so on.

Specific examples of the aliphatic diamine include ethylenediamine, propylenediamine, hydroxypropylenediamine, butanediamine, pentanediamine, hexamethylenediamine, diaminodiethylamine, and diaminopropylamine. Cyclopentanediamine, cyclohexanediamine, azapentanediamine, triazaundecanediamine, and the like. These aromatic diamines and aliphatic diamines may be used alone or in combination of two or more.

Examples of the dicarboxylic acid used for producing the resin having a mercaptoamine group or a quinone imine group include an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and an oligomer having a carboxyl group at both terminals.

Specific examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, biphenyl dicarboxylic acid, methylene dibenzoic acid, thiodibenzoic acid, and carbonyl dibenzoic acid. Sulfonyl dibenzoic acid, naphthalene dicarboxylic acid, hydroxyisophthalic acid, hydroxyphthalic acid, hydroxy terephthalic acid, dihydroxyisophthalic acid, dihydroxyterephthalic acid, and the like. These aromatic dicarboxylic acids may be used alone or in combination of two or more.

Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, and (methyl group). Acrylic methoxy succinic acid, di(methyl) propylene decoxy succinic acid, (meth) propylene methoxy methoxy malic acid, (meth) acrylamide succinic acid, (meth) acrylamide phthalic acid Wait. These aliphatic dicarboxylic acids may be used alone or in combination of two or more.

The oligomer having a carboxyl group at both terminals may be an oligomer having a number average molecular weight of 200 to 10,000, preferably a number average molecular weight of 500 to 5,000. Specific examples thereof include a polybutadiene having a carboxyl group at both terminals, a butadiene-acrylonitrile copolymer, a styrene-butadiene copolymer, a polyisoprene, an ethylene propylene copolymer, a polyether, and a poly Ester, polycarbonate, polyacrylate, polymethacrylate, polyurethane, anthrone rubber, and the like. These aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and oligomers having a carboxyl group at both terminals may be used alone or in combination of two or more. The "quantitative average molecular weight (Mn)" and the "weight average molecular weight (Mw)" described later are values measured by a calibration curve using standard polystyrene according to the Gel Permeation Chromatography (GPC) method, and more specifically. In the case of the pump (manufactured by Hitachi, Ltd., model L-6200), the column (TSKgel-G5000HXL and TSKgel-G2000HXL, both manufactured by Tosoh Co., Ltd., trade name) and detector (Hitachi The product manufactured by Seiko Co., Ltd., model L-3300RI) was measured as a GPC measuring device using tetrahydrofuran as a dissolving solution at a temperature of 30 ° C and a flow rate of 1.0 mL/min.

In the case where polyamine is contained as the component (C), a copolymer of polyamine and polybutadiene may also be used from the viewpoint of further improving the adhesion of copper plating (may also be referred to as "polybutylene". Diene modified polyamine resin"). The polybutadiene-modified polyamine resin may be a polybutadiene containing a phenolic hydroxyl group obtained by polycondensing a diamine, a dicarboxylic acid having a phenolic hydroxyl group, and a polybutadiene having a carboxyl group at both terminals. Modification of polyamine. The phenolic hydroxyl group-containing polybutadiene modified polyamine can be obtained, for example, by a diamine, a phenolic hydroxyl group-containing dicarboxylic acid, and a polybutadiene having a carboxyl group at both terminals, in N-A. In an organic solvent such as N-methyl-2-pyrrolidinone (NMP), a carboxyl group and an amine group are polycondensed in the presence of a phosphite and a pyridine derivative as a catalyst. Further, in addition to a diamine, a dicarboxylic acid having a phenolic hydroxyl group, and a polybutadiene having a carboxyl group at both terminals, a dicarboxylic acid having no phenolic hydroxyl group may be added. A commercially available product of such a phenolic hydroxyl group-containing polybutadiene-modified polyamine resin is BPAM-155 manufactured by Nippon Kayaku Co., Ltd., and the like.

Examples of the polyamidoximine which may be contained as the component (C) include polyamidoximine synthesized by a so-called isocyanate method using a reaction product of trimellitic anhydride or trimellitic anhydride and a diamine, and an aromatic second. The reaction of isocyanate. Specific examples of the isocyanate method for synthesizing polyamidoximine are a method in which an aromatic tricarboxylic acid anhydride and a diamine compound are reacted in excess of a diamine compound, and then a diisocyanate is reacted (for example, Japanese Patent No. 2897186) The method described in the publication) is a method of reacting an aromatic diamine compound with trimellitic anhydride (for example, the method described in JP-A-2004-182466).

Commercially available products of such polyamidoximine resins include, for example, Vylomax HR11NN manufactured by Toyobo Co., Ltd., Vylomax HR16NN, and the like.

The polyimine which can be contained as the component (C) can also be synthesized by a usual synthesis method currently used in the industry. For example, a tetracarboxylic dianhydride and the diamine are used as a raw material to carry out polymerization in a molar manner to obtain a polylysine which is a precursor of polyimine, and then a dehydration reaction is carried out using heating or a catalyst at 200 ° C or higher. The cyclization reaction, whereby polyimine is obtained. In the case of using a catalyst, an amine compound may be used, or a carboxylic anhydride may be used in combination as a dehydrating agent for rapidly removing water produced by imidization. Further, the component (C) described above may be used alone or in combination of two or more.

The content of the component (C) is preferably from 3% by mass to 30% by mass, and more preferably from 15% by mass to 255% by mass based on the total of the solid components of the component (A), the component (B-1) and the component (C). %.

<Component (D)> The resin composition may contain the component (D): an inorganic filler from the viewpoint of stabilizing the roughened shape and improving the adhesion. In the case of containing an inorganic filler, the thermal expansion coefficient of the cured film obtained by heating may be lowered corresponding to the content of the component (D) after the pattern is formed. The component (D) may be used alone or in combination of two or more.

Examples of the inorganic fillers include inorganic fillers derived from mineral products such as alumina, aluminum hydroxide, calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, cerium oxide or talc, and mica. Further, examples of the cerium oxide include molten spherical cerium oxide, melt pulverized cerium oxide, smoky cerium oxide, and sol-gel cerium oxide.

The type of the inorganic filler is not particularly limited, and the coefficient of thermal expansion is preferably 5.0 × 10 ^-6 / ° C or less. From the viewpoint of particle diameter, molten spherical cerium oxide, smog cerium oxide, sol gel is preferred. Antimony dioxide such as cerium oxide. Among them, more preferred is aerosol-like cerium oxide or sol-gel cerium oxide. A decane coupling agent can also be used in order to disperse in a resin without agglomeration.

When measuring the particle diameter of each inorganic filler, a well-known particle size distribution meter can be used.

When the resin composition for forming the non-photosensitive layer contains the component (D), it is preferably 1 part by mass to 40 parts by mass, more preferably 1 part by mass, based on 100 parts by mass of the total solid content of the resin composition. Parts to 10 parts by mass.

In addition, the inorganic filler contained in the non-photosensitive layer (or the photosensitive layer to be described later) preferably has an average value of the primary particle diameter of 100 nm or less, and is preferably 50 nm or less in terms of more excellent photosensitivity. When the average value of the primary particle diameter is 100 nm or less, the resolution tends to be further improved. In addition, the "primary particle diameter" is a value obtained by converting the specific surface area of the particles actually measured by the Brunauer-Emmett-Teller (BET) method. In the BET method, an adsorbate (for example, an inert gas such as nitrogen) can be physically adsorbed on the surface of a solid particle at a low temperature, and the specific surface area can be estimated from the molecular cross-sectional area of the adsorbate and the amount of adsorption. The component (D) dispersed in the resin composition is suppressed from the viewpoint of suppressing light scattering in the exposure wavelength range (for example, 300 nm to 450 nm) of the resin composition, that is, suppressing a decrease in transmittance in the exposure wavelength range. The average particle diameter is preferably 80 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less. The lower limit of the average particle diameter of the component (D) in the resin composition is not particularly limited, and may be, for example, 5 nm or more. From the viewpoint of suppressing the decrease in the transmittance, the inorganic filler is preferably dispersed in a maximum particle diameter of 1 μm or less when dispersed in a resin composition, and more preferably dispersed at a maximum particle diameter of 0.5 μm or less. Further, it is preferably dispersed with a maximum particle diameter of 0.1 μm or less. In addition, the "average particle diameter" of the component (D) is an average particle diameter of the inorganic filler in a state of being dispersed in the resin composition, and is set to a value measured as follows. First, after diluting (or dissolving) the resin composition to 1000 times with methyl ethyl ketone, a submicron particle analyzer (manufactured by Beckman-Coulter Co., Ltd., trade name: N5) was used. According to the International Standardization Organization (ISO) 13321, the particles dispersed in the solvent are measured at a refractive index of 1.38, and the particle size distribution is 50% (volume basis) of the particle size as the average particle diameter. . Further, the particle diameter of the cumulative value of the particle size distribution of 99.9% (volume basis) was taken as the maximum particle diameter. Further, even if it is a cured film of a non-photosensitive layer or a resin composition provided on a support, after the dry film is subjected to total exposure to prevent elution of the photosensitive layer, the solvent is diluted (or dissolved) as described above. After 1000 times (volume ratio), the measurement was carried out using the sub-micro particle analyzer.

<(E) Component> The resin composition may further contain the component (E): an ester group-containing compound. Specifically, a compound containing one or more ester groups in one molecule and containing no hydroxyl group and curing the epoxy resin may, for example, be an ester obtained from an aliphatic or aromatic carboxylic acid and an aliphatic or aromatic hydroxy compound. Compounds, etc. Among these compounds, an ester compound composed of an aliphatic carboxylic acid, an aliphatic hydroxy compound or the like can improve solubility in an organic solvent and compatibility with an epoxy resin by containing an aliphatic chain. On the other hand, an ester compound composed of an aromatic carboxylic acid, an aromatic hydroxy compound or the like has an aromatic ring, and the heat resistance of the resin composition can be improved.

A preferred compound of the ester group-containing compound is, for example, a mixture of an aromatic carboxylic acid, a monohydric phenol compound, and a polyhydric phenol compound, and the aromatic carboxylic acid, the monohydric phenol compound, and the polyphenol compound. An aromatic ester obtained by a condensation reaction of a phenolic hydroxyl group.

Examples of the aromatic carboxylic acid include two to four aromatic rings such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, diphenylphosphonium, and benzophenone. A compound in which a hydrogen atom is substituted with a carboxyl group. The monovalent phenol-based compound may be a compound in which one hydrogen atom of the aromatic ring is substituted with a hydroxyl group. The polyhydric phenol compound may be a compound in which two to four hydrogen atoms of the aromatic ring are substituted with a hydroxyl group.

Examples of the aromatic carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, and benzenetricarboxylic acid. Examples of the monohydric phenol compound include phenol, various cresols, α-naphthol, and β-naphthol. Examples of the polyhydric phenol compound include hydroquinone, resorcin, catechol, 4,4'-biphenol, 4,4'-dihydroxydiphenyl ether, bisphenol A, and double Phenol, bisphenol S, bisphenol Z, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, methylated bisphenol S, various dihydroxy naphthalenes, various dihydroxybenzophenones, various three Hydroxybenzophenone, various tetrahydroxybenzophenones, fluoroglycine, and the like.

The ester group-containing compound may be a resin having one or more ester groups in one molecule, or may be obtained as a commercially available product. For example, "EXB-9460", "EXB-9460S", "EXB-9470", "EXB-9480", and "EXB-9420" manufactured by Dickson (DIC) Co., Ltd., manufactured by Mitsui Chemicals Co., Ltd. "BPN80" and so on. These ultraviolet-active ester group-containing compounds may be used alone or in combination of two or more.

In the case of containing an ester group-containing compound, it is preferably one equivalent of the epoxy group of the component (A), and the content of the ester group-containing compound is from 0.75 equivalent to 1.25 equivalent. When it is 0.75 equivalent or more, the adhesion and the curability of the support and the non-photosensitive layer are easily obtained, and when it is 1.25 equivalent or less, sufficient curability, heat resistance, and chemical resistance are easily obtained.

In the resin composition, other components are added as needed in the components (A) to (E), and the components are sufficiently stirred and mixed, and then left to stand until the bubbles disappear. In addition, in order to uniformly disperse the inorganic filler contained in the resin composition, a known kneading or dispersion method such as a kneader, a ball mill, a bead mill, a three-roll mill, or a nanomizer may be used.

The resin composition is preferably in the form of a varnish which is mixed in a solvent and diluted or dispersed in terms of workability. Examples of the solvent include methyl ethyl ketone, xylene, toluene, acetone, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxy propionate, N,N-dimethylformamide, and N. , N-dimethylacetamide, and the like. These solvents may be used alone or in combination of two or more. The ratio of the solvent to the resin composition can also be set to a previously used ratio, and the amount of use can be adjusted according to the apparatus for forming the non-photosensitive layer. On the other hand, after the dispersion preparation, the resin composition may be further diluted or dispersed by the solvent to prepare a varnish.

[Photosensitive Composition] The photosensitive composition for forming the photosensitive layer of the present embodiment can be used depending on the intended purpose as long as the property is changed (for example, hardened) by light irradiation, and may be negative or positive. type. In addition, the term "photosensitivity" refers to a case where the photosensitive layer is exposed to light, and then heat treatment after exposure is performed as needed, and then a developing solution for removing the photosensitive composition is used for development (removal). A resin pattern can be formed. The photosensitive composition may further contain (F) a component: a resin having a phenolic hydroxyl group, a (G') component: a crosslinking agent, and (I) a component: a photo-sensitive acid generator. (G') component: The crosslinking agent is a compound which forms a bond with a resin or a bond of a crosslinking agent by the action of heat, an acid, or the like. The (G') component may comprise a component (G): a compound having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring and having a methylol group or an alkoxyalkyl group, and may also contain ( H) component: an aliphatic compound having two or more functional groups selected from the group consisting of an acryloxy group, a methacryloxy group, a glycidoxy group, and a hydroxyl group, and may further contain the component (G) and H) Both components. Further, the photosensitive composition of the present embodiment may optionally contain a (D') component: an inorganic filler, (J) component: an amine, (K) component: an organic peroxide, (L) component: a decane coupling agent, (M) component: leveling agent, (N) component: sensitizer, and the like. Further, in addition to the component (F), a phenolic low molecular compound may be contained.

Further, as the (D') component: the inorganic filler, the same component as the component (D) described above can be used. When the photosensitive composition contains the component (D'), it is preferably 1 part by mass to 70 parts by mass, more preferably 3 parts by mass to 65 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive composition. Share.

The (D') component contained in the photosensitive composition of the present embodiment preferably has an average value of the primary particle diameter of 100 nm or less. Further, the average particle diameter of (D') is preferably 100 nm or less. Thereby, the thermal expansion coefficient of the cured film can be lowered in accordance with the content of the (D') component. (D' is dispersed in the photosensitive composition from the viewpoint of suppressing light scattering in the exposure wavelength range (for example, 300 nm to 450 nm) of the photosensitive composition, that is, suppressing a decrease in transmittance in the exposure wavelength range. The average particle diameter of the component is preferably 80 nm or less, more preferably 50 nm or less, and still more preferably 30 nm or less. The lower limit of the average particle diameter of the component (D') is not particularly limited, and may be, for example, 5 nm or more. From the viewpoint of suppressing the decrease in the transmittance, the inorganic filler is preferably dispersed at a maximum particle diameter of 1 μm or less when dispersed in a photosensitive composition, and more preferably dispersed at a maximum particle diameter of 0.5 μm or less. Further, it is preferably dispersed with a maximum particle diameter of 0.1 μm or less. In addition, the "average particle diameter" and the "maximum particle diameter" of the (D') component mean the cumulative value of the particle size distribution of the inorganic filler in a state of being dispersed in the photosensitive composition, 50% (volume basis). The particle size and the cumulative value of the particle size of 99.9% (volume basis). Further, even if it is a photosensitive layer provided on a support or a cured film of a photosensitive composition, the submicron particles may be used after being diluted (or dissolved) to 1000 times (volume ratio) using a solvent as described above. The analyzer performs the measurement.

<Component (F): The component (F) used in the photosensitive composition of the present embodiment: the resin having a phenolic hydroxyl group is not particularly limited, and is preferably a resin soluble in an aqueous alkaline solution, particularly preferably a phenolic resin. Varnish resin. Such a novolak resin can be obtained by condensing a phenol with an aldehyde in the presence of a catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, and p-butylene. Phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, biphenyltriol, α-naphthol, β-naphthol, and the like.

Further, examples of the aldehydes include formaldehyde, trioxane, acetaldehyde, benzaldehyde, and the like.

Specific examples of such a novolak resin include a phenol/formaldehyde condensed novolac resin, a cresol/formaldehyde condensed novolac resin, a phenol-naphthol/formaldehyde condensed novolac resin, and the like.

Further, examples of the component (F) other than the novolak resin include polyhydroxystyrene and copolymers thereof, phenol-o-phthalaldehyde condensation resin, cresol-o-phthalaldehyde condensation resin, and phenol-dicyclopentadiene. Condensation resin, etc. The component (F) may be used alone or in combination of two or more.

The component (F) preferably has a weight average molecular weight of 100,000 or less, more preferably 1,000 to 80,000, and more preferably from the viewpoint of further improving the resolution, developability, thermal shock resistance, heat resistance and the like of the obtained insulating film. 2000 to 50000, especially preferably 2000 to 20000, and excellent 4000 to 15000.

The content of the component (F) is preferably 30 parts by mass to 90% by mass based on the total amount of the solid content of the photosensitive composition (excluding the component (D') when the component (D') is used). The mass part is more preferably 40 parts by mass to 80 parts by mass. When the content of the component (F) is within this range, the film formed using the obtained photosensitive composition tends to have more excellent developability of the alkaline aqueous solution.

<(G) component> The photosensitive composition of this embodiment may contain the component (G): It has at least one selected from the group consisting of an aromatic ring, a heterocyclic ring, and an alicyclic, and has a hydroxymethyl group or alkoxy Alkyl-based compound. Here, the aromatic ring means an aromatic hydrocarbon group (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic ring refers to a cyclic group having at least one nitrogen atom, oxygen atom, sulfur atom or the like (for example, a cyclic group having 3 to 10 carbon atoms), and examples thereof include a pyridine ring, an imidazole ring, and a pyrrolidone ring. , oxazolidinone ring, imidazolidinone ring and pyrimidinone ring. In addition, the alicyclic ring means a cyclic hydrocarbon group which does not have aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), and examples thereof include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane. Alkane ring. The alkoxyalkyl group means a group in which an alkyl group is bonded to an alkyl group via an oxygen atom. Further, the two alkyl groups may be different from each other, and are, for example, an alkyl group having 1 to 10 carbon atoms.

When the photosensitive layer after the formation of the resin pattern is cured by the component (G), the component (G) reacts with the component (F) to form a crosslinked structure, thereby preventing the resin pattern from being weakened and melted. Further, specifically, a compound having a phenolic hydroxyl group (excluding the component (F)) or a compound having a hydroxymethylamino group or an alkoxymethylamino group can be used as a preferred compound.

The "compound having a phenolic hydroxyl group" used as the component (G) has a methylol group or an alkoxymethyl group, and can be used not only as a crosslinking agent but also in an unexposed portion when developing with an aqueous alkaline solution. The dissolution rate is increased to increase the sensitivity. The molecular weight of the phenolic hydroxyl group-containing compound is preferably from 94 to 2,000, more preferably from 108 to 2,000, in terms of weight average molecular weight, in consideration of balance of solubility, photosensitivity, and mechanical properties in an aqueous alkaline solution. And then the best is 108 to 1500. Further, when the compound having a low molecular weight is difficult to be measured by the measurement method of the weight average molecular weight, the molecular weight may be measured by another method, and the average value thereof may be calculated.

The compound having a phenolic hydroxyl group can be a conventionally known compound, and is preferably a compound represented by the following formula (1) because the effect of promoting the dissolution of the unexposed portion and the prevention of melting of the photosensitive composition film during hardening are caused. The balance of the effect is excellent. [Chemical 1] [In the formula (1), Z represents a single bond or a divalent group, and R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent organic group, and R ²⁶ and R ²⁷ each independently represent a monovalent organic group, a and b each independently represents an integer of 1 to 3, and c and d each independently represent an integer of 0 to 3. Here, examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group and a propyl group; an alkenyl group having 2 to 10 carbon atoms such as a vinyl group; and a carbon atom such as a phenyl group. An aryl group having a number of 6 to 30; a group in which a part or all of a hydrogen atom of the hydrocarbon group is substituted with a halogen atom such as a fluorine atom. When there are a plurality of R ²⁴ to R ²⁷ , they may be the same or different from each other]

The compound represented by the formula (1) is preferably a compound represented by the formula (2). [Chemical 2]

In the formula (2), X ¹ represents a single bond or a divalent group, and a plurality of R each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

Further, as the compound having a phenolic hydroxyl group, a compound represented by the formula (3) can also be used. [Chemical 3] In the formula (3), a plurality of R each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

In the formula (1), the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. Further, examples of the divalent group represented by Z include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylidene group and a propyl group, and an alkylene group having 2 to 10 carbon atoms such as an ethylene group. a aryl group having 6 to 30 carbon atoms such as a phenyl group, a group in which a part or all of a hydrogen atom of the hydrocarbon group is substituted with a halogen atom such as a fluorine atom, a sulfonyl group, a carbonyl group, an ether bond, or a thioether bond. , guanamine bond, etc. Among these groups, Z is preferably a divalent group represented by the following formula (4).

[Chemical 4] [In the formula (4), X ² represents a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylene group (for example, an alkylene group having 2 to 10 carbon atoms), Some or all of the hydrogen atoms of the groups are substituted with a halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a thioether bond or a guanamine bond. R ²⁸ represents a hydrogen atom, a hydroxyl group, an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms) or a halogenated alkyl group, and e represents an integer of 1 to 10. The plurality of R ²⁸ and X ² may be the same or different from each other. Here, the halogenated alkyl group means an alkyl group substituted with a halogen atom]

The compound having a hydroxymethylamino group or an alkoxymethylamino group may, for example, be (poly)(N-hydroxymethyl)melamine, (poly)(N-hydroxymethyl)acetyleneurea, (poly)( N-hydroxymethyl)benzoguanamine, (poly)(N-hydroxymethyl)urea, and the like. Further, a nitrogen-containing compound obtained by alkylating all or a part of the hydroxymethylamino group of these compounds may be used. Here, the alkyl group of the alkyl ether may, for example, be a methyl group, an ethyl group, a butyl group or a mixture of such groups, or may contain an oligomer component which is partially self-condensed. Specific examples thereof include hexa(methoxymethyl)melamine, hexakis(butoxymethyl)melamine, tetrakis(methoxymethyl)acetyleneurea, tetrakis(butoxymethyl)acetyleneurea, and tetrakis(methoxy). Methyl) urea and the like.

The compound having an alkoxymethylamino group is specifically preferably a compound represented by the formula (5) or a compound represented by the formula (6). [Chemical 5]

In the formula (5), a plurality of R each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). [Chemical 6] In the formula (6), a plurality of R each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

The content of the component (G) is preferably from 5 parts by mass to 60 parts by mass, more preferably from 10 parts by mass to 45 parts by mass, even more preferably from 10 parts by mass to 35 parts by mass, per 100 parts by mass of the component (F). When the content of the component (G) is 5 parts by mass or more, the crosslinking of the exposed portion is sufficient, so that the resolution is further improved. When the content is 60 parts by mass or less, the photosensitive composition is easily formed on the desired support. The film has a further improved resolution.

<(H) component> The photosensitive composition of this embodiment may contain (H) component: the one which has two or more types selected from a acryloxy group, a methacryloxy group, a glycidyloxy group, and a hydroxyl group. The above functional aliphatic compound. Further, the component (H) may have two or more different functional groups each, and may have two or more functional groups. The compound is preferably an aliphatic compound having three or more of the functional groups. The upper limit of the number of functional groups is not particularly limited and is, for example, 12.

From the viewpoint of the workability in the case where the photosensitive layer is formed on the substrate, the photosensitive composition is also required to have excellent adhesion to the substrate (viscosity). When a photosensitive composition which does not have sufficient adhesiveness is used, the photosensitive layer of the exposed portion is easily removed by the development treatment, and the adhesion between the substrate and the resist pattern tends to be deteriorated. When the photosensitive layer contains the component (H), the adhesion between the photosensitive composition and the substrate, that is, the viscosity tends to increase. Further, the dissolution rate of the exposed portion at the time of development by the alkaline aqueous solution can be increased, and the resolution can be further improved. The molecular weight is preferably from 92 to 2,000, more preferably from 106 to 2,000, still more preferably from 106 to 1,500, even more preferably from 134 to 1300, in terms of weight average molecular weight, from the viewpoint of viscosity and solubility in an aqueous alkaline solution. . Further, when the compound having a low molecular weight is difficult to be measured by the measurement method of the weight average molecular weight, the molecular weight may be measured by another method, and the average value thereof may be calculated.

Specific examples of the component (H) include compounds represented by the formula (7) to the formula (10). In addition, the "aliphatic compound" means a compound whose main skeleton is an aliphatic skeleton and does not contain an aromatic ring or an aromatic hetero ring. [Chemistry 7] [化8] [Chemistry 9] [化10] [11] [化12] [Chemistry 13] In the general formulae (7) to (10), R ¹ , R ⁵ , R ¹⁶ and R ¹⁹ each represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group or a group represented by the formula (11), and R ²¹ represents a hydroxyl group, a glycidoxy group, an acryloxy group or a methacryloxy group, and R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² And R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ²⁰ each represent a hydroxyl group, a glycidoxy group, an acryloxy group, a methacryloxy group, a group represented by the formula (12) or In the group represented by the formula (13), R ²² and R ²³ each represent a hydroxyl group, a glycidoxy group, an acryloxy group or a methacryloxy group, and n and m are each an integer of 1 to 10]

Examples of the compound having a glycidyloxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and neopentyl glycol diglycidyl ether. 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, pentaerythritol tetraglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, propoxylated glycerol Triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, and the like.

Among the compounds having a glycidyloxy group, trishydroxymethylethane triglycidyl ether or trimethylolpropane triglycidyl ether is preferred in terms of sensitivity and resolution.

Compounds having a glycidyloxy group are commercially available, for example, as Epolight 40E, Epolight 100E, Epolight 70P, Epolight 200P, Epolight 1500NP, Epolight 1600, Epolight 80MF, Epolight 100MF (above, manufactured by Kyoei Chemical Co., Ltd., trade name), alkyl type Epoxy resin ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, and Denacol EX-850L (above, manufactured by Nagase Chemtex Co., Ltd., trade name). These glycidoxy group-containing compounds may be used alone or in combination of two or more.

Examples of the compound having an acryloxy group include ethylene oxide (EO) modified dipentaerythritol hexaacrylate, propylene oxide (PO) modified dipentaerythritol hexaacrylate, and dipentaerythritol hexaacrylate. Ester, EO modified di-trimethylolpropane tetraacrylate, PO modified di-trimethylolpropane tetraacrylate, di-trimethylolpropane tetraacrylate, EO modified pentaerythritol tetraacrylate, PO Modified pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, EO modified pentaerythritol triacrylate, PO modified pentaerythritol triacrylate, pentaerythritol triacrylate, EO modified trimethylolpropane acrylate, PO modified trihydroxyl Propane acrylate, trimethylolpropane acrylate, EO modified glycerin triacrylate, PO modified glycerin triacrylate, glycerin triacrylate, and the like. These compounds having an acryloxy group may be used alone or in combination of two or more. EO represents an ethoxy group and PO represents a propoxy group.

Examples of the compound having a methacryloxycarbonyl group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, and EO-modified di-trishydroxyl. Methyl propane tetramethacrylate, PO modified di-trimethylolpropane tetramethacrylate, di-trimethylolpropane tetramethacrylate, EO modified pentaerythritol tetramethacrylate, PO modification Pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, EO modified pentaerythritol trimethacrylate, PO modified pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, EO modified trimethylolpropane Methacrylate, PO modified trimethylolpropane methacrylate, trimethylolpropane methacrylate, EO modified glycerol trimethacrylate, PO modified glyceryl trimethacrylate, glycerol Methacrylate and the like. These compounds having a methacryloxycarbonyl group may be used alone or in combination of two or more. EO represents an ethoxy group and PO represents a propoxy group.

Examples of the compound having a hydroxyl group include polyhydric alcohols such as dipentaerythritol, pentaerythritol, and glycerin. These compounds having a hydroxyl group may be used alone or in combination of two or more.

The functional group of the component (H) is preferably a glycidoxy group, an acryloxy group or a methacryloxy group, more preferably a glycidoxy group or an acrylonitrile group, and further preferably an acryloxy group. Further, from the viewpoint of developability, the component (H) is preferably an aliphatic compound having two or more glycidoxy groups, more preferably an aliphatic compound having three or more glycidoxy groups, and further preferably It is an aliphatic compound having a glycidoxy group having a weight average molecular weight of 1,000 or less.

When the component (H) is contained, the content of the component (H) is preferably 20 parts by mass to 70 parts by mass, more preferably 25 parts by mass to 65 parts by mass, even more preferably 100 parts by mass of the component (F). It is 35 parts by mass to 55 parts by mass. When the content of the component (H) is 20 parts by mass or more, sufficient viscosity can be obtained, and when the amount is 70 parts by mass or less, the photosensitive composition can be easily formed on a desired support, and the resolution can be suppressed. reduce.

<(I) Component> The photosensitive composition of this embodiment may contain the component (I): a photo-sensitive acid generator. The component (I) is a compound which generates an acid by irradiation with an actinic ray or the like, and the (G) component is cross-linked with each other not only by the generated acid but also with the phenolic hydroxyl group of the component (F). The solubility in the developer is drastically lowered. Further, the hydroxyl group in the (G) component or the alkoxyalkyl group or the methylol group or the alkoxyalkyl group in the (G) component is (F) by the catalytic action of the generated acid. The component reacts with the dealcoholation, whereby a negative pattern can be formed.

The component (I) is not particularly limited as long as it is an acid which generates an acid by irradiation with an actinic ray or the like, and examples thereof include an onium salt compound, a halogen-containing compound, a diazoketone compound, an anthraquinone compound, and a sulfonic acid compound. , sulfonium imine compounds, diazomethane compounds, and the like. Specific examples thereof are shown below.

Onium salt compound: The onium salt compound may, for example, be a phosphonium salt, a phosphonium salt, a phosphonium salt, a diazonium salt or a pyridinium salt. Preferable specific examples of the onium salt compound include diphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate, and diphenylsulfonium hexafluorophosphate. a diarylsulfonium salt such as diphenylphosphonium tetrafluoroborate; a triarylsulfonium salt such as triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate or triphenylsulfonium hexafluoroantimonate; Salt; 4-tert-butylphenyl-diphenylfluorene trifluoromethanesulfonate; 4-tert-butylphenyl-diphenylphosphonium p-toluenesulfonate; 4,7-di-n-butoxy Naphthyltetrahydrothiophene trifluoromethanesulfonate and the like.

Sulfonimide compound: Specific examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)butaneimine, N-(trifluoromethylsulfonyloxy) phthalate Formammine, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene- 2,3-dicarboxy quinone imine, N-(trifluoromethylsulfonyloxy)naphthyl quinone imine, N-(p-toluenesulfonyloxy)-1,8-naphthyldimethylimine and N-(10-camphorsulfonyloxy)-1,8-naphthyldimethylimine.

In the present embodiment, the component (I) preferably has a triflate group, a hexafluoroantimonate group, a hexafluorophosphate group or a tetrafluoroborate group in terms of excellent sensitivity and analytical properties. compound of. Further, the component (I) may be used alone or in combination of two or more.

In the case of containing the component (I), the component (I) is further improved in terms of sensitivity, resolution, pattern shape, and the like of the photosensitive composition of the present embodiment. The content is preferably from 0.1 part by mass to 15 parts by mass, more preferably from 0.3 part by mass to 10 parts by mass.

<Solvent> A solvent may be added to the photosensitive composition of the present embodiment in order to improve the handleability of the photosensitive composition or to adjust the viscosity and storage stability. The solvent is preferably an organic solvent. The organic solvent is not particularly limited, and examples thereof include ethylene glycol monomethyl ether acetate such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether and propylene glycol single Propylene glycol monoalkyl ethers such as diethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene glycol monomethyl ether a propylene glycol monoalkyl ether acetate such as an acid ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate or propylene glycol monobutyl ether acetate; a cellosolve such as ethyl cellosolve or butyl cellosolve; Carbitol such as butyl carbitol; lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, and isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate Aliphatic carboxylic acid esters such as ester, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate; 3-methoxypropionic acid Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Other esters such as methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone ; N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone and other guanamines; γ-butyrolactone Esters. These organic solvents may be used alone or in combination of two or more.

The content of the solvent is preferably from 30 parts by mass to 200 parts by mass, more preferably from 60 parts by mass to 120 parts by mass, per 100 parts by mass of the total amount of the photosensitive composition excluding the solvent.

[Method of Forming Resist Pattern] Next, a method of forming the resist pattern of the present embodiment will be described.

First, a substrate (a copper foil with a resin, a copper clad laminate, a tantalum wafer with a metal sputter film, an alumina substrate, etc.) on which a resist is to be formed is laminated in such a manner that the photosensitive layer is in contact with the substrate. The dry film having the non-photosensitive layer and the photosensitive layer. Thus, a laminate in which a substrate and a photosensitive layer and a non-photosensitive layer are formed on the substrate in this order can be formed. Further, in the laminate, the photosensitive composition may be applied onto a substrate to form a photosensitive layer, and then the resin composition may be applied onto the photosensitive layer to form a non-photosensitive layer. Further, when the photosensitive composition contains a solvent, the applied photosensitive composition may be dried to form a photosensitive layer. Further, when the resin composition contains a solvent, the applied resin composition may be dried to form a non-photosensitive layer.

Then, the photosensitive layer is exposed in a predetermined pattern by a predetermined mask pattern. Examples of the radiation used for the exposure include ultraviolet rays, electron beams, and laser rays of a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a g-ray stepper, an i-ray stepper, and the like, and the exposure amount is based on the light source used. The thickness of the photosensitive layer, the thickness of the non-photosensitive layer, the transmittance of the non-photosensitive layer, and the like are appropriately selected, for example, when the ultraviolet ray is irradiated from the high-pressure mercury lamp, and when the thickness of the photosensitive layer is 10 μm to 50 μm, The exposure amount is about 100 mJ/cm ² to 5000 mJ/cm ² . Further, in the case of using the dry film of the present embodiment, the photosensitive layer is exposed by irradiating the non-photosensitive layer with radiation. Further, when the support exhibits light-shielding properties to the actinic rays, the actinic rays are irradiated after the support is removed.

Further, heat treatment (post-exposure baking) is performed after the exposure as needed. By performing post-exposure baking, it is possible to promote the hardening reaction using the (F) component and the (G) component of the generated acid. The preferred range of the photosensitive composition varies depending on the composition of the photosensitive composition, the thickness of the photosensitive layer, etc., and is usually preferably heated at 60 to 150 ° C for 1 minute to 60 minutes, more preferably 70 to 100 minutes. Heat at °C for about 1 minute to 60 minutes.

Then, the photosensitive layer subjected to the post-exposure baking is developed by an alkaline developing solution, and the region other than the photocured portion of the photosensitive layer (unexposed portion) is dissolved and removed. The developing method in this case may, for example, be a spray method, a high pressure spray method, a dipping method, a liquid coating method or the like, and is preferably a high pressure spray method. On the other hand, the non-photosensitive layer has a lower solubility in a developing solution than a photosensitive layer, and also lacks a change in solubility of an exposed portion. Therefore, a resin pattern of a clear non-photosensitive layer such as a photosensitive layer is not formed, or a resin pattern is not formed at all. The development conditions are usually from 20 ° C to 40 ° C and from about 1 minute to 10 minutes. In the laminate of the present embodiment, as shown in FIG. 3, the unexposed portion of the photosensitive layer is eluted to rupture the non-photosensitive layer on the unexposed portion, and a hole penetrating the photosensitive layer and the non-photosensitive layer is formed.

The alkaline developing solution is, for example, a basic compound such as sodium hydroxide, potassium hydroxide, aqueous ammonia, tetramethylammonium hydroxide or choline dissolved in water at a concentration of about 1% by mass to 10% by mass. An alkaline aqueous solution. In the alkaline aqueous solution, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. Further, after development with an alkaline developing solution, it was washed with water and dried. In terms of excellent analytical properties, the alkaline developing solution is preferably tetramethylammonium hydroxide.

Further, in order to exhibit the properties of the insulating film, in order to improve the resolution, heat treatment is performed to obtain a cured film (resist pattern). The curing conditions at this time are not particularly limited, and the photosensitive composition can be cured by heating at 50 ° C to 250 ° C for 30 minutes to 10 hours depending on the use of the cured product.

Further, in order to sufficiently carry out the hardening or to prevent deformation of the obtained pattern shape, it is also possible to perform heating in two stages. For example, in the first stage, it may be heated at 50 to 120 ° C for 5 minutes to 2 hours, and further heated in the second stage at 80 to 200 ° C for 10 minutes to 10 hours to be cured.

As long as it is such a hardening condition, an oven, an infrared furnace or the like which is usually used as a heating device can be used. In the laminate of the present embodiment, by performing heat treatment after development, as shown in FIG. 4, the ruptured non-photosensitive layer is welded to the wall surface of the hole to form a channel. Further, in the case where the non-photosensitive layer is broken in the same shape as the shape of the hole, the non-photosensitive layer may not necessarily be welded to the wall surface of the hole.

The method for forming the circuit is not particularly limited, and a photosensitive layer and a non-photosensitive layer are formed on the inner layer circuit, and an outer layer circuit is formed on the non-photosensitive layer by a plating method. When forming the outer layer circuit, it is preferred to first roughen the non-photosensitive layer. As the roughening liquid, an oxidizing roughening liquid such as a chromium/sulfuric acid roughening liquid, an alkaline permanganic acid roughening liquid, a sodium fluoride/chromium/sulfuric acid roughening liquid, or a fluoroboric acid roughening liquid can be used. For the roughening treatment, for example, first, an aqueous solution of diethylene glycol monobutyl ether and NaOH as a swelling liquid is heated to 80 ° C, and the laminate or multilayer wiring board is immersed for 5 minutes. Then, an aqueous solution of KMnO ₄ and NaOH as a roughening solution was heated to 80 ° C, and immersed for 10 minutes. Then, immersion treatment was carried out for 5 minutes at room temperature in a neutralized liquid, for example, a solution of stannous chloride (SnCl ₂ ) in hydrochloric acid to reduce KMnO ₄ .

After the roughening treatment, a plating catalyst application treatment for adhering palladium is performed. The plating catalyst treatment is carried out by immersing in a palladium chloride-based plating catalyst liquid. Then, an electroless plating layer (conductor layer) having a thickness of 0.1 μm to 1.5 μm is deposited on the entire surface of the non-photosensitive layer by immersion in an electroless plating solution. Further plating is performed as necessary to set the necessary thickness. A known electroless plating solution can be used for the electroless plating solution used for the electroless plating, and is not particularly limited. Further, a known method can be used for the plating, and is not particularly limited. The plating is preferably copper plating. Further, an unnecessary portion can be removed by etching to form a circuit layer. Further, a multilayer wiring board having a large number of layers can be produced by repeating the same steps.

Further, the roughening treatment may be performed in order to remove the smear of the channel.

[Multilayer printed wiring board] The cured product formed of the resin composition and the photosensitive composition of the present embodiment can be preferably used as a surface protective film (overcoat film) and/or an interlayer insulating film of a semiconductor element, for example. Passivation film), or a solder resist of a multilayer printed wiring board and/or an interlayer insulating layer. Among them, since it is excellent in adhesion to copper plating, it can be preferably used as an interlayer insulating layer. (a) to (f) of FIG. 2 are views showing a method of manufacturing a multilayer printed wiring board including a cured resin composition of the present embodiment and a cured product of the photosensitive composition as an interlayer insulating material. The multilayer printed wiring board 100A shown in Fig. 2(f) has a wiring pattern on the surface and inside. Hereinafter, a method of manufacturing the multilayer printed wiring board 100A according to the embodiment of the present invention will be briefly described with reference to Fig. 2 .

First, an interlayer insulating layer 103 is formed on both surfaces of a substrate 101 on which a wiring pattern 102 is formed (see FIG. 2(a)). The dry film can be prepared in advance, and the photosensitive layer and the non-photosensitive layer of the dry film are attached to the printed wiring board by a laminator to form an interlayer insulating layer 103. Alternatively, instead of using a dry film, the photosensitive composition may be coated on the substrate to form a photosensitive layer, and then the resin composition may be coated on the photosensitive layer to form a non-photosensitive layer, thereby forming interlayer insulation. Layer 103. Further, the photosensitive composition or the resin composition may be dried. Further, in FIG. 2, the interlayer insulating layer 103 is represented as a single layer for the sake of simplicity, but is substantially divided into two layers of a photosensitive layer and a non-photosensitive layer.

Then, an area other than the portion to be electrically connected to the outside is exposed, and development processing is performed, followed by heat treatment to form the opening 104 (see FIG. 2(b)). The slag (residue) around the opening 104 is removed by degreasing treatment. Then, the seed layer 105 is formed by electroless plating (see FIG. 2(c)). A photosensitive layer of a semi-additive photosensitive element is formed on the seed layer 105, and a predetermined portion is exposed and developed to form a resin pattern 106 (see FIG. 2(d)). Then, the wiring pattern 107 is formed on the portion of the seed layer 105 where the resin pattern 106 is not formed by electroplating, and after the resin pattern 106 is removed by the stripping liquid, the wiring of the seed layer 105 is not formed by etching. Part of the pattern 107 is removed (see Fig. 2(e)). By repeating the above operation, the solder resist 108 is formed on the outermost surface, whereby the multilayer printed wiring board 100A can be produced (see FIG. 2(f)).

The multilayer printed wiring board 100A thus obtained can mount a semiconductor element at a corresponding portion to ensure electrical connection.

(Second embodiment) Hereinafter, a second embodiment of the present invention will be described. The dry film of the second embodiment is a dry film including a photosensitive layer and a non-photosensitive layer, and has a function of sequentially forming a photosensitive layer and a non-photosensitive layer on a substrate, exposing the photosensitive layer, and developing the dry film. Thereby, the unexposed portion of the photosensitive layer is eluted to rupture the non-photosensitive layer on the unexposed portion, and a channel can be formed at a portion where the non-photosensitive layer is broken by heat treatment after development.

Here, in the dry film of the present embodiment, for example, a photosensitive layer and a non-photosensitive layer are sequentially formed on a substrate, and the photosensitive layer is exposed in a predetermined pattern by the above method to correspond to the shortest development time (will 2 times of the shortest time of removal of the unexposed portion of the photosensitive layer), the non-photosensitive layer and the photosensitive layer were sprayed using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, whereby the photosensitive layer was formed as shown in FIG. The unexposed portion is eluted to rupture the non-photosensitive layer on the unexposed portion. In the developed dry film, pores penetrating the photosensitive layer and the non-photosensitive layer are formed. Further, the development described herein can also be carried out by a method other than the spraying method. Alternatively, the exposed photosensitive layer may be subjected to heat treatment prior to development of the dry film. The post-exposure heat treatment is preferably the same as the conditions of the post-exposure heat treatment of the first embodiment.

Thereafter, the developed dry film is subjected to heat treatment, whereby as shown in Fig. 4, the cracked non-photosensitive layer is welded to the wall surface of the hole to form a channel. The heat treatment can be carried out, for example, at a temperature of from 50 ° C to 250 ° C for about 30 minutes to 10 hours, or in the first stage at 50 ° C to 120 ° C for 5 minutes to 2 hours, and further to the second. In the stage, it is heated at 80 ° C to 200 ° C in two stages of about 10 minutes to 10 hours.

The non-photosensitive layer and the photosensitive layer of the dry film of the present embodiment are not particularly limited as long as they have the above functions, and examples thereof include the photosensitive layer and the non-photosensitive layer described in the first embodiment. Further, by using the dry film of the present embodiment, the resist pattern and the multilayer printed wiring board can be formed by the above method. Further, when the photosensitive layer is a positive type, the exposed portion of the photosensitive layer is eluted and the non-photosensitive layer on the exposed portion is broken, and by the heat treatment after development, a channel can be formed at a portion where the non-photosensitive layer is broken. [Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples. In addition, the parts in the following examples and comparative examples are used in the meaning of the mass part unless otherwise indicated.

<Examples A1 to A13 and Comparative Examples A1 to A15> (Synthesis Example A1) Synthesis of Polyamine A First, a Dean-Stark reflux condenser, a thermometer, and a stirring were provided. In a 1 L separable flask, 22 g (132 mmol) of isophthalic acid, 26.4 g (132 mmol) of 3,4'-oxydiphenylamine, 3.9 g of lithium chloride, 12.1 g were added. Calcium chloride, 240 ml of N-methyl-2-pyrrolidone and 54 ml of pyridine were dissolved and dissolved, and then 74 g of triphenyl phosphite was added and reacted at 90 ° C for 4 hours to obtain polyfluorene. A solution of an amine resin. This solution was poured into 20 L of methanol to precipitate a polyamide resin, thereby obtaining polyamine A.

(Synthesis Example A2) Synthesis of Polyamidiamine A. First, 45 mmol of saturated fat was added to a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer and a stirrer. (4,4'-diamino)dicyclohexylmethane of a cyclic hydrocarbon-based diamine compound A (Wandamin HM (WHM), manufactured by Nippon Chemical and Chemical Co., Ltd., trade name), 5 mmol as a helium oxygen Alkyldiamine compound B is a reactive eucalyptus oil (X-22-161-B, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent: 1500, trade name), 105 mmol of trimellitic anhydride (TMA), and 145 g as an aprotic N-methyl-2-pyrrolidone (NMP) in a polar solvent, after setting the temperature in the flask to 80 ° C and stirring for 30 minutes, further adding 100 mL of toluene as an aromatic hydrocarbon azeotropeable with water The temperature in the flask was raised to 160 ° C and refluxed for about 2 hours. The theoretical amount of water was stored in the moisture quantitative receiver, and it was confirmed that the water in the water quantitative meter was removed while the water was not distilled off, and the temperature in the flask was raised to 190 ° C to be in the reaction solution. Toluene removal. After returning the solution in the flask to room temperature, 60 mmol of 4,4'-diphenylmethane diisocyanate (MDI) as a diisocyanate was added, and the temperature in the flask was raised to 190 ° C and reacted for 2 hours. NMP was diluted to obtain a solution of polyamidoquinone in NMP. The NMP solution was poured into 20 L of methanol to precipitate a polyamidoximine resin to obtain a polyamidoximine A.

[Preparation of a solution (varnish) for forming a resin composition of a non-photosensitive layer] (varnish aI) 15.9 g of N was formulated in 1.8 g of the polyamidamine A obtained in Synthesis Example A1 as the component (C), After N-dimethylacetamide (DMAc), 5.0 g of a biphenyl aralkyl type epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd., trade name) and 2.1 as (A) component were added. a cresol novolac type phenol resin (KA1165, manufactured by Dianesei Co., Ltd., trade name) as a component (B-1), and further added 0.050 g of 2-phenylimidazole as a hardening accelerator ( 2PZ, manufactured by Shikoku Chemicals Co., Ltd., trade name), diluted with a mixed solvent containing DMAc and methyl ethyl ketone, and added 0.50 g of inorganic filler (D) as component (D) (AEROSIL) R972, manufactured by AEROSIL JAPAN Co., Ltd., trade name), obtained a varnish aI using a disperser (nine pulverizer, manufactured by Yoshida Machinery Co., Ltd., trade name) (solid content concentration is about 25 quality%).

(Varnish a-II) A varnish a-II was obtained by the same method as the varnish a-I except that the component (D) of the varnish a-I was removed.

(Varnish a-III) In a 1.8 g phenolic hydroxyl group-containing polyamine (BPAM-155, manufactured by Nippon Kayaku Co., Ltd., trade name), 15.9 g of N, N-di After methyl acetamide (DMAc), 5.0 g of a biphenyl aralkyl type epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd., trade name) and 2.1 g of (A) component were added. (B-1) component cresol novolac type phenol resin (KA1165, manufactured by Di Ai Sheng (DIC) Co., Ltd., trade name), and further added 0.050 g of 2-phenylimidazole (2PZ, four as a hardening accelerator) Manufactured by Guohuacheng Industrial Co., Ltd., trade name), diluted with a mixed solvent containing DMAc and methyl ethyl ketone, and then added 0.50 g of an inorganic filler as component (D) (AEROSIL R202, Japan) Manufactured by AEROSIL JAPAN Co., Ltd., trade name), using a dispersing machine (nine pulverizer, manufactured by Yoshida Machinery Co., Ltd., trade name) to obtain varnish a-III (solid content concentration is about 25 mass) %).

(varnish a-IV) In a 1.8 g phenolic hydroxyl group-containing polyamine (BPAM-155, manufactured by Nippon Kayaku Co., Ltd., trade name), 15.9 g of N, N-di After methyl acetamide (DMAc), 0.27 g of a crosslinked organic filler (EXL-2655, manufactured by Rohm & Haas Japan Co., Ltd., trade name) and 5.0 g (5.0) were added. Biphenyl aralkyl type epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd.), and 2.0 g of bisphenol A novolac type phenol resin (YLH129, oily) as component (B-1) Manufactured by Shell Epoxy Co., Ltd., and further added 0.050 g of 2-phenylimidazole (2PZ, manufactured by Shikoku Chemicals Co., Ltd., trade name) as a hardening accelerator to contain DMAc and methyl ethyl ketone. After diluting the mixed solvent, 0.52 g of an inorganic filler (AEROSIL R202, manufactured by AEROSIL JAPAN Co., Ltd., trade name) was added as a component (D), and a dispersing machine was used ( Nano crusher, Yoshida Machinery Industrial Co., Ltd. The company manufactured, trade name) obtained varnish a-IV (solid content concentration was about 25% by mass).

(varnish aV) After dissolving 1.3 g of N,N-dimethylacetamide (DMAc) in 0.30 g of the polyamidoximine A obtained in Synthesis Example A2 as the component (C), 0.96 was added thereto. g crosslinked organic filler (EXL-2655, manufactured by Rohm & Haas Japan Co., Ltd., trade name), 5.0 g of phenol novolac type epoxy resin (N770, as component (A) A phenol novolac type phenol resin (trade name) manufactured by Aisheng (DIC) Co., Ltd. and 2.8 g as a component (B-1) (TD2090, manufactured by Dianesei Co., Ltd., trade name), and further added 0.050 g After 2-phenylimidazole (2PZ, manufactured by Shikoku Chemicals Co., Ltd., trade name), which is a hardening accelerator, it is diluted with a mixed solvent containing DMAc and methyl ethyl ketone, and 0.54 g is added as (D). Inorganic filler of the composition (AEROSIL R972, manufactured by AEROSIL JAPAN Co., Ltd., trade name), using a dispersing machine (nine pulverizer, manufactured by Yoshida Machinery Co., Ltd., Name) get varnish aV The solid content of about 25% by mass).

(varnish a-VI) 49 g of polyamido A and 0.15 g of 1-cyanoethyl-2-phenylimidazolium trimellitate (manufactured by Shikoku Chemical Industry Co., Ltd., trade name "2PZ" -CNS") was dissolved in 40 g of methyl ethyl ketone as a solvent to obtain varnish a-VI.

(varnish a-VII) Dissolve 49 g of polyamido A and 27 g of ester-containing resin (Dioxin (DIC) Co., Ltd., trade name "EXB-9460S", ester equivalent: 223) in 40 g In the methyl ethyl ketone as a solvent, varnish a-VII was obtained.

<Preparation of a solution (varnish) of a photosensitive composition> The alkoxy alkane is adjusted to the quantity (unit: parts by mass) shown in Table 1 with respect to 100 mass parts of the novolak resin (F-1 - F-2). A basal compound (G-1), a compound having a glycidoxy group or a propylene oxy group (H-1 to H-3), a photo-sensitive acid generator (I-1), and a solvent to obtain a varnish bI-varnish bV . [Table 1]

F-1: cresol novolac resin (manufactured by Asahi Organic Materials Co., Ltd., trade name; TR4020G) F-2: cresol novolak resin (manufactured by Asahi Organic Materials Co., Ltd., trade name; TR4080G) G- 1:1,3,4,6-tetrakis(methoxymethyl)acetylene urea (manufactured by Sanwa Chemical Co., Ltd., trade name "MX-270") H-1: trimethylolpropane Triglycidyl ether (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name: ZX-1542, refer to the following formula (3))

[Chemistry 14]

H-2: Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: TMPTA) H-3: pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: PET-30) I-1: Triarylsulfonium salt (manufactured by San-Apro Co., Ltd., trade name: CPI-310B) Solvent: methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) D'-1: Sol-gel cerium oxide with a mean primary particle size of 15 nm coupled by 3-methylpropenyloxypropyltrimethoxydecane

<Preparation of dry film> The solution of the obtained resin composition for forming a non-photosensitive layer was applied to a polyethylene terephthalate film in a uniform thickness (Teijin-Dupont Film) ) manufactured by the company, the product name "Purex A53" (support), dried by a hot air convection dryer at 100 ° C ~ 140 ° C for 10 minutes, the film thickness after drying becomes Table 2 A non-photosensitive layer was formed in a manner as shown in Table 3. Then, the solution of the obtained photosensitive composition was applied to the non-photosensitive layer so that the thickness thereof became uniform, and dried by a hot air convection dryer at 90° C. for 10 minutes, and the film thickness after drying was Table 2 and The photosensitive layer was formed in the manner shown in Table 3. A polypropylene film (manufactured by Tamapoly Co., Ltd., product name "NF-15") (protective layer) was attached to the photosensitive layer to obtain a dry film. The composition of the produced dry film is shown in Table 2 and Table 3. Further, in Table 2, Example A1 is that the following dry film was formed on a support, and the dry film was sequentially provided with a non-photosensitive layer (thickness: 0.5 μm) formed using varnish aI, and sensitized by using varnish bI. Layer (thickness: 10 μm) and protective layer. In the other examples and comparative examples, a dry film was also prepared using a solution of the corresponding resin composition.

<Preparation of laminated body for evaluation> The protective layer of the dry film was peeled off, and the protective layer was peeled off while the photosensitive layer was in contact with the surface of the crucible of the 6-inch wafer. The lamination is a continuous pressure vacuum laminator (manufactured by Nago Seisakusho Co., Ltd., trade name "MVLP-500"), with a crimping pressure of 0.4 MPa, a hot plate temperature of 90 ° C, and a vacuum suction time of 20 seconds. The lamination press time was 20 seconds and the gas pressure was 4 kPa or less. Then, the support was peeled off to obtain a laminate for evaluation.

<Evaluation of Analytical Property> The laminate for evaluation produced by the above method was exposed. At the time of exposure, an i-ray stepper (manufactured by Canon Co., Ltd., trade name "FPA-3000iW") was used to reduce the projection exposure with an i-ray (365 nm) barrier. The mask is a mask having a channel pattern size z μmf (z=8, 10, 15, 20, 30, 40, 50, 60, 70). Further, while reducing the exposure amount in the range of 100 mJ/cm ² to 3000 mJ/cm ² in units of 100 mJ/cm ² , the reduction projection exposure is performed.

Then, the exposed photosensitive layer was heated at 65 ° C for 1 minute, followed by heating at 75 ° C for 8 minutes (baked after exposure), using a 2.38 mass % aqueous solution of tetramethylammonium hydroxide to correspond to the shortest development time (will Spraying is performed twice as long as the shortest time of removal of the unexposed portion of the photosensitive layer, whereby the unexposed portion of the photosensitive layer is removed (developing treatment). After the development treatment, heat treatment was performed at 180 ° C for 60 minutes. After the heat treatment, the formed channel pattern was observed using a metal microscope, and the resolution was evaluated with a minimum channel pattern size. The evaluation results are shown in Table 2 and Table 3. Further, scanning electron microscope (SEM) photographs of the channels after the development treatment and the heat treatment in Example A3 are shown in FIGS. 3 and 4, respectively. As shown in FIG. 3, when the unexposed portion of the photosensitive layer is removed by development, the non-photosensitive layer on the unexposed portion is broken, and a hole penetrating the developed photosensitive layer and the non-photosensitive layer is formed. Further, as shown in FIG. 4, when heat treatment is performed after development, the rupture portion of the non-photosensitive layer shown in FIG. 3 is welded to the wall surface of the hole to form a channel. Further, in the case of Comparative Example A14 and Comparative Example 15 in which a non-photosensitive layer containing varnish a-VI to varnish a-VII was used, it was sprayed for 120 seconds, followed by heat treatment, but the non-photosensitive layer was not broken and could not be obtained. Form a channel. Further, development was carried out by using a nozzle of a developing machine using a full cone type and spraying at a pressure of 0.15 MPa. The distance between the laminated body and the tip end of the nozzle was 6 cm, and the center of the test piece was arranged to coincide with the center of the nozzle.

<Evaluation of Strength (Peel Strength) and Surface Roughness> The laminate for evaluation produced by the above method was exposed. At the time of exposure, an exposure machine having a high-pressure mercury lamp (manufactured by ORC Manufacturing Co., Ltd., trade name "EXM-1201") was used, and the amount of irradiation energy was 3,000 mJ/cm ² for the non-photosensitive layer or the photosensitive layer. Exposure. The exposed laminate for evaluation was heated on a hot plate at 65 ° C for 2 minutes, followed by heating at 95 ° C for 8 minutes (bake after exposure). Further, the film was heat-treated at 180 ° C for 60 minutes using a hot air convection dryer to obtain a cured film.

Then, in order to carry out chemical coarsening, an aqueous solution of diethylene glycol monobutyl ether of 200 ml/L and sodium hydroxide of 5 g/L was prepared as a swelling liquid, and the mixture was heated to 80 ° C and immersed for 10 minutes. Then, an aqueous solution of potassium permanganate of 60 g/L and sodium hydroxide of 40 g/L was prepared as a roughening liquid, and the mixture was heated to 80 ° C and immersed for 15 minutes. Then, an aqueous solution of a neutralizing liquid (tin (SnCl ₂ ): 30 g/L, hydrogen chloride: 300 ml/L) was prepared, and the mixture was heated to 40 ° C and immersed for 5 minutes to reduce potassium permanganate.

The surface of the chemically roughened insulating resin was measured using a Micromap Model MN5000 manufactured by Ryoka System Co., Ltd. (a non-photosensitive layer after heat treatment (a photosensitive layer in the absence of a non-photosensitive layer) )) Surface roughness Ra. The evaluation results are shown in Table 2 and Table 3.

In order to form a conductor layer on the surface of the hardened insulating resin, Neoganth 834 (Atotech Japan), a catalyst activator for electroless plating containing lead chloride (PdCl ₂ ), was first used. The company's manufacture, trade name) is heated to 35 ° C and immersed for 5 minutes, in the plating solution for electroless copper, Print Gant MSK-DK (manufactured by Atotech Japan Co., Ltd., trade name) The copper sulfate plating was further carried out by immersing for 15 minutes at room temperature. Thereafter, annealing was performed at 180 ° C for 60 minutes to form a conductor layer having a thickness of 20 μm. A region having a width of 10 mm and a length of 50 mm was formed in the conductor layer by etching, and one end of the region was peeled off by 10 mm at the interface of the conductor layer (copper layer) and the hardened insulating resin. Then, the peeled conductor layer was sandwiched by a jig, and the load (peel strength) at the time of peeling at room temperature at a tensile speed of 50 mm/min along the thickness direction (vertical direction) of the tantalum wafer was measured. The evaluation results are shown in Table 2 and Table 3. In addition, in this specification, the room temperature shows 25 degreeC.

[Table 2]

[table 3]

As shown in Table 2, Examples A1 to A13 have good analytical properties and exhibit a peel strength of up to 0.3 kN/m or more. On the other hand, it was found that the peeling strengths of Comparative Examples A1 to A5 were lower than those of the Examples, and the resolutions of Comparative Examples A6 to A15 were inferior.

<Examples B1 to B8, Comparative Example B1 to Comparative Example B7> (Synthesis Example B1) Synthesis of epoxy resin In a flask equipped with a thermometer and a stirrer, 228 g (1.00 mol) of bisphenol A and 92 g (0.85 mol) of 1,6-hexanediol divinyl ether, after heating to 120 ° C for 1 hour, and further reacting at 120 ° C for 6 hours to obtain 400 g of transparent semi-solid modified polyphenols . Then, 400 g of the modified polyhydric phenol and 925 g (10 mol) of epichlorohydrin were dissolved in 185 g of n-butanol in a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer. in. Thereafter, the mixture was heated to 65 ° C while being purged with nitrogen, and then the pressure was reduced to azeotropic pressure, and 122 g (1.5 mol) of a 49% by mass aqueous sodium hydroxide solution was added dropwise over 5 hours. Then, the mixture was stirred under the same conditions (65 ° C, azeotropic pressure) for 0.5 hour. During this period, the distillate fraction distilled by azeotropy was separated by a Dean-Stark trap, and the aqueous layer was removed to return the organic layer to the reaction system. reaction. Thereafter, unreacted epichlorohydrin was distilled under reduced pressure and distilled to obtain a crude epoxy resin. To the obtained crude epoxy resin, 1000 g of methyl isobutyl ketone and 100 g of n-butanol were added and dissolved. 20 g of a 10% by mass aqueous sodium hydroxide solution was added to the obtained solution, and the mixture was reacted at 80 ° C for 2 hours, and then washed three times with 300 g of water. After washing 3 times, it was confirmed that the pH of the washing liquid was neutral. Then, the system was dehydrated by azeotropy, and the solvent was distilled off under reduced pressure after microfiltration to obtain 457 g of a transparent liquid epoxy resin A-1. The epoxy equivalent is 403.

<Preparation of Solution (Varnish) of Resin Composition> (Preparation Example 1) 24.2 g of epoxy resin A-1 as component (A) and 17.4 g of a biphenyl aralkyl type ring as component (A) Oxygen resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 290), 0.3 g of 1-cyanoethyl-2-phenylimidazolium trimellitate as component (B-2) Ester-containing resin (manufactured by Chemical Industry Co., Ltd., trade name "2PZ-CNS") and 27 g (E) component (Di-Aisheng (DIC) Co., Ltd., trade name "EXB-9460S", ester equivalent : 223) Dissolved in 40 g of methyl ethyl ketone as a solvent to obtain a varnish cI.

(Preparation Example 2) 49 g of epoxy resin A-1 as component (A) and 0.15 g of 1-cyanoethyl-2-phenylimidazolium trimellitic acid as component (B-2) Salt (manufactured by Shikoku Chemical Industry Co., Ltd., trade name "2PZ-CNS") and 27 g of ester-containing resin as component (E) (Di-Aisheng (DIC) Co., Ltd., trade name "EXB-9460S" The ester equivalent: 223) was dissolved in 40 g of methyl ethyl ketone as a solvent to obtain a varnish c-II.

(Preparation Example 3) Further, 0.25 g of cerium oxide (D) as a component (D) (manufactured by AEROSIL JAPAN Co., Ltd., trade name "AEROSIL R202", primary particle diameter) was added. The average value of the varnish c- was obtained by the same operation as in Preparation Example 1 except that the dispersion was carried out using a disperser (manufactured by Yoshida Machinery Co., Ltd., trade name "Nano Crusher"). III.

<Preparation of a solution (varnish) of a photosensitive composition> The alkoxyalkyl group is adjusted to the quantity (unit: mass part) shown in Table 4 with respect to 100 mass parts of the novolak resin (F-1 - F-2). Base compound (G-1), compound having glycidoxy group or propylene methoxy group (H-1, H-3), photo-sensitive acid generator (I-1), solvent (methyl ethyl ketone) And inorganic filler (D'-1), obtaining varnish dI ~ varnish d-III.

[Table 4]

<Production of dry film 1: Example B1 to Example B7 and Comparative Example B1 to Comparative Example B6> The solution of the obtained resin composition was applied to polyethylene terephthalate in a uniform thickness. The membrane (manufactured by Unitica Co., Ltd.), product name "TR-1" (support), was dried by a hot air convection dryer at 100 ° C to 140 ° C for 10 minutes to dry the film. The non-photosensitive layer was formed in such a manner that the thickness became 0.5 μm, 1 μm, and 1.5 μm. Then, the solution of the obtained photosensitive composition was applied to the non-photosensitive layer so as to have a uniform thickness, and dried by a hot air convection dryer at 90 ° C for 10 minutes to form a dried film on the non-photosensitive layer. A photosensitive layer with a thickness of 10 μm. A polypropylene film (manufactured by Tamapoly Co., Ltd., product name "NF-15") (protective layer) was attached to the photosensitive layer to obtain a dry film. The composition of the produced dry film is shown in Table 5. Further, in Table 5, for example, Example B1 means that a dry film having a non-photosensitive layer (thickness: 1 μm) formed by using varnish cI and sensitized by using varnish dI is formed on the support. Layer (thickness: 10 μm) and protective layer. In the other examples and comparative examples, a dry film was also prepared by using a solution of the corresponding resin composition and/or a solution of the photosensitive composition.

<Preparation of laminated body for evaluation> The protective layer of the dry film was peeled off, and the photosensitive layer was laminated so as to be in contact with the surface of the crucible of the 6-inch silicon wafer. Lamination is performed using a continuous pressure vacuum laminator (manufactured by Nago Seisakusho Co., Ltd., trade name "MVLP-500") at a pressure of 0.4 MPa, a hot plate temperature of 90 ° C, and a vacuum suction time of 30 seconds. The lamination press time was 40 seconds and the gas pressure was 4 kPa or less. Then, the support was peeled off to obtain a laminate for evaluation.

<Evaluation of Analytical Property> The laminate for evaluation produced by the above method was exposed. At the time of exposure, an i-ray stepper (manufactured by Canon Co., Ltd., trade name "FPA-3000iW") was used to reduce the projection exposure with an i-ray (365 nm) barrier. The mask is a mask having a channel pattern size z μmf (z = 20, 30, 80). Further, while reducing the exposure amount in the range of 100 mJ/cm ² to 3000 mJ/cm ² in units of 100 mJ/cm ² , the reduction projection exposure is performed.

Then, the exposed photosensitive layer was heated at 75 ° C for 8 minutes (baked after exposure), using a 2.38 mass % aqueous solution of tetramethylammonium hydroxide to correspond to the shortest development time (the shortest removal of the unexposed portion of the photosensitive layer) The spraying was performed four times as long as the time, thereby removing the unexposed portion of the photosensitive layer (developing treatment). After the development treatment, heat treatment was performed at 180 ° C for 60 minutes using a hot air convection dryer. After the heat treatment, the formed channel pattern was observed using a metal microscope. The case where the channel pattern of 20 μmf was opened including the non-photosensitive layer was evaluated as "A", the case where the channel pattern of 30 μmf was opened was evaluated as "B", and the case where the channel pattern of 80 μmf was opened was evaluated as " C", the case where the opening is not performed is evaluated as "D". The evaluation results are shown in Table 5. Further, scanning electron microscope (SEM) photographs of the channels after the development treatment and the heat treatment in Example B6 are shown in Figs. 5 and 6, respectively. As shown in FIG. 5, when the unexposed portion of the photosensitive layer is removed by development, the non-photosensitive layer on the unexposed portion is broken, and a hole penetrating the developed photosensitive layer and the non-photosensitive layer is formed. Further, as shown in FIG. 6, when heat treatment is performed after development, the rupture portion of the non-photosensitive layer shown in FIG. 5 is welded to the wall surface of the hole to form a channel. Further, regarding development, the nozzle of the developing machine was sprayed at a pressure of 0.15 MPa using a full taper type. The distance between the test piece and the tip end of the nozzle was 6 cm, and the center of the test piece was arranged to coincide with the center of the nozzle.

<Evaluation of the bonding strength (peeling strength) after chemical roughening> For the evaluation laminated body produced by the above method, in order to carry out chemical roughening, diethylene glycol monobutyl ether was prepared to be 200 ml/L, sodium hydroxide A 5 g/L aqueous solution was used as the swelling liquid, and the mixture was heated to 70 ° C and immersed for 10 minutes. Then, an aqueous solution of potassium permanganate of 60 g/L and sodium hydroxide of 40 g/L was prepared as a roughening liquid, and the mixture was heated to 70 ° C and immersed for 5 minutes. Then, an aqueous solution of a neutralizing liquid (tin (SnCl ₂ ): 30 g/L, hydrogen chloride: 300 ml/L) was prepared, and the mixture was heated to 40 ° C and immersed for 5 minutes to reduce potassium permanganate.

The pretreatment of the electroless plating was carried out in a conditioning liquid "CLC-601" (manufactured by Hitachi Chemical Co., Ltd., trade name) at 60 ° C for 5 minutes, and then washed with water in the prepreg "PD-201" ( Immersed at room temperature for 2 minutes in a product manufactured by Hitachi Chemical Co., Ltd., trade name. Then, it was immersed in an electroless plating catalyst "HS-202B" (manufactured by Hitachi Chemical Co., Ltd., trade name) containing lead chloride (PdCl ₂ ) for 10 minutes at room temperature, and then washed with water. The electroless copper plating solution "CUST-201 plating liquid" (manufactured by Hitachi Chemical Co., Ltd., trade name) was immersed at room temperature for 15 minutes to further perform copper sulfate plating. Thereafter, annealing was performed at 180 ° C for 60 minutes to form a conductor layer having a thickness of 20 μm. A region having a width of 10 mm and a length of 50 mm was formed in the conductor layer by etching, and one end of the region was peeled off by 10 mm at the interface of the conductor layer (copper layer) and the hardened insulating resin. Then, the peeled conductor layer was sandwiched by a jig, and the load (peel strength) at the time of peeling at room temperature at a tensile speed of 50 mm/min along the thickness direction (vertical direction) of the tantalum wafer was measured. The evaluation results are shown in Table 5. In addition, in this specification, the room temperature shows 25 degreeC.

<Evaluation of the bonding strength (peeling strength) after the ultraviolet irradiation> In the evaluation of the bonding strength of the example B1 to the example B7 and the comparative example B1 to the comparative example B6, ultraviolet irradiation was performed instead of chemical coarsening, and electroless plating was performed. The conditions of the pretreatment of the application were locally changed and the same evaluation was performed. The evaluation of the subsequent strength will be described below.

The cured film produced by the above method is subjected to ultraviolet irradiation. Ultraviolet irradiation was carried out using a conveyor type ultraviolet irradiation device using a metal halide lamp (maximum wavelength of 350 nm to 380 nm) at an exposure amount of 3000 mJ/cm ² .

Then, an aqueous solution of diethylene glycol monobutyl ether of 200 ml/L and sodium hydroxide of 5 g/L was prepared, and the mixture was heated to 70 ° C and immersed for 10 minutes. Thereafter, it was washed with water and immersed in a conditioning liquid "CLC-601" (manufactured by Hitachi Chemical Co., Ltd., trade name) at 60 ° C for 5 minutes, and then washed with water in the prepreg. PD-201 (manufactured by Hitachi Chemical Co., Ltd., trade name) was immersed at room temperature for 2 minutes. Then, it was immersed in an electroless plating catalyst "HS-202B" (manufactured by Hitachi Chemical Co., Ltd., trade name) containing lead chloride (PdCl ₂ ) for 10 minutes at room temperature, and then washed with water. The electroless copper plating solution "CUST-201 plating liquid" (manufactured by Hitachi Chemical Co., Ltd., trade name) was immersed at room temperature for 15 minutes to further perform copper sulfate plating. Thereafter, annealing was performed at 180 ° C for 60 minutes to form a conductor layer having a thickness of 20 μm. A region having a width of 10 mm and a length of 50 mm was formed in the conductor layer by etching, and one end of the region was peeled off by 10 mm at the interface between the conductor layer (copper layer) and the hardened resin film. Then, the peeled conductor layer was sandwiched by a jig, and the load (peel strength) at the time of peeling at room temperature at a tensile speed of 50 mm/min along the thickness direction (vertical direction) of the tantalum wafer was measured. The evaluation results are shown in Table 5. Further, in the present specification, the room temperature means 25 °C.

<Evaluation of Surface Roughness (Ra) of Insulating Resin Layer After Conductive Layer Etching> The conductor layer produced by the above method was subjected to an etching treatment to thereby produce a test piece from which the conductor layer was removed. Using an ultra-depth shape measuring microscope "VK-8500" manufactured by Keyence Co., Ltd., three points of different parts in the test piece were measured at a measurement length of 149 μm, a magnification of 2000 times, and a resolution of 0.05 μm. The surface roughness (Ra) of the insulating resin was measured. The evaluation results are shown in Table 5.

[table 5]

<Production of Dry Film 2: Example B8 and Comparative Example B7> The solution of the obtained resin composition was applied to a polyethylene terephthalate film in a uniform thickness (Unitica) ) (product name "TR-1") (support) is dried by a hot air convection dryer at 100 ° C to 140 ° C for 10 minutes, and the film thickness after drying is 1 μm. Photosensitive layer. Then, the photosensitive composition was laminated on a non-photosensitive layer at 100 ° C and 0.5 Mpa (manufactured by Hitachi Chemical Co., Ltd., trade name: Raytec (registered trademark) FZ-2700GA) (d-IV) Thereby, the bonding is performed to obtain a dry film. The composition of the produced dry film is shown in Table 6. In addition, in Table 3, Example B8 is that the dry film which has a non-photosensitive layer (thickness: 1 μm) formed using varnish cI and a photosensitive composition (d) was produced on the support. -IV) The formed photosensitive layer (thickness: 10 μm) and a protective layer. In Comparative Example B7, a photosensitive composition (manufactured by Hitachi Chemical Co., Ltd., trade name: Raytec (registered trademark) FZ-2700GA) (d-IV) was used as it was. The analyticity, surface roughness, and peel strength were evaluated by the method described above. The evaluation results are shown in Table 6.

[Table 6]

As shown in Tables 5 and 6, the examples B1 to B8 had good analytical properties, and showed a peel strength of up to 0.4 kN/m or more after chemical roughening and ultraviolet irradiation. The surface roughness (Ra) of the base resin was smoothed by 0.1 μm in the ultraviolet irradiation process. Comparative Examples B1 to B3 were inferior in analytical properties as compared with the examples, and the channels could not be opened. Further, Comparative Examples B4 to B7 were the result of poor peel strength. [Industrial availability]

The dry film of the present invention is suitably used as an interlayer insulating film of a wiring board material or a member for an interlayer insulating film (passivation film) such as a semiconductor element. In particular, since the dry film is excellent in adhesion to copper plating and resolution, it can be preferably used for a high-density package substrate which is thinned and densified.

1‧‧‧Support
3‧‧‧ non-photosensitive layer
5‧‧‧Photosensitive layer
7‧‧‧Protective layer
10‧‧‧ dry film
100A‧‧‧Multilayer printed wiring board
101‧‧‧Substrate
102, 107‧‧‧ wiring pattern
103‧‧‧Interlayer insulation
104‧‧‧ openings
105‧‧‧ seed layer
106‧‧‧ resin pattern
108‧‧‧Soldering agent

Fig. 1 is a schematic cross-sectional view showing a dry film of the embodiment. 2(a) to 2(f) are views showing a method of manufacturing the multilayer printed wiring board of the embodiment. Fig. 3 is a scanning electron microscope (SEM) photograph of a developer obtained by developing a dry film of the present embodiment. Fig. 4 is a SEM photograph of a person who obtained a heat treatment after developing a dry film of the present embodiment. Fig. 5 is a SEM photograph of a person who developed the dry film of the present embodiment. Fig. 6 is a SEM photograph of a person who has developed a dry film of the present embodiment and heat-treated it.

1‧‧‧Support

3‧‧‧ non-photosensitive layer

5‧‧‧Photosensitive layer

7‧‧‧Protective layer

10‧‧‧ dry film

Claims (19)

A dry film comprising a photosensitive layer and a non-photosensitive layer, wherein the non-photosensitive layer contains a thermosetting resin. The dry film according to claim 1, wherein the non-photosensitive layer comprises: (A) component: epoxy resin, (B-1) component: epoxy resin hardener, and (C) component: Amidino or quinone based resin. The dry film according to claim 2, wherein the non-photosensitive layer further contains (E) a component: an ester group-containing compound. The dry film according to claim 1, wherein the non-photosensitive layer comprises: (A) component: epoxy resin, (B-2) component: epoxy resin hardening accelerator, and (E) component: An ester group-containing compound. The dry film according to any one of claims 1 to 4, wherein the non-photosensitive layer further contains a component (D): an inorganic filler. The dry film according to any one of claims 1 to 5, wherein the photosensitive layer has a thickness of from 1 μm to 50 μm. The dry film according to any one of claims 1 to 6, wherein the non-photosensitive layer has a thickness of 10 μm or less. The dry film according to any one of the preceding claims, wherein the photosensitive layer comprises: (F) a component: a resin having a phenolic hydroxyl group; (G) a component: having an aromatic ring selected from the group consisting of a compound having at least one of a heterocyclic ring and an alicyclic group and having a methylol group or an alkoxyalkyl group; (H) component: having two or more selected from the group consisting of acryloxyl groups and methacrylic groups An aliphatic compound having one or more functional groups of a decyloxy group, a glycidoxy group, and a hydroxyl group; and (I) a component: a photo-sensitive acid generator. The dry film according to claim 8, wherein the (H) component is contained in an amount of 20 parts by mass to 70 parts by mass based on 100 parts by mass of the component (F). The dry film according to any one of claims 1 to 9, wherein the photosensitive layer further contains a (D') component: an inorganic filler. The dry film according to claim 10, wherein the (D') component is an inorganic filler having an average primary particle diameter of 100 nm or less. The dry film of claim 10, wherein the (D') component is cerium oxide. The dry film according to any one of claims 1 to 12, which is used for forming an interlayer insulating layer. A cured product obtained by using the dry film according to any one of claims 1 to 13. A method of forming a resist pattern, comprising the steps of: sequentially forming a photosensitive layer and a non-photosensitive layer on a substrate by using the dry film according to any one of claims 1 to 13 a step of exposing the photosensitive layer in a predetermined pattern; and a step of developing the exposed photosensitive layer and performing a heat treatment. The method for forming a resist pattern according to claim 15, further comprising the step of performing heat treatment before developing the exposed photosensitive layer. A dry film comprising a photosensitive layer and a non-photosensitive layer, wherein the dry film is formed by sequentially forming the photosensitive layer and the non-photosensitive layer on a substrate, exposing the photosensitive layer, and performing the dry film Development is performed to dissolve the unexposed portion of the photosensitive layer to rupture the non-photosensitive layer on the unexposed portion, and a channel can be formed at a portion where the non-photosensitive layer is broken by heat treatment after development. A laminated body obtained by sequentially laminating a substrate, a photosensitive layer, and a non-photosensitive layer containing a thermosetting resin. A method for forming a resist pattern, comprising the steps of: applying a photosensitive composition onto a substrate to form a photosensitive layer; and coating a resin composition containing a thermosetting resin on the photosensitive layer a step of forming a non-photosensitive layer; a step of exposing the photosensitive layer in a predetermined pattern; and a step of developing the exposed photosensitive layer and performing a heat treatment.