WO2016157622A1 - Dry film, cured product, semiconductor device, and method for forming resist pattern - Google Patents

Abstract

The purpose of the present invention is to provide a dry film capable of forming a resist pattern having excellent resolution and heat resistance, even when a photosensitive layer having a thickness exceeding 20 μm is formed. Provided is a dry film provided, in the following order, with: a support body; a silicone resin layer or an alkyd resin layer; and a photosensitive layer. The photosensitive layer contains a component (A), a component (D), and at least one of a component (B) and a component (C).

Description

Dry film, cured product, semiconductor device, and resist pattern forming method

The present disclosure relates to a dry film, a cured product, a semiconductor device, and a resist pattern forming method.

In the manufacture of semiconductor elements or printed wiring boards, for example, a negative photosensitive resin composition is used to form a fine pattern. In this method, a photosensitive layer is formed on a base material (a chip in the case of a semiconductor element, a substrate in the case of a printed wiring board) by application of a photosensitive resin composition, and actinic rays are irradiated through a predetermined pattern. Furthermore, a resin pattern is formed on a base material by selectively removing unexposed portions using a developer. Therefore, the photosensitive resin composition is required to have a short development time (development property), photosensitivity to actinic rays, excellent ability to form a fine pattern (resolution), and the like. Therefore, a photosensitive resin composition containing a novolak resin soluble in an alkaline aqueous solution, an epoxy resin and a photoacid generator, a photosensitive resin composition containing an alkali-soluble epoxy compound having a carboxyl group and a photocationic polymerization initiator, etc. Has been proposed (see, for example, Patent Documents 1 to 3). With the recent increase in the density of printed wiring boards, there is an increasing demand for a photosensitive resin composition capable of forming a resist pattern with excellent resolution.

In addition, from the viewpoint of workability when forming a photosensitive layer on a substrate, the photosensitive resin composition is also required to have excellent adhesion (tackiness) to the substrate. When using the photosensitive resin 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.

Furthermore, the surface protective film and the interlayer insulating film used in the semiconductor element are required to have insulation reliability such as heat resistance, electrical characteristics, and mechanical characteristics. Therefore, a photosensitive resin composition further containing a crosslinkable monomer has been proposed (see, for example, Patent Document 4).

Also, by forming a thick interlayer insulating film, the insulation between the wirings in the thickness direction of the layer can be improved and the short circuit of the wiring can be prevented, so that the reliability regarding the insulation between the wirings is improved. Further, when mounting a chip, since the semiconductor element has a thick interlayer insulating film, the stress applied to the pads of the solder bumps can be relieved, so that poor connection is unlikely to occur during mounting. Therefore, from the viewpoint of insulation reliability and productivity when mounting a chip, it is also required that a film of a thick photosensitive resin composition exceeding 20 μm can be formed.

Japanese Patent Application Laid-Open No. 06-059444 Japanese Patent Laid-Open No. 09-087366 International Publication No. 2008/010521 JP 2003-215802 A

In particular, in manufacturing a package substrate, it is difficult to form a resist pattern having an L / S (line width / space width) of 10/10 (unit: μm) or less. Therefore, there is a strong demand to improve the resolution by reducing the resolution of the resist pattern even in units of 1 μm.

However, the photosensitive resin composition described in the above prior art document is excellent in insulation reliability and the like, but it is difficult to achieve high resolution when the film is thickened. For example, in the photosensitive resin composition described in Patent Document 2, when the thickness of the coating film is 50 μm, the resolution is such that the space width is about 40 μm, which is insufficient for highly integrated semiconductor elements. is there. In addition, the photosensitive resin composition described in Patent Document 3 may not exhibit sufficient heat resistance. Moreover, in the photosensitive resin composition of patent document 1 or 4, when the thickness of the coating film is 10 μm, good resolution with a space width of about 5 μm is obtained. In this case, good resolution cannot be obtained.

The purpose of the present disclosure is to solve the problems associated with the prior art as described above, and to form a resist pattern having excellent resolution and heat resistance even when a photosensitive layer having a thickness exceeding 20 μm is formed. It is to provide a possible dry film. Another object of the present disclosure is to provide a cured product obtained using the photosensitive layer in the dry film, a semiconductor device using the cured product, and a method for forming a resist pattern using the dry film. is there.

The dry film of the present disclosure includes a support, a silicone resin layer or an alkyd resin layer, and a photosensitive layer in this order. The photosensitive layer has a component (A): a resin having a phenolic hydroxyl group, and component (B): aroma. A compound having at least one selected from the group consisting of a ring, a heterocyclic ring and an alicyclic ring and having a methylol group or an alkoxyalkyl group, and (C) component: an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group An aliphatic compound having two or more functional groups selected from hydroxyl groups and (D) component: a light-sensitive acid generator.

The thickness of the photosensitive layer may be less than 50 μm.

The photosensitive layer may contain 20 to 70 parts by mass of the component (C) with respect to 100 parts by mass of the component (A).

The component (C) may have three or more functional groups.

The present disclosure provides a cured product obtained using the photosensitive layer in the dry film. The present disclosure also provides a semiconductor device provided with the cured product as a surface protective film or an interlayer insulating film.

Further, the present disclosure includes a step of forming a photosensitive layer on a substrate using a dry film, a step of exposing the photosensitive layer to a predetermined pattern and performing a post-exposure heat treatment, and a photosensitive layer after the heat treatment. And a step of heat-treating the obtained resin pattern. A method for forming a resist pattern is provided.

According to the dry film of the present disclosure, it is possible to form a resist pattern excellent in resolution and heat resistance even when a photosensitive layer having a thickness exceeding 20 μm is formed. Moreover, according to this indication, the hardened | cured material obtained using the photosensitive layer in the said dry film, the semiconductor device using the said hardened | cured material, and the formation method of the resist pattern using the said dry film can be provided.

1 is a schematic cross-sectional view of a dry film according to an embodiment of the present disclosure. It is a mimetic diagram showing a manufacturing method of a multilayer printed wiring board concerning one embodiment of this indication.

Hereinafter, an embodiment of the present disclosure will be specifically described with reference to the drawings. However, the present disclosure is not limited thereto. In the following description, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.

In the present specification, “EO modification” means a compound having a (poly) oxyethylene group, and “PO modification” means a compound having a (poly) oxypropylene group. means. Here, the (poly) oxyethylene group means at least one kind of polyoxyethylene group in which an oxyethylene group or two or more ethylene groups are linked by an ether bond. The (poly) oxypropylene group means at least one of an oxypropylene group or a polyoxypropylene group in which two or more propylene groups are linked by an ether bond.

Further, in this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term is used as long as the intended action of the process is achieved. include. In the present 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. In addition, in this specification, the term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when viewed in plan.

Furthermore, in the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.

[Dry film]
The dry film of this embodiment is demonstrated referring FIG. FIG. 1 is a schematic cross-sectional view of a dry film 10 according to this embodiment. As shown in FIG. 1, the dry film according to the present embodiment includes a support 1, a silicone resin layer or alkyd resin layer 3, and a 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.

<Photosensitive resin composition>
The photosensitive resin composition forming the photosensitive layer 5 of the present embodiment contains the component (A), one or both of the component (B) and the component (C), and the component (D). Here, the component (A) is a resin having a phenolic hydroxyl group, the component (B) has at least one selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and a methylol group or (C) component is an aliphatic compound having two or more functional groups selected from acryloyloxy group, methacryloyloxy group, glycidyloxy group and hydroxyl group. Component D) is a photosensitive acid generator. In addition, the photosensitive resin composition may contain, as necessary, (E) component: solvent, (F) component: inorganic filler, (G) component: silane coupling agent, (H) component: sensitizer, (I ) Component: amine, (J) component: organic peroxide, (K) component: leveling agent and the like.

The present inventors consider that the reason why a resin pattern having excellent resolution and heat resistance can be formed by the photosensitive resin composition is as follows. When the component (C) is contained, the solubility of the component (A) in the developer is significantly improved by the component (C) in the unexposed area. In the case where the component (B) is contained, in the exposed area, the methylol group or alkoxyalkyl group in the component (B) reacts with the phenolic hydroxyl group in the component (A) by the acid generated from the component (D), and photosensitivity to the developer. The solubility of the conductive resin composition is greatly reduced. When both (B) component and (C) component are contained, the methylol group or alkoxyalkyl group in (B) component can also react with (C) component. By including the component (B) and / or the component (C) as described above, sufficient resolution can be obtained due to a remarkable difference in solubility in the developing solution between the unexposed area and the exposed area when developed. . Depending on the structure of component (C), a negative pattern can be formed even if the photosensitive resin composition does not contain component (B). Moreover, the heat resistance of a resin pattern can be improved by including any one of (B) component and (C) component, but it is photosensitive resin from a viewpoint of forming a negative type pattern with higher heat resistance. The composition may contain both the component (B) and the component (C). For this reason, the reaction between the component (B) and the component (C) or the component (A) further proceeds by heat treatment of the resin pattern after development, and a cured product having sufficient heat resistance is obtained. The present inventors speculate.

<(A) component>
(A) Although it does not specifically limit as resin which has the phenolic hydroxyl group which is a component, A resin soluble in alkaline aqueous solution may be sufficient, and a novolak resin may be sufficient. 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.

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

Component (A) has a weight average molecular weight of 100,000 or less, 1000 to 80000, 2000 to 50000, 2000 to 20000, from the viewpoint of further improving the resolution, developability, thermal shock resistance, heat resistance and the like of the resulting resin pattern. Or it may be 5000-15000. “Weight average molecular weight” refers to a value measured using a standard polystyrene calibration curve in accordance with a gel permeation chromatography (GPC) method. More specifically, a pump (manufactured by Hitachi, Ltd., L -6200 type), column (TSKgel-G5000HXL and TSKgel-G2000HXL, both manufactured by Tosoh Corporation, trade name) and detector (Hitachi, Ltd., L-3300RI type) with tetrahydrofuran as eluent And measured at a temperature of 30 ° C. and a flow rate of 1.0 mL / min.

In the photosensitive resin composition, the content of the component (A) is 30 with respect to 100 parts by mass of the total amount of the photosensitive resin composition (excluding the component (E) when the component (E) is used). It may be ~ 90 parts by mass, or 40-80 parts by mass. When the content of the component (A) is within this range, the film formed using the resulting photosensitive resin composition tends to have further developability with an alkaline aqueous solution.

<(B) component>
The photosensitive resin composition contains, as the component (B), 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. Also good. 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 hetero atom such as a nitrogen atom, oxygen atom, sulfur atom (for example, a cyclic group having 3 to 10 carbon atoms), such as a pyridine ring, an imidazole ring, Examples include a pyrrolidinone ring, 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. Two alkyl groups may be the same or different. The alkyl group is, for example, an alkyl group having 1 to 10 carbon atoms.

By containing the component (B), when the photosensitive layer after the resin pattern is formed is heated and cured, the component (B) reacts with the component (A) to form a bridge structure, and the resin pattern is weak. And deformation of the resin pattern can be prevented, and heat resistance can be improved. Further, as the component (B), specifically, a compound further having a phenolic hydroxyl group, a compound further having a hydroxymethylamino group, or a compound further having an alkoxymethylamino group can be used. The component (C) is not included. (B) A component can be used individually by 1 type or in mixture of 2 or more types.

As will be described later, by including the component (D) in the photosensitive resin composition, an acid is generated by irradiation with actinic rays or the like. Due to the catalytic action of the generated acid, the alkoxyalkyl groups in component (B) or the alkoxyalkyl groups in component (B) react with component (A) with dealcoholization to form a negative pattern. can do. Further, due to the catalytic action of the generated acid, the methylol groups in the component (B) or the methylol groups in the component (B) react with the component (A) with dealcoholization to form a negative pattern. Can be formed.

The “compound further having a phenolic hydroxyl group” used as the component (B) has a methylol group or an alkoxyalkyl group, so that not only the reaction with the component (C) or the component (A) but also the development with an alkaline aqueous solution. It is possible to increase the dissolution rate of the unexposed portion of the film and improve the resolution. The molecular weight of the compound having a phenolic hydroxyl group is 94 to 2000, 108 to 2000, or 108 to 108 in terms of weight average molecular weight in consideration of improving the solubility, resolution, mechanical properties and the like in an alkaline aqueous solution in a balanced manner. 1500 may be sufficient. 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.

As the compound further having a phenolic hydroxyl group, conventionally known compounds can be used, but the balance between the effect of promoting dissolution of the unexposed area and the effect of preventing melting during development (heat treatment) of the resin pattern after development. Therefore, it may be a compound represented by the following general formula (1).

In general formula (1), Z represents a single bond or a divalent organic 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) may be a compound represented by the following general formula (2).

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

Moreover, you may use the compound represented by following General formula (3) as a compound which further 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 the general formula (1), the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic 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 having 2 to 10 carbon atoms such as an ethylidene group An arylene group having 6 to 30 carbon atoms such as a phenylene group; a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms; a sulfonyl group; a carbonyl group; an ether bond A sulfide bond; an amide bond and the like. Among these, Z may be a divalent organic group represented by the following general formula (4).

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), A group in which part or all of the hydrogen atoms are substituted with a halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond or an amide bond is shown. 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 further having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) ( N-hydroxymethyl) urea and the like. 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 further having an alkoxymethylamino group may be a compound represented by the following general formula (5) or a compound represented by the following general formula (6).

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 the component (B) may be 5 to 60 parts by mass, 10 to 45 parts by mass, or 10 to 35 parts by mass with respect to 100 parts by mass of the component (A). When the content of the component (B) is 5 parts by mass or more, the reaction of the exposed part becomes sufficient, so that the resolution is hardly deteriorated and the chemical resistance and heat resistance tend to be good, and 60 parts by mass. When it is below, it becomes easy to form a photosensitive resin composition on a desired support, and the resolution tends to be good.

<(C) component>
Component (C): An aliphatic compound having two or more functional groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group is an adhesive between the photosensitive resin composition and the support. Property, that is, tackiness can be improved. Furthermore, it is possible to increase the dissolution rate of the unexposed area when developing with an alkaline aqueous solution, and to improve the resolution. In addition, (C) 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. From the viewpoint of tackiness and solubility in an aqueous alkali solution, the molecular weight of component (C) may be 92 to 2000, 106 to 1500, or 134 to 1300 in terms of weight average molecular weight in consideration of balance. When it is difficult to measure a compound having a low molecular weight by the above-described method for measuring the weight average molecular weight, the average can be calculated by measuring the molecular weight by another method. 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.

The functional group of component (C) may be a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, a glycidyloxy group or an acryloyl group, or an acryloyloxy group. Moreover, (C) component may have 3 or more of the said functional groups. The upper limit of the number of functional groups is not particularly limited, but is 12 for example. Specific examples of the component (C) include compounds represented by the following general formulas (7) to (10).

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), and 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 a general formula (13). shows a group each R ²² and R ²³ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, n and m are the integer of 1 to 10

Examples of the compound having a glycidyloxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl. Ether, glycerin diglycidyl ether, dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerin triglycidyl ether, Glycerol propoxyle Totori glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, diglycidyl 1,2-cyclohexane dicarboxylate, and the like. These compounds having a glycidyloxy group can be used singly or in combination of two or more.

Among the compounds having a glycidyloxy group, trimethylolethane triglycidyl ether or trimethylolpropane triglycidyl ether may be used in terms of excellent photosensitivity 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 (product name) manufactured by Kyoeisha Chemical Co., Ltd., alkyl type epoxy resin ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L and Denacol EX-850L Name).

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, and ditrimethylolpropane. 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 Trimethylo Propane acrylate, trimethylol propane 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.

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, and ditrimethylolpropane. 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 Over DOO, 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.

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 content of component (C) may be 20 to 70 parts by mass, 25 to 65 parts by mass, or 35 to 55 parts by mass with respect to 100 parts by mass of component (A). If the content of the component (C) is 20 parts by mass or more, there is a tendency that crosslinking in the exposed part is sufficient and tackiness is sufficient, and if it is 70 parts by mass or less, the photosensitive resin composition is supported as desired. It tends to form a film on the body, and the resolution tends not to decrease.

<(D) component>
The photosensitive acid generator which is (D) component is a compound which generate | occur | produces an acid by irradiation of actinic rays. In addition, when the component (B) is included, not only the components (B) react with each other due to the generated acid, but the component (B) also reacts with the component (A) or the component (C), and is sensitive to the developer. By reducing the solubility of the resin composition, a negative pattern can be formed. In the case where the component (C) is a compound having an acryloyloxy group or a methacryloyloxy group, radical polymerization of the acryloyloxy group or methacryloyloxy group also proceeds by irradiation with an actinic ray or the like.

The component (D) is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or the like. Etc. Among them, an onium salt compound or a sulfonimide compound may be used from the viewpoint of availability. In particular, when a solvent is used as the component (E), an onium salt compound may be used from the viewpoint of solubility in the solvent. 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. Specific examples of onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate and the like diaryliodonium salts; triphenylsulfonium trifluoride Triarylsulfonium salts such as lomethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate; 4-t-butylphenyl-diphenylsulfonium trifluoromethanesulfonate; 4-t-butylphenyl-diphenylsulfonium p-toluene Sulfonate; 4,7-di-n Such as 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) naphthalimide, N- (p-toluenesulfonyloxy) -1,8- And naphthalimide and N- (10-camphorsulfonyloxy) -1,8-naphthalimide.

In the present embodiment, the component (D) is a compound having a trifluoromethanesulfonate group, a hexafluoroantimonate group, a hexafluorophosphate group, or a tetrafluoroborate group in that the photosensitivity and resolution are further improved. There may be. Moreover, (D) component can be used individually by 1 type or in mixture of 2 or more types.

The content of the component (D) is 0.1 to 15 parts by mass with respect to 100 parts by mass of the component (A), or 0.1 to 0.1 parts by mass from the viewpoint of improving photosensitivity, resolution, pattern shape and the like. It may be 3 to 10 parts by mass.

<(E) component>
The photosensitive resin composition may further contain a solvent as the component (E) in order to improve the handleability of the photosensitive resin composition or to adjust the viscosity and storage stability. The component (E) may be an organic solvent. Such an organic solvent is not particularly limited as long as it can exhibit the above-mentioned performance. For example, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, etc. Propylene glycol dialkyl ethers; Propylene glycol monoalkyl ether acetates such as coal monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; Lactic acid esters such as methyl lactate, 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 and 3-methoxy Other esters such as ethyl lopionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; 2-butanone, 2-heptanone, 3 -Ketones such as heptanone, 4-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 component (E) is 30 to 200 parts by weight, 50 to 120 parts by weight, or 60 to 120 parts by weight with respect to 100 parts by weight of the total amount of the photosensitive resin composition excluding the component (E). Also good.

<(F) component>
The photosensitive resin composition contains an inorganic filler as the component (F), and according to the content of the component (F), the thermal expansion of the cured product obtained by heating the photosensitive layer after the resin pattern is formed. The coefficient can be reduced. (F) A component can be used individually by 1 type or in mixture of 2 or more types. The inorganic filler may have a maximum particle size of 2 μm or less when dispersed in the resin composition.

Examples of the inorganic filler include aluminum compounds such as aluminum oxide and aluminum hydroxide; alkali metal compounds; alkaline earth metal compounds such as calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide and magnesium hydroxide; talc And inorganic compounds derived from mines such as mica; silica such as fused spherical silica, fused and ground silica, fumed silica, and sol-gel silica. These are pulverized by a pulverizer, classified according to circumstances, and can be dispersed with a maximum particle size of 2 μm or less.

Any inorganic filler can be used, but silica may be used. Silica may have a thermal expansion coefficient of 5.0 × 10 ⁻⁶ / ° C. or less, and may be silica such as fused spherical silica, fumed silica, sol-gel silica from the viewpoint of particle diameter, It may be fumed silica or sol-gel silica. As the silica, silica (nanosilica) having an average primary particle diameter in the range of 5 nm to 100 nm may be used. These may be dispersed in the photosensitive resin composition with a maximum particle size of 2 μm or less. At that time, a silane coupling agent can be used in order to disperse the resin in the resin without aggregation.

When measuring the particle diameter of each inorganic filler, a known particle size distribution meter may be used. For example, the maximum particle diameter of the inorganic filler is the maximum particle diameter of the inorganic filler in a state dispersed in the photosensitive resin composition, and is a value obtained by measurement as follows. First, after diluting (or dissolving) the photosensitive resin composition 1000 times (volume ratio) with methyl ethyl ketone, using a submicron particle analyzer (Beckman Coulter, trade name, model: N5), In accordance with the standard ISO 13321, particles dispersed in a solvent with a refractive index of 1.38 are measured, and the particle size at an integrated value of 99.9% (volume basis) in the particle size distribution is defined as the maximum particle size. Moreover, even if it is the hardened | cured material of the photosensitive layer provided on the support body or the photosensitive resin composition, after diluting (or melt | dissolving) 1000 times (volume ratio) using a solvent as mentioned above, It can be measured using a submicron particle analyzer.

The content of the component (F) may be 1% by mass or more and 70% by mass or less based on the total amount of the photosensitive resin composition excluding the component (E), or 3% by mass or more and 65% by mass or less. There may be.

The average primary particle diameter of the inorganic filler used in the present embodiment may be 100 nm or less, or 80 nm or less, and may be 50 nm or less from the viewpoint of photosensitivity. When the average primary particle size is 100 nm or less, the photosensitive resin composition is less likely to become cloudy, light such as an actinic ray for exposure is easily transmitted through the resin composition, and unexposed portions are easily removed. There is a tendency that the resolution is not easily lowered.

The average primary particle diameter is a value obtained by conversion from the BET specific surface area.

<(G) component>
The photosensitive resin composition may contain a silane coupling agent as the component (G). By containing the component (G), the adhesion strength between the photosensitive layer and the substrate after the resin pattern is formed can be improved.

As the component (G), generally available compounds can be used. For example, alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acryloyl silane, methacrylo silane, mercapto silane, sulfide silane, isocyanate silane, Sulfur silane, styryl silane, alkylchlorosilane, and the like can be used.

Specific examples of the component (G) include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyl. Trimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, Diphenyldimethoxysilane, triphenylsilanol, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, n-octi Dimethylchlorosilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane , 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane Vinyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane, and aminosilane.

(G) The component may be an epoxy silane having one or more glycidyloxy groups, or an epoxy silane having a trimethoxysilyl group or a triethoxysilyl group. Further, acryloylsilane or methacryloylsilane may be used.

The content of the component (G) may be 1 to 20 parts by mass, or 3 to 10 parts by mass with respect to 100 parts by mass of the component (A).

<(H) component>
The photosensitive resin composition may contain a sensitizer as the component (H). Examples of the sensitizer include 9,10-dibutoxyanthracene. Moreover, (H) component can be used individually by 1 type or in mixture of 2 or more types. By containing the component (H), the photosensitivity of the photosensitive resin composition can be improved.

The content of the component (H) may be 0.01 to 1.5 parts by mass, or 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the component (A).

In addition to the component (A), the photosensitive resin composition may contain a phenolic low molecular compound having a molecular weight of less than 1000 (hereinafter referred to as “phenol compound (a)”). For example, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, tris (4-hydroxyphenyl) ) Ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6 -Bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) ) -1-methylethyl} phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane and the like. These phenolic compounds (a) can be contained in an amount of 0 to 40% by mass, particularly 0 to 30% by mass, based on the component (A).

Moreover, the photosensitive resin composition may contain other components other than the above-mentioned components. Examples of the other components include inhibitors for reactions accompanying irradiation with active rays, adhesion assistants, and the like.

<Support>
As the support, for example, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used. In addition, you may use the said polymer film by laminating | stacking on both surfaces of a photosensitive layer so that a photosensitive layer may be pinched | interposed using one as a support body and the other as a protective layer.

<Silicone resin layer or alkyd resin layer>
The dry film according to this embodiment includes a silicone resin layer or an alkyd resin layer on a support. Thereby, when a photosensitive layer is laminated on a substrate, the photosensitive layer can be easily transferred to the substrate, and in particular, the resolution can be improved. In the dry film 10, a silicone resin layer or alkyd resin layer 3 is formed on the support 1. In addition, when the support body 1 and the photosensitive layer 5 are peeled, the silicone resin layer or the alkyd resin layer 3 should just be provided on the support body 1. FIG. That is, it can be said that the support 1 may or may not be integrated with the silicone resin layer or the alkyd resin layer 3. At least one surface of the support may be treated with a silicone resin or an alkyd resin. Here, the treatment with the silicone resin or alkyd resin refers to a chemical treatment in which the silicone resin or alkyd resin is thinly applied (coated) to the surface of the support. Examples of the silicone resin include silicone-modified resin and polydimethylsiloxane.

When the silicone resin or alkyd resin is applied to the support, it may be thinly applied as long as the release effect is obtained. After application, a silicone resin or alkyd resin may be fixed to the support by heat or UV treatment. Before applying the silicone resin or alkyd resin, an undercoat layer may be applied to the support.

Further, from the viewpoint of the peelability (release property) of the photosensitive layer, the 180 ° C peel strength at 23 ° C of the silicone resin-treated surface or alkyd resin-treated surface of the support is 5 to 300 gf / inch (1.97 to 118 gf / inch). cm or 19.3 × 10 ⁻³ to 1156.4 × 10 ⁻³ N / cm), 5 to 200 gf / inch (1.97 to 78.7 gf / cm or 19.3 × 10 ⁻³ to 771.3 × 10 ⁻³ N / cm), or 100 to 200 gf / inch (39.4 to 78.7 gf / cm or 386.1 × 10 ⁻³ to 771.3 × 10 ⁻³ N / cm). The 180 ° peel strength can be measured by a general method (for example, a method according to JIS K6854-2) using an adhesive tape (manufactured by Nitto Denko Corporation, product name: “NITTO31B”). .

The thickness of the silicone resin layer or alkyd resin layer may be about 0.005 to 1 μm, particularly 0.01 to 0.1 μm. When the thickness of the silicone resin layer or alkyd resin layer is in the above range, the adhesion between the support and the silicone resin layer or alkyd resin layer is improved. Note that the dry film may include both a silicone resin layer and an alkyd resin layer.

Examples of PET films having at least one surface treated with silicone resin or alkyd resin include, for example, product names “Purex A53”, “Purex A70”, “Purex A31-25” manufactured by Teijin DuPont Films Ltd. “Purex A51-25” and “Purex A53-38” are commercially available (“Purex” is a registered trademark). The support in the dry film according to the present embodiment may be provided with a silicone resin layer on the support from the viewpoint of easy availability.

The thickness of the support having at least one surface treated with silicone resin or alkyd resin may be 15 to 50 μm, or 25 to 40 μm. When the thickness of the support is 15 μm or more, distortion during treatment with a silicone resin or an alkyd resin hardly remains, and generation of wrinkles tends to be suppressed when the dry film is wound into a roll. There is. When the thickness of the support is 50 μm or less, bubbles tend not to be caught between the substrate and the photosensitive layer during thermocompression bonding when the photosensitive layer is laminated on the substrate.

<Protective layer>
As the protective layer 7, polymer films, such as polyester, such as polyethylene, a polypropylene, a polyethylene terephthalate, can be used, for example. Moreover, you may use the polymer film which processed with the silicone resin or the alkyd resin like the support body. From the viewpoint of flexibility when winding the dry film into a roll, a polyethylene film may be used as the protective layer. Further, the protective layer may be a low fish eye film because it can reduce dents on the surface of the photosensitive layer.

The thickness of the protective layer 7 may be 10 to 100 μm, or 15 to 80 μm.

The photosensitive layer may be formed by applying the photosensitive resin composition onto a silicone resin-treated surface or alkyd resin-treated surface of a support, a silicone resin layer or alkyd resin layer on a support, or a protective layer. it can. 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. Although the thickness of the photosensitive layer varies depending on the use, the photosensitive layer of the dry film should be 1 to 100 μm, 3 to 60 μm, 5 to 50 μm, 5 to 50 μm, or 5 to 25 μm after drying the photosensitive layer. This is particularly preferable in that the film-forming property on the body and the resolution of the photosensitive layer are good.

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

First, a photosensitive layer is formed using a dry film as described above on a substrate (resin-coated copper foil, copper-clad laminate, silicon wafer with a metal sputtered film, alumina substrate, etc.) on which a resist pattern is to be formed.

Next, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. Examples of actinic rays used for exposure include visible rays from g-line steppers and the like; ultraviolet rays from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, i-line steppers, and the like; electron beams; The amount of exposure is appropriately selected depending on the light source used, the thickness of the photosensitive layer, and the like. For example, when irradiating ultraviolet rays from a high-pressure mercury lamp, when the thickness of the photosensitive layer is 10 to 50 μm, about 100 to 5000 mJ / cm ^2. It is. In addition, when exposing a photosensitive layer, a photosensitive layer may be exposed through a support body, and a photosensitive layer may be exposed after peeling a support body.

Furthermore, heat treatment (post exposure bake) is performed after exposure. By performing post-exposure baking, the curing reaction between the component (A) and the component (B) by the acid generated from the photosensitive acid generator can be promoted. The post-exposure baking conditions vary depending on the composition of the photosensitive resin composition, the content of each component, the thickness of the photosensitive layer, etc., but it may usually be heated at 70 to 150 ° C. for 1 to 60 minutes, and 80 to 120 You may heat at 1 degreeC for 1 to 60 minutes.

Next, the photosensitive layer that has been baked after exposure is developed with an alkaline developer, and the unexposed areas are dissolved and removed to obtain a desired resin pattern. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The development conditions are usually 20 to 40 ° C. and 1 to 10 minutes.

Examples of the alkaline developer include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and choline is dissolved in water to have a concentration of about 1 to 10% by mass, or Examples include alkaline aqueous solutions such as aqueous ammonia. 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 this alkaline developing solution, it wash | cleans with water and dries. The alkaline developer may be an aqueous tetramethylammonium hydroxide solution in terms of excellent resolution.

Furthermore, a cured product (resist pattern) of the photosensitive resin composition is obtained by heat-treating the resin pattern obtained to develop the insulating film characteristics. The curing conditions are not particularly limited, but the resin pattern can be cured by heating at 50 to 250 ° C. for 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 resin pattern. For example, it can be cured by heating at 50 to 120 ° C. for 5 minutes to 2 hours in the first stage, and further at 80 to 200 ° C. for 10 minutes to 10 hours in the second stage.

If it is the above-mentioned curing conditions, there is no particular limitation on the heating equipment, and a general oven, infrared furnace, or the like can be used.

[Multilayer printed wiring board]
The cured product containing the photosensitive resin composition can be suitably used as, for example, a solder resist and / or an interlayer insulating film in a multilayer printed wiring board. FIG. 2 is a diagram illustrating a method for manufacturing a multilayer printed wiring board including the cured product of the present embodiment as a solder resist and / or an interlayer insulating film. The multilayer printed wiring board 100A shown in FIG. 2 (f) has a wiring pattern on the surface and inside. Hereinafter, a method for 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 film 103 is formed on both surfaces of a base material 101 having a wiring pattern 102 on the surface (see FIG. 2A). The interlayer insulating film 103 is formed by preparing the above-described dry film in advance and attaching the photosensitive layer in the dry film to the surface of the substrate 101 using a laminator. Next, an opening 104 is formed using a YAG laser or a carbon dioxide gas laser in a place that needs to be electrically connected to the outside (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 containing a semi-additive photosensitive resin composition is laminated on the seed layer 105, and a predetermined portion is exposed and developed to form a resin pattern 106 (see FIG. 2D). An adhesion layer, for example, a titanium layer having a thickness of about 30 nm is formed on the seed layer, and a Cu layer having a thickness of about 100 nm is further formed. These adhesion layers can be formed by sputtering. 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, the resin pattern 106 is removed with a stripping solution, and then the seed layer 105 is removed by etching (FIG. 2 (e)). By repeating the above operation and forming a solder resist 108 containing a cured product of the above-described photosensitive resin composition on the outermost surface, the multilayer printed wiring board 100A can be produced (see FIG. 2 (f)).

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

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.

<Preparation of photosensitive resin composition>
Compound (B-1 to B-3) having two or more methylol groups or alkoxyalkyl groups, acryloyloxy group, methacryloyloxy group, glycidyloxy with respect to 100 parts by mass of novolak resin (A-1 to A-2) Compounds having two or more functional groups selected from a group and a hydroxyl group (C-1 to C-8, C′-9 to C′-10), photosensitive acid generator (D-1) Then, the solvent (E-1) and the inorganic filler (F-1) were blended in the predetermined amounts shown in Table 1 to obtain a photosensitive resin composition.

<Production of dry film>
As the support, those having a silicone resin layer or an alkyd resin layer formed on the support and those not formed were prepared. The photosensitive resin composition is applied on a support or a silicone resin layer or an alkyd resin layer so that the thickness of the photosensitive resin composition is uniform, and dried for 10 minutes in a hot air convection dryer at 90 ° C. Then, a photosensitive layer having a thickness after drying shown in Table 1 was formed. A polyethylene film (product name: NF-15, manufactured by Tamapoly Co., Ltd.) is bonded as a protective layer on the photosensitive layer, and the photosensitive layer and the protective layer are formed on the support or the silicone resin layer or the alkyd resin layer. The dry films laminated in order were obtained.

<Releasability evaluation>
While peeling off the protective layer, the dry film was laminated on a 6-inch silicon wafer so that the photosensitive layer of the dry film was in contact with the silicon surface. Next, after the support is peeled off, the surface of the support and the surface of the silicon wafer are observed, and “A” on which the photosensitive layer is formed on the silicon wafer is indicated on the support (or the silicone resin layer or the alkyd resin layer). In the above, the release property was evaluated as “B” where even a part of the photosensitive layer remained. Lamination was performed using a 120 ° C. heat roll at a pressure of 0.4 MPa and a roll speed of 1.0 m / min.

<Evaluation of resolution>
While removing the protective layer of the dry film, the dry film was laminated on a 6-inch silicon wafer so that the photosensitive layer was in contact with the silicon surface. After peeling off the support, the photosensitive layer was subjected to reduced projection exposure with a i-line stepper (manufactured by Canon Inc., product name: FPA-3000iW) with i-line (365 nm) through a mask. As the mask, a mask having a pattern in which the width of the exposed portion and the unexposed portion is 1: 1 is from 2 μm: 2 μm to 30 μm: 30 μm in 1 μm increments. The exposure amount is in the range of 100 ~ 3000mJ / cm ^2, was subjected to the reduction projection exposure while changing by 100 mJ / cm ^2.

Next, the exposed photosensitive layer is heated at 65 ° C. for 1 minute and then at 95 ° C. for 4 minutes (post-exposure baking), and a 2.38 mass% tetramethylammonium hydroxide aqueous solution is used to develop the shortest development time (unexposed area is Development was performed by immersing in a time corresponding to twice the shortest time to be removed, and the unexposed portion was removed and development processing was performed. After the development process, the resin pattern formed using a metal microscope was observed. Among the patterns in which the space portion (unexposed portion) is removed cleanly and the line portion (exposed portion) is formed without meandering or chipping, the smallest space width in the range of 100 to 3000 mJ / cm ² exposure amount Was evaluated as the minimum resolution.

<Evaluation of heat resistance>
A dry film having a photosensitive layer thickness of 40 μm was prepared by the method described above. The protective layer of the dry film is peeled off, and then the photosensitive layer is formed so that the irradiation energy amount is 3000 mJ / cm ² using an exposure machine having a high-pressure mercury lamp (product name: EXM-1201, manufactured by Oak Manufacturing Co., Ltd.). Exposed. The exposed photosensitive layer is heated on a hot plate at 65 ° C. for 2 minutes and then at 95 ° C. for 8 minutes, heat-treated at 180 ° C. for 60 minutes in a hot air convection dryer, and the support is peeled off and cured. A membrane was obtained. Using a thermomechanical analyzer (product name: TMA / SS6000, manufactured by Seiko Instruments Inc.), the amount of thermal expansion of the cured film is measured when the temperature is increased at a rate of temperature increase of 5 ° C./min. Was obtained as the glass transition temperature Tg. If Tg is 145 ° C. or higher, it can be said that the heat resistance is excellent, and if Tg is 170 ° C. or higher, it can be said that the heat resistance is excellent.

PET-1: Polyethylene terephthalate film (manufactured by Teijin DuPont Films, Ltd., product name: PUREX A53, thickness: 25 μm): Film comprising a silicone resin layer formed using a silicone-modified resin PET-2: Polyethylene terephthalate film (Manufactured by Teijin DuPont Films, Ltd., product name: PUREX A70, thickness: 25 μm): film with a silicone resin layer formed using polydimethylsiloxane PET-3: polyethylene terephthalate film (manufactured by Toray Industries, Inc., product Name “FB-40”, thickness: 16 μm): Film not provided with silicone resin layer or alkyd resin layer A-1: Cresol novolak resin (manufactured by Asahi Organic Materials Co., Ltd., product name: TR4020G, weight average molecular weight: 15300)
A-2: Cresol novolak resin (manufactured by Asahi Organic Materials Co., Ltd., product name: TR4080G, weight average molecular weight: 4800)
B-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., product name: MX-270)
B-2: Methylated urea resin (manufactured by Sanwa Chemical Co., Ltd., product name: MX-280)
B-3: 4,4 ′-(1,1,1,3,3,3-hexafluoroisopropylidene) bis [2,6-bis (hydroxymethyl) phenol] (product name, manufactured by Honshu Chemical Industry Co., Ltd.) : TML-BPAF)
C-1: Trimethylolpropane triglycidyl ether (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name: ZX-1542, see formula (14) below)

C-2: Trimethylolethane triglycidyl ether (Aldrich)
C-3: Pentaerythritol polyglycidyl ether (manufactured by Nagase Chemtech, product name: EX-411)
C-4: Trimethylolpropane (Wako Pure Chemical Industries, Ltd.)
C-5: Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., product name: TMPTA)
C-6: Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., product name: PET-30)
C-7: Dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light acrylate DPE-6A)
C-8: EO-modified trimethylolpropane trimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name: FA-137M)
C′-9: 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (manufactured by Hitachi Chemical Co., Ltd., product name: FA-324M, aromatic compound)
C′-10: 2,2-bis (4- (methacryloxyethoxy) phenyl) propane (manufactured by Hitachi Chemical Co., Ltd., product name: FA-320M, aromatic compound)
D-1: Triarylsulfonium salt (manufactured by San Apro, product name: CPI-310B)
E-1: Methyl ethyl ketone (Wako Pure Chemical Industries, Ltd.)
F-1: Silica having an average primary particle size of 15 nm coupled with 3-methacryloyloxypropyltrimethoxysilane.

As is apparent from Table 1, the dry films (Examples 1 to 22) in which the photosensitive layer is formed on the silicone resin layer of the support treated with the silicone resin have a releasability between the laminated photosensitive layer and the support. The minimum resolution was 10 μm or less, and the Tg was 145 ° C. or more. When a photosensitive layer was formed on a support not treated with a silicone resin or an alkyd resin, the releasability between the photosensitive layer and the support deteriorated as in Comparative Examples 1 and 2.

The dry film of the present disclosure can be suitably used when forming a solder resist or an interlayer insulating film of a printed wiring board, or a surface protective film (overcoat film) or an interlayer insulating film (passivation film) such as a semiconductor element. it can. In particular, since the photosensitive layer of the dry film of the present disclosure has both good resolution and heat resistance after curing, the dry film of the present disclosure can be applied to a high-density package substrate that has been thinned and densified. Preferably used.

DESCRIPTION OF SYMBOLS 1 ... Support body, 3 ... Silicone resin layer or alkyd resin layer, 5 ... Photosensitive layer, 7 ... Protective layer, 10 ... Dry film, 100A ... Multilayer printed wiring board, 101 ... Base material, 102, 107 ... Wiring pattern, 103 ... Interlayer insulating film 104 ... Opening part 105 ... Seed layer 106 ... Resin pattern 108 ... Solder resist.

Claims (7)

1. A support, a silicone resin layer or alkyd resin layer, and a photosensitive layer are provided in this order,
   The photosensitive layer is
   (A) component: a resin having a phenolic hydroxyl group;
   (B) 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, and (C) component: an acryloyloxy group, methacryloyloxy One or both components of an aliphatic compound having two or more functional groups selected from a group, a glycidyloxy group and a hydroxyl group;
   (D) component: a photosensitive acid generator;
   A dry film containing
2. The dry film according to claim 1, wherein the photosensitive layer has a thickness of less than 50 μm.
3. 3. The dry film according to claim 1, wherein the photosensitive layer contains 20 to 70 parts by mass of the component (C) with respect to 100 parts by mass of the component (A).
4. The dry film according to any one of claims 1 to 3, wherein the component (C) has three or more functional groups.
5. A cured product obtained by using the photosensitive layer in the dry film according to any one of claims 1 to 4.
6. A semiconductor device comprising the cured product according to claim 5 as a surface protective film or an interlayer insulating film.
7. Using the dry film according to any one of claims 1 to 4 to form a photosensitive layer on a substrate;
   Exposing the photosensitive layer to a predetermined pattern and performing a post-exposure heat treatment;
   Developing the photosensitive layer after the heat treatment, and heat-treating the resulting resin pattern.

Images