JP2017201345A - Photosensitive resin composition, photosensitive element, cured product, method for forming resist pattern, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which can give a cured product having excellent mechanical characteristics even when cured at a low temperature.SOLUTION: The photosensitive resin composition contains a component (A): a resin having a phenolic hydroxyl group, a component (B): a compound having at least one selected from the group consisting of a methylol group and an alkoxyalkyl group, a component (C): a polyfunctional monomer having three or more structural units derived from caprolactone in the molecule, and a component (D): a photosensitive acid generator.SELECTED DRAWING: None

Description

  The present disclosure relates to a photosensitive resin composition, a photosensitive element, a cured product, a resist pattern forming method, and a semiconductor device.

  In the production of a semiconductor element or a printed wiring board, 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 (for example, a chip in the case of a semiconductor element or a substrate in the case of a printed wiring board) by application of a photosensitive resin composition, and irradiated with actinic rays through a predetermined pattern. By doing so, the exposed portion is cured. Furthermore, the resist pattern which is a cured film of the photosensitive resin composition is formed on a base material by selectively removing an unexposed part using a developing solution.

  For example, a photosensitive resin composition containing a novolak resin soluble in an alkaline aqueous solution, an acrylic 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 Document 1 below).

International Publication No. 2014/103516

  A material used for a protective film (solder resist, surface protective film, etc.) or an interlayer insulating film of a semiconductor element or a printed wiring board is required to have excellent mechanical properties. On the other hand, since the heat resistance temperature of other materials used in combination with a protective film or an interlayer insulating film is not sufficiently high in recent years, the thermosetting temperature of the material used to obtain the protective film or the interlayer insulating film Decrease is demanded, and in particular, thermosetting property at 220 ° C. or less is often demanded. However, when the thermosetting temperature is lowered, the mechanical properties tend to decrease.

  The present disclosure has been made in view of the above problems in the prior art, and provides a photosensitive resin composition capable of obtaining a cured product having excellent mechanical properties even when cured at a low temperature. For the purpose. Moreover, this indication aims at providing the photosensitive element and hardened | cured material which are obtained using the said photosensitive resin composition. Furthermore, this indication aims at providing the formation method of the resist pattern using the said photosensitive resin composition or the said photosensitive element. An object of this indication is to provide a semiconductor device provided with the above-mentioned hardened material.

  The present disclosure is derived from (A) component: a resin having a phenolic hydroxyl group, (B) component: a compound having at least one selected from the group consisting of a methylol group and an alkoxyalkyl group, and (C) component: caprolactone. There is provided a photosensitive resin composition comprising a polyfunctional monomer having three or more structural units in the molecule, and a component (D): a photosensitive acid generator.

  According to the photosensitive resin composition of the present disclosure, a cured product having excellent mechanical properties can be obtained even when cured at a low temperature. For example, according to the photosensitive resin composition of the present disclosure, a cured product having excellent mechanical properties can be obtained even when cured at 220 ° C. or lower. According to the photosensitive resin composition of the present disclosure, a cured product having excellent mechanical properties can be obtained, and excellent resolution can be achieved.

  By the way, as a mechanical characteristic required for the protective film or the interlayer insulating film, even if the resin is deformed by stress, it is required to exhibit high elongation in a range in which elastic deformation is restored when the stress is relaxed. A material that exceeds the range showing elastic deformation and exhibits high elongation due to plastic deformation does not return from the deformed state when the stress is relaxed, and therefore may have poor reliability. In response to these requirements, mechanical properties have not been sufficiently studied in conventional photosensitive resin compositions such as the photosensitive resin composition described in Patent Document 1. On the other hand, according to the photosensitive resin composition of the present disclosure, a cured product having good elongation can be obtained in a range showing elastic deformation even when cured at a low temperature.

［一般式（１）中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６は、それぞれ独立に、下記一般式（２）で表される基、又は、下記一般式（３）で表される基を示す］

［一般式（２）中、Ｒ^２は、水素原子又はメチル基を示し、ｎは、１又は２を示す。］

［一般式（３）中、Ｒ^３は、水素原子又はメチル基を示す。］ The component (C) preferably contains a compound represented by the following general formula (1).

[In General Formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a group represented by the following General Formula (2) or the following General Formula (3 Is a group represented by

[In General Formula (2), R ² represents a hydrogen atom or a methyl group, and n represents 1 or 2. ]

[In General Formula (3), R ³ represents a hydrogen atom or a methyl group. ]

  The content of the component (C) is preferably 20 to 100 parts by mass with respect to 100 parts by mass of the component (A).

  Moreover, this indication provides the photosensitive element provided with the support body and the photosensitive layer provided on the said support body, and the said photosensitive layer contains the said photosensitive resin composition.

  Moreover, this indication provides the hardened | cured material of the said photosensitive resin composition. The cured product can be suitably used as a protective film (solder resist, surface protective film, etc.) or an interlayer insulating film.

  The present disclosure also includes a step of forming a photosensitive layer on a substrate using the photosensitive resin composition or the photosensitive element, and a step of performing a heat treatment after exposing the photosensitive layer to a predetermined pattern. And a step of heat-treating a resin pattern obtained by developing the photosensitive layer after the heat treatment.

  Moreover, this indication provides the semiconductor device provided with the hardened | cured material of the said photosensitive resin composition as a protective film or an interlayer insulation film.

  According to the present disclosure, it is possible to provide a photosensitive resin composition capable of obtaining a cured product having excellent mechanical properties even when cured at a low temperature. Moreover, according to this indication, the photosensitive element and hardened | cured material which are obtained using the said photosensitive resin composition can be provided. Furthermore, according to this indication, the formation method of the resist pattern using the said photosensitive resin composition or the said photosensitive element can be provided. According to the present disclosure, a semiconductor device including the cured product can be provided. According to the present disclosure, a cured product (resist pattern or the like) having excellent reliability can be formed by exhibiting a high elongation of 10% or more in a range showing elastic deformation.

It is a schematic diagram which shows the manufacturing method of a multilayer printed wiring board.

  Hereinafter, although embodiment of this indication is described concretely, this indication is not limited to this.

  The materials exemplified in the present specification can be used singly or in combination of two or more unless otherwise specified. In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means. In this specification, “(meth) acrylic acid” means at least one of acrylic acid and methacrylic acid corresponding thereto. The same applies to other similar expressions such as “(meth) acrylate”. Further, the term “layer” includes a structure formed in a part in addition to a structure formed over the entire surface when observed as a plan view. Moreover, the numerical value range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a 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.

<Photosensitive resin composition and cured product>
The photosensitive resin composition of the present embodiment comprises (A) component: a resin having a phenolic hydroxyl group, and (B) component: a compound having at least one selected from the group consisting of a methylol group and an alkoxyalkyl group; Component C): a polyfunctional monomer having three or more structural units derived from caprolactone in the molecule; and component (D): a photosensitive acid generator. Moreover, the photosensitive resin composition of this embodiment is (E) component: solvent, (F) component: inorganic filler, (G) component: Silane coupling agent, (H) component: sensitization as needed. Agent, component (I): An epoxy resin, an acryloyl compound, a methacryloyl compound or a polyhydric alcohol can also be contained. The photosensitive resin composition of this embodiment can be used as a negative photosensitive resin composition. The photosensitive resin composition of this embodiment can have thermosetting properties. The cured product of the present embodiment is a cured product of the photosensitive resin composition of the present embodiment.

  The present inventors speculate that the photosensitive resin composition of the present embodiment can form a cured product (resin pattern or the like) that is excellent in resolution and mechanical properties (particularly, elongation). doing.

  First, in the unexposed area, the solubility of the component (A) in the developer is improved by the component (C). Next, in the exposed portion, 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 the photosensitive resin composition for the developer Solubility is greatly reduced. Thereby, when it develops, sufficient resolution is acquired by the remarkable difference of the solubility of the unexposed part with respect to a developing solution, and an exposed part.

  Further, even when the heat treatment temperature is low, the reaction between the component (B) and the component (A) is likely to proceed, and the component (C) has three flexible structural units derived from caprolactone in the molecule. By having the above, it is assumed that high elongation is exhibited.

  Furthermore, according to the photosensitive resin composition of this embodiment, it is guessed that cured | curing material (resin pattern etc.) which has sufficient heat resistance is obtained because reaction of (C) component advances.

((A) component)
Although it does not specifically limit as (A) component (resin which has a phenolic hydroxyl group), Resin soluble in alkaline aqueous solution is preferable, and novolak resin is more preferable. Such a novolak resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst.

  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-trimethylphenol, Catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like can be mentioned.

  Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

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

  Examples of the component (A) other than the novolak resin include polyhydroxystyrene and a copolymer thereof, a phenol-xylylene glycol condensation resin, a cresol-xylylene glycol condensation resin, and a phenol-dicyclopentadiene condensation resin.

  (A) A component can be used individually by 1 type or in combination of 2 or more types.

  The weight average molecular weight of the component (A) is preferably 100000 or less, more preferably 1000 to 80000, from the viewpoint of further improving the resolution, thermal shock resistance, heat resistance and the like of the resulting cured product. More preferably, it is 2000-50000, It is especially preferable that it is 2000-20000, It is very preferable that it is 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 a detector (Hitachi, Ltd., L-3300RI type) and tetrahydrofuran as an eluent And measured at a temperature of 30 ° C. and a flow rate of 1.0 mL / min. 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.

  The content of the component (A) is preferably 30 to 90 parts by mass and more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition excluding the component (E). preferable. When the content of the component (A) is within this range, a photosensitive layer (film formed using a photosensitive resin composition) having sufficient resolution with an alkaline aqueous solution can be obtained.

((B) component)
The photosensitive resin composition of this embodiment contains the compound which has at least 1 sort (s) chosen from the group which consists of a methylol group and an alkoxyalkyl group as (B) component. (B) As a component, the component applicable to (A) component or (C) component is remove | excluded.

  When the photosensitive resin composition contains the component (B), when the photosensitive layer containing the photosensitive resin composition (such as a photosensitive layer (resin pattern) after pattern formation) is heated and cured, (B) The component reacts with the component (A) to form a bridge structure, and weakening and deformation of the photosensitive layer (resin pattern or the like) can be prevented.

  As will be described later, when the photosensitive resin composition contains the component (D), an acid is generated by irradiation with actinic rays or the like. Due to the catalytic action of the generated acid, the methylol groups in component (B), or the methylol groups in component (B) react with components (A) with dealcoholization to form a negative pattern. can do. Moreover, the negative type is caused by the reaction between the alkoxyalkyl groups in the component (B) or the alkoxyalkyl groups in the component (B) and the component (A) with dealcoholization due to the catalytic action of the generated acid. The pattern can be formed.

  The component (B) preferably further has at least one selected from the group consisting of a phenolic hydroxyl group and a hydroxymethylamino group. When the component (B) has a phenolic hydroxyl group or a hydroxymethylamino group in addition to a methylol group or an alkoxyalkyl group (alkoxymethyl group, etc.), it is not only insolubilized by reaction with the component (A) but also an unexposed portion. Then, the dissolution rate at the time of developing with alkaline aqueous solution increases, and a sensitivity can be improved.

  The weight average molecular weight of the component (B) having a phenolic hydroxyl group is preferably 94 to 2000, and preferably 108 to 2000 in consideration of the balance of solubility in alkali aqueous solution, photosensitivity, mechanical properties, and the like. More preferably, it is 108-1500.

  As the component (B) having a phenolic hydroxyl group, a conventionally known component can be used, but it is excellent in the balance between the effect of promoting the dissolution of the unexposed area and the effect of preventing the melting of the photosensitive resin composition. From the viewpoint, a compound represented by the following general formula (4) is preferable.

［一般式（４）中、Ｚは、単結合又は２価の有機基を示し、Ｒ^４１及びＲ^４２は、それぞれ独立に水素原子又は１価の有機基を示し、Ｒ^４３及びＲ^４４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。］

[In General Formula (4), Z represents a single bond or a divalent organic group, R ⁴¹ and R ⁴² each independently represent a hydrogen atom or a monovalent organic group, and R ⁴³ and R ⁴⁴ represent Each independently represents a monovalent organic group, a and b each independently represent an integer of 1 to 3, and c and d each independently represent an integer of 0 to 3. ]

  In the general formula (4), 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 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; Bond; Amide bond and the like can be mentioned. Among these, Z is preferably a divalent organic group represented by the following general formula (5).

［一般式（５）中、Ｘ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、炭素数が２〜１０のアルキリデン基）、こ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し、Ｒ^５は、水素原子、水酸基（ヒドロキシ基）、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^５は、互いに同一でも異なっていてもよい。］

[In general formula (5), X is 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), or hydrogen thereof. A group in which part or all of the atoms are substituted with a halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond or an amide bond; R ⁵ represents a hydrogen atom, a hydroxyl group (hydroxy group), an alkyl group or a haloalkyl group; E represents an integer of 1 to 10. Several R < ⁵ > may mutually be same or different. ]

  As the component (B) having a hydroxymethylamino group, (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N-hydroxymethyl) urea and the like, and nitrogen-containing compounds obtained by alkylating all or part of the hydroxymethylamino group may be used. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, or a mixture thereof. The component (B) having a hydroxymethylamino group may be an oligomer component that is partially self-condensed, and specifically includes hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxy). And methyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl) urea and the like.

  (B) A component can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (B) is preferably 5 to 60 parts by mass, more preferably 10 to 45 parts by mass, and 10 to 35 parts by mass with respect to 100 parts by mass of the component (A). More preferably. When the content of the component (B) is 5 parts by mass or more, the exposed part is likely to react sufficiently, so that the resolution tends to be difficult to decrease. When the content is 60 parts by mass or less, the photosensitive resin composition is It becomes easy to form (for example, film formation) the photosensitive layer containing on a desired support body, and there exists a tendency for a resolution to fall easily.

((C) component)
The photosensitive resin composition of this embodiment contains a polyfunctional monomer having three or more structural units derived from caprolactone in the molecule as the component (C). Component (C) is a monomer having two or more polymerizable unsaturated bonds, and a compound having three or more structural units derived from caprolactone in the molecule. When structural units derived from caprolactone are bonded to each other, each structural unit corresponds to a “structural unit derived from caprolactone”. For example, n is 2 in the group represented by the general formula (2) described later. In some cases, two “structural units derived from caprolactone” are included.

  As the component (C), for example, a polyfunctional (meth) acrylate (a structural unit derived from caprolactone) obtained by esterifying a polyhydric alcohol, (meth) acrylic acid and caprolactone (for example, ε-caprolactone) is used. And polyfunctional (meth) acrylate having polyhydric alcohol, (meth) acrylic acid and caprolactone ester compound).

  Examples of the polyhydric alcohol include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine and the like.

  As the component (C), a compound represented by the following general formula (1) is preferable from the viewpoint of obtaining better elongation.

［一般式（１）中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６は、それぞれ独立に、下記一般式（２）で表される基、又は、下記一般式（３）で表される基を示す。Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６のうち少なくとも３つが、前記一般式（２）で表される基であってもよい。］

[In General Formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a group represented by the following General Formula (2) or the following General Formula (3 ) Is represented. At least three of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be a group represented by the general formula (2). ]

［一般式（２）中、Ｒ^２は、水素原子又はメチル基を示し、ｎは、１又は２の整数を示す。式（１）において、式（２）のＲ^２及びｎのそれぞれは、互いに同一であってもよく、異なっていてもよい。］

[In General Formula (2), R ² represents a hydrogen atom or a methyl group, and n represents an integer of 1 or 2. In Formula (1), each of R ² and n in Formula (2) may be the same as or different from each other. ]

［一般式（３）中、Ｒ^３は、水素原子又はメチル基を示す。式（１）において、式（３）のＲ^３は、互いに同一であってもよく、異なっていてもよい。］

[In General Formula (3), R ³ represents a hydrogen atom or a methyl group. In Formula (1), R ³ in Formula (3) may be the same as or different from each other. ]

The compound represented by the formula (1) needs to be a compound having two or more groups represented by the formula (2), and a compound having three or more groups represented by the formula (2) is preferable. A compound having six groups represented by the formula (2) is more preferable. Such compounds are commercially available, for example, under the trade name “KAYARAD DPCA series” manufactured by Nippon Kayaku Co., Ltd. Examples of such commercially available products include DPCA-30 (number of groups (n = 1) represented by formula (2): 3, R ² : all hydrogen atoms), DPCA-60 (represented by formula (2)). Number of groups (n = 1): 6, R ² : all hydrogen atoms), DPCA-120 (number of groups represented by formula (2) (n = 2): 6, R ² : all hydrogen atoms) Etc.

  (C) A component can be used individually by 1 type or in combination of 2 or more types.

  (C) Content of a component can be suitably selected from 20-100 mass parts, 20-70 mass parts, 25-65 mass parts, or 35-55 mass parts with respect to 100 mass parts of (A) component. When the content of the component (C) is 20 parts by mass or more, the elongation tends to be further improved, and when it is 100 parts by mass or less, the adhesion to the base material (substrate or the like) tends to be improved.

((D) component)
The component (D) (photosensitive acid generator) is a compound that generates an acid upon irradiation with an actinic ray or the like. Due to the acid generated from the component (D), the methylol group or alkoxyalkyl group in the component (B) reacts with the phenolic hydroxyl group of the component (A), and the solubility of the photosensitive resin composition in the developer is greatly reduced. Thus, 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, but it is an onium salt compound, a sulfonimide compound, a halogen-containing compound, a diazo ketone compound, a sulfone compound, a sulfonic acid compound, a diazomethane compound Etc. Among these, an onium salt compound or a sulfonimide compound is preferable from the viewpoint of excellent availability. In particular, when a solvent is used as the component (E), an onium salt compound is preferable from the viewpoint of excellent solubility in the solvent. Specific examples of the onium salt compound and the sulfonimide compound are shown below.

[Onium salt compound]
Examples of the onium salt compound include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Preferred examples of the onium salt compound include diaryl iodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diaryliodonium salts such as 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 compound]
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.

  As the component (D), a compound having a trifluoromethanesulfonate group, a hexafluoroantimonate group, a hexafluorophosphate group, or a tetrafluoroborate group is preferable from the viewpoint of further excellent sensitivity and resolution.

  (D) A component can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (D) is 0.1 with respect to 100 parts by mass of the component (A) from the viewpoint that the sensitivity, resolution, pattern shape, and the like of the photosensitive resin composition of the present embodiment are even better. It is preferable that it is -15 mass parts, and it is more preferable that it is 0.3-10 mass parts.

((E) component)
The photosensitive resin composition of this embodiment can 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) is preferably an organic solvent.

  The organic solvent is not particularly limited as long as it can exhibit the above performance. For example, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl Propylene glycol monoalkyl ethers such as ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether Dialkyl ethers; propylene glycol Propylene glycol monoalkyl ether acetates such as methyl ether acetate, 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, propionic acid aliphatic carboxylic acid esters such as n-butyl and isobutyl propionate; methyl 3-methoxypropionate and 3-methoxypropion Other esters such as ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; 2-butanone (methyl ethyl ketone), 2-heptanone, Examples include ketones such as 3-heptanone, 4-heptanone, and cyclohexanone; amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; and lactones such as γ-butyrolactone.

  (E) A component can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (E) is preferably 30 to 200 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition excluding the component (E), from the viewpoint of excellent storage stability. More preferably, it is 120 parts by mass.

((F) component)
The photosensitive resin composition of this embodiment can contain an inorganic filler as (F) component. Thereby, according to content of (F) component, the thermal expansion coefficient of the hardened | cured material obtained by heating a photosensitive layer (photosensitive layer etc. after pattern formation) can be reduced. (F) A component can be used individually by 1 type or in combination of 2 or more types. The component (F) is preferably dispersed in the resin composition with a maximum particle size of 2 μm or less.

  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 mineral products such as mica; particles containing fused spherical silica, fused ground silica, fumed silica, sol-gel silica and the like. These are pulverized by a pulverizer, classified according to circumstances, and can be dispersed in a state where the maximum particle diameter is 2 μm or less.

Any of the constituents of the inorganic filler can be used, but silica is preferred. Moreover, it is preferable that the thermal expansion coefficient of the inorganic filler containing silica is 5.0 × 10 ⁻⁶ / ° C. or less. As a constituent component of the inorganic filler, silica such as fused spherical silica, fumed silica, and sol-gel silica is preferable, and fumed silica or sol-gel silica is more preferable from the viewpoint that a suitable particle size can be easily obtained. It is preferable to use silica (nanosilica) having an average primary particle diameter in the range of 5 to 100 nm. These are preferably 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, it is preferable to use a known particle size distribution meter. For example, a laser diffraction scattering type particle size distribution meter that calculates particle size distribution from the intensity distribution pattern of diffracted / scattered light emitted from a particle group; particle size distribution using frequency analysis by dynamic light scattering method Examples thereof include a particle size distribution meter of nanoparticles for which distribution is obtained.

  The average primary particle diameter of the inorganic filler is preferably 100 nm or less, more preferably 80 nm or less, and further preferably 50 nm or less from the viewpoint of further improving the photosensitivity. When the average primary particle diameter is 100 nm or less, the resin composition is less likely to become cloudy, so that the exposure light is easily transmitted through the resin composition, so that unexposed portions are easily removed and resolution is not easily lowered. Tend. The average primary particle diameter can be a value obtained by conversion from the BET specific surface area.

  (F) As for content of a component, 1-70 mass parts is preferable with respect to 100 mass parts of whole quantity of the photosensitive resin composition except (E) component, and 3-65 mass parts is more preferable.

((G) component)
The photosensitive resin composition of this embodiment may contain a silane coupling agent as the component (G). When the photosensitive resin composition contains the component (G), the adhesion strength between the photosensitive layer (such as the photosensitive layer after the resin pattern is formed) and the substrate can be improved.

  As the component (G), generally available compounds can be used. Alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acryloyl silane, methacryloyl silane, mercapto silane, sulfide silane, isocyanate silane, sulfur silane , Styrylsilane, alkylchlorosilane, and the like can be used.

  Specific compound names include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxy. Silane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxy Silane, triphenylsilanol, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, n-octyldi Tylchlorosilane, 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, Lutriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3 -Mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane, aminosilane and the like.

  As the silane coupling agent, an epoxy silane having one or more glycidyloxy groups is preferable, and an epoxy silane having a trimethoxysilyl group or a triethoxysilyl group is more preferable. Further, acryloylsilane or methacryloylsilane may be used.

  (G) A component can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (G) is preferably 1 to 20 parts by mass and more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the component (A).

((H) component)
The photosensitive resin composition of this embodiment may contain a sensitizer as the component (H). When the photosensitive resin composition contains the component (H), the photosensitivity of the photosensitive resin composition can be further improved. Examples of the sensitizer include 9,10-dibutoxyanthracene. (H) component can be used individually by 1 type or in combination of 2 or more types.

  The content of component (H) is preferably 0.01 to 1.5 parts by mass and more preferably 0.05 to 0.5 parts by mass with respect to 100 parts by mass of component (A). .

((I) component)
The photosensitive resin composition of this embodiment can also contain (I) component: an epoxy resin, an acryloyl compound, a methacryloyl compound, or a polyhydric alcohol. Thereby, the adhesiveness (namely, tackiness) of the photosensitive resin composition and a support body can be made favorable. Furthermore, it is possible to further increase the dissolution rate of the unexposed area when developing with an alkaline aqueous solution, and to further improve the resolution. As the component (I), components corresponding to the components (A) to (D) are excluded. (I) A component can be used individually by 1 type or in combination of 2 or more types.

  The weight average molecular weight of the component (I) is preferably 92 to 2000, more preferably 106 to 1500, and more preferably 134 to 1300 from the viewpoint of excellent balance between tackiness and solubility in an aqueous alkali solution. More preferably it is.

  Examples of epoxy resins include dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerin triglycidyl ether, and the like. It is done. An epoxy resin can be used individually by 1 type or in combination of 2 or more types.

  Examples of the acryloyl compound include EO-modified dipentaerythritol hexaacrylate, PO-modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO-modified ditrimethylolpropane tetraacrylate, PO-modified ditrimethylolpropane tetraacrylate, 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 trimethylolpropane acrylic Les DOO, trimethylolpropane acrylate, EO-modified glycerol tri acrylate, PO-modified glycerol triacrylate, glycerin triacrylate. An acryloyl compound can be used individually by 1 type or in combination of 2 or more types. EO represents an oxyethylene group, and PO represents an oxypropylene group.

  Examples of the methacryloyl compound include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, 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, PO modified Trimethylol propane dimethacrylate, trimethylol propane dimethacrylate, EO modified glycerol trimethacrylate, PO-modified glycerol trimethacrylate, glycerine trimethacrylate and the like. A methacryloyl compound can be used individually by 1 type or in combination of 2 or more types. EO represents an oxyethylene group, and PO represents an oxypropylene group.

  Examples of the polyhydric alcohol include dipentaerythritol, pentaerythritol, pentaerythritol, and glycerin. A polyhydric alcohol can be used individually by 1 type or in combination of 2 or more types.

  The content of component (I) is preferably 5 to 50 parts by mass, more preferably 8 to 40 parts by mass, and 10 to 35 parts by mass with respect to 100 parts by mass of component (A). More preferably. When the content of component (I) is 5 parts by mass or more, sufficient tackiness tends to be obtained, and when it is 50 parts by mass or less, a photosensitive layer containing the photosensitive resin composition is formed as a desired support. It is easy to form (for example, film formation) on the top, and the resolution is not easily lowered.

(Other ingredients)
The photosensitive resin composition of this embodiment may contain other components other than the above-mentioned components. Examples of the other components include amines, organic peroxides, inhibitors for reactions accompanying irradiation with actinic rays, and leveling agents. Further, in addition to the component (C), in the formula (1), the number of groups (n = 1) represented by the formula (2) is 2, and all R ² are hydrogen atoms (Nipponization) Yakuhin Co., Ltd., trade name: KAYARAD DPCA-20) may be used.

  In addition to the component (A), the photosensitive resin composition of the present embodiment may contain a phenolic low molecular compound having a molecular weight of less than 1000 (hereinafter referred to as “phenol compound (a)”). . As the phenolic compound (a), 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) Tan, and the like. Content of a phenol compound (a) can be 0-40 mass parts (especially 0-30 mass parts) with respect to 100 mass parts of (A) component.

<Photosensitive element>
Next, the photosensitive element of this embodiment will be described.

  The photosensitive element of this embodiment is equipped with the support body and the photosensitive layer provided on the said support body, and the said photosensitive layer contains the above-mentioned photosensitive resin composition. The photosensitive layer is formed on the support using the above-described photosensitive resin composition. The photosensitive element may be provided with a protective layer covering the photosensitive layer on the photosensitive layer.

  As the support, for example, a polymer film having heat resistance and solvent resistance such as a polyethylene terephthalate film, a polypropylene film, a polyethylene film, and a polyester film can be used. The thickness of the support (polymer film) is preferably 5 to 25 μm. In addition, a polymer film may be used by laminating on both sides of the photosensitive layer so as to sandwich the photosensitive layer, using one as a support and the other as a protective film.

  As the protective layer, for example, a polymer film having heat resistance and solvent resistance such as a polyethylene terephthalate film, a polypropylene film, a polyethylene film, and a polyester film can be used.

  The photosensitive layer can be formed by applying a photosensitive resin composition on a support or a protective layer. 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 a photosensitive layer changes with uses, after drying a photosensitive layer, it is preferable that it is 5-100 micrometers, It is more preferable that it is 8-60 micrometers, It is still more preferable that it is 10-50 micrometers.

<Method for forming resist pattern>
The resist pattern forming method of the present embodiment includes a photosensitive layer forming step of forming a photosensitive layer on a substrate using the photosensitive resin composition or photosensitive element of the present embodiment, and the photosensitive layer having a predetermined pattern. A step of performing heat treatment after exposure to (hereinafter, this heat treatment is also referred to as “post-exposure baking”), a step of heat-treating a resin pattern obtained by developing the photosensitive layer after the heat treatment, Is provided. In the photosensitive layer forming step, after the photosensitive resin composition is applied on the substrate, the applied photosensitive resin composition may be dried to form the photosensitive layer. The photosensitive layer of the photosensitive element is used as the substrate. You may arrange on top.

  Next, the resist pattern forming method of this embodiment will be further described.

  First, a photosensitive layer containing the above-described photosensitive resin composition is formed on a substrate on which a resist is to be formed (a copper foil with resin, a copper clad laminate, a silicon wafer with a metal sputtered film, an alumina substrate, etc.). . As a method for forming the photosensitive layer, a method in which a photosensitive resin composition is applied to a substrate and dried to volatilize a solvent or the like to form a coating film (photosensitive layer); Examples thereof include a method of transferring onto a substrate.

  As a method for applying the photosensitive resin composition to the substrate, for example, a coating method such as a dipping method, a spray method, a bar coating method, a roll coating method, or a spin coating method can be used. The thickness of the coating film can be appropriately controlled by adjusting the coating means and the solid content concentration and viscosity of the photosensitive resin composition.

Next, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. Examples of the actinic rays used for exposure include g-line stepper rays; ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and i-line steppers; electron beams; The exposure amount is appropriately selected depending on the light source to be used, the thickness of the coating film, and the like. For example, in the case of ultraviolet irradiation from a high pressure mercury lamp, the coating thickness is about 100 to 5000 mJ / cm ² when the coating thickness is 10 to 50 μm. is there.

  Further, a heat treatment (post exposure bake) is performed after the exposure. By performing post-exposure baking, the curing reaction of the component (A) and the component (B) by the generated acid can be promoted. The post-exposure baking conditions vary depending on the content of the photosensitive resin composition, the thickness of the coating film, etc., but it is usually preferable to heat at 70 to 150 ° C. for 1 to 60 minutes, and 1 to 70 to 120 ° C. It is more preferable to heat for 60 minutes.

  Next, the exposed and / or post-exposure baked coating film is developed with an alkaline developer, and a region other than the cured portion (unexposed portion) is dissolved and removed to obtain a desired resist 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 obtained by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and choline in water so that the concentration is about 1 to 10% by mass; Can be 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, for example. In addition, after developing with an alkaline developer, it can be washed with water and dried. As the alkaline developer, a tetramethylammonium hydroxide aqueous solution is preferable from the viewpoint of further excellent resolution.

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

  Moreover, in order to fully advance hardening and to prevent the deformation | transformation of the obtained resin pattern shape, it can also heat in two steps. For example, it can be cured by heating at 50 to 120 ° C. for 5 minutes to 2 hours in the first stage and heating at 80 to 200 ° C. for 10 minutes to 10 hours in the second stage.

  In the above-described curing conditions, the heating equipment is not particularly limited, and a general oven, infrared furnace, or the like can be used.

<Semiconductor device>
The semiconductor device of this embodiment includes a cured product of the photosensitive resin composition as a protective film or an interlayer insulating film. Examples of the semiconductor device include a multilayer printed wiring board.

  The cured product of the photosensitive resin composition of the present embodiment can be suitably used as, for example, a protective film (solder resist or the like) and / or an interlayer insulating film in a multilayer printed wiring board. FIG. 1 is a view showing a method for producing a multilayer printed wiring board including a cured product of the photosensitive resin composition of the present embodiment as a solder resist and an interlayer insulating film. A multilayer printed wiring board 100 shown in FIG. 1F has a wiring pattern on the surface and inside. The multilayer printed wiring board 100 is obtained by laminating a copper clad laminate, an interlayer insulating film, a metal foil, and the like, and appropriately forming a wiring pattern by an etching method or a semi-additive method. Hereinafter, the manufacturing method of the multilayer printed wiring board 100 is demonstrated easily based on FIG.

  First, an interlayer insulating film 103 is formed on both surfaces of a copper clad laminate 101 having a wiring pattern 102 on the surface (see FIG. 1A). The interlayer insulating film 103 may be formed by printing a photosensitive resin composition using a screen printer or a roll coater. The above-described photosensitive element is prepared in advance, and a laminator is used to form the photosensitive element in the photosensitive element. It can also be formed by attaching a photosensitive layer to the surface of a printed wiring board. 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. 1B). Smear (residue) around the opening 104 can be removed by desmear treatment. Next, a seed layer 105 is formed by an electroless plating method (see FIG. 1C). A photosensitive layer containing the above-described photosensitive resin composition is laminated on the seed layer 105, and a predetermined portion is exposed and developed to form a wiring pattern 106 (see FIG. 1D). After forming an adhesion layer (for example, a titanium layer having a thickness of about 30 nm) on the seed layer 105, a Cu layer having a thickness of about 100 nm may be formed. These adhesion layers can be formed by sputtering. Next, the wiring pattern 107 is formed by electrolytic plating, and the cured product of the photosensitive resin composition is removed by a peeling solution, and then the seed layer 105 is removed by etching (see FIG. 1E). The multilayer printed wiring board 100 can be produced by repeating the above operations and forming the solder resist 108 made of the cured product of the above-described photosensitive resin composition on the outermost surface (see FIG. 1 (f)).

  In the multilayer printed wiring board 100 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.

<Preparation of photosensitive resin composition>
50 parts by mass of cresol novolac resin (Asahi Organic Materials Co., Ltd., trade name: TR4020G), 50 parts by mass of cresol novolac resin (product of Asahi Organic Materials Co., Ltd., trade name: TR4080G), 1, 3, 4, 6-tetrakis (methoxymethyl) glycoluril (a compound having a methylol group, manufactured by Sanwa Chemical Co., Ltd., trade name: MX-270) 28 parts by mass, the following component (X) 50 parts by mass, and a triarylsulfonium salt ( Photosensitive acid generator, manufactured by San Apro Co., Ltd., trade name: CPI-310B) 8 parts by mass and methyl ethyl ketone (solvent, Wako Pure Chemical Industries, Ltd., trade name: 2-butanone) 100 parts by mass are mixed. Thus, the photosensitive resin compositions of Example 1 and Comparative Examples 1 to 9 were obtained.

(Ingredient (X))
Example 1: Compound represented by the above formula (1) (number of groups represented by the formula (2) (n = 1): 6, R ² : a compound in which all are hydrogen atoms. Structural unit derived from caprolactone A polyfunctional monomer having 6 in the molecule, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPCA-60)
Comparative Example 1: Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: PET-30)
Comparative Example 2: Trimethylolpropane triglycidyl ether (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: ZX-1542)
Comparative Example 3: Trimethylolpropane trimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: TMPT)
Comparative Example 4: Trimethylolpropane EO-modified triacrylate, a compound in which 9 mol of ethylene oxide (EO) group was added in one molecule (manufactured by Hitachi Chemical Co., Ltd., trade name: TMPT-9)
Comparative Example 5: Trimethylolpropane EO-modified triacrylate, compound obtained by adding 21 mol of ethylene oxide (EO) group in one molecule (trade name: TMPT-21, manufactured by Hitachi Chemical Co., Ltd.)
Comparative Example 6: EO-modified polypropylene glycol # 700 dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-023M)
Comparative Example 7: 1,6 hexanediol diglycidyl ether (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., trade name: SR16HL)
Comparative Example 8: 3-Glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403)
Comparative Example 9: A compound in which the number of groups (n = 1) represented by the formula (2) is 2 and R ² is all hydrogen atoms in the formula (1) (Nippon Kayaku Co., Ltd., product Name: KAYARAD DPCA-20)

<Production of photosensitive element>
After applying the photosensitive resin composition on a polyethylene terephthalate film (trade name: Purex A53, manufactured by Teijin DuPont Films Ltd.) so that the thickness of the photosensitive resin composition becomes uniform, a hot air convection type at 90 ° C. By drying with a dryer for 10 minutes, photosensitive layers having a dried photosensitive layer thickness of 10 μm and 40 μm were formed, respectively. On this photosensitive layer, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name: NF-15) is bonded as a protective layer, and a polyethylene terephthalate film (support), a photosensitive layer, and a protective layer are sequentially laminated. Each sex element was obtained.

<Evaluation of minimum resolution (resolution)>
While peeling off the protective layer of the photosensitive element (photosensitive layer thickness: 10 μm), the photosensitive element was laminated on a 6-inch silicon wafer so that the photosensitive layer was in contact with the surface of the silicon wafer. Next, the support was peeled off to obtain uniform photosensitive layers having a thickness of 10 μm on the silicon wafer. Lamination is performed by 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., vacuuming time 30 seconds, laminating press. The time was 30 seconds.

Subsequently, the i-line stepper (manufactured by Canon Inc., trade name: FPA-3000iW) was used to perform reduction projection exposure on the photosensitive layer with i-line (365 nm) through a mask. As the mask, a mask having a pattern in which an unexposed portion exists in a circular shape in an exposed portion and the diameter of a circle of the unexposed portion is in a range of 2 to 30 μm and used is 1 μm. 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 was heated at 75 ° C. for 8 minutes (post-exposure baking), and then 2.38 mass% tetra in a time corresponding to twice the shortest development time (the shortest time for removing the unexposed portion). The development process was performed by removing unexposed portions by dipping in an aqueous solution of methylammonium hydroxide. After the development treatment, the formed resist pattern was observed using a metal microscope. Among the patterns in which the unexposed portions were removed cleanly, the smallest via diameter value was evaluated as the minimum resolution when the exposure amount was in the range of 100 to 3000 mJ / cm ² . The evaluation results are shown in Table 1.

<Evaluation of mechanical properties>
While removing the protective layer of the photosensitive element (photosensitive layer thickness: 40 μm), the fluororesin sheet (manufactured by NICHIAS Corporation, trade name: Naflon (R) sheet) so that the photosensitive layer is in contact with the surface of the fluororesin sheet. ) Was laminated with a photosensitive element. Next, the support was peeled off to obtain a uniform photosensitive layer having a thickness of 40 μm on the fluororesin sheet. Lamination is performed by 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., vacuuming time 30 seconds, laminating press. The time was 30 seconds.

Subsequently, using an i-line stepper (trade name: UX-2240SM-XJ01, manufactured by Ushio Inc.), the projection exposure to the photosensitive layer was performed at the same magnification with i-line (365 nm) through a mask. The sample was exposed to a length of 50 mm and a width of 20 mm. Moreover, the exposure amount was set to 5000 mJ / cm ² .

  Next, the exposed photosensitive layer was heated at 75 ° C. for 8 minutes (post-exposure baking), and then 2.38 mass% tetra in a time corresponding to twice the shortest development time (the shortest time for removing the unexposed portion). The development process was performed by removing unexposed portions by dipping in an aqueous solution of methylammonium hydroxide. After the development process, using an inert gas oven (manufactured by Koyo Thermo System Co., Ltd.), heat treatment is performed in a nitrogen atmosphere at a temperature of 220 ° C. (temperature increase time: 1.0 hour) for 1 hour, and then peeled from the fluororesin sheet and cured. A membrane was obtained.

  The elongation of the obtained cured film was measured using “Autograph AGS-H100N” manufactured by Shimadzu Corporation. The width of the sample was 10 mm, the film thickness was 25 to 40 μm, and the distance between chucks was 20 mm. The pulling speed was 5 mm / min, and the measurement temperature was 20-25 ° C. The elongation in the range showing the elastic deformation of five or more test pieces obtained from the cured film obtained under the same conditions was measured, and the maximum value was defined as the elongation value of the cured film. The evaluation results are shown in Table 1.

  As shown in Table 1, in the examples, the minimum resolution is 9 μm or less, and the elongation is 10% or more in the range showing the elastic deformation while maintaining the excellent resolution (pattern property) equivalent to the comparative example. Indicates the value of. On the other hand, in Comparative Examples 1-8 using a polyfunctional monomer (PET-30, TMPT-9, TMPT-21, etc.) having no structural unit derived from caprolactone, the elongation in the range showing elastic deformation is 10 Less than%. Moreover, in the comparative example 9 using the polyfunctional monomer (DPCA-20) which has two structural units derived from caprolactone in a molecule | numerator, the elongation in the range which shows an elastic deformation is less than 10%. Therefore, by using a polyfunctional monomer having three or more structural units derived from caprolactone in the molecule, excellent mechanical properties can be obtained, and the occurrence of product defects such as cracks can be remarkably suppressed.

  The photosensitive resin composition of the present disclosure is applied to a protective film (such as a solder resist) or an interlayer insulating film such as 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 be applied as a material to be used. In particular, since the photosensitive resin composition of the present disclosure has good resolution and mechanical properties, it can be suitably used for high-density package substrates that are thinned and densified.

  DESCRIPTION OF SYMBOLS 100 ... Multilayer printed wiring board, 101 ... Copper clad laminated body, 102, 106, 107 ... Wiring pattern, 103 ... Interlayer insulation film, 104 ... Opening part, 105 ... Seed layer, 108 ... Solder resist.

Claims (7)

(A) component: a resin having a phenolic hydroxyl group;
(B) component: a compound having at least one selected from the group consisting of a methylol group and an alkoxyalkyl group;
(C) component: a polyfunctional monomer having three or more structural units derived from caprolactone in the molecule;
(D) component: The photosensitive resin composition containing a photosensitive acid generator. The photosensitive resin composition of Claim 1 in which the said (C) component contains the compound represented by following General formula (1).

[In General Formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a group represented by the following General Formula (2) or the following General Formula (3 ) Is represented. ]

[In General Formula (2), R ² represents a hydrogen atom or a methyl group, and n represents 1 or 2. ]

[In General Formula (3), R ³ represents a hydrogen atom or a methyl group. ]   The photosensitive resin composition of Claim 1 or 2 whose content of the said (C) component is 20-100 mass parts with respect to 100 mass parts of said (A) component. A support, and a photosensitive layer provided on the support,
The photosensitive element in which the said photosensitive layer contains the photosensitive resin composition as described in any one of Claims 1-3.   Hardened | cured material of the photosensitive resin composition as described in any one of Claims 1-3. A step of forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 3 or the photosensitive element according to claim 4, and
Performing a heat treatment after exposing the photosensitive layer to a predetermined pattern;
And a step of heat-treating a resin pattern obtained by developing the photosensitive layer after the heat treatment.   A semiconductor device comprising the cured product of the photosensitive resin composition according to claim 5 as a protective film or an interlayer insulating film.

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