JP2018091877A - Photosensitive resin composition, photosensitive element, cured product and method for forming resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which allows for formation of a resist pattern excellent in resolution and heat resistance and having low thermal expansion coefficient, even when a coating film with a thickness of more than 20 μm is formed.SOLUTION: The photosensitive resin composition is provided that contains component (A): a resin having a phenolic hydroxyl group, component (B): an aliphatic compound having two or more of one or more kinds of functional groups selected from among an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group, component (C): a photosensitive acid generator, and component (D): an inorganic filler which has an average particle diameter of 100 nm or less and is surface-treated with a silane coupling agent.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element, a cured product, and a method for forming a resist pattern.

  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 (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 high sensitivity to actinic rays and to be able to form a fine pattern (resolution). 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 and 2).

  Furthermore, the surface protection 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. Thus, a photosensitive resin composition that further contains a crosslinkable monomer in the photosensitive resin composition has been proposed (see, for example, Patent Document 3).

On the other hand, in recent years, with the improvement in performance of electronic devices, higher integration and higher reliability of semiconductor elements are progressing year by year. As semiconductor devices are highly integrated, it is required to form finer patterns and reduce the thickness of the entire semiconductor device. However, when the entire semiconductor element is thinned, warpage caused by the difference in thermal expansion coefficient between the chip and the surface protective film or the interlayer insulating film becomes a serious problem. There is a strong demand to have a thermal expansion coefficient close to the thermal expansion coefficient (3 × 10 ⁻⁶ / ° C.), that is, to lower the thermal expansion coefficient. Then, in order to achieve the low thermal expansion of the photosensitive resin composition, for example, a photosensitive resin composition containing an inorganic filler has been proposed (see, for example, Patent Document 4).

  Further, by forming the interlayer insulating film thick, 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.

JP 09-087366 A International Publication No. 2008/010521 JP 2003-215802 A JP 2011-13622 A

  However, for example, in the photosensitive resin composition described in Patent Document 1, when the thickness of the coating film is 50 μm, the space width is about 40 μm and the resolution is not good for highly integrated semiconductor elements. It is enough. Moreover, in the photosensitive resin composition of patent document 2, sufficient heat resistance may not be expressed. Moreover, in the photosensitive resin composition of patent document 3, when the thickness of the coating film is 10 μm, a good resolution with a space width of about 5 μm is obtained. Good resolution cannot be obtained. Further, when the photosensitive resin composition described in Patent Document 4 is used to highly fill an inorganic filler in order to lower the thermal expansion coefficient, light scattering or light absorption tends to increase, leading to a decrease in resolution. There is.

  The object of the present invention is to solve the problems associated with the prior art as described above, and is excellent in resolution and heat resistance even when a coating film (photosensitive layer) having a thickness exceeding 20 μm is formed. Furthermore, it is providing the photosensitive resin composition which can form a resist pattern with a low thermal expansion coefficient. Another object of the present invention is to provide a cured product of the photosensitive resin composition, and a photosensitive element and a method for forming a resist pattern using the photosensitive resin composition.

  The photosensitive resin composition of the present invention comprises (A) component: a resin having a phenolic hydroxyl group, and (B) component: one or more functional groups selected from acryloyloxy group, methacryloyloxy group, glycidyloxy group and hydroxyl group. An aliphatic compound having two or more, (C) component: a photosensitive acid generator, and (D) component: an inorganic filler surface-treated with a silane coupling agent having an average particle diameter of 100 nm or less. To do.

  The silane coupling agent preferably has an alkoxy group and a phenyl group, vinyl group, epoxy group, methacryloyl group, amino group, ureido group, mercapto group, isocyanate group, or acryloyl group.

  The silane coupling agent is phenyltrimethoxysilane, vinyltrimethoxysilane, epoxytrimethoxysilane, methacryltrimethoxysilane, aminotrimethoxysilane, ureidotrimethoxysilane, mercaptotrimethoxysilane, isocyanate, and acryltrimethoxysilane. It is preferable that it is at least one selected.

  The maximum particle size of the component (D) is preferably less than 1000 nm.

  The component (B) is preferably an aliphatic compound having three or more functional groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group.

  The photosensitive resin composition of the present invention further comprises (E) 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. It is preferable.

  The photosensitive resin composition of the present invention preferably contains 20 to 70 parts by mass of the component (B) with respect to 100 parts by mass of the component (A).

  The present invention provides a photosensitive element comprising a support and a photosensitive layer provided on the support, wherein the photosensitive layer is formed using the photosensitive resin composition.

  Moreover, this invention provides the hardened | cured material of the said photosensitive resin composition.

  The present invention also includes a step of applying the photosensitive resin composition onto a substrate, drying the photosensitive resin composition to form a photosensitive layer, exposing the photosensitive layer to a predetermined pattern, and heating after exposure. Provided is a method for forming a resist pattern, which includes a step of performing a process and a step of developing the photosensitive layer after the heat treatment and heat-treating the obtained resin pattern.

  The present invention also includes a step of forming a photosensitive layer on the base material using the photosensitive element, a step of exposing the photosensitive layer to a predetermined pattern and performing a post-exposure heat treatment, and a post-heat treatment step. And a step of developing the photosensitive layer and heat-treating the obtained resin pattern.

  According to the photosensitive resin composition of the present invention, even when a coating film having a thickness exceeding 20 μm is formed, a resist pattern having excellent resolution and heat resistance and a low thermal expansion coefficient is formed. It is possible. Moreover, according to this invention, the cured | curing material of the said photosensitive resin composition, the photosensitive element using the said photosensitive resin composition, and the formation method of a resist pattern can be provided.

It is a schematic cross section which shows the photosensitive element of one Embodiment of this invention. It is a schematic diagram which shows the manufacturing method of the multilayer printed wiring board of this embodiment.

  Hereinafter, one embodiment of the present invention will be specifically described with reference to the drawings as necessary, but the present invention 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.

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment comprises (A) component: a resin having a phenolic hydroxyl group, (B) component: one or more functional groups selected from acryloyloxy group, methacryloyloxy group, glycidyloxy group and hydroxyl group. An aliphatic compound having two or more groups, (C) component: a photosensitive acid generator, and (D) component: an inorganic filler surface-treated with a silane coupling agent having an average particle size of 100 nm or less. contains.

  The present inventors consider that the reason why a resist pattern having high resolution and heat resistance can be formed by the photosensitive resin composition of the present embodiment is as follows. First, in the unexposed area, the solubility of (A) a resin having a phenolic hydroxyl group in a developer is greatly improved by the addition of the component (B). Thereby, when developed, sufficient resolution is obtained due to the remarkable difference in solubility in the unexposed and exposed portion of the developer, and the (B) component is crosslinked by heat treatment of the pattern after development, (A The present inventors infer that the reaction with the component) further proceeds and sufficient heat resistance is obtained.

  The photosensitive resin composition of this embodiment has at least one selected from the group consisting of component (E): an aromatic ring, a heterocyclic ring, and an alicyclic ring as necessary, and a methylol group or an alkoxyalkyl group. (F) component: sensitizer, (G) component: solvent, (H) component: silane coupling agent, (I) component: amine, (J) component: organic peroxide, (K) Ingredients: Can contain leveling agents and the like.

<(A) component>
Although it does not specifically limit as resin which has the phenolic hydroxyl group which is (A) component, It is preferable that it is resin soluble in alkaline aqueous solution, and a novolak resin is especially preferable from a viewpoint of improving resolution. The novolak resin can be obtained, for example, 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.

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

  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 copolymers thereof, 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.

  The component (A) preferably has a weight average molecular weight of 100,000 or less, more preferably 1000 to 80,000, from the viewpoint of further improving the resolution, developability, thermal shock resistance, heat resistance and the like of the resulting resin pattern. More preferably, it is more preferably 2000 to 50000, particularly preferably 2000 to 20000, and most preferably 5000 to 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.

  When the component (A) is used, the content of the component (A) is preferably 10 to 80% by mass based on the total amount of the photosensitive resin composition excluding the component (G), and is preferably 15 to 60% by mass. % Is more preferable, and 20 to 40% by mass is even more preferable. When the content of the component (A) is in the above range, a film formed using the resulting photosensitive resin composition tends to be more excellent in developability with an alkaline aqueous solution.

［一般式（７）〜（１０）中、Ｒ^１、Ｒ^５、Ｒ^１６及びＲ^１９は、それぞれ水素原子、メチル基、エチル基、水酸基又は一般式（１１）で表される基を示し、Ｒ^２１は水酸基、グリシジルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を示し、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１７、Ｒ^１８及びＲ^２０は、それぞれ水酸基、グリシジルオキシ基、アクリロイルオキシ基、メタクリロイルオキシ基、一般式（１２）で表される基又は一般式（１３）で表される基を示し、Ｒ^２２及びＲ^２３はそれぞれ水酸基、グリシジルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を示し、ｎ及びｍはそれぞれ１〜１０の整数である。］ <(B) component>
Component (B): An aliphatic compound having two or more functional groups selected from acryloyloxy group, methacryloyloxy group, glycidyloxy group and hydroxyl group is an aliphatic compound having three or more functional groups. Preferably there is. In addition, (B) component may have 2 or more types of different functional groups one by one, and may have 2 or more of 1 type of functional groups. The upper limit of the number of functional groups is not particularly limited, but is 12 for example. Specific examples of the component (B) include compounds represented by general formulas (7) to (10). The “aliphatic compound” refers to a compound in which the main skeleton is an aliphatic skeleton and does not contain an aromatic ring or an aromatic heterocyclic ring.

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

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

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

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

  Examples of the compound having a methacryloyloxy group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, 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 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. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

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

  (B) As a functional group of a component, a glycidyloxy group, an acryloyloxy group, or a methacryloyloxy group is preferable, a glycidyloxy group or an acryloyl group is more preferable, and an acryloyloxy group is still more preferable. From the viewpoint of developability, the component (B) is preferably an aliphatic compound having two or more glycidyloxy groups, and more preferably an aliphatic compound having three or more glycidyloxy groups. More preferably, the aliphatic compound has a glycidyloxy group having a weight average molecular weight of 1000 or less. In addition, since the component (B) has a glycidyloxy group, in the exposed area, not only is the two or more oxirane rings in the component (B) reacted and cross-linked by the acid generated from the component (C), but (A It is preferable because it also reacts with the phenolic hydroxyl group of the component to further reduce the solubility of the composition in the developer.

  The content of the component (B) is preferably 20 to 70 parts by mass, more preferably 25 to 65 parts by mass, and 35 to 55 parts by mass with respect to 100 parts by mass of the component (A). More preferably. When the content of the component (B) is 20 parts by mass or more, the crosslinking in the exposed part is sufficient, so that the resolution is more easily improved. When the content is 70 parts by mass or less, the photosensitive resin composition is placed on a desired support. The film can be easily formed, and the resolution tends not to decrease.

<(C) component>
The photosensitive acid generator as component (C) is a compound that generates an acid upon irradiation with actinic rays or the like.

  The component (C) is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or the like. For example, an onium salt compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound Is mentioned. Among them, it is preferable to use an onium salt compound or a sulfonimide compound from the viewpoint of availability. In particular, when a solvent is used as the component (G), it is preferable to use an onium salt compound 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 preferred onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate and the like diaryliodonium salts; triphenylsulfonium Triarylsulfonium salts such as trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate; 4-t-butylphenyl-diphenylsulfonium trifluoromethanesulfonate; 4-t-butylphenyl-diphenylsulfonium p- Toluenesulfonate; 4, 7 And di -n- butoxy naphthyl tetrahydrothiophenium trifluoromethanesulfonate, and the like.

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

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

  The content of the component (C) is 0.1 to 15 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of ensuring the sensitivity, resolution, pattern shape and the like of the photosensitive resin composition of the present embodiment. Preferably, 0.3-10 mass parts is more preferable.

<(D) component>
In the photosensitive resin composition of the present embodiment, the content of the component (D) by including an inorganic filler surface-treated with a silane coupling agent having an average particle size of 100 nm or less as the component (D). Accordingly, the thermal expansion coefficient of the obtained cured film can be reduced. The photosensitive resin composition was dispersed in the photosensitive resin composition from the viewpoint of suppressing light scattering in the exposure wavelength region (for example, 300 to 450 nm), that is, suppressing a decrease in transmittance in the exposure wavelength region. The average particle size of the component (D) is preferably 80 nm or less, more preferably 50 nm or less, and still more preferably 30 nm or less. Although the minimum of the average particle diameter in (D) component is not specifically limited, For example, it can be 5 nm or more.

  From the viewpoint of suppressing a decrease in transmittance, the inorganic filler is preferably dispersed with a maximum particle size of less than 1000 nm and more preferably 500 nm or less when dispersed in the resin composition. Preferably, it is more preferably dispersed at 300 nm or less, and particularly preferably at 100 nm or less.

  The average particle diameter of the inorganic filler is an average 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 with methyl ethyl ketone, using a submicron particle analyzer (trade name: N5, manufactured by Beckman Coulter Co., Ltd.), conforming to the international standard ISO 13321. Then, the particles dispersed in the solvent at a refractive index of 1.38 are measured, and the particle size at an integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle size. Further, the particle diameter at the integrated value 99.9% (volume basis) in the particle size distribution is defined as the maximum particle diameter. Further, even if the photosensitive layer or the cured film of the photosensitive resin composition provided on the support is diluted (or dissolved) by 1000 times (volume ratio) using a solvent as described above, the sub It can be measured using a micron particle analyzer.

  The primary particle diameter of the inorganic filler before being dispersed in the photosensitive resin composition is preferably 80 nm or less. The primary particle diameter is a value obtained by conversion from the BET specific surface area.

  An inorganic filler will not be restrict | limited especially if the said performance can be exhibited, 1 type can be used individually or in mixture of 2 or more types. 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; Examples include inorganic compounds derived from mines such as talc and mica; silica such as fused spherical silica, fused and ground silica, fumed silica, and sol-gel silica. These can be pulverized by a pulverizer, classified according to circumstances, and dispersed with a maximum particle size of less than 1000 nm.

As the kind of the inorganic filler, an inorganic filler having a thermal expansion coefficient of 5.0 × 10 ⁻⁶ / ° C. or less is preferable, and from the viewpoint of particle diameter, silica is more preferable, fused spherical silica, fumed silica or Sol gel silica is more preferred. Among them, fumed silica or sol-gel silica is more preferable, and silica (nanosilica) having an average primary particle size of 5 nm to 100 nm is more preferable.

  Since the inorganic filler has a maximum particle size of less than 1000 nm and is dispersed in the photosensitive resin composition, the dispersibility can be improved by using a surfactant such as a silane coupling agent. The inorganic filler surface-treated with the silane coupling agent has a functional group X (phenyl group, vinyl group, epoxy group, methacryloyl group, amino group, ureido group, mercapto group, isocyanate group, or acryloyl group) on the surface. The surface treatment method is not particularly limited. In addition, it can be said that (D) component is an inorganic filler which has the functional group X with an average particle diameter of 100 nm or less. The ratio of the number of hydroxyl groups and functional groups X on the surface of the surface-treated inorganic filler may be 9: 1 to 1:60. Within this range, excellent affinity for the resin composition and inorganic filler particles Aggregation between each other can be suppressed.

The inorganic filler surface-treated with the silane coupling agent can confirm the presence or absence of surface treatment by the infrared absorption spectrum. Specifically, the inorganic filler is separated from the photosensitive resin composition with a solvent. The infrared absorption spectrum of the inorganic filler is measured by a solid diffuse reflection method, and the presence or absence of the maximum absorption peak of C—H stretching vibration near 2962 cm ⁻¹ and the presence or absence of the surface treatment of the inorganic filler can be confirmed.

  Moreover, it is preferable that content of an inorganic filler is 20-300 mass parts with respect to 100 mass parts of (A) component, It is more preferable that it is 50-300 mass parts, It is 100-300 mass parts. Is more preferable. By setting the content of the inorganic filler to 20 parts by mass or more, the thermal expansion coefficient can be reduced, and by setting the content of the inorganic filler to 300 parts by mass or less, good resolution can be expressed.

  As the silane coupling agent, the silane coupling agent is an alkoxy group and a functional group X (phenyl group, vinyl group, epoxy group, methacryloyl group, amino group, ureido group, mercapto group, isocyanate group, or acryloyl group). Those having the following are preferred. Such silane coupling agents include phenyltrimethoxysilane, vinyltrimethoxysilane, epoxytrimethoxysilane, methacryltrimethoxysilane, aminotrimethoxysilane, ureidotrimethoxysilane, mercaptotrimethoxysilane, isocyanate, acrylic trimethoxy. Silane etc. are mentioned.

<(E) component>
The photosensitive resin composition of the present embodiment includes, as the component (E), 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. You may contain. 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 (for example, a cyclic group having 3 to 10 carbon atoms) having at least one nitrogen atom, oxygen atom, sulfur atom, etc., for example, a pyridine ring, an imidazole ring, a pyrrolidinone ring, Examples include an oxazolidinone ring, an imidazolidinone ring, and a pyrimidinone ring. The alicyclic ring means a cyclic hydrocarbon group having no aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), for example, 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. Further, the two alkyl groups may be different from each other, for example, an alkyl group having 1 to 10 carbon atoms.

  By containing the component (E), when the photosensitive layer after the resin pattern is formed is heated and cured, the component (E) 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. Specifically, a compound further having a phenolic hydroxyl group or a compound having a hydroxymethylamino group or an alkoxymethylamino group can be preferably used, and the component (A) and the component (B) are not included. (E) A component can be used individually by 1 type or in mixture of 2 or more types.

  As described above, acid is generated from the component (C) by irradiation with actinic rays or the like. Then, by the catalytic action of the generated acid, the alkoxyalkyl groups in the component (E) or the alkoxyalkyl groups in the component (E) react with the component (A) with dealcoholization, thereby causing a negative pattern. Can be formed more efficiently. In addition, due to the catalytic action of the generated acid, the methylol groups in the component (E) or the methylol groups in the component (E) react with the component (A) with dealcoholization to form a negative pattern. Can be formed.

  Further, as the component (E), a compound having a phenolic hydroxyl group (however, the component (A) is not included) or a compound having a hydroxymethylamino group can be preferably used. (E) A component can be used individually by 1 type or in mixture of 2 or more types.

  The “compound having a phenolic hydroxyl group” used as the component (E) can increase the dissolution rate of the unexposed area when developing with an alkaline aqueous solution and improve the sensitivity. The molecular weight of the compound having a phenolic hydroxyl group is preferably 94 to 2000, more preferably 108 to 2000 in terms of weight average molecular weight in consideration of improving the solubility in alkali aqueous solution, photosensitivity, mechanical properties and the like in a balanced manner. 108-1500 are more preferable. In addition, about the compound with a low molecular weight, when it is difficult to measure by the above-mentioned measuring method of the weight average molecular weight, the molecular weight can be measured by another method, and the average can be calculated.

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

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 valent organic group, a and b each independently represent 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 an ethenyl 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 as or different from each other.

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

In General Formula (2), X ¹ represents a single bond or a divalent 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).

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

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

  In 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 group 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 a halogen atom such as a fluorine atom; a sulfonyl group; a carbonyl group; an ether bond; Sulfide bond; amide bond and the like. Among these, Z is preferably a divalent organic group represented by the following general formula (4).

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

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

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

一般式（６）中、複数のＲは、それぞれ独立にアルキル基（例えば、炭素原子数が１〜１０のアルキル基）を示す。 In general formula (5), several R shows an alkyl group (for example, a C1-C10 alkyl group) each independently.

In general formula (6), several R shows an alkyl group (for example, a C1-C10 alkyl group) each independently.

  The content of the component (E) is preferably 5 to 50 parts by mass and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the component (A). When the content of the component (E) is 5 parts by mass or more, the reaction of the exposed part becomes sufficient, so that the resolution tends to be difficult to decrease. When the content is 50 parts by mass or less, a photosensitive resin composition is desired. It tends to be easy to form a film on the support, and the resolution tends not to decrease.

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

  The content of the component (F) 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 the component (A). .

<(G) component>
The photosensitive resin composition of this embodiment further contains a solvent as the component (G) in order to improve the handleability of the photosensitive resin composition or to adjust the viscosity and storage stability. Can do. The component (G) 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 acetate such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene Propylene glycol monoalkyl ethers such as glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene Glycol monomethyl ether Cetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monoalkyl ether acetate such as propylene glycol monobutyl ether acetate; cellosolve such as ethyl cellosolve and butyl cellosolve; carbitol such as butyl carbitol; methyl lactate, lactic acid Lactic acid esters such as ethyl, n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate Aliphatic carboxylic acid esters such as isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-eth Esters such as methyl cypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone Ketones such as N; N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, amides such as N-methylpyrrolidone, and lactones such as γ-butyrolactone. The said organic solvent can be used individually by 1 type or in mixture of 2 or more types.

  The content of the component (G) is preferably 30 to 200 parts by mass and more preferably 60 to 120 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition excluding the component (G). preferable.

<(H) component>
The photosensitive resin composition of this embodiment may contain a silane coupling agent as the component (H) as a component different from the silane coupling agent used for the surface modification of the inorganic filler. By containing the component (H), the adhesion strength between the photosensitive layer and the substrate after the resin pattern is formed can be improved.

  As the component (H), 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 (H) 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-octyl Methylchlorosilane, 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, Nyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane, and aminosilane.

  As the component (H), 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.

  The component (H) is preferably epoxy silane, mercapto silane, isocyanate silane, acryloyl silane, or methacryloyl silane, and more preferably acryloyl silane or methacryloyl silane, from the viewpoint of high resolution.

  The content of the component (H) 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).

  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)”). . Examples of the phenolic low molecular weight compound include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenyl. Ethane, 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-hydroxy Eniru) ethane and the like. These phenol compounds (a) can be contained in an amount of 0 to 40 parts by mass, particularly 0 to 30 parts by mass with respect to 100 parts by mass of the component (A).

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

[Photosensitive element]
The photosensitive element of this embodiment is demonstrated based on FIG. FIG. 1 is a schematic cross-sectional view of a photosensitive element 10 according to this embodiment. As shown in FIG. 1, the photosensitive element 10 of the present embodiment includes a support 1 and a photosensitive layer 3 including the above-described photosensitive resin composition formed on the support 1. Good. A protective film 5 that covers the photosensitive layer may be further provided on the photosensitive layer 3.

  As the support 1, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. The thickness of the support 1 (polymer film) is preferably 5 to 25 μm. In addition, you may laminate | stack the said polymer film on both surfaces of the photosensitive layer 3, using one as the support body 1 and the other as the protective film 5.

  As the protective film 5, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used.

  The photosensitive layer 3 can be formed by applying the photosensitive resin composition on a support or a protective film. 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, it is preferably 10 to 100 μm, more preferably 15 to 60 μm, and particularly preferably 20 to 50 μm after the photosensitive layer 3 is dried.

[Method of forming resist pattern]
Next, a resist pattern forming method of this embodiment will be 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.). . The photosensitive layer may be formed by coating the photosensitive resin composition on a substrate and drying to volatilize the solvent to form a coating film (photosensitive layer). Examples include a method of transferring a layer 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. Moreover, the thickness of the coating film can be appropriately controlled by adjusting the coating means, the solid content concentration and the viscosity of the photosensitive resin composition.

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

  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 composition of the photosensitive resin composition, the content of each component, the thickness of the photosensitive layer, and the like, but for example, heating at 70 to 150 ° C. for 1 to 60 minutes is preferable, and 80 to 120 It is more preferable to heat at a temperature of 1 to 60 minutes.

  Next, the exposed and / or post-exposure baked photosensitive layer 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, for example, 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 so as to have a concentration of 1 to 10% by mass, aqueous ammonia, and the like. And an alkaline aqueous solution. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, after developing with this alkaline developing solution, it wash | cleans with water and dries. The alkaline developer is preferably tetramethylammonium hydroxide in terms of excellent resolution.

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

  Moreover, in order to fully advance hardening, or in order 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 further heating at 80 to 200 ° C. for 10 minutes to 10 hours in the second stage.

  If it is the above-mentioned hardening conditions, there will be no restriction | limiting in particular as a heating equipment, A general oven, an infrared furnace, etc. can be used.

[Multilayer printed wiring board]
The cured product formed from the photosensitive resin composition of the present embodiment is preferably used as, for example, a surface protective film or an interlayer insulating film of a semiconductor element, or a solder resist and / or an interlayer insulating film in a multilayer printed wiring board. it can. FIG. 2 is a view showing a method for producing a multilayer printed wiring board containing a cured product of the photosensitive resin composition of the present embodiment as a solder resist and / or an interlayer insulating material. The multilayer printed wiring board 100A shown in FIG. 2 (f) has a wiring pattern on the surface and inside. Hereinafter, a method 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, the interlayer insulating film 103 is formed on both surfaces of the base material 101 having the wiring pattern 102 on the surface (see FIG. 2A). The interlayer insulating film 103 may be formed by printing a photosensitive resin composition using a screen printer or a roll coater. Alternatively, the photosensitive element described above is prepared in advance, and the photosensitive resin composition is prepared using a laminator. The photosensitive layer in the element can also be formed on the surface of the 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. 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 formed on the seed layer 105, and a predetermined portion is exposed and developed to form a resin pattern 106 (see FIG. 2D). Next, the 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 by a peeling 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 thus obtained, semiconductor elements are mounted at corresponding locations, and electrical connection can be ensured.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these 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, B-2) having a methacryloyloxy group and a glycidyloxy group, photosensitive acid generator (C-1), silane with respect to 100 parts by mass of the novolak resin (A-1, A-2) Table 1 shows silica that has been surface-treated with a coupling agent and silica that has not been surface-treated (inorganic filler 1 to inorganic filler 6), a compound (E-1) having an alkoxyalkyl group, and a solvent (G-1). A predetermined amount was blended to obtain a photosensitive resin composition.
The photosensitive resin composition was applied on a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd., product name: Purex A53) (support) so that the thickness of the photosensitive resin composition was uniform, and 90 ° C. Was dried for 10 minutes with a hot air convection dryer to prepare a photosensitive element having a dried photosensitive layer thickness of 25 μm.

<Measurement of average particle size and maximum particle size>
The photosensitive resin composition is diluted 1000 times (volume ratio) with methyl ethyl ketone and refracted using a submicron particle analyzer (trade name: N5, manufactured by Beckman Coulter, Inc.) according to international standard ISO 13321. The particle size at an integrated value of 50% (volume basis) in the particle size distribution was measured at a rate of 1.38, and the average particle size of the inorganic filler dispersed in the photosensitive resin composition. Further, the particle diameter at the integrated value 99.9% (volume basis) in the particle size distribution was taken as the maximum particle diameter.

<Evaluation of transparency>
The transmittance of the photosensitive element was measured with a UV-visible spectrophotometer (trade name: U-3310, manufactured by Hitachi, Ltd.) at a wavelength of 365 nm (i-line) at a film thickness of 25 μm.

<Evaluation of resolution>
The photosensitive element is laminated on a 6-inch silicon wafer so that the photosensitive layer and the silicon wafer are in contact with each other, using a heat roll at 100 ° C., with a pressure bonding pressure of 0.4 MPa and a roll speed of 1.0 m / min. Lamination was performed. The produced coating film was subjected to reduced projection exposure through a mask with i-line (365 nm) using an i-line stepper (manufactured by Canon Inc., trade name: FPA-3000iW). As the mask, a mask having a pattern in which the width of the exposed part and the unexposed part 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 coating film was heated at 65 ° C. for 1 minute and then at 95 ° C. for 4 minutes (post-exposure bake), and the shortest development time (with the unexposed area was reduced by using 2.38 mass% tetramethylammonium hydroxide aqueous solution). Development was performed by immersing in a time corresponding to 1.5 times the shortest time to be removed), and development was performed by removing unexposed portions. 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 causing meandering or chipping, the smallest space width value is set as the minimum resolution, and at that time The amount of exposure was evaluated.

<Evaluation of heat resistance>
The photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were placed on a polyethylene terephthalate film (manufactured by Teijin DuPont Films, product name: Purex A53) (support), and the thickness of the photosensitive resin composition. Was applied with a hot air convection dryer at 90 ° C. for 10 minutes to produce a photosensitive element having a dried photosensitive layer thickness of 40 μm. Subsequently, the photosensitive layer was exposed using an exposure machine having a high-pressure mercury lamp (trade name: EXM-1201, manufactured by Oak Manufacturing Co., Ltd.) so that the irradiation energy amount was 3000 mJ / cm ² . The exposed photosensitive layer was heated on a hot plate at 65 ° C. for 2 minutes, then at 95 ° C. for 8 minutes, and then heated at 180 ° C. for 60 minutes in a hot air convection dryer to obtain a cured film. Using a thermomechanical analyzer (trade name: TMA / SS6000, manufactured by Seiko Instruments Inc.), the amount of thermal expansion of the cured film was measured when the temperature was increased at a rate of temperature increase of 5 ° C./min. The inflection point obtained from the curve was determined as the glass transition temperature Tg. The thermal expansion coefficient was calculated from the amount of thermal expansion from 40 ° C. to 150 ° C. at a tensile load of 5 g. The 3% thermogravimetric decrease temperature was measured under the conditions of a temperature increase rate of 10 ° C./min under air using a differential thermothermal gravimetric simultaneous measurement device (manufactured by Seiko Instruments Inc., trade name: TG / DTA6300). The temperature was reduced by 3%. The evaluation results are shown in Table 1.

A-1: Cresol novolac resin (Asahi Organic Materials Co., Ltd., trade name: TR4020G)
A-2: Cresol novolac resin (Asahi Organic Materials Co., Ltd., trade name: TR4080G)
B-1: Trimethylolpropane triglycidyl ether (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: ZX-1542, see formula (14) below)

Ｂ−２：ペンタエリスリトールトリアクリレート（日本化薬株式会社製、商品名：ＰＥＴ−３０）
Ｃ−１：トリアリールスルホニウム塩（サンアプロ株式会社製、商品名：ＣＰＩ−３１０Ｂ）
無機フィラー１：３−メタクリロイルオキシプロピルトリメトキシシランでカップリング処理した、平均一次粒子径が１５ｎｍであるゾルゲルシリカ
無機フィラー２：３−メタクリロイルオキシプロピルトリメトキシシランでカップリング処理した、平均一次粒子径が４５ｎｍであるゾルゲルシリカ
無機フィラー３：２−（３，４―エポキシシクロヘキシル）エチルトリメトキシシランでカップリング処理した、平均一次粒子径が１５ｎｍであるゾルゲルシリカ
無機フィラー４：３−グリシドキシプロピルトリメトキシシランでカップリング処理した、平均一次粒子径が１５ｎｍであるゾルゲルシリカ
無機フィラー５：３−メタクリロイルオキシプロピルトリメトキシシランでカップリング処理した、平均一次粒子径が１２０ｎｍであるゾルゲルシリカ
無機フィラー６：平均一次粒子径が１５ｎｍであるゾルゲルシリカ
Ｅ−１：グリコールウリル誘導体（株式会社三和ケミカル製、商品名：ＭＸ−２７０）
Ｇ−１：メチルエチルケトン（和光純薬工業株式会社製、商品名：２−ブタノン）

B-2: Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: PET-30)
C-1: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-310B)
Inorganic filler 1: Sol-gel silica inorganic filler having an average primary particle size of 15 nm coupled with 3-methacryloyloxypropyltrimethoxysilane 2: Average primary particle size coupled with 3-methacryloyloxypropyltrimethoxysilane Sol-gel silica inorganic filler 3: having a mean primary particle size of 15 nm coupled with 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 4: 3-glycidoxypropyl Sol-gel silica inorganic filler 5 having an average primary particle diameter of 15 nm coupled with trimethoxysilane 5: Sol having an average primary particle diameter of 120 nm coupled with 3-methacryloyloxypropyltrimethoxysilane Rushirika inorganic filler 6: average primary particle diameter of 15nm sol-gel silica E-1: glycoluril derivative (Sanwa Chemical Co., trade name: MX-270)
G-1: Methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 2-butanone)

  As is clear from Table 1, Examples 1 to 8 in which the average particle diameter of the inorganic filler in the photosensitive resin composition is 100 nm or less have a high transmittance of 70% or more, and the resolution is 15 μm or less. It was good. On the other hand, Comparative Examples 1 and 4 containing no inorganic filler have a high coefficient of thermal expansion and a low 3% thermal weight loss temperature, and are inferior in heat resistance. In Comparative Example 10 in which the average particle size of the inorganic filler in the photosensitive resin composition exceeded 100 nm, the transmittance was as low as 40% or less, and the resolution exceeded 30 μm and was insufficient. In Comparative Example 11, aggregation of silica occurred, and a series of evaluations could not be performed. Further, in Examples 1 to 3, as the content of the inorganic filler increases, the thermal expansion coefficient decreases, the 3% thermal weight loss temperature increases, and the balance between resolution, heat resistance, and thermal expansion coefficient is achieved. I found it excellent.

  The photosensitive resin composition of this invention is applied as a material used for the surface protection film or interlayer insulation film of a semiconductor element. Moreover, it is applied as a material used for a solder resist of a wiring board material or an interlayer insulating film. In particular, since the photosensitive resin composition has good resolution and heat resistance after curing, and also has a low thermal expansion coefficient, it is highly integrated package that is thinned and densified. It is suitably used for substrates and the like.

DESCRIPTION OF SYMBOLS 1 ... Support body, 3 ... Photosensitive layer, 5 ... Protective film, 10 ... Photosensitive element, 100A ... Multilayer printed wiring board, 101 ... Base material, 102, 107 ... Wiring pattern, 103 ... Interlayer insulating film, 104 ... Opening , 105 ... seed layer, 106 ... resin pattern, 108 ... solder resist.

Claims (11)

(A) component: resin having phenolic hydroxyl group,
(B) component: an aliphatic compound having two or more functional groups of at least one selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group;
(C) component: a photosensitive acid generator, and (D) component: an inorganic filler surface-treated with a silane coupling agent having an average particle size of 100 nm or less,
The photosensitive resin composition containing this.   The photosensitive resin according to claim 1, wherein the silane coupling agent has an alkoxy group, a phenyl group, a vinyl group, an epoxy group, a methacryloyl group, an amino group, a ureido group, a mercapto group, an isocyanate group, or an acryloyl group. Composition.   The silane coupling agent includes phenyltrimethoxysilane, vinyltrimethoxysilane, epoxytrimethoxysilane, methacryltrimethoxysilane, aminotrimethoxysilane, ureidotrimethoxysilane, mercaptotrimethoxysilane, isocyanate, and acryltrimethoxysilane. The photosensitive resin composition of Claim 1 or 2 which is at least 1 type chosen.   The photosensitive resin composition as described in any one of Claims 1-3 whose maximum particle diameter of the said (D) component is less than 1000 nm.   The component (B) is an aliphatic compound having three or more functional groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and a hydroxyl group. The photosensitive resin composition according to item.   (E) component: It has at least 1 sort (s) chosen from the group which consists of an aromatic ring, a heterocyclic ring, and an alicyclic ring, and further contains the compound which has a methylol group or an alkoxyalkyl group. The photosensitive resin composition of one term.   The photosensitive resin composition as described in any one of Claims 1-6 which contains 20-70 mass parts of said (B) components with respect to 100 mass parts of said (A) components. A support and a photosensitive layer provided on the support;
The said photosensitive layer is a photosensitive element formed using the photosensitive resin composition as described in any one of Claims 1-7.   Hardened | cured material of the photosensitive resin composition as described in any one of Claims 1-7. Applying the photosensitive resin composition according to any one of claims 1 to 7 on a substrate, and drying the photosensitive resin composition to form a photosensitive layer;
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. A step of forming a photosensitive layer on the substrate using the photosensitive element according to claim 8;
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