WO2016158362A1 - 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

Dry film, cured product, laminate, and method for forming resist pattern

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

In recent years, as electronic devices become more sophisticated (smaller, lighter, and more multifunctional), semiconductor components such as LSIs and chips have become more highly integrated, and the form of semiconductor components has rapidly increased in number and size. Has changed. Further, packaging forms such as a package-on-package in which a semiconductor device is stacked on a semiconductor device are actively performed, and it is expected that the mounting density of the semiconductor device will be further increased in the future.

The printed wiring board is, for example, a structure in which a plurality of wiring layers are formed on a core substrate, and is provided on the outermost surface with an interlayer insulating film provided between the core substrate, each wiring layer (also referred to as a conductor pattern layer). Solder resist (surface protective film).

It is necessary to provide vias (openings) for electrically connecting the upper and lower wiring layers in the interlayer insulating film of the printed wiring board. If the number of flip chip pins mounted on a printed wiring board increases, it is necessary to provide as many vias as the number of pins. However, conventional printed wiring boards have a low mounting density, and the semiconductor to be mounted Since the number of pins of the device is designed from several thousand pins to around 10,000 pins, it is not necessary to provide vias having a small diameter and a narrow pitch. However, as the miniaturization of semiconductor elements progresses and the number of pins increases from tens of thousands to hundreds of thousands of pins, the vias formed in the interlayer insulating film of the printed wiring board are also narrowed according to the number of pins of the semiconductor elements. There is a growing need.

As a method of forming a via and a wiring layer in an interlayer insulating film, for example, after forming an insulating layer on an inner layer circuit board (base material having a first conductor pattern) using a thermosetting resin material, laser A method of forming a second conductor pattern by forming a via by processing and then performing an electroless copper plating process on an insulating layer is known (see, for example, Patent Document 1).

Japanese Patent Laid-Open No. 2002-3705

However, in the conventional method described above, that is, in the method of providing vias using a laser, each via must be formed one by one, and it takes time to provide a large number of vias. There are problems that it is necessary to use different lasers according to the situation, and it is difficult to provide fine vias.

Also, when the conductor pattern is formed on the insulating layer by electroless copper plating, the adhesive force between the insulating layer and the plated copper is not sufficient, and the conductor pattern may peel off.

An object of the present disclosure is to solve the above-described problems and to form a dry film that can form a resist pattern that has excellent adhesion to plated copper and that has excellent resolution, and a cured product, laminate, and the dry film. It is to provide a method of forming a resist pattern using

As a result of intensive studies to solve the above problems, the present inventors have found a dry film having excellent characteristics. That is, the dry film of the present disclosure includes a photosensitive layer and a non-photosensitive layer, and the non-photosensitive layer includes a thermosetting resin.

Here, the non-photosensitive layer is used as an insulating layer when, for example, a multilayer wiring board is manufactured, and a conductor pattern (wiring layer) can be formed by plating the surface thereof. In the dry film of the present disclosure, the non-photosensitive layer improves the adhesion between the insulating layer formed from the non-photosensitive layer and the conductor pattern formed by plating on the insulating layer, and the electric circuit of the formed circuit Reliability can be improved. The non-photosensitive layer can also be called an adhesion auxiliary layer.
Since the non-photosensitive layer of the present disclosure has low solubility in a chemical solution such as a developer, it has been found that the surface roughness after the roughening treatment is small. In addition, the present inventors have shown that the non-photosensitive layer in the dry film of the present disclosure has better adhesion to the plated copper than the single insulating layer obtained by mixing the non-photosensitive layer and the photosensitive layer of the present disclosure. It was found that it can be secured.

Furthermore, by using the dry film of the present disclosure, not only the via can be formed without using a laser, but also a finer via pattern can be formed as compared with the case where a laser is used. That is, it has been found that by using the above-described dry film, a fine via can be formed by combining the non-photosensitive layer and the photosensitive layer. Furthermore, by forming an insulating layer using the dry film of the present disclosure, the generation of via residues can be suppressed, and the insulation reliability between layers can be improved.

The non-photosensitive layer preferably contains (A) component: epoxy resin, (B-1) component: epoxy resin curing agent, and (C) component: resin having amide group or imide group.

It is preferable that the non-photosensitive layer further contains (E) component: an ester group-containing compound.

The non-photosensitive layer preferably contains (A) component: epoxy resin, (B-2) component: epoxy resin curing accelerator, and (E) component: ester group-containing compound. The non-photosensitive layer has a small surface roughness after the ultraviolet irradiation treatment and can ensure good adhesion to the plated copper.

It is preferable that the non-photosensitive layer further contains (D) component: an inorganic filler.

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

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

The photosensitive layer has (F) 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 a methylol group or an alkoxyalkyl group. A compound having (H) component: an aliphatic compound having two or more functional groups selected from acryloyloxy group, methacryloyloxy group, glycidyloxy group and hydroxyl group, and (I) component: photo-sensitive acid generation It is preferable to contain an agent.

The dry film according to claim 8, comprising 20 to 70 parts by mass of the component (H) with respect to 100 parts by mass of the component (F).

It is preferable that the photosensitive layer further contains a component (D ′): an inorganic filler.

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

The component (D ′) is preferably silica.

The above dry film can be used for forming an interlayer insulating layer.

The present disclosure also provides a cured product obtained using the dry film.

The method for forming a resist pattern of the present disclosure includes a step of forming a photosensitive layer and a non-photosensitive layer on a substrate in this order using the dry film, a step of exposing the photosensitive layer to a predetermined pattern, And developing the exposed photosensitive layer and subjecting it to a heat treatment.

Preferably, the resist pattern forming method further includes a heat treatment step before the exposed photosensitive layer is developed.

Further, the present disclosure is a dry film including a photosensitive layer and a non-photosensitive layer, wherein a photosensitive layer and a non-photosensitive layer are formed in this order on a substrate, the photosensitive layer is exposed, and the dry film is formed. By providing development, a dry film is provided in which an unexposed portion of a photosensitive layer is eluted and a non-photosensitive layer on the unexposed portion is broken, and a via can be formed at a location where the non-photosensitive layer is broken by heat treatment after development. . According to such a dry film, vias can be formed without using a laser, and a large number of vias can be easily formed at a time.

The present disclosure provides a laminate in which a base material, a photosensitive layer, and a non-photosensitive layer containing a thermosetting resin are laminated in this order.

The resist pattern forming method of the present disclosure includes a step of forming a photosensitive layer by applying a photosensitive composition on a substrate, and a non-photosensitive layer by applying a resin composition containing a thermosetting resin on the photosensitive layer. A step of exposing the photosensitive layer to a predetermined pattern, and a step of developing and heat-treating the exposed photosensitive layer.

According to the present disclosure, it is possible to provide a dry film capable of forming a resist pattern that is excellent in adhesiveness with plated copper and excellent in resolution. Moreover, according to this indication, the formation method of the resist pattern using the hardened | cured material of this dry film, a laminated body, and this dry film can be provided.

It is a schematic cross section of the dry film which concerns on this embodiment. It is a figure which shows the manufacturing method of the multilayer printed wiring board of this embodiment. It is a SEM photograph of what developed the dry film concerning this embodiment. It is a SEM photograph of what heat-processed after developing the dry film which concerns on this embodiment. It is a SEM photograph of what developed the dry film concerning this embodiment. It is a SEM photograph of what heat-processed after developing the dry film which concerns on this embodiment.

(First embodiment)
Hereinafter, although 1st Embodiment of this indication is described concretely, this indication is not limited to this. In the present specification, (meth) acrylate means at least one of acrylate and methacrylate corresponding thereto. The same applies to other similar expressions such as (meth) acrylic compounds.

In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. It is. In this specification, the term “layer” includes not only a structure having a shape formed on the entire surface but also a structure having a shape formed on a part when observed as a plan view. Further, in this specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In addition, in the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.

[Dry film]
The dry film of this embodiment is demonstrated based on FIG. FIG. 1 is a schematic cross-sectional view of a dry film 10 according to this embodiment.

The dry film 10 according to this 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. The dry film 10 may be formed on the support 1 so that the non-photosensitive layer 3 and the support 1 are in contact with each other. That is, the dry film 10 according to the present embodiment may include the support 1, the non-photosensitive layer 3, and the photosensitive layer 5 in this order. A protective layer 7 that covers 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 5 to 25 μm. One polymer film may be used as the support 1 and the other polymer film as the protective layer 7. Moreover, you may use as the support body 1 what shows light-shielding property (copper foil etc.).

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. Moreover, you may use as the protective layer 7 what shows light-shielding property (copper foil etc.).

The non-photosensitive layer 3 and the photosensitive layer 5 can be formed by applying a resin composition and a photosensitive composition on 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 this embodiment can be obtained by the following method.
First, the non-photosensitive layer 3 is formed by coating and drying on a polymer film or copper foil serving as a support using the resin composition. Next, the photosensitive composition is applied on the non-photosensitive layer 3 and dried to form the photosensitive layer 5, whereby the dry film of this embodiment is obtained. In addition, the dry film of this embodiment may be obtained by bonding the non-photosensitive layer 3 formed on the support 1 and the protective layer 7 formed with the photosensitive layer 5 together.

The thickness of the non-photosensitive layer 3 may be 10 μm or less, 0.1 to 10 μm, 0.1 to 5 μm, or 0.2 to 1.5 μm. 0.3 to 1 μm. By reducing the thickness of the non-photosensitive layer 3 to 10 μm or less, the developability with respect to the alkaline aqueous solution is improved, or the sensitivity reduction of the photosensitive layer 5 due to the non-photosensitive layer 3 absorbing actinic rays can be suppressed. Improves. When the thickness of the non-photosensitive layer 3 is 0.1 μm or more, workability is improved.

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

The preferable range of the thickness of the photosensitive layer 5 varies depending on the application, but the thickness of the photosensitive layer 5 is preferably 1 to 50 μm, more preferably 5 to 40 μm, and still more preferably 10 to 30 μm. . By setting the thickness of the photosensitive layer 5 in the above-described range, the resolution tends to be further improved.

[Resin composition used to form non-photosensitive layer]
The resin composition of the present embodiment does not have photosensitivity and is used for forming a non-photosensitive layer. The resin composition of this embodiment contains a thermosetting resin. The thermosetting resin is not particularly limited as long as it is a component composed of a reactive compound that causes a crosslinking reaction by heat. For example, epoxy resin, cyanate ester resin, maleimide resin, allyl nadiimide resin, phenol resin, Urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, resorcinol formaldehyde resin, xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, Examples include resins containing tris (2-hydroxyethyl) isocyanurate, resins containing triallyl trimellitate, thermosetting resins synthesized from cyclopentadiene, thermosetting resins by trimerization of aromatic dicyanamide, etc. It is. The resin composition may contain a curing agent for a thermosetting resin.

The resin composition of this embodiment may contain (A) component: epoxy resin, (B-1) component: epoxy resin curing agent, and (C) component: resin having amide group or imide group. In addition, the resin composition used to form the resin layer of the present embodiment includes (A) component: epoxy resin, (B-2) component: epoxy resin curing accelerator, and (E) component: ester group-containing compound. It may contain. In the present specification, these components may be simply referred to as (A) component, (B-1) component, (B-2) component, (C) component, (E) component and the like. In addition, the resin layer of this embodiment can be used suitably in the formation method provided with a plating process.

<(A) component>
As an epoxy resin, although a preferable compound changes with uses, it is preferable that it is a polyfunctional epoxy resin. Specific examples of preferable epoxy resins include cresol novolak type epoxy resins, phenol novolak type epoxy resins, naphthol novolak type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol T type epoxy resins, bisphenol Z type epoxy resins. , Tetrabromobisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, tetramethylbiphenyl type epoxy resin, triphenyl type epoxy resin, tetraphenyl type epoxy resin, naphthol aralkyl type epoxy resin, naphthalenediol aralkyl type epoxy Resin, fluorene type epoxy resin, epoxy resin having dicyclopentadiene skeleton, epoxy having skeleton derived from butanediol Resin, epoxy resin having a skeleton derived from pentadiol, epoxy resin having a skeleton derived from hexanediol, epoxy resin having a skeleton derived from heptanediol, epoxy resin having a skeleton derived from octanediol, alicyclic epoxy resin, etc. It is done. Among these, a biphenyl aralkyl epoxy resin or an epoxy resin having a skeleton derived from hexanediol is more preferable. Examples of commercially available products include biphenyl aralkyl type epoxy resins (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000). These epoxy resins may be used in combination of two or more from the viewpoint of further improving the insulation reliability and heat resistance.

The content of the component (A) is preferably 20 to 90 parts by weight, and preferably 30 to 80 parts by weight with respect to 100 parts by weight of the total solid content of the resin composition used for forming the non-photosensitive layer. It is more preferable. In addition, in this specification, solid content refers to the component in compositions other than volatile substances, such as a water | moisture content and the solvent mentioned later. That is, the solid content includes liquid, water tank-like and wax-like substances at room temperature around 25 ° C., and does not necessarily mean solid.

<(B-1) component>
As an epoxy resin hardening | curing agent, although a preferable compound changes with uses, for example, phenol resins, acid anhydrides, amines, hydragits, etc. are mentioned. 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 anhydrides, phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic anhydride and the like can be used. As the amines, dicyandiamide, diaminodiphenylmethane, guanylurea and the like can be used.

The content of component (B-1) is preferably 0.5 to 1.5 equivalents relative to the epoxy group of component (A). When the content of the epoxy resin curing agent is 0.5 to 1.5 equivalents relative to the epoxy group of the component (A), it is possible to suppress a decrease in Tg (glass transition temperature) and insulation.

<(B-2) component>
Component (B-2) that can be used in the resin composition of the present embodiment: As an epoxy resin curing accelerator, a preferred compound varies depending on the use, but a general curing accelerator used for curing component (A) Can be used. Specific examples of the epoxy resin curing accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-undecylimidazole, 1-cyanoethyl- Imidazole compounds such as 2-phenylimidazolium trimellitate; Organic phosphite compounds such as triphenylphosphine and tributylphosphine; Organic phosphite compounds such as trimethylphosphite and triethylphosphite; Ethyltriphenylphosphonium bromide and tetraphenyl Phosphonium salt compounds such as phosphonium tetraphenylborate; Trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-to Amine compounds such as bis (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5.4.0) -undecene-7 (hereinafter abbreviated as “DBU”), and DBU and terephthalic acid or 2,6- Salts with naphthalenedicarboxylic acid, etc .; quaternary ammonium salt compounds such as tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrahexylammonium bromide, benzyltrimethylammonium chloride, etc. . These may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the component (B-2) is preferably 0.02 to 1.5 parts by mass, and 0.8 to 1.3 parts by mass with respect to 100 parts by mass of the component (A). It is more preferable. If the amount is 0.02 parts by mass or more, the component (A) tends to be sufficiently cured and heat resistance can be maintained. On the other hand, if the amount is 1.5 parts by mass or less, the storage stability of the resin composition, B The handleability of the staged resin composition is improved.

<(C) component>
Examples of the resin having an amide group or an imide group include polyamide, polyamideimide, and polyimide. Examples of diamines that can be used in these production include aromatic diamines and aliphatic diamines. The component (C) can be said to be a heat resistant resin.

Specific examples of aromatic diamines include diaminobenzene, diaminotoluene, diaminophenol, diaminodimethylbenzene, diaminomesitylene, diaminonitrobenzene, diaminodiazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether, diaminodimethyldiphenyl ether, methylene Diamine, methylenebis (dimethylaniline), methylenebis (methoxyaniline), methylenebis (dimethoxyaniline), methylenebis (ethylaniline), methylenebis (diethylaniline), methylenebis (ethoxyaniline), methylenebis (diethoxyaniline), isopropylidenedianiline, Diaminobenzophenone, diaminodimethylbenzophenone, diamy Anthraquinone, diamino diphenyl thioether, diaminodiphenyl dimethyl diphenyl thioether, diaminodiphenyl sulfone, diaminodiphenyl sulfoxide, diaminofluorene and the like.

Specific examples of the aliphatic diamine include ethylenediamine, propanediamine, hydroxypropanediamine, butanediamine, heptanediamine, hexanediamine, diaminodiethylamine, diaminopropylamine, cyclopentanediamine, cyclohexanediamine, azapentanediamine, and triazaundecadiamine. Etc. These aromatic diamines and aliphatic diamines may be used alone or in combination of two or more.

Examples of the dicarboxylic acid used for the production of a resin having an amide group or an imide group include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and oligomers having carboxyl groups at both ends.

Specific examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, methylene dibenzoic acid, thiodibenzoic acid, carbonyl dibenzoic acid, sulfonyl dibenzoic acid, naphthalenedicarboxylic acid, hydroxyisophthalic acid , Hydroxyphthalic acid, hydroxyterephthalic 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, (meth) acryloyloxysuccinic acid, di ( Examples include (meth) acryloyloxysuccinic acid, (meth) acryloyloxymalic acid, (meth) acrylamide succinic acid, (meth) acrylamide malic acid, and the like. These aliphatic dicarboxylic acids may be used alone or in combination of two or more.

Examples of the oligomer having a carboxyl group at both ends include oligomers having a number average molecular weight of 200 to 10,000, preferably a number average molecular weight of 500 to 5,000. Specific examples include polybutadiene having carboxyl groups at both ends, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, polyisoprene, ethylene propylene copolymer, polyether, polyester, polycarbonate, polyacrylate, polyacrylate. Examples include methacrylate, polyurethane, and silicone rubber. These aromatic dicarboxylic acids, aliphatic dicarboxylic acids and oligomers having carboxyl groups at both ends may be used alone or in combination of two or more. “Number average molecular weight (Mn)” and “weight average molecular weight (Mw)” described later refer to values measured using a standard polystyrene calibration curve according to the gel permeation chromatography (GPC) method, and more specifically. Is a pump (manufactured by Hitachi, Ltd., L-6200 type), column (TSKgel-G5000HXL and TSKgel-G2000HXL, both manufactured by Tosoh Corporation, trade name) and a detector (manufactured by Hitachi, Ltd.) L-3300RI type), tetrahydrofuran is used as an eluent, and measurement is performed at a temperature of 30 ° C. and a flow rate of 1.0 mL / min.

When a polyamide is included as the component (C), a copolymer of polyamide and polybutadiene (also referred to as “polybutadiene-modified polyamide resin”) can be used from the viewpoint of further improving the adhesion to the plated copper. Examples of such a polybutadiene-modified polyamide resin include a phenolic hydroxyl group-containing polybutadiene-modified polyamide obtained by polycondensation of a diamine, a dicarboxylic acid having a phenolic hydroxyl group, and a polybutadiene having a carboxyl group at both ends. A phenolic hydroxyl group-containing polybutadiene-modified polyamide is prepared by, for example, catalyzing a diamine, a phenolic hydroxyl group-containing dicarboxylic acid, and a polybutadiene having carboxyl groups at both ends in an organic solvent such as N-methyl-2-pyrrolidone (NMP). Can be obtained by polycondensation of a carboxyl group and an amino group in the presence of a phosphite ester and a pyridine derivative. In addition to diamine, dicarboxylic acid having a phenolic hydroxyl group and polybutadiene having a carboxyl group at both ends, a dicarboxylic acid having no phenolic hydroxyl group may be added. Examples of such a commercially available phenolic hydroxyl group-containing polybutadiene-modified polyamide resin include BPAM-155 manufactured by Nippon Kayaku Co., Ltd.

As the polyamideimide that can be contained as the component (C), for example, polyamideimide synthesized by a so-called isocyanate method by reaction of trimellitic anhydride or a reaction product of trimellitic anhydride and diamine with an aromatic diisocyanate. Is mentioned. As a specific example of the isocyanate method for synthesizing polyamideimide, a method in which an aromatic tricarboxylic acid anhydride and the above diamine compound are reacted in the presence of excess diamine compound and then a diisocyanate is reacted (for example, as described in Japanese Patent No. 2897186). Method) and a method of reacting an aromatic diamine compound and trimellitic anhydride (for example, a method described in JP-A No. 04-182466).

Examples of commercially available polyamide imide resins include Bilomax HR11NN and Bilomax HR16NN manufactured by Toyobo Co., Ltd.

The polyimide that can be contained as the component (C) may be synthesized by a general synthesis method currently used industrially. For example, tetracarboxylic dianhydride and the above diamine are polymerized in equimolar amounts to obtain a polyamic acid that is a polyimide precursor, and then subjected to a dehydration reaction and a cyclization reaction using heating at 200 ° C. or higher or using a catalyst. By proceeding, polyimide can be obtained. When using a catalyst, an amine compound can be used, and a carboxylic acid anhydride may be used in combination as a dehydrating agent for quickly removing water generated by imidization. In addition, (C) component mentioned above may each be used independently, and may be used in combination of 2 or more types.

The content of the component (C) is preferably 3 to 30% by mass, preferably 15 to 25% by mass with respect to the total solid content of the component (A), the component (B-1) and the component (C). More preferably.

<(D) component>
The said resin composition may contain (D) component: an inorganic filler from a viewpoint of stabilizing a roughening shape and improving adhesiveness. When containing an inorganic filler, the thermal expansion coefficient of the cured film obtained by heating after pattern formation can be reduced according to the content of the component (D). (D) component can be used individually by 1 type or in mixture of 2 or more types.

Examples of inorganic fillers include aluminum oxide, aluminum hydroxide, calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, silica, or inorganic fillers derived from mineral products such as talc and mica. Can be mentioned. Examples of the silica include fused spherical silica, fused and ground silica, fumed silica, and sol-gel silica.

The type of the inorganic filler is not particularly limited, but the thermal expansion coefficient is preferably 5.0 × 10 ⁻⁶ / ° C. or less. From the viewpoint of particle size, silica such as fused spherical silica, fumed silica, sol-gel silica, and the like is used. preferable. Among them, fumed silica or sol-gel silica is more preferable. In order to disperse in the resin without aggregation, a silane coupling agent may be used.

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

When the resin composition used for forming the non-photosensitive layer contains the component (D), the amount is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition. More preferably, it is part by mass.

The inorganic filler contained in the non-photosensitive layer (or the photosensitive layer described later) preferably has an average primary particle size of 100 nm or less, and particularly 50 nm or less from the viewpoint of further excellent photosensitivity. Is preferred. When the average primary particle size is 100 nm or less, the resolution tends to be further improved. The “primary particle size” is a value obtained by conversion from the specific surface area of particles actually measured by the BET method. In the BET method, an adsorbate (for example, an inert gas such as nitrogen) is physically adsorbed on the surface of solid particles at a low temperature, and the specific surface area can be estimated from the molecular cross-sectional area and adsorbed amount of the adsorbate. Component (D) dispersed in the resin composition from the viewpoint of suppressing light scattering in the exposure wavelength region (for example, 300 to 450 nm) of the resin composition, that is, suppressing a decrease in transmittance in the exposure wavelength region. The average particle diameter is preferably 80 nm or less, more preferably 50 nm or less, and still more preferably 30 nm or less. Although the minimum of the average particle diameter of (D) component in a resin composition is not specifically limited, For example, it can be 5 nm or more. From the viewpoint of suppressing a decrease in transmittance, the inorganic filler is preferably dispersed with a maximum particle size of 1 μm or less when dispersed in the resin composition, and is dispersed within 0.5 μm or less. More preferably, it is more preferable to be dispersed to 0.1 μm or less. The “average particle diameter” of the component (D) is the average particle diameter of the inorganic filler in a state dispersed in the resin composition, and is a value obtained by measurement as follows. First, after diluting (or dissolving) the resin composition 1000 times with methyl ethyl ketone, using a submicron particle analyzer (trade name: N5, manufactured by Beckman Coulter Co., Ltd.), in accordance with the international standard ISO 13321, The particles dispersed in the solvent at a refractive index of 1.38 are measured, and the particle size at an integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle size. Further, the particle diameter at the integrated value 99.9% (volume basis) in the particle size distribution is defined as the maximum particle diameter. Further, even for a non-photosensitive layer or a cured film of a resin composition provided on a support, the dry film is exposed to the entire surface to prevent elution of the photosensitive layer, and then 1000 times using a solvent as described above. After dilution (or dissolution) in (volume ratio), measurement can be performed using the submicron particle analyzer.

<(E) component>
The resin composition may contain (E) component: ester group-containing compound. Specifically, one or more ester groups are contained in one molecule, and an epoxy resin can be cured without containing a hydroxyl group. For example, aliphatic or aromatic carboxylic acid and aliphatic or aromatic hydroxy Examples include ester compounds obtained from the compounds. Among these, an ester compound composed of an aliphatic carboxylic acid, an aliphatic hydroxy compound, or the like can increase the solubility in an organic solvent and the compatibility with an epoxy resin by including an aliphatic chain. On the other hand, an ester compound composed of an aromatic carboxylic acid, an aromatic hydroxy compound, or the like can improve the heat resistance of the resin composition by having an aromatic ring.

Suitable examples of the ester group-containing compound include, for example, a mixture of an aromatic carboxylic acid, a monohydric phenol compound, and a polyhydric phenol compound as raw materials, the aromatic carboxylic acid, the monohydric phenol compound, and a polyhydric compound. An aromatic ester obtained by a condensation reaction with a phenolic hydroxyl group of a polyhydric phenol compound is mentioned.

Examples of the aromatic carboxylic acid include those in which 2 to 4 hydrogen atoms of an aromatic ring such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, diphenylsulfone, and benzophenone are substituted with a carboxyl group. As said monohydric phenol type compound, what substituted one hydrogen atom of the above-mentioned aromatic ring by the hydroxyl group is mentioned. Examples of the polyhydric phenol compound include those in which 2 to 4 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, β-naphthol and the like. Examples of the polyhydric phenol compounds include hydroquinone, resorcin, catechol, 4,4′-biphenol, 4,4′-dihydroxydiphenyl ether, bisphenol A, bisphenol, bisphenol S, bisphenol Z, brominated bisphenol A, and brominated. Examples thereof include bisphenol F, brominated bisphenol S, methylated bisphenol S, various dihydroxynaphthalenes, various dihydroxybenzophenones, various trihydroxybenzophenones, various tetrahydroxybenzophenones, and phloroglycine.

The ester group-containing compound may be a resin having one or more ester groups in one molecule, and is also available as a commercial product. Examples include “EXB-9460”, “EXB-9460S”, “EXB-9470”, “EXB-9480”, “EXB-9420” manufactured by DIC Corporation, and “BPN80” manufactured by Mitsui Chemicals, Inc. . These ultraviolet active ester group-containing compounds may be used alone or in combination of two or more.

When the ester group-containing compound is contained, the content of the ester group-containing compound is preferably 0.75 to 1.25 equivalents with respect to 1 equivalent of the epoxy group of the component (A). When it is 0.75 equivalent or more, sufficient tackiness and curability between the support and the non-photosensitive layer can be obtained sufficiently, and when it is 1.25 equivalent or less, sufficient curability, heat resistance and chemical resistance are obtained. It becomes easy to obtain.

The above resin composition is obtained by adding other components to the components (A) to (E) as necessary, sufficiently stirring and mixing them, and then standing until there are no bubbles. For the purpose of uniformly dispersing the inorganic filler contained in the resin composition, a known kneading and dispersing method such as a kneader, ball mill, bead mill, three rolls, or nanomizer may be used.

It is preferable from the viewpoint of workability that the resin composition is mixed or diluted or dispersed in a solvent to form a varnish. Examples of the solvent include methyl ethyl ketone, xylene, toluene, acetone, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide and the like. These solvents may be used singly or in combination of two or more. The ratio of the solvent to the resin composition may be a conventionally used ratio, and the amount used can be adjusted according to the equipment for forming the non-photosensitive layer. On the other hand, after the dispersion preparation, the resin composition can be further diluted or dispersed with the above solvent to prepare a varnish.

[Photosensitive composition]
The photosensitive composition used to form the photosensitive layer of the present embodiment can be used in accordance with a desired purpose as long as its properties change (for example, it cures) when irradiated with light. It may be negative or positive. The term “photosensitive” means that the photosensitive layer is exposed, then subjected to heat treatment after exposure, if necessary, and then developed (removed) using a developer for removing the photosensitive composition. ) Means that a resin pattern can be formed. The photosensitive composition may contain (F) component: a resin having a phenolic hydroxyl group, (G ′) component: a crosslinking agent, and (I) component: a photosensitive acid generator. Component (G ′): A crosslinking agent is a compound that forms a bond with a resin or a bond between crosslinkers by the action of heat, acid, or the like. (G ′) component may contain a compound having (G) component: 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, Component (H): An aliphatic compound having two or more functional groups of one or more selected from acryloyloxy group, methacryloyloxy group, glycidyloxy group and hydroxyl group may be included. (G) Component and (H) Both components may be included. Moreover, the photosensitive composition of this embodiment is (D ') component: an inorganic filler, (J) component: Amine, (K) component: Organic peroxide, (L) component: Silane cup as needed. A ring agent, (M) component: leveling agent, (N) component: sensitizer can also be contained. Moreover, in addition to (F) component, a phenolic low molecular weight compound can also be contained.

In addition, (D ') component: As an inorganic filler, the thing similar to the above-mentioned (D) component can be used. When the photosensitive composition contains the component (D ′), the amount is preferably 1 to 70 parts by mass and preferably 3 to 65 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition. More preferred.

As the component (D ′) contained in the photosensitive composition of the present embodiment, the average primary particle size is preferably 100 nm or less. Moreover, it is preferable that the average particle diameter of (D ') is 100 nm or less. Thereby, the thermal expansion coefficient of the cured film can be reduced according to the content of the component (D ′). From the viewpoint of suppressing light scattering in the exposure wavelength region (for example, 300 to 450 nm) of the photosensitive composition, that is, suppressing a decrease in transmittance in the exposure wavelength region, it was dispersed in the photosensitive composition (D The average particle size of the component ') 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 in the component (D ′) is not particularly limited, but can be, for example, 5 nm or more. From the viewpoint of suppressing a decrease in transmittance, the inorganic filler is preferably dispersed with a maximum particle diameter of 1 μm or less when dispersed in the photosensitive composition, and is dispersed within 0.5 μm or less. More preferably, it is more preferably dispersed to 0.1 μm or less. The “average particle diameter” and “maximum particle diameter” of the component (D ′) are 50% (volume basis) of the integrated value in the particle size distribution of the inorganic filler dispersed in the photosensitive composition, respectively. And the integrated value of 99.9% (volume basis). In addition, even a cured film of a photosensitive layer or a photosensitive composition provided on a support is diluted (or dissolved) 1000 times (volume ratio) with a solvent as described above, and then the submicron. It can be measured using a particle analyzer.

<(F) component>
Component (F) used in the photosensitive composition of the present embodiment: The resin having a phenolic hydroxyl group is not particularly limited, but is preferably a resin that is soluble in an alkaline aqueous solution, and particularly preferably a novolak resin. Such a novolak resin can be obtained by condensing phenols and aldehydes 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, p-butylphenol, 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- Examples include trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like.

In addition, examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and the like.

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

Examples of the component (F) other than the novolak resin include polyhydroxystyrene and copolymers thereof, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, and the like. It is done. (F) A component can be used individually by 1 type or in mixture of 2 or more types.

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

The content of the component (F) is 30 to 90 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition (excluding the component (D ′) when the component (D ′) is used). It is preferably 40 to 80 parts by mass. When the content of the component (F) is within this range, a film formed using the resulting photosensitive composition tends to be more excellent in developability with an alkaline aqueous solution.

<(G) component>
The photosensitive composition of this embodiment contains (G) component: the compound which has at least 1 type chosen from the group which consists of an aromatic ring, a heterocyclic ring, and an alicyclic ring, and has a methylol group or an alkoxyalkyl group. May be. 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 means a cyclic group having at least one nitrogen atom, oxygen atom, sulfur atom and the like (for example, a cyclic group having 3 to 10 carbon atoms), such as a pyridine ring, an imidazole ring, a pyrrolidinone ring, Examples include an oxazolidinone ring, an imidazolidinone ring, and a pyrimidinone ring. The alicyclic ring means a cyclic hydrocarbon group having no aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and A cyclohexane ring is mentioned. An alkoxyalkyl group means a group in which an alkyl group is bonded to an alkyl group through an oxygen atom. The two alkyl groups may be different from each other, for example, an alkyl group having 1 to 10 carbon atoms.

By containing the component (G), when the photosensitive layer after the resin pattern is formed is heated and cured, the component (G) reacts with the component (F) to form a bridge structure, and the resin pattern is weak. And melting can be prevented. Specifically, a compound having a phenolic hydroxyl group (however, the component (F) is not included) or a compound having a hydroxymethylamino group or an alkoxymethylamino group can be preferably used.

The “compound having a phenolic hydroxyl group” used as the component (G) has a methylol group or an alkoxymethyl group, thereby increasing the dissolution rate of the unexposed area when developing with an alkaline aqueous solution as well as a crosslinking agent. , Sensitivity can be improved. The molecular weight of the compound having a phenolic hydroxyl group is preferably 94 to 2000, and preferably 108 to 2000 in terms of weight average molecular weight in consideration of the balance of solubility in alkali aqueous solution, photosensitivity, mechanical properties, and the like. More preferably, it is 108 to 1500. In addition, about the compound with a low molecular weight, when it is difficult to measure by the above-mentioned measuring method of the weight average molecular weight, the molecular weight can be measured by another method, and the average can be calculated.

［一般式（１）中、Ｚは単結合又は２価の基を示し、Ｒ^２４及びＲ^２５はそれぞれ独立に水素原子又は１価の有機基を示し、Ｒ^２６及びＲ^２７はそれぞれ独立に１価の有機基を示し、ａ及びｂはそれぞれ独立に１～３の整数を示し、ｃ及びｄはそれぞれ独立に０～３の整数を示す。ここで、１価の有機基としては、例えば、メチル基、エチル基、プロピル基等の炭素原子数が１～１０であるアルキル基；ビニル基等の炭素原子数が２～１０であるアルケニル基；フェニル基等の炭素原子数が６～３０であるアリール基；これら炭化水素基の水素原子の一部又は全部をフッ素原子等のハロゲン原子で置換した基が挙げられる。Ｒ^２４～Ｒ^２７が複数ある場合には、互いに同一でも異なっていてもよい。］ As the compound having a phenolic hydroxyl group, conventionally known compounds can be used, but the compound represented by the following general formula (1) is effective in promoting the dissolution of the unexposed area and curing the photosensitive composition film. It is preferable because it has an excellent balance of effects for preventing melting.

[In General Formula (1), Z represents a single bond or a divalent group, 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 1 A and b each independently represents an integer of 1 to 3, and c and d each independently represents 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. An aryl group having 6 to 30 carbon atoms such as a phenyl group; a group in which some or all of the hydrogen atoms of these hydrocarbon groups are 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. ]

The compound represented by the general formula (1) is preferably a compound represented by the general formula (2).

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

　一般式（３）中、複数のＲは、それぞれ独立にアルキル基（例えば、炭素原子数が１～１０のアルキル基）を示す。 Moreover, you may use the compound represented by General formula (3) as a compound which has the said phenolic hydroxyl group.

In general formula (3), a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

In general formula (1), the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent group represented by Z include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group, an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group, Arylene groups having 6 to 30 carbon atoms such as phenylene groups, groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms, sulfonyl groups, carbonyl groups, ether bonds, sulfides Examples include a bond and an amide bond. Among these, Z is preferably a divalent group represented by the following general formula (4).

［一般式（４）中、Ｘ^２は、単結合、アルキレン基（例えば、炭素原子数が１～１０のアルキレン基）、アルキリデン基（例えば、炭素原子数が２～１０のアルキリデン基）、それらの水素原子の一部又は全部をハロゲン原子で置換した基、スルホニル基、カルボニル基、エーテル結合、スルフィド結合又はアミド結合を示す。Ｒ^２８は、水素原子、水酸基、アルキル基（例えば、炭素原子数が１～１０のアルキル基）又はハロアルキル基を示し、ｅは１～１０の整数を示す。複数のＲ^２８及びＸ^２は互いに同一でも異なっていてもよい。ここで、ハロアルキル基とは、ハロゲン原子で置換されたアルキル基を意味する。］

[In the general formula (4), X ² represents a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), these Or a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond or an amide bond in which part or all of the hydrogen atoms are substituted with a halogen atom. 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 haloalkyl group, and e represents an integer of 1 to 10. The plurality of R ²⁸ and X ² may be the same as or different from each other. Here, the haloalkyl group means an alkyl group substituted with a halogen atom. ]

Examples of the compound having a hydroxymethylamino group or an alkoxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, And (poly) (N-hydroxymethyl) urea. Moreover, you may use the nitrogen-containing compound etc. which alkyl-etherified all or one part of the hydroxymethylamino group of these compounds. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed. Specific examples include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl) urea and the like.

Specifically, the compound having an alkoxymethylamino group is preferably a compound represented by the general formula (5) or a compound represented by the general formula (6).

　一般式（６）中、複数のＲは、それぞれ独立にアルキル基（例えば、炭素原子数が１～１０のアルキル基）を示す。 In general formula (5), a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

In general formula (6), a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

The content of component (G) is preferably 5 to 60 parts by mass, more preferably 10 to 45 parts by mass, and more preferably 10 to 35 parts by mass with respect to 100 parts by mass of component (F). More preferably. When the content of the component (G) is 5 parts by mass or more, the exposed part is sufficiently crosslinked, so that the resolution is further improved. When the content is 60 parts by mass or less, the photosensitive composition is placed on a desired support. It becomes easier to form a film, and the resolution is further improved.

<(H) component>
The photosensitive composition of this embodiment contains an aliphatic compound having two or more functional groups selected from component (H): acryloyloxy group, methacryloyloxy group, glycidyloxy group and hydroxyl group. Also good. In addition, (H) component may have 2 or more types of different functional groups one by one, and may have 2 or more of 1 type of functional groups. The compound is preferably an aliphatic compound having three or more functional groups. The upper limit of the number of functional groups is not particularly limited, but is 12 for example.

From the viewpoint of workability when a photosensitive layer is formed on a substrate, the photosensitive composition may be required to have excellent adhesion (tackiness) to the substrate. When using the photosensitive composition which does not have sufficient tackiness, the photosensitive layer of an exposed part is easy to be removed by development processing, and there exists a tendency for the adhesiveness of a base material and a resist pattern to deteriorate. When the photosensitive layer contains the component (H), the adhesiveness between the photosensitive composition and the substrate, that is, the tackiness tends to be improved. Furthermore, it is possible to increase the dissolution rate of the exposed area when developing with an alkaline aqueous solution, and to further improve the resolution. From the viewpoint of tackiness and solubility in an aqueous alkali solution, the molecular weight is preferably 92 to 2000, more preferably 106 to 1500, and still more preferably 134 to 1300 in terms of weight average molecular weight in consideration of balance. In addition, about the compound with a low molecular weight, when it is difficult to measure by the above-mentioned measuring method of the weight average molecular weight, the molecular weight can be measured by another method, and the average can be calculated.

［一般式（７）～（１０）中、Ｒ^１、Ｒ^５、Ｒ^１６及びＲ^１９は、それぞれ水素原子、メチル基、エチル基、水酸基又は一般式（１１）で表される基を示し、Ｒ^２１は水酸基、グリシジルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を示し、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１７、Ｒ^１８及びＲ^２０は、それぞれ水酸基、グリシジルオキシ基、アクリロイルオキシ基、メタクリロイルオキシ基、一般式（１２）で表される基又は一般式（１３）で表される基を示し、Ｒ^２２及びＲ^２３はそれぞれ水酸基、グリシジルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を示し、ｎ及びｍはそれぞれ１～１０の整数である。］ Specific examples of the component (H) include compounds represented by general formulas (7) to (10). The “aliphatic compound” refers to a compound in which the main skeleton is an aliphatic skeleton and does not contain an aromatic ring or an aromatic heterocyclic ring.

[In the general formulas (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 general formula (11); R ²¹ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, and R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ²⁰ are each a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the general formula (12), or the general formula (13). a group represented, respectively, R ²² and R ²³ represents a hydroxyl group, a glycidyloxy group, acryloyloxy indicates group or methacryloyloxy group, integers der of n and m are each 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, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl. Ether, glycerin diglycidyl ether, pentaerythritol tetraglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol propoxylate triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, diglycidyl-1,2 -Cyclohexane dicarboxylate and the like.

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

The compound having a glycidyloxy group includes, for example, Epolite 40E, Epolite 100E, Epolite 70P, Epolite 200P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), alkyl type epoxy resin ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L and Denacol EX-850L Name). These compounds having a glycidyloxy group can be used singly or in combination of two or more.

Examples of the compound having an acryloyloxy group include EO-modified dipentaerythritol hexaacrylate, PO-modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO-modified ditrimethylolpropane tetraacrylate, PO-modified ditrimethylolpropane tetraacrylate, ditrile Methylolpropane 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 birds Chi triacrylate, trimethylolpropane acrylate, EO-modified glycerol tri acrylate, PO-modified glycerol triacrylate, glycerin triacrylate. These compounds having an acryloyloxy group can be used singly or in combination of two or more. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

Examples of the compound having a methacryloyloxy group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, ditriethyl. Methylolpropane tetramethacrylate, EO-modified pentaerythritol tetramethacrylate, PO-modified pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, EO-modified pentaerythritol trimethacrylate, PO-modified pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, EO-modified trimethylolpropane Methacrylate, PO-modified trimethylolpropane dimethacrylate, trimethylolpropane dimethacrylate, EO modified glycerol trimethacrylate, PO-modified glycerol trimethacrylate, glycerine trimethacrylate and the like. These compounds having a methacryloyloxy group can be used singly or in combination of two or more. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

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

The functional group of the component (H) is preferably a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, more preferably a glycidyloxy group or an acryloyl group, and even more preferably an acryloyloxy group. From the viewpoint of developability, the component (H) is preferably an aliphatic compound having two or more glycidyloxy groups, more preferably an aliphatic compound having three or more glycidyloxy groups. More preferably, the aliphatic compound has a glycidyloxy group having a weight average molecular weight of 1000 or less.

When the component (H) is contained, the content of the component (H) is preferably 20 to 70 parts by mass, more preferably 25 to 65 parts by mass with respect to 100 parts by mass of the component (F). Preferably, the amount is 35 to 55 parts by mass. When the content of the component (H) is 20 parts by mass or more, sufficient tackiness can be obtained, and when the content is 70 parts by mass or less, a photosensitive composition is formed on a desired support. It becomes easy and the fall of resolution can be controlled.

<(I) component>
The photosensitive composition of this embodiment may contain (I) component: a photosensitive acid generator. The component (I) is a compound that generates an acid upon irradiation with actinic rays and the like, and not only the (G) component is cross-linked by the generated acid, but also reacts with the phenolic hydroxyl group of the (F) component to develop a developer. The solubility of the composition with respect to is greatly reduced. Further, due to the catalytic action of the generated acid, methylol groups or alkoxyalkyl groups in component (G) or methylol groups or alkoxyalkyl groups in component (G) react with (F) component with dealcoholization. By doing so, a negative pattern can be formed.

The component (I) is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or the like. For example, an onium salt compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and diazomethane. Compounds and the like. Specific examples are shown below.

Onium salt compounds:
Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts. Preferred examples of the onium salt compound include diaryl iodonium salts such as diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, and diphenyliodonium tetrafluoroborate; triphenylsulfonium Triarylsulfonium salts such as trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate; 4-t-butylphenyl-diphenylsulfonium trifluoromethanesulfonate; 4-t-butylphenyl-diphenylsulfonium p- Toluenesulfonate; 4, 7 And di -n- butoxy naphthyl tetrahydrothiophenium trifluoromethanesulfonate, and the like.

Sulfonimide compounds:
Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) -1,8- And naphthalimide and N- (10-camphorsulfonyloxy) -1,8-naphthalimide.

In the present embodiment, the component (I) is preferably a compound having a trifluoromethanesulfonate group, a hexafluoroantimonate group, a hexafluorophosphate group or a tetrafluoroborate group in terms of excellent sensitivity and resolution. Moreover, (I) component can be used individually by 1 type or in mixture of 2 or more types.

When component (I) is contained, the content of component (I) is based on 100 parts by mass of component (F) from the viewpoint of further improving the sensitivity, resolution, pattern shape, and the like of the photosensitive composition of the present embodiment. 0.1 to 15 parts by mass, and more preferably 0.3 to 10 parts by mass.

<Solvent>
In order to improve the handleability of the photosensitive composition or adjust the viscosity and storage stability, a solvent may be added to the photosensitive composition of this embodiment. The solvent is preferably an organic solvent. Such an organic solvent is not particularly limited. For example, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl Propylene glycol monoalkyl ethers such as 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 acete Propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; Lactic acid esters such as methyl, ethyl lactate, n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, propion Aliphatic carboxylic acid esters such as n-butyl acid and isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Other esters such as methyl toxipropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; 2-butanone, 2-heptanone, 3-heptanone, 4 -Ketones such as heptanone and cyclohexanone; Amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; Lactones such as γ-butyrolactone. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.

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

[Method of forming resist pattern]
Next, a resist pattern forming method of this embodiment will be described.

First, on a base material (resin-coated copper foil, copper-clad laminate, silicon wafer with a metal sputtered film, alumina substrate, etc.) on which a resist is to be formed, a dry film comprising the above-mentioned non-photosensitive layer and photosensitive layer is prepared. Lamination is performed so that the photosensitive layer is in contact with the substrate. Thus, a base material and a laminate in which a photosensitive layer and a non-photosensitive layer are formed in this order on the base material can be formed. Moreover, the said laminated body may apply | coat the said photosensitive composition to a base material, and form a photosensitive layer, Then, the said resin composition may be apply | coated on this photosensitive layer, and a non-photosensitive layer may be formed. In addition, when a photosensitive composition contains a solvent, you may dry the apply | coated photosensitive composition and may form a photosensitive layer. Moreover, when a resin composition contains a solvent, you may dry the apply | coated resin composition and form a non-photosensitive layer.

Next, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. Examples of radiation used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-ray steppers, i-line steppers and other ultraviolet rays or electron beams, laser beams, and the like. The thickness is selected as appropriate depending on the thickness, the thickness of the non-photosensitive layer, the transmittance of the non-photosensitive layer, etc. For example, in the case of UV irradiation from a high-pressure mercury lamp, when the photosensitive layer thickness is 10-50 μm, 100-5000 mJ / cm. It is about ² . In the case where the dry film of this embodiment is used, the photosensitive layer is exposed by irradiating the non-photosensitive layer with radiation. In addition, when a support body shows a light-shielding property with respect to actinic light, after removing a support body, actinic light is irradiated.

Furthermore, if necessary, heat treatment (post-exposure baking) is performed after exposure. By performing post-exposure baking, the curing reaction of the (F) component and the (G) component by the generated acid can be promoted. The preferable range varies depending on the composition of the photosensitive composition, the thickness of the photosensitive layer, and the like, but it is usually preferable to heat at 60 to 150 ° C. for about 1 to 60 minutes, and at 1 to 60 at 70 to 100 ° C. It is more preferable to heat for about a minute.

Next, the photosensitive layer that has been baked after exposure is developed with an alkaline developer to dissolve and remove the region other than the photocured portion (unexposed portion) of the photosensitive layer. Examples of the developing method in this case include a shower method, a high-pressure spray method, a dipping method, a paddle method, and the like, and a high-pressure spray method is preferable. On the other hand, the non-photosensitive layer has a lower solubility in a developer than the photosensitive layer, and the solubility change in the exposed area is poor. Therefore, a clear resin pattern of the non-photosensitive layer like the photosensitive layer is not formed, or no resin pattern is formed at all. The development conditions are usually 20 to 40 ° C. for about 1 to 10 minutes. By developing the laminate of the present embodiment, as shown in FIG. 3, the unexposed portion of the photosensitive layer is eluted, the non-photosensitive layer on the unexposed portion is broken, and penetrates the photosensitive layer and the non-photosensitive layer. A hole is formed.

Examples of the alkaline developer include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, and choline is dissolved in water so as to have a concentration of about 1 to 10% by mass. Is mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline aqueous solution. In addition, after developing with an alkaline developer, it is washed with water and dried. The alkaline developer is preferably tetramethylammonium hydroxide in terms of excellent resolution.

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

Also, heating can be performed in two stages in order to sufficiently advance the curing or to prevent deformation of the obtained pattern shape. For example, it can be cured by heating at 50 to 120 ° C. for about 5 minutes to 2 hours in the first stage and further heating at 80 to 200 ° C. for about 10 minutes to 10 hours in the second stage.

Under such curing conditions, a general oven, infrared furnace, or the like can be used as a heating facility. The laminated body of the present embodiment is heat-treated after development, whereby the non-photosensitive layer torn as shown in FIG. 4 is fused to the wall surface of the hole to form a via. When the non-photosensitive layer is torn in a shape similar to the shape of the hole, the non-photosensitive layer does not necessarily have to be fused 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. In forming the outer layer circuit, it is preferable 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 borofluoric acid roughening liquid can be used. As the roughening treatment, for example, an aqueous solution of diethylene glycol monobutyl ether and NaOH is first heated as a swelling solution to 80 ° C., and the laminate or multilayer wiring board is immersed for 5 minutes. Next, as a roughening solution, an aqueous solution of KMnO ₄ and NaOH is heated to 80 ° C. and immersed for 10 minutes. Subsequently, KMnO ₄ is reduced by immersing in a neutralizing solution, for example, an aqueous hydrochloric acid solution of stannous chloride (SnCl ₂ ) at room temperature for 5 minutes.

After the roughening treatment, a plating catalyst applying treatment for adhering palladium is performed. The plating catalyst treatment is performed by immersing in a palladium chloride plating catalyst solution. Next, it is immersed in an electroless plating solution to deposit an electroless plating layer (conductor layer) having a thickness of 0.1 to 1.5 μm on the entire surface of the non-photosensitive layer. If necessary, further electroplating is performed to obtain a necessary thickness. As the electroless plating solution used for electroless plating, a known electroless plating solution can be used, and there is no particular limitation. Also, electroplating can be performed by a known method and is not particularly limited. These platings are preferably copper platings. Furthermore, unnecessary portions can be removed by etching to form a circuit layer. Furthermore, a multilayer wiring board with many layers can be manufactured by repeating the same process.

The roughening treatment can also be performed to remove via smear.

[Multilayer printed wiring board]
The cured product formed from the resin composition and the photosensitive composition of the present embodiment is, for example, a surface protection film (overcoat film) and / or an interlayer insulating film (passivation film) of a semiconductor element, or a multilayer printed wiring board. It can be said that it can be suitably used as a solder resist and / or an interlayer insulating layer. Especially, since it is excellent in adhesiveness with copper plating, it can be used suitably as an interlayer insulation layer. FIG. 2 is a view showing a method for producing a multilayer printed wiring board including the cured resin composition and photosensitive composition of the present embodiment 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 an embodiment of the present disclosure will be briefly described with reference to FIG.

First, an interlayer insulating layer 103 is formed on both surfaces of a base material 101 having a wiring pattern 102 formed on the surface (see FIG. 2A). The interlayer insulating layer 103 can be formed by preparing the above-described dry film in advance and using a laminator to attach the photosensitive layer and the non-photosensitive layer of the dry film so that the photosensitive layer is in contact with the printed wiring board. . Alternatively, without using a dry film, the photosensitive composition is applied to the substrate to form a photosensitive layer, and then the resin composition is applied onto the photosensitive layer to form a non-photosensitive layer. Thus, the interlayer insulating layer 103 may be formed. Moreover, you may dry the photosensitive composition or the resin composition. In FIG. 2, the interlayer insulating layer 103 is expressed as a single layer for simplification, but is actually divided into a photosensitive layer and a non-photosensitive layer.

Next, an opening 104 is formed by exposing a region other than a portion that needs to be electrically connected to the outside, developing, and then performing heat treatment (see FIG. 2B). Smear (residue) around the opening 104 is removed by desmear treatment. Next, a seed layer 105 is formed by an electroless plating method (see FIG. 2C). A photosensitive layer of the 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. 2D). Next, a wiring pattern 107 is formed on the portion of the seed layer 105 where the resin pattern 106 is not formed by electrolytic plating, and the resin pattern 106 is removed using a stripping solution, and then the wiring pattern 107 of the seed layer 105 is formed. Unexposed portions are removed by etching (see FIG. 2E). The multilayer printed wiring board 100A can be manufactured by repeating the above operation and forming the solder resist 108 on the outermost surface (see FIG. 2F).

In the multilayer printed wiring board 100A obtained in this way, semiconductor elements are mounted at corresponding locations, and electrical connection can be ensured.

(Second embodiment)
Hereinafter, a second embodiment of the present disclosure will be described. The dry film according to the second embodiment is a dry film including a photosensitive layer and a non-photosensitive layer, and a photosensitive layer and a non-photosensitive layer are formed on a substrate in this order, and the photosensitive layer is exposed to dry By developing the film, the unexposed portion of the photosensitive layer is eluted and the non-photosensitive layer on the unexposed portion is broken, and a via can be formed at a location where the non-photosensitive layer is broken by the heat treatment after development. Is.

Here, the dry film according to the present embodiment includes, for example, a photosensitive layer and a non-photosensitive layer formed in this order on a substrate, and after exposing the photosensitive layer in a predetermined pattern by the above-described method, the non-photosensitive layer And by spraying the photosensitive layer with an aqueous 2.38 mass% tetramethylammonium hydroxide solution for a time corresponding to twice the shortest development time (the shortest time for removing the unexposed portion of the photosensitive layer). As shown in FIG. 3, the unexposed portion of the photosensitive layer is eluted and the non-photosensitive layer on the unexposed portion is broken. In the developed dry film, a hole penetrating the photosensitive layer and the non-photosensitive layer is formed. The development here can also be performed by a method other than the spray method described above. Moreover, you may heat-process the photosensitive layer exposed before developing a dry film. The post-exposure heat treatment is preferably performed under the same conditions as the post-exposure heat treatment in the first embodiment described above.

Thereafter, the developed dry film is heat-treated, so that the torn non-photosensitive layer is fused to the wall surface of the hole as shown in FIG. 4 to form a via. The heat treatment can be performed, for example, at 50 to 250 ° C. for about 30 minutes to 10 hours in one stage. In the first stage, heating is performed at 50 to 120 ° C. for about 5 minutes to 2 hours, and then the second treatment. The heating may be performed in two steps at 80 to 200 ° C. for about 10 minutes to 10 hours.

The non-photosensitive layer and the photosensitive layer in the dry film of the present embodiment are not particularly limited as long as they have the functions described above, and examples thereof include the photosensitive layer and the non-photosensitive layer described in the first embodiment. It is done. Moreover, a resist pattern and a multilayer printed wiring board can be formed by the above-mentioned method by using the dry film of this embodiment. When the photosensitive layer is a positive type, the exposed portion of the photosensitive layer elutes and the non-photosensitive layer on the exposed portion is broken, but vias can be formed at locations where the non-photosensitive layer is broken by the heat treatment after development.

Hereinafter, the present disclosure will be described in detail with reference to examples, but the present disclosure is not limited to the examples. In addition, unless otherwise indicated, the part in a following example and a comparative example is used by the meaning of a mass part.

<Examples A1 to A13 and Comparative Examples A1 to A15>
(Synthesis Example A1) Synthesis of Polyamide A First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, 22 g (132 mmol) of isophthalic acid, 3,4′-oxydianiline 26. 4 g (132 mmol), lithium chloride 3.9 g, calcium chloride 12.1 g, N-methyl-2-pyrrolidone 240 ml and pyridine 54 ml were added and dissolved by stirring. Then, 74 g of triphenyl phosphite was added, and the mixture was heated at 90 ° C. Reaction was performed for 4 hours to obtain a polyamide resin solution. This solution was added to 20 L of methanol to precipitate a polyamide resin, and polyamide A was obtained.

(Synthesis Example A2) Synthesis of Polyamidoimide A First, a diamine compound A having a saturated alicyclic hydrocarbon group (4, 4) was added to a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer. 4'-diamino) dicyclohexylmethane (Wandamine HM (WHM), manufactured by Shin Nippon Chemical Co., Ltd., trade name) 45 mmol, reactive silicone oil as siloxane diamine compound B (X-22-161-B, manufactured by Shin-Etsu Chemical Co., Ltd.) Amine equivalent: 1500, trade name: 5 mmol, trimellitic anhydride (TMA) 105 mmol, and 145 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent were added, and the temperature in the flask was set to 80 ° C. After stirring for 30 minutes, add 100 mL of toluene as an aromatic hydrocarbon azeotropic with water. It added, the temperature in the flask was refluxed heated to approximately 2 hours to 160 ° C.. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.
After returning the solution in the flask to room temperature, 60 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C. and reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide was obtained. This NMP solution was added to 20 L of methanol to precipitate a polyamideimide resin, and polyamideimide A was obtained.

[Preparation of resin composition solution (varnish) used to form non-photosensitive layer]
(Varnish a-1)
After blending 15.9 g of N, N-dimethylacetamide (DMAc) with 1.8 g of the polyamide A obtained in Synthesis Example A1 as the component (C), the biphenyl aralkyl epoxy resin (A) as the component (A) is subsequently added. NC3000H, Nippon Kayaku Co., Ltd., trade name) 5.0 g, (B-1) component cresol novolac type phenol resin (KA1165, DIC Corporation, trade name) 2.1 g is added, and further curing accelerator After adding 0.050 g of 2-phenylimidazole (2PZ, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), it is diluted with a mixed solvent consisting of DMAc and methyl ethyl ketone, and (D) component inorganic filler (AEROSIL R972, Japan) Aerosil Co., Ltd., trade name: 0.50 g was added, and the disperser (Nanomizer, Yoshida Machine Industry Co., Ltd.) Product, product name) was used to obtain varnish a-I (solid content concentration of about 25% by mass).

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

(Varnish a-III)
After blending 15.9 g of N, N-dimethylacetamide (DMAc) with 1.8 g of the phenolic hydroxyl group-containing polyamide (BPAM-155, Nippon Kayaku Co., Ltd., trade name) as component (C), (A) component biphenyl aralkyl type epoxy resin (NC3000H, Nippon Kayaku Co., Ltd., trade name) 5.0 g, (B-1) component cresol novolac type phenol resin (KA1165, manufactured by DIC Corporation, product) Name) 2.1 g was added, and further, 0.050 g of 2-phenylimidazole (2PZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) was added as a curing accelerator, and diluted with a mixed solvent consisting of DMAc and methyl ethyl ketone. D) 0.50 g of inorganic filler (AEROSIL R202, Nippon Aerosil Co., Ltd., trade name) as a component In addition, varnish a-III (solid content concentration: about 25 mass%) was obtained using a disperser (Nanomizer, trade name, manufactured by Yoshida Kikai Kogyo Co., Ltd.).

(Varnish a-IV)
After blending 15.9 g of N, N-dimethylacetamide (DMAc) with 1.8 g of the phenolic hydroxyl group-containing polyamide (BPAM-155, Nippon Kayaku Co., Ltd., trade name) as component (C), Cross-linked organic filler (EXL-2655, manufactured by Rohm and Haas Japan Co., Ltd., trade name) 0.27 g, biphenylaralkyl type epoxy resin (NC3000H, manufactured by Nippon Kayaku Co., Ltd., trade name) as component (A) 5.0 g of bisphenol A novolak type phenolic resin (YLH129, manufactured by Yuka Shell Epoxy Co., Ltd., trade name) as component (B-1) was added, and 2-phenylimidazole (2PZ, Shikoku) was further added as a curing accelerator. Made by Kasei Kogyo Co., Ltd., trade name) 0.050 g is added, and it is a mixed solvent consisting of DMAc and methyl ethyl ketone. After adding 0.52 g of inorganic filler (AEROSIL R202, Nippon Aerosil Co., Ltd., trade name) as component (D), using a disperser (Nanomizer, Yoshida Kikai Co., Ltd., trade name), Varnish a-IV (solid content concentration of about 25% by mass) was obtained.

(Varnish aV)
After blending 1.3 g of N, N-dimethylacetamide (DMAc) with 0.32 g of polyamideimide A obtained in Synthesis Example A2 as component (C), subsequently, a crosslinked organic filler (EXL-2655, Rohm and -Hearth Japan Co., Ltd., trade name: 0.96 g, (A) component phenol novolac epoxy resin (N770, DIC, trade name) 5.0 g, (B-1) component phenol novolac After adding 2.8 g of type phenolic resin (TD2090, manufactured by DIC Corporation, trade name), and further adding 0.050 g of 2-phenylimidazole (2PZ, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator, Dilute with a mixed solvent consisting of DMAc and methyl ethyl ketone, and (D) component inorganic filler (AEROSIL R972, JP 0.54 g of this Aerosil Co., Ltd., trade name) was added, and varnish a-V (solid content concentration of about 25% by mass) was obtained using a disperser (Nanomizer, Yoshida Kikai Kogyo Co., Ltd., trade name). .

(Varnish a-VI)
49 g of polyamide A and 0.15 g of 1-cyanoethyl-2-phenylimidazolium trimellitate (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “2PZ-CNS”) were dissolved in 40 g of methyl ethyl ketone as a solvent to obtain varnish. a-VI was obtained.

(Varnish a-VII)
49 g of polyamide A and 27 g of ester group-containing resin (DIC Corporation, trade name “EXB-9460S”, ester equivalent: 223) were dissolved in 40 g of methyl ethyl ketone as a solvent to obtain varnish a-VII.

<Preparation of solution (varnish) of photosensitive composition>
An alkoxyalkyl compound (G-1), a compound having a glycidyloxy group or an acryloyloxy group (H-1 to H-3), a photo-sensitive acid with respect to 100 parts by mass of the novolak resin (F-1 to F-2) The generator (I-1) and the solvent were blended in the predetermined amounts (unit: parts by mass) shown in Table 1 to obtain varnishes bI to bV.

F-1: Cresol novolak resin (Asahi Organic Materials Co., Ltd., trade name: TR4020G)
F-2: Cresol novolac resin (Asahi Organic Materials Co., Ltd., trade name: TR4080G)
G-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name “MX-270”)
H-1: Trimethylolpropane triglycidyl ether (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: ZX-1542, see formula (3) below)

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.)
Sol-gel silica having an average primary particle size of 15 nm, which is coupled with D′-1: 3-methacryloyloxypropyltrimethoxysilane

<Production of dry film>
The solution of the resin composition used for forming the non-photosensitive layer obtained above becomes uniform in thickness on a polyethylene terephthalate film (product name “Purex A53” manufactured by Teijin DuPont Films Ltd.) (support). And dried for 10 minutes with a hot air convection dryer at 100 to 140 ° C. to form a non-photosensitive layer so that the film thickness after drying was as shown in Tables 2 and 3. Next, the solution of the photosensitive composition obtained above is applied onto the non-photosensitive layer so that the thickness is uniform, and dried for 10 minutes in a hot air convection dryer at 90 ° C., and the film thickness after drying The photosensitive layer was formed so as to have the thicknesses shown in Tables 2 and 3. A polypropylene film (manufactured by Tamapoly Co., Ltd., product name “NF-15”) (protective layer) was bonded onto the photosensitive layer to obtain dry films. The composition of the produced dry film is shown in Tables 2 and 3. In Table 2, in Example A1, a non-photosensitive layer (thickness: 0.5 μm) formed using varnish a-I and a photosensitive layer (thickness) formed using varnish b-I on the support. : 10 μm) and a dry film comprising a protective layer in this order. In other examples and comparative examples, dry films were prepared using solutions of the corresponding resin compositions.

<Preparation of evaluation laminate>
While peeling off the protective layer of the dry film, lamination was performed while peeling off the protective layer so that the photosensitive layer was in contact with the silicon surface of the 6-inch silicon wafer. Lamination is performed using a continuous press type vacuum laminator (trade name “MVLP-500”, manufactured by Meiki Seisakusho Co., Ltd.), pressure bonding pressure 0.4 MPa, press hot plate temperature 90 ° C., evacuation time 20 seconds, laminating press time. The test was performed for 20 seconds and at a pressure of 4 kPa or less. Subsequently, the support was peeled off to obtain an evaluation laminate.

<Evaluation of resolution>
The evaluation laminated body produced by the above-mentioned method was exposed. Exposure was reduced projection exposure through a mask with i-line (365 nm) using an i-line stepper (trade name “FPA-3000iW” manufactured by Canon Inc.). A mask having a via pattern size z μmφ (z = 8, 10, 15, 20, 30, 40, 50, 60, 70) was used. The exposure amount is in the range of 100 ~ 3000mJ / cm ^2, while changing by 100 mJ / cm ^2, was subjected to the reduction projection exposure.

The exposed photosensitive layer is then heated at 65 ° C. for 1 minute and then at 75 ° C. for 8 minutes (post-exposure bake), using a 2.38% by weight aqueous tetramethylammonium hydroxide solution to develop the shortest development time (the photosensitive layer The unexposed portion of the photosensitive layer was removed (development process) by spraying for a time corresponding to twice the shortest time for removing the exposed portion). After the development processing, heat treatment was performed at 180 ° C. for 60 minutes. After the heat treatment, the via pattern formed using a metal microscope was observed, and the resolution was evaluated with the minimum via pattern size. The evaluation results are shown in Tables 2 and 3. Moreover, the scanning electron microscope (SEM) photograph of the via | veer after development processing and heat processing of Example A3 is shown in FIG.3 and FIG.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 torn and a hole that penetrates the developed photosensitive layer and the non-photosensitive layer is formed. It had been. As shown in FIG. 4, when heat treatment was performed after development, the torn part of the non-photosensitive layer shown in FIG. 3 was fused to the wall surface of the hole to form a via. In the case of Comparative Examples A14 and 15 using the non-photosensitive layer composed of varnish a-VI to VII, spraying was performed for 120 seconds and then heat treatment was performed, but the non-photosensitive layer was not broken and a via could not be formed. I understood.
The development was performed by spraying at a pressure of 0.15 MPa using a full cone type nozzle of the developing machine. The distance between the laminate and the tip of the nozzle was 6 cm, and the center of the test piece and the center of the nozzle were aligned.

<Evaluation of adhesive strength (peel strength) and surface roughness>
The evaluation laminated body produced by the above-mentioned method was exposed. For the exposure, the non-photosensitive layer or the photosensitive layer was exposed using an exposure machine having a high-pressure mercury lamp (trade name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.) so that the irradiation energy amount was 3000 mJ / cm ² . The exposed evaluation laminate was heated on a hot plate at 65 ° C. for 2 minutes and then at 95 ° C. for 8 minutes (post exposure bake). Furthermore, it heat-processed for 60 minutes at 180 degreeC with the hot air convection type dryer, and obtained the cured film.

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

The surface roughness Ra of the surface of the insulating resin (non-photosensitive layer (photosensitive layer when no non-photosensitive layer is present) after the heat treatment) after chemical roughening is measured using a micromap MN5000 model manufactured by Ryoka System Co., Ltd. And measured. The evaluation results are shown in Tables 2 and 3.

In order to form a conductor layer on the cured insulating resin surface, first, an electroless plating catalyst activator Neogant 834 (Atotech Japan Co., Ltd., trade name) containing lead chloride (PdCl ₂ ) is set to 35 ° C. Heat and immerse for 5 minutes, immerse in plating solution Print Gantt MSK-DK (trade name, manufactured by Atotech Japan Co., Ltd.) for electroless copper plating for 15 minutes at room temperature, and perform copper sulfate electrolytic plating It was. 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 on the conductor layer by etching, and one end of this region was peeled off by 10 mm at the interface between the conductor layer (copper layer) and the cured insulating resin. Next, the peeled conductor layer was pinched with a gripper, and the load (peel strength) when peeled at room temperature at a pulling speed of 50 mm / min in the thickness direction (vertical direction) of the silicon wafer was measured. The evaluation results are shown in Tables 2 and 3. In this specification, room temperature means 25 ° C.

As is clear from Table 2, Examples A1 to A13 had good resolution and high adhesive strength with a peel strength of 0.3 kN / m or more. On the other hand, it was found that Comparative Examples A1 to A5 had lower peel strength and Comparative Examples A6 to A15 had inferior resolution as compared with the Examples.

<Examples B1 to B8, Comparative Examples B1 to B7>
(Synthesis Example B1) Synthesis of Epoxy Resin A flask equipped with a thermometer and a stirrer was charged with 228 g (1.00 mol) of bisphenol A and 92 g (0.85 mol) of 1,6-hexanediol divinyl ether at 120 ° C. The mixture was heated up to 1 hour, and further reacted at 120 ° C. for 6 hours to obtain 400 g of a transparent semi-solid modified polyhydric phenol. Next, 400 g of the modified polyphenols 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. Thereafter, the temperature was raised to 65 ° C. while purging with nitrogen gas, and then the pressure was reduced to an azeotropic pressure, and 122 g (1.5 mol) of a 49 mass% sodium hydroxide aqueous solution was added dropwise over 5 hours. Subsequently, it stirred for 0.5 hour under the same conditions (65 degreeC, the pressure to azeotrope). During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the organic layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled by distillation under reduced pressure 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. After adding 20 g of 10 mass% sodium hydroxide aqueous solution to the obtained solution and making it react at 80 degreeC for 2 hours, the water washing with 300 g of water was repeated 3 times. After washing three times with water, it was confirmed that the pH of the cleaning solution was neutral. Subsequently, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain 457 g of a transparent liquid epoxy resin A-1. The epoxy equivalent was 403.

<Preparation of resin composition solution (varnish)>
(Preparation Example 1)
(A) component epoxy resin A-1: 24.2 g, (A) component biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 290) 17.4 g, component (B-2) 1-cyanoethyl-2-phenylimidazolium trimellitate (trade name “2PZ-CNS” manufactured by Shikoku Kasei Kogyo Co., Ltd.) and ester group-containing resin (DIC Co., Ltd., product) 27 g of the name “EXB-9460S”, ester equivalent: 223) was dissolved in 40 g of methyl ethyl ketone as a solvent to obtain varnish c-I.

(Preparation Example 2)
Component (A): Epoxy resin A-1: 49 g, Component (B-2): 1-cyanoethyl-2-phenylimidazolium trimellitate (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “2PZ-CNS”) 0.15 g and 27 g of ester group-containing resin (DIC Corporation, trade name “EXB-9460S”, ester equivalent: 223) as component (E) were dissolved in 40 g of methyl ethyl ketone as a solvent to obtain varnish c-II. .

(Preparation Example 3)
Further, 0.25 g of silica (made by Nippon Aerosil Co., Ltd., trade name “AEROSIL R202”, average primary particle size: about 14 nm) is added as a component (D), and a disperser (made by Yoshida Kikai Co., Ltd., trade name “ A varnish c-III was obtained in the same manner as in Preparation Example 1 except that the dispersion was performed using a nanomizer ").

<Preparation of solution (varnish) of photosensitive composition>
Alkoxyalkyl compound (G-1), compound having glycidyloxy group or acryloyloxy group (H-1, H-3), photosensitive acid with respect to 100 parts by mass of novolak resins (F-1 to F-2) A generator (I-1), a solvent (methyl ethyl ketone), and an inorganic filler (D′-1) were blended in predetermined amounts (unit: parts by mass) shown in Table 4, and varnishes dI to d-III were added. Obtained.

<Preparation of Dry Film 1: Examples B1 to B7 and Comparative Examples B1 to B6>
The solution of the resin composition obtained above was applied on a polyethylene terephthalate film (manufactured by Unitika Co., Ltd.) product name “TR-1”) (support) so as to have a uniform thickness, and was heated at 100 to 140 ° C. It dried for 10 minutes with the hot air convection type dryer, and formed the non-photosensitive layer so that the film thickness after drying might be 0.5 micrometer, 1 micrometer, and 1.5 micrometers. Next, the solution of the photosensitive composition obtained above is applied on the non-photosensitive layer so that the thickness is uniform, and dried for 10 minutes in a hot air convection dryer at 90 ° C. A photosensitive layer having a thickness of 10 μm after drying was formed. A polypropylene film (manufactured by Tamapoly Co., Ltd., product name “NF-15”) (protective layer) was bonded onto the photosensitive layer to obtain dry films. Table 5 shows the configuration of the produced dry film. In Table 5, for example, in Example B1, a non-photosensitive layer (thickness: 1 μm) formed using varnish c-I and a photosensitive layer (thickness: formed using varnish d-I) on the support. 10 μm) and a dry film provided with a protective layer in this order. In other examples and comparative examples, dry films were prepared using the corresponding resin composition solution and / or the photosensitive composition solution, respectively.

<Preparation of evaluation laminate>
While peeling off the protective layer of the dry film, lamination was performed so that the photosensitive layer was in contact with the silicon surface of a 6-inch silicon wafer. Lamination is performed using a continuous press type vacuum laminator (trade name “MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.), pressure bonding pressure 0.4 MPa, press hot plate temperature 90 ° C., evacuation time 30 seconds, laminating press time. Forty seconds, the pressure was 4 kPa or less. Subsequently, the support was peeled off to obtain an evaluation laminate.

<Evaluation of resolution>
The evaluation laminated body produced by the above-mentioned method was exposed. Exposure was reduced projection exposure through a mask with i-line (365 nm) using an i-line stepper (trade name “FPA-3000iW” manufactured by Canon Inc.). A mask having a via pattern size z μmφ (z = 20, 30, 80) was used. The exposure amount is in the range of 100 ~ 3000mJ / cm ^2, while changing by 100 mJ / cm ^2, was subjected to the reduction projection exposure.

Next, the exposed photosensitive layer is heated at 75 ° C. for 8 minutes (post-exposure baking), and the shortest development time using the 2.38 mass% tetramethylammonium hydroxide aqueous solution (the shortest time at which the unexposed portion of the photosensitive layer is removed) The unexposed portion of the photosensitive layer was removed (development processing) by spraying for a time corresponding to four times the (time). After the development process, the film was heat-treated at 180 ° C. for 60 minutes in a hot air convection dryer. After the heat treatment, the via pattern formed using a metal microscope was observed. Including the non-photosensitive layer, “A” indicates that the via pattern of 20 μmφ is opened, “B” indicates that the via pattern of 30 μmφ is opened, and “C” indicates that the via pattern of 80 μmφ is opened. ”, Those not opened were evaluated as“ D ”. The evaluation results are shown in Table 5. Moreover, the scanning electron microscope (SEM) photograph of the via | veer after development processing and heat processing of Example B6 is shown in FIG.5 and FIG.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 torn and a hole that penetrates the developed photosensitive layer and the non-photosensitive layer is formed. It had been. As shown in FIG. 6, when heat treatment was performed after development, the torn part of the non-photosensitive layer shown in FIG. 5 was fused to the wall surface of the hole to form a via. In the development, a full cone type nozzle was used and sprayed at a pressure of 0.15 MPa. The distance between the test piece and the nozzle tip was 6 cm, and the center of the test piece was aligned with the center of the nozzle.

<Evaluation of adhesive strength (peel strength) after chemical roughening>
To chemically roughen the evaluation laminate produced by the above method, an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L, sodium hydroxide: 5 g / L was prepared as a swelling liquid and heated to 70 ° C. It was heated and immersed for 10 minutes. Next, an aqueous solution of potassium permanganate: 60 g / L and sodium hydroxide: 40 g / L was prepared as a roughening solution, heated to 70 ° C. and immersed for 5 minutes. Subsequently, an aqueous solution of a neutralizing solution (tin chloride (SnCl ₂ ): 30 g / L, hydrogen chloride: 300 ml / L) was prepared, heated to 40 ° C. and immersed for 5 minutes to reduce potassium permanganate. .

As a pretreatment for electroless plating, it was immersed in conditioner solution “CLC-601” (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 5 minutes at 60 ° C., then washed with water, and pre-dip solution “PD-201” (Hitachi Chemical Co., Ltd.). The product was immersed in a product (trade name) for 2 minutes at room temperature. Next, it was immersed in “HS-202B” (trade name, manufactured by Hitachi Chemical Co., Ltd.), a catalyst for electroless plating containing lead chloride (PdCl ₂ ), at room temperature for 10 minutes, washed with water, and electroless copper The plate was immersed in “CUST-201 plating solution” (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 15 minutes at room temperature, and further subjected to copper sulfate electrolytic 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 on the conductor layer by etching, and one end of this region was peeled off by 10 mm at the interface between the conductor layer (copper layer) and the cured insulating resin. Next, the peeled conductor layer was pinched with a gripper, and the load (peel strength) when peeled at room temperature at a pulling speed of 50 mm / min in the thickness direction (vertical direction) of the silicon wafer was measured. The evaluation results are shown in Table 5. In this specification, room temperature means 25 ° C.

<Evaluation of adhesive strength (peel strength) after UV irradiation>
In the evaluation of the adhesive strengths of Examples B1 to B7 and Comparative Examples B1 to B6, UV irradiation was performed instead of chemical roughening, and the same evaluation was performed by partially changing the pretreatment conditions for electroless plating. It was. The evaluation of adhesive strength will be described below.

The cured film produced by the above method was irradiated with ultraviolet rays. The ultraviolet irradiation was performed using a conveyor type ultraviolet irradiation apparatus with a metal halide lamp (maximum wavelength 350 to 380 nm) at an exposure amount of 3000 mJ / cm ² .

Next, an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L, sodium hydroxide: 5 g / L was prepared, heated to 70 ° C. and immersed for 10 minutes. Thereafter, it is washed with water, and immersed in a conditioner solution “CLC-601” (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 5 minutes at 60 ° C. as a pretreatment for electroless plating, then washed with water, and pre-dip solution “PD- 201 "(trade name, manufactured by Hitachi Chemical Co., Ltd.) for 2 minutes at room temperature. Next, it was immersed in “HS-202B” (trade name, manufactured by Hitachi Chemical Co., Ltd.), a catalyst for electroless plating containing lead chloride (PdCl ₂ ), at room temperature for 10 minutes, washed with water, and electroless copper The plate was immersed in “CUST-201 plating solution” (trade name, manufactured by Hitachi Chemical Co., Ltd.) for 15 minutes at room temperature, and further subjected to copper sulfate electrolytic 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 on the conductor layer by etching, and one end of this region was peeled off by 10 mm at the interface between the conductor layer (copper layer) and the cured resin film. Next, the peeled conductor layer was pinched with a gripper, and the load (peel strength) when peeled at room temperature at a pulling speed of 50 mm / min in the thickness direction (vertical direction) of the silicon wafer was measured. The evaluation results are shown in Table 5. In addition, in this specification, room temperature shows 25 degreeC.

<Evaluation of surface roughness (Ra) of insulating resin layer after conductor layer etching>
A test piece from which the conductor layer was removed was produced by performing an etching process on the conductor layer produced by the method described above. Using an ultra-deep shape measurement microscope “VK-8500 type” manufactured by Keyence Corporation, three different points in the test piece were measured under conditions of a measurement length of 149 μm, a magnification of 2000 times, and a resolution of 0.05 μm. The surface roughness (Ra) of was measured. The evaluation results are shown in Table 5.

<Preparation of Dry Film 2: Example B8 and Comparative Example B7>
The solution of the resin composition obtained above was applied on a polyethylene terephthalate film (manufactured by Unitika Co., Ltd.) product name “TR-1”) (support) so as to have a uniform thickness, and was heated at 100 to 140 ° C. It dried for 10 minutes with the hot air convection type dryer, and formed the non-photosensitive layer so that the film thickness after drying might be set to 1 micrometer. Next, a photosensitive composition (manufactured by Hitachi Chemical Co., Ltd., trade name: Raytec (registered trademark) FZ-2700GA) (d-IV) is laminated on the non-photosensitive layer under the conditions of 100 ° C. and 0.5 MPa. Lamination was performed to obtain a dry film. Table 6 shows the structure of the produced dry film. In Table 3, in Example B8, a non-photosensitive layer (thickness: 1 μm) formed using varnish c-I and a photosensitive composition (d-IV) formed on the support were used. It means that a dry film comprising a layer (thickness: 10 μm) and a protective layer in this order was produced. 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 resolution, surface roughness and peel strength were evaluated by the methods described above. The evaluation results are shown in Table 6.

As is clear from Tables 5 and 6, Examples B1 to B8 have good resolution, and have high peel strength of 0.4 kN / m or more after both chemical roughening and ultraviolet irradiation. showed that. The surface roughness (Ra) of the base resin was as smooth as 0.1 μm in the ultraviolet irradiation process. Compared with the examples, Comparative Examples B1 to B3 were inferior in resolution, and the vias could not be opened. Further, Comparative Examples B4 to B7 resulted in poor peel strength.

The dry film of the present disclosure is applied as a member used for an interlayer insulating film of a wiring board material or an interlayer insulating film (passivation film) of a semiconductor element or the like. In particular, the above-mentioned dry film is suitable for high-density package substrates and the like that are thinned and densified because both the adhesiveness and resolution with the plated copper are good.

DESCRIPTION OF SYMBOLS 1 ... Support body, 3 ... Non-photosensitive layer, 5 ... Photosensitive layer, 7 ... Protective layer, 10 ... Dry film, 100A ... Multilayer printed wiring board, 101 ... Base material, 102, 107 ... Wiring pattern, 103 ... Interlayer insulation layer 104, opening, 105, seed layer, 106, resin pattern, 108, solder resist.

Claims (19)

A dry film comprising a photosensitive layer and a non-photosensitive layer, wherein the non-photosensitive layer contains a thermosetting resin. The non-photosensitive layer is
(A) component: epoxy resin,
The dry film according to claim 1, comprising (B-1) component: an epoxy resin curing agent, and (C) component: a resin having an amide group or an imide group. The non-photosensitive layer is
(E) Component: The dry film of Claim 2 which further contains an ester group containing compound. The non-photosensitive layer is
(A) component: epoxy resin,
The dry film according to claim 1, comprising (B-2) component: an epoxy resin curing accelerator, and (E) component: an ester group-containing compound. The non-photosensitive layer is
Component (D): The dry film according to any one of claims 1 to 4, further comprising an inorganic filler. 6. The dry film according to claim 1, wherein the photosensitive layer has a thickness of 1 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 photosensitive layer is (F) component: a resin having a phenolic hydroxyl group,
(G) component: 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,
(H) component: an aliphatic compound having two or more functional groups selected from acryloyloxy group, methacryloyloxy group, glycidyloxy group and hydroxyl group, and (I) component: containing a photosensitive acid generator The dry film according to any one of claims 1 to 7, wherein The dry film according to claim 8, comprising 20 to 70 parts by mass of the component (H) with respect to 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 (D ') component: an inorganic filler. The dry film according to claim 10, wherein the component (D ') is an inorganic filler having an average primary particle size of 100 nm or less. The dry film according to claim 10 or 11, wherein the component (D ') is silica. 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 using the dry film according to any one of claims 1 to 13. Using the dry film according to any one of claims 1 to 13 to form a photosensitive layer and a non-photosensitive layer in this order on a substrate;
Exposing the photosensitive layer to a predetermined pattern;
A method for forming a resist pattern, comprising a step of developing and heat-treating an exposed photosensitive layer. The method for forming a resist pattern according to claim 15, further comprising a step of performing a heat treatment before developing the exposed photosensitive layer. A dry film comprising a photosensitive layer and a non-photosensitive layer,
The photosensitive layer and the non-photosensitive layer are formed in this order on the substrate, the photosensitive layer is exposed, and the dry film is developed. A dry film in which vias can be formed where the non-photosensitive layer is broken and the non-photosensitive layer is broken by heat treatment after development. A laminate in which a base material, a photosensitive layer, and a non-photosensitive layer containing a thermosetting resin are laminated in this order. Applying a photosensitive composition on a substrate to form a photosensitive layer;
Applying a resin composition containing a thermosetting resin on the photosensitive layer to form a non-photosensitive layer;
Exposing the photosensitive layer to a predetermined pattern;
A method for forming a resist pattern, comprising a step of developing and heat-treating an exposed photosensitive layer.

Images