TW201642038A - Photosensitive resin composition, photosensitive element, cured product, and method for forming resist pattern - Google Patents

Abstract

The purpose of the present invention is to provide a photosensitive resin composition capable of forming a resist pattern that has excellent resolution and heat resistance and has a low thermal expansion coefficient, even when a coating film having a thickness exceeding 20 [mu]m is formed. Provided is a photosensitive resin composition that contains the following components: (A) a resin having a phenolic hydroxyl group; (B) an aliphatic compound having at least two functional groups of at least one type selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and a hydroxyl group; (C) a photosensitive acid-generating agent; and (D) an inorganic filler that is surface-treated with a silane coupling agent and has an average particle diameter of 100 nm or less.

Description

Photosensitive resin composition, photosensitive element, cured product, and method for forming resist pattern

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

In the production of a semiconductor element or a printed wiring board, for example, a negative photosensitive resin composition is used in order to form a fine pattern. In this method, a photosensitive layer is formed on a substrate (a chip in the case of a semiconductor element or a substrate in the case of a printed wiring board) by applying a photosensitive resin composition or the like, and a predetermined layer is formed. The pattern illuminates the actinic ray. Further, the unexposed portion is selectively removed using a developing solution, whereby a resin pattern is formed on the substrate. Therefore, the photosensitive resin composition is required to have excellent photosensitivity to actinic rays, properties (analytical properties) capable of forming fine patterns, and the like. Therefore, a photosensitive resin composition containing a novolac resin, an epoxy resin, and a photoacid generator which are soluble in an aqueous alkaline solution, an alkali-soluble epoxy compound having a carboxyl group, and a photocationic polymerization initiator are proposed. A resin composition or the like (for example, refer to Patent Document 1 and Patent Document 2).

Further, as the surface protective film and the interlayer insulating film used in the semiconductor element, insulation reliability such as heat resistance, electrical properties, and mechanical properties is required. Therefore, a photosensitive resin composition further containing a crosslinkable monomer has been proposed (for example, see Patent Document 3).

On the other hand, in recent years, with the increase in the performance of electronic devices, the integration and high reliability of semiconductor devices have progressed year by year. As the semiconductor element is highly integrated, formation of a finer pattern and thinning of the entire semiconductor element are required. However, when the entire semiconductor element is thinned, warpage caused by a difference in thermal expansion coefficient between the wafer and the surface protective film or the wafer and the interlayer insulating film becomes a big problem, and therefore, there is a strong demand for a photosensitive resin composition. It has a coefficient of thermal expansion close to the coefficient of thermal expansion of the wafer (3 × 10 ^-6 / ° C), that is, a coefficient of thermal expansion. Therefore, in order to achieve a low thermal expansion of the photosensitive resin composition, for example, a photosensitive resin composition containing an inorganic filler has been proposed (for example, see Patent Document 4).

In addition, by forming a thick interlayer insulating film, the insulation between the wirings in the thickness direction of the layer is improved, and the short circuit of the wiring can be prevented, so that the reliability related to the insulation between the wirings is improved. Further, in the case of mounting a wafer, since the semiconductor element has a thick interlayer insulating film, the stress applied to the pad of the solder bump can be alleviated, so that connection failure is less likely to occur at the time of mounting. Therefore, from the viewpoint of insulation reliability and productivity in the case of mounting a wafer, a film which can form a photosensitive resin composition having a thickness of more than 20 μm is also required. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. -13622

[Problems to be Solved by the Invention] 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. It is not sufficient for a highly integrated semiconductor element. Further, in the photosensitive resin composition described in Patent Document 2, sufficient heat resistance cannot be exhibited. Further, in the photosensitive resin composition described in Patent Document 3, when the thickness of the coating film is 10 μm, good resolution with a gap width of about 5 μm can be obtained, but it is not good at the time of thick film formation. Analytical. In addition, when the photosensitive resin composition described in Patent Document 4 is used and the inorganic filler is highly filled in order to lower the thermal expansion coefficient, the influence of light scattering tends to increase, and the resolution tends to be lowered.

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide an excellent thermal conductivity and thermal expansion even when a coating film (photosensitive layer) having a thickness of more than 20 μm is formed. A photosensitive resin composition of a resist pattern having a low coefficient. Further, another object of the present invention is to provide a cured product of the photosensitive resin composition and a method of forming a photosensitive element and a resist pattern using the photosensitive resin composition. [Means for solving the problem]

The photosensitive resin composition of the present invention contains (A) a component: a resin having a phenolic hydroxyl group, and (B) a component: two or more selected from the group consisting of an acryloxy group, a methacryloxy group, a glycidoxy group, and a hydroxyl group. One or more functional group aliphatic compounds, (C) component: photo-sensitive acid generator, and (D) component: an average particle diameter of 100 nm or less and surface-surfaced with a silane coupling agent Treated inorganic filler.

The decane coupling agent may have an alkoxy group and have a phenyl group, a vinyl group, an epoxy group, a methacryl oxime group, an amine group, a ureido group, a fluorenyl group, an isocyanate group, or an acrylonitrile group.

The decane coupling agent may be selected from the group consisting of phenyl trimethoxy decane, vinyl trimethoxy decane, epoxy trimethoxy decane, methacryl fluorenyl trimethoxy decane, amine trimethoxy decane, urea group At least one of trimethoxydecane, decyltrimethoxydecane, isocyanate decane, and acrylonitrile trimethoxy decane.

The (D) component may have a maximum particle diameter of less than 1000 nm.

The component (B) may be an aliphatic compound having three or more functional groups selected from the group consisting of an acryloxy group, a methacryloxy group, a glycidoxy group, and a hydroxyl group.

The photosensitive resin composition of the present invention may further contain (E) a 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. .

The photosensitive resin composition of the present invention may contain 20 parts by mass to 70 parts by mass of the component (B) based on 100 parts by mass of the component (A).

The component (D) may be silica.

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

The photosensitive element may further include an fluorenone resin layer or an alkyd resin layer between the support and the photosensitive layer.

The photosensitive layer may have a thickness of less than 50 μm.

Further, the present disclosure provides a cured product which is a cured product of the photosensitive resin composition.

Further, the present disclosure provides a cured product obtained by using a photosensitive layer in the photosensitive element.

Further, the present disclosure provides a method of forming a resist pattern, comprising: a step of applying the photosensitive resin composition onto a substrate, and drying the photosensitive resin composition to form a photosensitive layer; a step of exposing to a predetermined pattern and performing heat treatment after exposure; and a step of developing the heat-treated photosensitive layer and subjecting the obtained resin pattern to heat treatment.

Further, the present disclosure provides a method of forming a resist pattern, comprising: forming a photosensitive layer using the photosensitive element on a substrate; exposing the photosensitive layer to a predetermined pattern, and performing heat treatment after exposure And a step of developing the heat-treated photosensitive layer and subjecting the obtained resin pattern to heat treatment. [Effects of the Invention]

According to the photosensitive resin composition of the present invention, even when a coating film having a thickness of more than 20 μm is formed, a resist pattern having excellent resolution and heat resistance and a low thermal expansion coefficient can be formed. Further, according to the present disclosure, it is possible to provide a cured product of the photosensitive resin composition, a photosensitive element using the photosensitive resin composition, and a method of forming a resist pattern.

Hereinafter, the embodiments of the present disclosure will be specifically described with reference to the drawings, but the present disclosure is not limited thereto. In the following description, the same or corresponding components are designated by the same reference numerals, and the repeated description is omitted.

In the present specification, "EO modification" means a compound having a (poly)oxyethyl group, and "PO modification" means a compound having a (poly)oxypropyl group. Here, the (poly)oxyl extended ethyl group means at least one of an oxygen-extended ethyl group or two or more polyoxyethylene groups in which an ethyl group is bonded by an ether bond. The (poly)oxypropanyl group means at least one of an oxygen-extended propyl group or a polyoxyl-propyl group in which two or more exopropyl groups are linked by an ether bond.

In addition, in the present specification, the term "step" refers not only to an independent step but also to the intended function of the step as long as it can not be clearly distinguished from other steps. In addition, in the present specification, the numerical range indicated by "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. Further, regarding the numerical range recited in the present specification, the upper limit value or the lower limit value of the numerical range of a certain stage may be replaced with the upper limit value or the lower limit value of the numerical range of the other stage. In addition, in the numerical range described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment. In addition, in this specification, the term "layer" includes a structure formed in a shape of a part of a surface, in addition to a structure having a shape formed on the entire surface in plan view.

Further, in the present specification, when a plurality of substances corresponding to the respective components are present in the composition, the content of each component in the composition means the plurality of substances present in the composition unless otherwise specified. Total amount.

[Photosensitive Resin Composition] The photosensitive resin composition of the present embodiment contains (A) a component: a resin having a phenolic hydroxyl group, and (B) a component: two or more selected from the group consisting of acryloxy group and methacryloxy group An aliphatic compound having one or more functional groups of a glycidyloxy group and a hydroxyl group; (C) component: a photo-sensitive acid generator; and (D) component: an average particle diameter of 100 nm or less and a decane coupling agent An inorganic filler that has been surface treated.

The reason why the present inventors have found that a resist pattern having high resolution and high heat resistance can be formed by the photosensitive resin composition of the present embodiment is as follows. The inventors of the present invention presumed that the solubility of the component (A) in the developer in the unexposed portion is greatly improved by the addition of the component (B). Thereby, at the time of development, sufficient resolution can be obtained by a significant difference in solubility in the developer in the unexposed portion and the exposed portion, and the component (B) is obtained by heat treatment of the resin pattern after development. The crosslinking, the reaction of the component (B) and the component (A) are further carried out, whereby a resist pattern having sufficient heat resistance can be obtained.

The photosensitive resin composition of the present embodiment may optionally contain (E) a 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. (F) component: sensitizer, (G) component: solvent, (H) component: decane coupling agent, (I) component: amine, (J) component: organic peroxide, (K) component: leveling Leveling agent, etc.

<Component (A)> The resin having a phenolic hydroxyl group as the component (A) is not particularly limited, and may be a resin which is soluble in an aqueous alkaline solution, and may be a novolak resin from the viewpoint of further improving the resolution. . The novolak resin is obtained, for example, by condensing a phenol with an aldehyde in the presence of a catalyst.

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

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

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

Further, examples of the component (A) other than the novolac resin include polyhydroxystyrene and a copolymer thereof, a phenol-benzene dimethanol condensation resin, a cresol-benzene dimethanol condensation resin, and a phenol-dicyclopentadiene condensation resin. Wait. The component (A) may be used alone or in combination of two or more. The component (A) other than the novolak resin may be less than 50% by mass, 30% by mass or less, 10% by mass or less, or 5% by mass or less based on the total amount of the component (A). Or 1% by mass or less. Further, the component (A) other than the novolak resin may be substantially not contained.

The weight average molecular weight of the component (A) may be 100,000 or less, 1,000 to 80,000, 2,000 to 50,000, or 2,000 Å from the viewpoint of further improving the resolution, developability, thermal shock resistance, heat resistance, and the like of the obtained resin pattern. 20000, 4000-16000 or 5000-15000. In addition, from the viewpoint of improving the resolution, developability, thermal shock resistance, heat resistance, and the like of the obtained resin pattern with good balance, two or more kinds of (A) components having different weight average molecular weights can be used in combination. The component (A) having a weight average molecular weight of less than 10,000 may be used in combination with the component (A) having a weight average molecular weight of 10,000 or more. Further, from the same viewpoint, the distribution of the weight average molecular weight of the component (A) may have two or more peaks. Further, from the viewpoint of more excellent analytical properties, the weight average molecular weight of the component (A) may be less than 20,000 or 16,000 or less. "Weight average molecular weight" means a value measured by a gel permeation chromatography (GPC) method using a calibration curve based on a standard polystyrene, and more specifically, a pump (a limited number of Hitachi Ltd. shares) The company manufactures, L-6200 type), column (TSKgel-G5000HXL and TSKgel-G2000HXL, all manufactured by Tosoh Co., Ltd., trade name) and detector (manufactured by Hitachi, Ltd., L -3300RI type) As a GPC measuring apparatus, tetrahydrofuran was used as a washing liquid, and it measured by the temperature of 30 degreeC, and the flow rate of 1.0 mL / min.

When the component (A) is used, the component (G) may be 10% by mass to 80% by mass or 15% by mass based on the total amount of the photosensitive resin composition other than the component (G). ～60% by mass, 15% by mass to 50% by mass, or 20% by mass to 40% by mass. When the content of the component (A) is within the above range, the film formed using the obtained photosensitive resin composition tends to be more excellent in developability by using an alkaline aqueous solution.

<Component (B)> (B) component: an aliphatic compound having two or more functional groups selected from the group consisting of an acryloxy group, a methacryloxy group, a glycidoxy group, and a hydroxyl group may have An aliphatic compound having three or more of the above functional groups. Further, the component (B) may have one or two different functional groups, and may have two or more functional groups. The upper limit of the number of functional groups is not particularly limited and is, for example, 12. Specific examples of the component (B) include a compound represented by the following formula (7) to formula (10). In addition, the "aliphatic compound" means that the main skeleton is an aliphatic skeleton and does not contain an aromatic ring or an aromatic heterocyclic ring. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] [Chemistry 7]

In the general formulae (7) to (10), R ¹ , R ⁵ , R ¹⁶ and R ¹⁹ each independently represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group or a group represented by the formula (11), and R ²¹ represents Hydroxy, glycidoxy, acryloxy or methacryloxy, 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 each represent a hydroxyl group, a glycidoxy group, an acryloxy group, a methacryloxy group, a group represented by the formula (12) or a formula ( 13) group, R ²² and R ²³ are represented by a hydroxyl group, a glycidyloxy group, methyl group, or Bing Xixi Bing Xixi group, n and m are each an integer of 1 to 10.

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

Among the compounds having a glycidyloxy group, trimethylolethane triglycidyl ether or trimethylolpropane triglycidyl ether may be used in terms of more excellent photosensitivity and resolution.

The glycidyloxy group-containing compound can be, for example, Epolight 40E, Epolight 100E, Epolight 70P, Epolight 200P, Epolight 1500NP, Epolight 1600, Epolight 80MF, Epolight 100MF (above is manufactured by Kyoeisha Chemical Co., Ltd., trade name), alkyl epoxy resin ZX-1542 (new Nippon Steel Sumitomo Chemical Co., Ltd., trade name), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Dana Kor (Denacol) EX-321L and Denacol EX-850L (above, manufactured by Nagase ChemteX Co., Ltd., trade name) are commercially available. These glycidoxy group-containing compounds may be used alone or in combination of two or more.

Examples of the compound having an acryloxy group include EO-modified dipentaerythritol hexaacrylate, PO-modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO-modified bis(trimethylolpropane) tetraacrylate, and PO. Modified bis(trimethylolpropane) tetraacrylate, bis(trimethylolpropane) tetraacrylate, EO modified pentaerythritol tetraacrylate, PO modified pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, EO modification Pentaerythritol triacrylate, PO modified pentaerythritol triacrylate, pentaerythritol triacrylate, EO modified trimethylolpropane acrylate, PO modified trimethylolpropane acrylate, trimethylolpropane acrylate, EO modification Glycerol triacrylate, PO modified glycerin triacrylate, glycerin triacrylate, and the like. These compounds having an acryloxy group may be used alone or in combination of two or more.

Examples of the compound having a methacryloxycarbonyl group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexa-methacrylate, dipentaerythritol hexa-methacrylate, and EO-modified bis (tris-hydroxyl). Propyl) tetramethacrylate, PO modified bis(trimethylolpropane) tetramethacrylate, bis(trimethylolpropane) tetramethacrylate, EO modified pentaerythritol tetramethacrylate, PO modified pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, EO modified pentaerythritol trimethacrylate, PO modified pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, EO modified trishydroxyl Propane methacrylate, PO modified trimethylolpropane methacrylate, trimethylolpropane methacrylate, EO modified glycerol trimethacrylate, PO modified glycerol trimethacrylate, Triglyceride, etc. These compounds having a methacryloxycarbonyl group may be used alone or in combination of two or more.

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

The functional group of the component (B) may be a glycidoxy group, an acryloxy group or a methacryloxy group, and may be a glycidoxy group or an acryloxy group, or may be an acryloxy group. Further, from the viewpoint of developability, the component (B) may be an aliphatic compound having two or more glycidoxy groups, and may be an aliphatic compound having three or more glycidoxy groups, or may be a weight. An aliphatic compound having a glycidoxy group having an average molecular weight of 1,000 or less. Further, the component (B) has a glycidoxy group, and the oxirane ring in the component (B) is reacted with each other in the exposed portion by an acid generated from the component (C). In addition, the oxirane ring of the component (B) also reacts with the phenolic hydroxyl group of the component (A) to further reduce the solubility of the composition in the developer, which is preferable. Further, from the viewpoint of analytical properties, the component (B) may be an aliphatic compound having two or more glycidoxy groups, or an aliphatic compound having three or more glycidoxy groups.

The content of the component (B) may be 20 parts by mass to 70 parts by mass, 25 parts by mass to 65 parts by mass, or 35 parts by mass to 55 parts by mass per 100 parts by mass of the component (A). When the content of the component (B) is 20 parts by mass or more, the crosslinking in the exposed portion is sufficient, and the analytical property is further improved. When the content is at least 70 parts by mass, the photosensitive resin composition can be easily formed into a film. On the desired support, the resolution is also less likely to decrease.

<Component (C)> The photo-sensitive acid generator as the component (C) is a compound which generates an acid by irradiation with an actinic ray or the like.

The component (C) is not particularly limited as long as it is an acid which generates an acid by irradiation with an actinic ray or the like, and examples thereof include an onium salt compound, a halogen-containing compound, a diazoketone compound, an anthraquinone compound, a sulfonic acid compound, and a sulfonate. A quinone imine compound and a diazomethane compound. Among them, an onium salt compound or a sulfonium imine compound can be used from the viewpoint of easy availability. In particular, when a solvent is used as the component (G), an onium salt compound can be used from the viewpoint of solubility in a solvent. Hereinafter, a specific example thereof will be described.

Onium salt compound: Examples of the onium salt compound include a phosphonium salt, a phosphonium salt, a phosphonium salt, a diazonium salt, and a pyridinium salt. Specific examples of the onium salt compound include diphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, diphenylsulfonium hexafluorophosphate, and a diarylsulfonium salt such as phenylphosphonium tetrafluoroborate; a triarylsulfonium salt such as triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate or triphenylsulfonium hexafluoroantimonate; 4-tert-butylphenyl-diphenylfluorene trifluoromethanesulfonate; 4-tert-butylphenyl-diphenylfluorene p-toluenesulfonate; 4,7-di-n-butoxynaphthalene Tetrahydrothiophene fluorene triflate or the like.

Sulfonimide compound: Specific examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy) succinimide, N-(trifluoromethylsulfonyloxy) phthalate Yttrium, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2 , 3-dimethylimine, N-(trifluoromethylsulfonyloxy)naphthoquinone imine, N-(p-toluenesulfonyloxy)-1,8-naphthyldimethylimine, N-(10-camphorsulfonyloxy)-1,8-naphthyldimethylimine and the like.

In the present embodiment, the component (C) may have a trifluoromethanesulfonate group, a hexafluoroantimonate group, a hexafluorophosphate group or a tetrafluoro group in terms of more excellent photosensitivity and resolution. Borate-based compound. Further, the component (C) may be used alone or in combination of two or more.

From the viewpoint of further improving the photosensitivity, the resolution, the pattern shape, and the like of the photosensitive resin composition of the present embodiment, the content of the component (C) may be 0.1 part by mass based on 100 parts by mass of the component (A). 15 parts by mass, or 0.3 parts by mass to 10 parts by mass.

<Component (D)> The inorganic filler having an average particle diameter of 100 nm or less and surface-treated with a decane coupling agent as the component (D) can be reduced by the photosensitive resin composition of the present embodiment. The coefficient of thermal expansion of the hardened material. The viewpoint of suppressing light scattering in an exposure wavelength region (for example, 300 nm to 450 nm) of the photosensitive resin composition, that is, suppressing a decrease in transmittance in the exposure wavelength region, is dispersed in a photosensitive resin composition The average particle diameter of the component (D) in the material may be 80 nm or less, 50 nm or less, or 30 nm or less. The lower limit of the average particle diameter of the component (D) is not particularly limited, and may be, for example, 5 nm or more.

The inorganic filler may have a maximum particle diameter of 2000 nm or less, 1000 nm or less, less than 1000 nm, 500 nm or less, 300 nm or less, or 100 in terms of suppressing a decrease in transmittance. Dispersed below nm.

The average particle diameter of the inorganic filler is an average particle diameter of the inorganic filler in a state of being dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows. First, after diluting (or dissolving) the photosensitive resin composition to 1000 times (volume ratio) with methyl ethyl ketone, a submicron particle analyzer (Beckman Coulter) is used. Co., Ltd. manufacture, trade name, model: N5), according to the international standard specification ISO13321, the particles dispersed in the solvent are measured at a refractive index of 1.38, and the particle size distribution is 50% (volume basis). Set to the average particle size. Further, the particle diameter at the cumulative value of 99.9% (volume basis) in the particle size distribution was defined as the maximum particle diameter. Further, even if the photosensitive layer or the cured product of the photosensitive resin composition provided on the support is diluted (or dissolved) into a 1000-fold (volume ratio) using the solvent in the manner described above, the submicron particle analysis is used. The instrument performs the measurement.

The primary particle diameter of the inorganic filler dispersed before the photosensitive resin composition may be 80 nm or less. The primary particle diameter is a value obtained by conversion from a specific surface area of a Brunauer-Emmett-Teller (BET).

The inorganic filler is not particularly limited as long as it exhibits the above properties, and may be used alone or in combination of two or more. Examples of the inorganic filler include aluminum compounds such as alumina 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; and talc (talc). Mineral-derived inorganic compounds such as mica; molten spherical cerium oxide, molten pulverized cerium oxide, aerosolized cerium oxide, sol-gel cerium oxide, and the like. These may be pulverized by a pulverizer, and classified as appropriate to be dispersed at a maximum particle diameter of 2000 nm or less or less than 1000 nm.

The type of the inorganic filler may be an inorganic filler having a thermal expansion coefficient of 5.0×10 ^-6 /° C. or less, and may be cerium oxide or molten spherical cerium oxide or smoky cerium oxide from the viewpoint of particle diameter. Or sol-gel cerium oxide. Among them, it may be fumed cerium oxide or sol-gel cerium oxide, or cerium oxide (nano-cerium oxide) having an average primary particle diameter of 5 nm to 100 nm. Further, sol-gel cerium oxide can also be used from the viewpoint of reducing impurities and improving insulation reliability. Further, from the viewpoint of improving the insulation reliability, the content of the impurities of the inorganic filler may be 10 ppm by mass or less or 5 ppm by mass or less based on the total amount of the inorganic filler. Further, from the viewpoint of the coefficient of thermal expansion, the void ratio of the inorganic filler may be less than 10%, 8% or less, 5% or less, or 0% (substantially no voids inside). The void ratio of the inorganic filler can be determined from the area ratio of the void portion of the electron microscopic cross-sectional image of the inorganic filler to the entire particle size (for example, the arithmetic mean of the area ratio of 200 inorganic fillers).

In the inorganic filler, in order to disperse it in the photosensitive resin composition at a maximum particle diameter of less than 1000 nm, the surface treatment of the inorganic filler can be carried out using a decane coupling agent, thereby improving the dispersibility in the photosensitive resin composition. The inorganic filler surface-treated with a decane coupling agent may have a functional group X (phenyl, vinyl, epoxy, methacryloyl, amine, ureido, sulfhydryl, isocyanate, or The inorganic filler of the acrylonitrile group is not particularly limited in its surface treatment method. Further, such a component (D) may be an inorganic filler having an average particle diameter of 100 nm or less and having a functional group X. The ratio of the number of hydroxyl groups on the surface of the surface-treated inorganic filler to the functional group X may be from 9:1 to 1:60, and if it is within this range, the affinity for the resin composition tends to be excellent, and The tendency of the inorganic filler particles to aggregate with each other can be suppressed.

The inorganic filler surface-treated with a decane coupling agent can confirm the presence or absence of surface treatment by an infrared absorption spectrum. Specifically, the inorganic filler is separated from the photosensitive resin composition containing the inorganic filler surface-treated with a decane coupling agent by a solvent. The infrared absorption spectrum of the inorganic filler was measured by a solid diffusion reflection method, and the presence or absence of the maximum absorption peak due to the CH stretching vibration in the vicinity of 2962 cm ^-1 and the height of the peak were confirmed.

In addition, the content of the inorganic filler may be 20 parts by mass to 300 parts by mass, 50 parts by mass to 300 parts by mass, or 100 parts by mass to 300 parts by mass per 100 parts by mass of the component (A). When the content of the inorganic filler is 20 parts by mass or more, the thermal expansion coefficient tends to be lowered, and when it is 300 parts by mass or less, good analytical properties tend to be exhibited.

The decane coupling agent may be an alkoxy group, and a functional group X (phenyl, vinyl, epoxy, methacryl oxime, amine, ureido, sulfhydryl, isocyanate, or propylene) Decane coupling agent. Examples of such a decane coupling agent include phenyltrimethoxydecane, vinyltrimethoxydecane, epoxytrimethoxydecane, methacryl fluorenyltrimethoxydecane, aminotrimethoxydecane, and ureido trimethyl. Oxydecane, decyltrimethoxydecane, isocyanate decane, propylene decyltrimethoxydecane, and the like. These compounds may also have an organic group between the functional group X and the ruthenium atom. The epoxytrimethoxydecane may be, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane or the like. The methacrylonitrile-trimethoxydecane may be, for example, 3-methylpropenyloxypropyltrimethoxydecane or the like.

<(E) Component> The photosensitive resin composition of the present embodiment may further contain, as the component (E), at least one selected from the group consisting of an aromatic ring, a hetero ring, and an alicyclic ring. Has a methylol or alkoxyalkyl group. Here, the aromatic ring means an aromatic hydrocarbon group (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic ring refers to a cyclic group having at least one hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom (for example, a cyclic group having 3 to 10 carbon atoms), and examples thereof include a pyridine ring, an imidazole ring, and a pyrrole group. A ketone ring, an oxazolidinone ring, an imidazolidinone ring, and a pyrimidinone ring. In addition, the alicyclic ring refers to a cyclic hydrocarbon group which does not have aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), and examples thereof include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and a ring. Hexane ring. The alkoxyalkyl group means a group in which an alkyl group is bonded to an alkyl group via an oxygen atom. Further, the two alkyl groups may be the same or different from each other. The alkyl group is, for example, an alkyl group having 1 to 10 carbon atoms.

When the photosensitive layer after the resin pattern is formed and cured by the component (E), the component (E) reacts with the component (A) to form a crosslinked structure, thereby preventing the resin pattern from being weakened. The deformation of the resin pattern tends to improve heat resistance. Further, specifically, a compound having a phenolic hydroxyl group, a compound further having a hydroxymethylamino group, or a compound having an alkoxymethylamino group, and not containing the components (A) and (B) may be used. . The component (E) may be used alone or in combination of two or more.

As described above, an acid is generated from the component (C) by irradiation with actinic rays or the like. Further, the alkoxyalkyl groups in the (E) component or the alkoxyalkyl group in the (E) component and the (A) component are subjected to dealcoholization by the catalytic action of the generated acid. The reaction is carried out, whereby a negative pattern can be formed more efficiently. Further, the hydroxymethyl group in the component (E) or the methylol group in the component (E) and the component (A) are reacted with dealcoholization by the catalytic action of the generated acid. A negative pattern can be formed.

The "compound having a phenolic hydroxyl group" as the component (E) tends to increase the dissolution rate of the unexposed portion when developing in an alkaline aqueous solution, and to improve the resolution. The molecular weight of the compound having a phenolic hydroxyl group is preferably 94 to 2000, 108 to 2000 by weight average molecular weight, in view of improving the solubility, the analytical property, the mechanical properties, and the like in an alkaline aqueous solution. Or 108 to 1500. Further, in the case where the compound having a low molecular weight is difficult to measure by the measurement method of the weight average molecular weight, the molecular weight may be measured by another method, and the average value thereof may be calculated.

In the compound having a phenolic hydroxyl group, a conventionally known compound can be used, but the effect of promoting the dissolution of the unexposed portion and the effect of preventing the deformation of the resin pattern after curing due to heating are also excellent. It may be a compound represented by the following formula (1). [化8]

In the formula (1), Z represents a single bond or a divalent organic group, and R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent organic group, and R ²⁶ and R ²⁷ each independently represent a monovalent organic group, a and b each independently represents an integer of 1 to 3, and c and d each independently represent an integer of 0 to 3. Here, examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group and a propyl group; an alkenyl group having 2 to 10 carbon atoms such as a vinyl group; and a carbon atom such as a phenyl group. An aryl group having a number of 6 to 30; a group in which a part or all of a hydrogen atom of the hydrocarbon group is substituted with a halogen atom such as a fluorine atom. When a plurality of R ²⁴ to R ²⁷ are present, they may be the same or different from each other.

The compound represented by the formula (1) may also be a compound represented by the following formula (2). [Chemistry 9]

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

Further, as the compound further having a phenolic hydroxyl group, a compound represented by the following formula (3) can also be used. [化10]

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

Further, in the formula (1), the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. Further, 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 exoethyl group and a propyl group; and an ethylene group having 2 to 10 carbon atoms. An alkyl group; a aryl group having 6 to 30 carbon atoms; a group in which a part or all of a hydrogen atom of the hydrocarbon group is substituted by a halogen atom such as a fluorine atom; a sulfonyl group; a carbonyl group; an ether bond; Thioether bond; guanamine bond, etc. Among these, Z may be a divalent organic group represented by the following formula (4). [11]

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

The compound further having a hydroxymethylamino group may, for example, be (poly)(N-hydroxymethyl)melamine, (poly)(N-hydroxymethyl)glycolil, (poly)(N-hydroxymethyl)benzene And decylamine, (poly) (N-hydroxymethyl) urea and the like. Further, a nitrogen-containing compound obtained by alkylating all or a part of the hydroxymethylamino group of these compounds with an alkyl group may also be used. Here, the alkyl group of the alkyl ether may, for example, be a methyl group, an ethyl group, a butyl group or a mixture of these groups, or may contain a part of an oligomer component obtained by self-condensation. Specific examples thereof include hexa(methoxymethyl)melamine, hexakis(butoxymethyl)melamine, tetrakis(methoxymethyl)glycoluril, tetrakis(butoxymethyl)glycolil, and four (Methoxymethyl) urea and the like.

Specifically, the compound having an alkoxymethylamino group may be a compound represented by the following formula (5) or a compound represented by the following formula (6). [化12]

In the formula (5), a plurality of R each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). [Chemistry 13]

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

The content of the component (E) may be 5 parts by mass to 50 parts by mass, or 5 parts by mass to 30 parts by mass, per 100 parts by mass of the component (A). When the content of the component (E) is 5 parts by mass or more, the reaction in the exposed portion is sufficient. Therefore, the resolution is not likely to be lowered. When the content is at least 50 parts by mass, the photosensitive resin composition can be easily formed into a film. On the desired support, the resolution is not easily lowered. In addition, when the component (E) is contained, the ratio of the content of the component (B) to the content of the component (E) (the content of the component (B) / the content of the component (E)) is analytically and heat resistant. In view of the fact that the coefficient of thermal expansion is more excellent, it may be 0.4 or more, 0.6 or more, 0.8 or more, 1.0 or more, 1.2 or more, or 1.4 or more, and from the same viewpoint, it may be 3.5 or less, 3.0 or less, 2.5 or less, or 2 or less. the following.

<Component (F)> The photosensitive resin composition of the present embodiment may further contain a sensitizer as the component (F), if necessary. When the component (F) is contained, the photosensitivity of the photosensitive resin composition tends to be improved. Examples of the sensitizer include 9,10-dibutoxyfluorene. Further, the component (F) may be used alone or in combination of two or more.

The content of the component (F) may be from 0.01 part by mass to 1.5 parts by mass, or from 0.05 part by mass to 0.5 part by mass, per 100 parts by mass of the component (A).

<(G) Component> The photosensitive resin composition of this embodiment may further contain a solvent as (G) component in order to improve the handleability of the photosensitive resin composition, or to adjust viscosity and storage stability. The component (G) may be an organic solvent. The organic solvent is not particularly limited as long as it exhibits the above properties, and examples thereof include ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; a propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether; propylene glycol dialkyl ether such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether or propylene glycol dibutyl ether; Propylene glycol monomethyl ether acetate such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; ethyl cellosolve, butyl cellosolve, etc. Cellulolytic agent; carbitol, such as butyl carbitol; lactate such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, An aliphatic carboxylic acid ester such as n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate or isobutyl propionate; 3-methoxypropane Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid An ester such as ester, methyl pyruvate or ethyl pyruvate; an aromatic hydrocarbon such as toluene or xylene; a ketone such as 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or cyclohexanone; , phthalamide such as N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide or N-methylpyrrolidone; lactones such as γ-butyrolactone. These organic solvents may be used alone or in combination of two or more.

The content of the component (G) may be 30 parts by mass to 200 parts by mass, 40 parts by mass to 120 parts by mass, or 60 parts by mass to 100 parts by mass based on the total amount of the photosensitive resin composition other than the component (G). 120 parts by mass.

<(H) component> The photosensitive resin composition of this embodiment may contain the component (H): a decane coupling agent is another component different from the decane coupling agent used for surface modification of the said inorganic filler. When the component (H) is contained, the adhesion strength between the photosensitive layer and the substrate after the resin pattern formation tends to be improved.

As the component (H), generally available components can be used, and for example, alkyl decane, alkoxy decane, vinyl decane, epoxy decane, amino decane, propylene decane, methacryl decyl decane, decyl decane can be used. , thioether decane, isocyanate decane, sulfide silane, styryl decane, alkyl chlorodecane, and the like.

Specific examples of the component (H) include methyltrimethoxydecane, dimethyldimethoxydecane, trimethylmethoxydecane, methyltriethoxydecane, and methyltriphenoxydecane. Ethyltrimethoxydecane, n-propyltrimethoxydecane, diisopropyldimethoxydecane, isobutyltrimethoxydecane, diisobutyldimethoxydecane, isobutyltriethoxy Decane, n-hexyltrimethoxydecane, n-hexyltriethoxydecane, cyclohexylmethyldimethoxydecane, n-octyltriethoxydecane, n-dodecylmethoxydecane, phenyltrimethoxy Baseline, diphenyldimethoxydecane, triphenylstanol, methyltrichlorodecane, dimethyldichlorodecane, trimethylchlorodecane, n-octyldimethylchlorodecane, tetraethoxy Decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane, 3-(2-amine Ethylethyl)aminopropylmethyldimethoxydecane, 3-phenylaminopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxy Methyldimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, bis(3-(triethoxydecyl)alkyl )propyl)disulfide, bis(3-(triethoxydecyl)propyl)tetrasulfide, vinyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane , vinyl triisopropoxy decane, allyl trimethoxy decane, diallyldimethyl decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-methyl propylene decyloxy Propylmethyldimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3 - mercaptopropyltriethoxydecane, N-(1,3-dimethylbutylidene)-3-aminopropyltriethoxydecane, aminodecane, and the like.

The component (H) may be an epoxy decane having one or more glycidoxy groups, or an epoxy decane having a trimethoxydecyl group or a triethoxydecyl group. Further, propylene decyl decane or methacryl decyl decane may also be used.

From the viewpoint of high resolution, the (H) component may be an epoxy decane, a mercapto decane, an isocyanate decane, an acrylonitrile decane or a methacryl decyl decane, or an acrylonitrile decane or a methacryl fluorenyl group. Decane.

The content of the component (H) may be from 1 part by mass to 20 parts by mass, or from 3 parts by mass to 10 parts by mass per 100 parts by mass of 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 1,000 (hereinafter referred to as "phenol compound (a)") in addition to the component (A). Examples of the phenolic low molecular compound include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris(4-hydroxyphenyl)methane, and 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-tetrakis(4-hydroxyphenyl)ethane and the like. The phenol compound (a) may be contained in an amount of from 0 part by mass to 40 parts by mass, particularly preferably from 0 part by mass to 30 parts by mass, per 100 parts by mass of the component (A).

Further, the photosensitive resin composition of the present embodiment may contain other components than the above components. Examples of the other components include an inhibitor accompanying the reaction of irradiating actinic rays, a adhesion aid, and the like.

[Photosensitive Element] The photosensitive element of the present embodiment will be described based on Fig. 1 . FIG. 1 is a schematic cross-sectional view of a photosensitive element 10 of the present embodiment. As shown in Fig. 1, the photosensitive element 10 of the present embodiment is a photosensitive element including a support 1 and a photosensitive layer 3 provided on the support 1, and the photosensitive layer 3 is used for the photosensitivity. It is formed by a resin composition. Further, the photosensitive layer 3 may further include a protective layer 5 covering the photosensitive layer.

Further, the photosensitive element of the present embodiment may further include an fluorenone resin layer or an alkyd resin layer 13 between the support 11 and the photosensitive layer 14 as in the photosensitive element 20 shown in FIG. 2 . Further, the photosensitive layer 14 may further include a protective layer 15 covering the photosensitive layer. In the photosensitive element 20, an fluorenone resin layer or an alkyd resin layer 13 may be formed on the support 11. In other words, when the photosensitive layer 14 is peeled off, the support 11 may be provided with the fluorenone resin layer or the alkyd resin layer 13, and the support 11 may be integrated with the fluorenone resin layer or the alkyd resin layer 13. Or not integrated. Further, the undercoat layer 12 may be further provided between the support 11 and the fluorenone resin layer or the alkyd resin layer 13.

<Support> For the support, for example, a polyester film such as polyethylene terephthalate, a polymer film having heat resistance and solvent resistance such as polypropylene or polyethylene can be used. The support may have a thickness of 5 μm to 50 μm, 5 μm to 25 μm, or 15 μm to 50 μm. Further, the polymer film may be used by using one as a support and the other as a protective layer on both sides of the photosensitive layer.

<Anthrone resin layer or alkyd resin layer> An anthrone resin layer or an alkyd resin layer may be provided on at least one surface of the support. Thereby, when the photosensitive layer is laminated on the substrate, the photosensitive layer is easily transferred to the substrate, and in particular, the resolution tends to be improved. Further, the support 11 may be treated with an fluorenone resin or an alkyd resin. Here, the treatment by the fluorenone resin or the alkyd resin refers to a chemical treatment in which the fluorenone resin or the alkyd resin is thinly coated on the surface of the support. Examples of the anthrone resin include an anthrone modified resin, polydimethylsiloxane, and the like.

When the fluorenone resin or the alkyd resin is applied to the support, it can be applied thinly within the limits of the effect of releasing the mold. After coating, the fluorenone resin or alkyd resin may also be fixed to the support by heat treatment or ultraviolet (UV) treatment. An undercoat layer may also be applied to the support before the coating of the fluorenone resin or the alkyd resin.

Further, from the viewpoint of the releasability (release property) of the photosensitive layer, the 180° peel strength at 23 ° C of the fluorenone resin-treated surface or the alkyd-treated surface of the support may be 5 gf/inch to 300 gf. /inch (1.97 gf/cm to 118 gf/cm or 19.3×10 ^-3 N/cm to 1156.4×10 ^-3 N/cm), 5 gf/inch to 200 gf/inch (1.97 gf/cm to 78.7 gf/ Cm or 19.3 × 10 ^-3 N / cm ~ 771.3 × 10 ^-3 N / cm), or 100 gf / inch ~ 200 gf / inch (39.4 gf / cm ~ 78.7 gf / cm or 386.1 × 10 ^-3 N / cm ~771.3×10 ^-3 N/cm). The 180° peel strength can be obtained by using an adhesive tape (manufactured by Nitto Denko Corporation, trade name: “NITTO31B”) by a usual method (for example, according to Japanese Industrial Standards (JIS) K6854-2. The method, etc.) is performed.

The thickness of the fluorenone resin layer or the alkyd resin layer may be from about 0.005 μm to 1 μm, and particularly from 0.01 μm to 0.1 μm. When the thickness of the fluorenone resin layer or the alkyd resin layer is within the above range, the adhesion between the support and the fluorenone resin layer or the alkyd resin layer is good. Further, the photosensitive element of the present embodiment may be provided with both an anthrone resin layer and an alkyd resin layer.

A polyethylene terephthalate (PET) film treated with at least one fluorenone resin or an alkyd resin, for example, as a commercial product, can be obtained as a trade name of Teijin Dupont Films Co., Ltd. Purex A53", "Purex A70", "Purex A31-25", "Purex A51-25" and "Pray" Purex A53-38" ("Purex" is a registered trademark). The support in the photosensitive element of the present embodiment may be provided with an fluorenone resin layer on the support in view of ease of availability.

The thickness of the support can be from 15 μm to 50 μm, or from 25 μm to 40 μm. When the thickness of the support 11 is 15 μm or more, strain at the time of treatment with an oxime resin or an alkyd resin is less likely to remain, and the support roll is treated with an oxime resin or an alkyd resin. When it is taken into a roll shape, it tends to be less likely to cause wrinkles. When the thickness of the support 11 is 50 μm or less, there is a tendency that air bubbles are less likely to be caught between the substrate and the photosensitive layer 14 during the thermal pressure bonding when the photosensitive layer 14 is laminated on the substrate.

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

Further, similarly to the support, a polymer film treated with an fluorenone resin or an alkyd resin can be used. The protective layer may be a polyethylene film from the viewpoint of flexibility in winding the photosensitive element into a roll shape. Further, in order to reduce the depression of the surface of the photosensitive layer, the protective layer may also be a film of a fisheye. The protective layer may have a thickness of 10 μm to 100 μm or 15 μm to 80 μm.

<Photosensitive Layer> The photosensitive layer can be formed, for example, by applying the photosensitive resin composition to a support (an oxime resin surface or an alkyd resin-treated surface of a support) or a protective layer. Examples of the coating method include a dipping method, a spray method, a bar coat method, a roll coat method, and a spin coat method. Method) and so on. The thickness of the photosensitive layer varies depending on the application, and after drying the photosensitive layer, it may be 10 μm to 100 μm, 15 μm to 60 μm, 20 μm to 50 μm or 20 μm or more and less than 50 μm.

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

First, the photosensitive resin composition is formed on a substrate on which a resist pattern is to be formed (a resin copper foil, a copper clad laminate, a silicon wafer with a metal sputter film, an alumina substrate, or the like). Photosensitive layer of matter. In the method of forming the photosensitive layer, a method in which the photosensitive resin composition is applied to a substrate, and the photosensitive resin composition is dried to volatilize a solvent or the like to form a photosensitive layer; A method of transferring a photosensitive layer onto a substrate or the like.

The method of applying the photosensitive resin composition to a substrate can be, 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. Further, the thickness of the photosensitive layer can be appropriately controlled by adjusting the solid concentration and viscosity of the coating means and the photosensitive resin composition.

Next, the photosensitive layer is exposed to a predetermined pattern via a predetermined mask pattern. Examples of the actinic rays used for the exposure include visible light rays from a g-ray stepper or the like; ultraviolet rays from a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an i-ray stepper, and the like. ; electron beam; laser light, etc. The exposure amount can be appropriately selected depending on the light source used and the thickness of the photosensitive layer, for example, in the case of irradiating ultraviolet rays from a high pressure mercury lamp, when the thickness of the photosensitive layer is from 10 μm to 50 μm, the exposure amount is 100 mJ/cm. ² to 5000 mJ/cm ² or so. Further, when the photosensitive layer is formed using a photosensitive element, the photosensitive layer may be exposed through the support, or the support may be peeled off and the photosensitive layer may be exposed.

Further, heat treatment (post-exposure baking) is performed after the exposure. By performing post-exposure baking, the hardening reaction of the (A) component and the (B) component by the acid by the photo-sensitive acid generator can be accelerated. The conditions for post-exposure baking vary depending on the composition of the photosensitive resin composition, the content of each component, the thickness of the photosensitive layer, and the like, and can be, for example, heated at 70 to 150 ° C for 1 minute to 60 minutes, or at 80 ° C. Heat at 120 ° C for 1 minute to 60 minutes.

Then, the photosensitive layer subjected to the post-exposure baking is developed by an alkaline developing solution, and the region of the unexposed portion is dissolved and removed, whereby a desired resin pattern is obtained. The development method in this case may, for example, be a shower development method, a spray development method, a immersion development method, a puddle development method, or the like. The developing conditions are, for example, 1 to 10 minutes at 20 to 40 °C.

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

Further, in order to exhibit the properties of the insulating film, the obtained resin pattern is subjected to heat treatment, whereby a cured product (resist pattern) of the photosensitive resin composition is obtained. The curing condition is not particularly limited, and the resin pattern can be cured by heating at 50 ° C to 250 ° C for 30 minutes to 10 hours depending on the use of the cured product.

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

In the case of the hardening conditions, the heating device is not particularly limited, and a general oven, an infrared furnace, or the like can be used.

[Multilayer printed wiring board] The cured product formed of the photosensitive resin composition of the present embodiment or the cured product obtained by using the photosensitive layer in the photosensitive element of the present embodiment can be preferably used as a surface of a semiconductor element, for example. A protective film or an interlayer insulating film, or a solder resist or an interlayer insulating film in a multilayer printed wiring board. 3(a) to 3(f) are views showing a method of manufacturing a multilayer printed wiring board including the cured product of the present embodiment as a solder resist and/or an interlayer insulating film. The multilayer printed wiring board 100A shown in FIG. 3(f) has a wiring pattern on the front surface and inside. Hereinafter, a method of manufacturing the multilayer printed wiring board 100A according to the embodiment of the present disclosure will be briefly described based on FIGS. 3(a) to 3(f).

First, an interlayer insulating film 103 is formed on both surfaces of a substrate 101 having a wiring pattern 102 on its surface (see FIG. 3(a)). The interlayer insulating film 103 can be formed by printing a photosensitive resin composition using a screen printer or a roll coater, or the photosensitive member can be prepared in advance, and a laminator can be used. The photosensitive layer in the photosensitive element is attached to the surface of the substrate 101 to be formed. Then, the opening portion 104 is formed using a yttrium aluminum garnet (YAG) laser or a carbon dioxide laser at a portion where electrical connection to the outside is required (see FIG. 3(b)). The smear (residue) around the opening portion 104 is removed by the desmear treatment. Then, a seed layer 105 is formed by an electroless plating method (refer to FIG. 3(c)). 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. 3(d) ). Then, the wiring pattern 107 is formed on the portion of the seed layer 105 where the resin pattern 106 is not formed by electrolytic plating, and after removing the resin pattern 106 by the stripping liquid, the seed layer 105 is removed by etching. Remove (refer to Figure 3 (e)). By repeating the above operation, the solder resist 108 containing the cured product of the photosensitive resin composition is formed on the outermost surface, whereby the multilayer printed wiring board 100A can be produced (see FIG. 3(f)).

The multilayer printed wiring board 100A thus obtained is mounted with a semiconductor element at a corresponding portion, so that electrical connection can be ensured. [Examples]

The disclosure is described in detail below by way of examples, but the disclosure is not limited by the examples. In addition, unless otherwise indicated, the parts in the following examples and comparative examples are used in the meaning of a mass part.

(Example 1-1 to Example 1-8 and Comparative Example 1-1 to Comparative Example 1-4) <Preparation of photosensitive resin composition> 100 mass with respect to novolak resin (A-1, A-2) The compound having two or more functional groups selected from the group consisting of acryloxy group, methacryloxy group, glycidoxy group and hydroxyl group is blended in an amount (unit: parts by mass) as shown in the following Table 1. Compound (B-1, B-2), photo-sensitive acid generator (C-1), cerium oxide surface-treated with decane coupling agent or cerium oxide which has not been surface-treated (inorganic filler 1 to inorganic The filler 6), the compound (E-1) having an alkoxyalkyl group, and the solvent (G-1) are used to obtain a photosensitive resin composition.

<Preparation of Photosensitive Element> The photosensitive resin composition is applied to a polyethylene terephthalate film in such a manner that the thickness of the photosensitive resin composition is uniform (Teijin Dupont Films Co., Ltd.) The product name: Prex A53) (support) was dried by a hot air convection dryer at 90 ° C for 10 minutes to prepare a photosensitive member having a thickness of 25 μm after drying.

<Measurement of Average Particle Diameter and Maximum Particle Diameter> The photosensitive resin composition was diluted to 1000 times (volume ratio) with methyl ethyl ketone, and a submicron particle analyzer (Beckman Coulter) was used. Co., Ltd. manufacture, trade name, model: N5), according to the international standard specification ISO13321, the particles dispersed in the solvent are measured at a refractive index of 1.38, and the cumulative value in the particle size distribution is 50% (volume basis). The diameter is an average particle diameter of the inorganic filler in a state of being dispersed in the photosensitive resin composition. Further, the particle diameter at the cumulative value of 99.9% (volume basis) in the particle size distribution was defined as the maximum particle diameter.

<Evaluation of Transparency> The transmittance of the photosensitive layer in the photosensitive element was measured by a UV-visible spectrophotometer (manufactured by Hitachi, Ltd., trade name: U-3310) to measure a photosensitive layer having a thickness of 25 μm. Transmittance at a wavelength of 365 nm (i-ray).

<Evaluation of Analyticity> The photosensitive element was laminated on a 6-inch tantalum wafer so that the photosensitive layer was in contact with the tantalum wafer, and a heat roll of 100 ° C was used to apply a pressure of 0.4 MPa. Lamination at a roll speed of 1.0 m/min. After the support was peeled off from the produced photosensitive layer, an i-ray stepper (manufactured by Canon Co., Ltd., trade name: FPA-3000iW) was used to reduce the projection exposure by masking with i-rays (365 nm). The mask is a mask having a pattern in which the width of the exposed portion and the unexposed portion is 1:1 at intervals of 1 μm in the range of 2 μm: 2 μm to 30 μm: 30 μm. Further, the reduction projection exposure is performed while changing the exposure amount in the range of 100 mJ/cm ² to 3000 mJ/cm ² per 100 mJ/cm ² .

Then, the exposed photosensitive layer was heated at 65 ° C for 1 minute, followed by heating at 95 ° C for 4 minutes (post-exposure baking). Development was carried out by using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for immersion at a time equivalent to 1.5 times the shortest development time (the shortest time for removing the unexposed portion), and the unexposed portion was removed to carry out development treatment. After the development treatment, the formed resin pattern was observed using a metal microscope. The value of the minimum gap width in the pattern in which the space portion (unexposed portion) is neatly removed and the line portion (exposure portion) is not bent or defective is evaluated as the minimum resolution.

<Evaluation of heat resistance> The photosensitive resin compositions of Examples 1-1 to 1-8, Comparative Example 1-1, and Comparative Example 1-4 were applied so that the thickness of the photosensitive resin composition was uniform. Polyethylene terephthalate film (manufactured by Teijin Dupont Films Co., Ltd., product name: Purex A53) (support), using a hot air convection dryer at 90 ° C After drying for 10 minutes, a photosensitive member having a thickness of 40 μm after drying was prepared. Then, an exposure apparatus having a high pressure mercury lamp (manufactured by ORC MANUFACTURING CO., LTD., trade name: EXM-1201) was used, and the photosensitive layer was exposed so that the irradiation energy became 3000 mJ/cm ² . The exposed photosensitive layer was heated on a hot plate at 65 ° C for 2 minutes, followed by heating at 95 ° C for 8 minutes, and heat-treated at 180 ° C for 60 minutes in a hot air convection dryer to peel off the support. A cured film is obtained. The thermal expansion amount of the cured film when the temperature was raised at a temperature increase rate of 5 ° C/min was measured using a thermomechanical analyzer (manufactured by Seiko Instruments Co., Ltd., trade name: TMA/SS6000), and the curve was determined according to the curve. The obtained inflection point is taken as the glass transition temperature Tg. Further, the coefficient of thermal expansion was calculated from the amount of thermal expansion of 40 ° C to 150 ° C at a tensile load of 5 g. The 3% by weight of the thermogravimetric reduction temperature was carried out by using a differential thermal and thermal weight simultaneous measuring device (manufactured by Seiko Instruments Co., Ltd., trade name: TG/DTA6300) under the conditions of a temperature rising rate of 10 ° C/min under air. The measurement was carried out to a temperature at which the weight was reduced by 3%. The evaluation results are shown in Table 1.

[Table 1]

A-1: cresol novolac resin (manufactured by Asahi Organic Materials Co., Ltd., trade name: TR4020G, weight average molecular weight: 15300) A-2: cresol novolak resin (manufactured by Asahi Organic Materials Co., Ltd., commodity Name: TR4080G, weight average molecular weight: 4800) B-1: Trimethylolpropane triglycidyl ether (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name: ZX-1542, refer to the following formula (14)) [ 14] 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 ceria inorganic filler 2 which was coupled by 3-methylpropenyloxypropyltrimethoxydecane and having an average primary particle diameter of 15 nm 2: using 3-methyl A sol-gel cerium oxide inorganic filler having a coupling treatment of acryloxypropyltrimethoxydecane and an average primary particle diameter of 45 nm: using 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Sol-gel cerium oxide inorganic filler 4 with coupling treatment of decane with an average primary particle size of 15 nm: coupling treatment with 3-glycidoxypropyltrimethoxy decane and average primary particle size of 15 nm Sol-gel cerium oxide inorganic filler 5: sol-gel cerium oxide inorganic filler 6 which is coupled by 3-methylpropenyloxypropyltrimethoxy decane and has an average primary particle diameter of 120 nm 6: average Sol-gel cerium oxide E-1 with a primary particle size of 15 nm Glycoluril derivatives (Sanwa Chemical (Sanwa Chemical) Co., Ltd., trade name: Cala d'Or neighborhood library (Nikalac) MX-270) G-1: Methyl ethyl ketone (Wako Pure Chemical Industries, Ltd.)

As is clear from Table 1, it is understood that in Examples 1-1 to 1-8 in which the average particle diameter of the inorganic filler in the photosensitive resin composition is 100 nm or less, the transmittance is as high as 70% or more, and the resolution is 15 μm or less and good resolution. On the other hand, in Comparative Example 1-1 and Comparative Example 1-4 which did not contain an inorganic filler, the thermal expansion coefficient was high, the 3% by weight thermal weight reduction temperature was also low, and heat resistance was inferior. In Comparative Example 1-2 in which the average particle diameter of the inorganic filler in the photosensitive resin composition exceeded 100 nm, the transmittance was as low as 40%, and the resin pattern could not be formed even in a mask pattern of 30 μm: 30 μm. Therefore, the evaluation of heat resistance was not performed. In Comparative Example 1-3, aggregation of cerium oxide was caused, and a series of evaluations could not be performed. Further, in Examples 1-1 to 1-3, the thermal expansion coefficient was lowered in accordance with the increase in the content of the inorganic filler, and the 3% by weight thermal weight reduction temperature was high, and the structility, heat resistance, and thermal expansion coefficient were high. Excellent balance.

(Example 2-1 to Example 2-11, Reference Example 2-1 to Reference Example 2-3, and Comparative Example 2-1 to Comparative Example 2-2) <Preparation of photosensitive resin composition> The following table will be used. Each of the components shown in Table 2 and Table 4 was prepared in an amount (unit: parts by mass) shown in the table, and a photosensitive resin composition was obtained.

<Preparation of Photosensitive Element> A support film (PET-1 to PET-2) having a support and an oxime resin layer and a support film (PET-3) not having an oxime resin layer or an alkyd resin layer were prepared. The photosensitive resin composition is applied onto the support film such that the thickness of the photosensitive resin composition is uniform (in the case of PET-1 to PET-2, on the fluorenone resin layer), and the temperature is 90 ° C. The hot air convection dryer was dried for 10 minutes to form a photosensitive layer having a thickness of the dried photosensitive layer of 10 μm to 100 μm. A polyethylene film (manufactured by Tamapoly Co., Ltd., product name: NF-15) was attached as a protective layer on the photosensitive layer, and photosensitivity of the support film, the photosensitive layer, and the protective layer were sequentially laminated. element.

<Evaluation of mold release property> The photosensitive layer of the photosensitive member having a thickness of 25 μm in the photosensitive layer was peeled off while the photosensitive layer was in contact with the surface of the tantalum wafer. The photosensitive element is pressed. Next, after peeling off the support film, the surface of the support film and the surface of the germanium wafer were observed, and the photosensitive layer was formed on the germanium wafer, and the photosensitive layer was not left on the support film, and "A" was left, and a part of the photosensitive film remained on the support film. The layer was set to "B" to evaluate the release property. The evaluation results are shown in Table 3 below. Further, lamination was carried out using a heating roll at 120 ° C at a pressure of 0.4 MPa and a roll speed of 1.0 m / min. Further, in Reference Examples 2-1 to 2-3, the mold release property was insufficient under the lamination conditions, and a good resin pattern could not be formed when the analytical property was evaluated, so that the resolution and heat resistance were not performed. evaluation of. However, since the compositions of the photosensitive layers of Reference Examples 2-1 to 2-3 are the same as those of Examples 2-1 to 2-3, respectively, they are supported as long as the photosensitive layer is not left on the support film. When the film was peeled off, it was considered that the same evaluation results as in Examples 2-1 to 2-3 were obtained.

<Analytical Evaluation> The protective layer of the photosensitive element having a thickness of 25 μm was peeled off, and the photosensitive layer was laminated on a 6-inch silicon wafer while the photosensitive layer was in contact with the surface of the germanium wafer. Sexual components. After peeling off the support film, the laminated photosensitive layer was subjected to reduction projection projection by i-ray (365 nm) via a mask using an i-ray stepper (manufactured by Canon Co., Ltd., trade name: FPA-3000iW). . The mask is a mask having a pattern in which the width of the exposed portion and the unexposed portion is 1:1 at intervals of 1 μm in the range of 2 μm: 2 μm to 30 μm: 30 μm. Further, the reduction projection exposure is performed while changing the exposure amount in the range of 100 mJ/cm ² to 3000 mJ/cm ² per 100 mJ/cm ² .

Then, the exposed photosensitive layer was heated at 65 ° C for 1 minute, followed by heating at 95 ° C for 4 minutes (post-exposure baking). Development was carried out by using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to immerse for twice the time corresponding to the shortest development time (the shortest time for removing the unexposed portion), and the unexposed portion was removed to carry out development treatment. After the development treatment, the formed resin pattern was observed using a metal microscope. The minimum gap width in the range of 100 mJ/cm ² to 3000 mJ/cm ² in the pattern formed by the gap portion (unexposed portion) being neatly removed and the line portion (exposure portion) is not bent or defective The value is evaluated as the minimum resolution. The evaluation results are shown in Tables 3 and 4 below.

<Evaluation of heat resistance> The protective layer of the photosensitive element having a thickness of 40 μm was peeled off, and then an exposure machine having a high-pressure mercury lamp (ORC MANUFACTURING CO., LTD., trade name: EXM) was used. -1201), the photosensitive layer was exposed so that the irradiation energy became 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 heat-treated at 180 ° C for 60 minutes in a hot air convection dryer to peel off the support film to obtain a cured film. The thermal expansion amount of the cured film when the temperature was raised at a temperature increase rate of 5 ° C/min was measured using a thermomechanical analyzer (manufactured by Seiko Instruments Co., Ltd., trade name: TMA/SS6000), and the curve was obtained. The obtained inflection point is taken as the glass transition temperature Tg. Further, the coefficient of thermal expansion was calculated from the amount of thermal expansion of 40 ° C to 150 ° C at a tensile load of 5 g. The 3% by weight of the thermogravimetric reduction temperature was carried out under the conditions of a temperature increase rate of 10 ° C/min under air using a differential thermal and thermal weight simultaneous measuring device (manufactured by Seiko Instruments Co., Ltd., trade name: TG/DTA6300). The measurement was carried out to a temperature at which the weight was reduced by 3%. The evaluation results are shown in Tables 3 and 4 below.

<Measurement of Average Particle Diameter> The photosensitive resin composition was diluted to 1000 times (volume ratio) with methyl ethyl ketone, and manufactured using a submicron particle analyzer (Beckman Coulter Co., Ltd.) , trade name, model: N5), according to the international standard specification ISO13321, the particles dispersed in the solvent are measured at a refractive index of 1.38, and the particle size under the cumulative value of 50% (volume basis) in the particle size distribution is dispersed in the photosensitive The average particle diameter of the inorganic filler in the state of the resin composition. The measurement results are shown in Tables 3 and 4 below.

<Evaluation of Transparency> The transmittance of the photosensitive layer in the photosensitive element was measured by a UV-visible spectrophotometer (manufactured by Hitachi, Ltd., trade name: U-3310) to measure a photosensitive layer having a thickness of 25 μm. Transmittance at a wavelength of 365 nm (i-ray). The measurement results are shown in Tables 3 and 4 below.

[Table 2]

[table 3]

[Table 4]

PET-1: polyethylene terephthalate film (manufactured by Teijin Dupont Films Co., Ltd., product name: Purex A53): formed by using an fluorenone modified resin Film PET-2 of an anthrone resin layer: polyethylene terephthalate film (manufactured by Teijin Dupont Films Co., Ltd., product name: Purex A70): Membrane PET-3 of an fluorenone resin layer formed of methyl decane: polyethylene terephthalate film (manufactured by Toray Co., Ltd., product name "FB-40"): no 矽Membrane A-11 of ketone resin layer or alkyd resin layer: novolac resin (manufactured by Asahi Organic Materials Co., Ltd., trade name: MXP5560BF, weight average molecular weight = 7800) A-12: cresol novolak resin (Xu has Manufactured by Machinery Industry Co., Ltd., trade name: TR4020G) A-13: Cresol novolac resin (manufactured by Asahi Organic Materials Co., Ltd., trade name: TR4080G) B-11: Trimethylolpropane triglycidyl ether ( Nippon Steel Corporation Manufactured by the company, trade name: ZX-1542, refer to the formula (14)) B-12: Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: PET-30) C-11: Triaryl Barium salt (manufactured by San-Apro Co., Ltd., trade name: CPI-101A) Inorganic filler 11: Coupling treatment with 3-methylpropenyloxypropyltrimethoxydecane and average primary particle Spherical sol-gel cerium oxide inorganic filler having a diameter of 15 nm 12: a spherical sol having a coupling treatment with 3-methylpropenyloxypropyltrimethoxydecane and an average primary particle diameter of 45 nm Gel cerium oxide inorganic filler 13: spherical sol-gel cerium oxide E-11 which was coupled by 3-methylpropenyloxypropyltrimethoxy decane and had an average primary particle diameter of 120 nm: Glycolide derivative (manufactured by Sanwa Chemical Co., Ltd., trade name: Nikalac MX-270) F-11: 9,10-dibutoxy oxime (Kawasaki Chemical Co., Ltd.) Manufactured, trade name: DBA) G-11: methyl ethyl ketone ( Manufactured by Wako Pure Chemical Industries, Ltd.)

As is clear from Tables 3 and 4, it is understood that Examples 2-1 to 2-11 of the inorganic filler in the photosensitive resin composition have an average particle diameter of 100 nm or less and a support film having an anthrone resin layer. Among them, the mold release property is good, and the transmittance is as high as 70% or more, and the resolution is 15 μm or less, and the resolution is good. On the other hand, in Comparative Example 2-1 containing no inorganic filler, the coefficient of thermal expansion was high, the thermal weight reduction temperature of 3% by weight was also low, and the heat resistance was poor. In Comparative Example 2-2 in which the average particle diameter of the inorganic filler in the photosensitive resin composition exceeded 100 nm, the transmittance was as low as 40%, and a resin pattern could not be formed even in a mask pattern of 30 μm: 30 μm. Therefore, the evaluation of heat resistance was not performed. Further, in Examples 2-1 to 2-4, the thermal expansion coefficient was lowered in accordance with the increase in the content of the inorganic filler, the 3% by weight thermal weight reduction temperature was increased, and the balance of analytic property, heat resistance, and thermal expansion coefficient was obtained. Excellent sex. [Industrial availability]

The photosensitive resin composition of the present disclosure can be suitably used as a material used for a surface protective film or an interlayer insulating film of a semiconductor element. Further, it can be suitably used as a material used for a solder resist or an interlayer insulating film of a wiring board material. In particular, the photosensitive resin composition is excellent in both analytical property and heat resistance after curing, and further has a low thermal expansion coefficient, so that it can be preferably used for high integration of fine lines and high density. Package substrate, etc.

1, 11‧‧‧ Support
3, 14‧‧‧Photosensitive layer
5, 15‧ ‧ protective layer
10, 20‧‧‧Photosensitive components
12‧‧‧Undercoat
13‧‧‧anthone resin layer or alkyd layer
100A‧‧‧Multilayer printed wiring board
101‧‧‧Substrate
102, 107‧‧‧ wiring pattern
103‧‧‧Interlayer insulating film
104‧‧‧ openings
105‧‧‧ seed layer
106‧‧‧ resin pattern
108‧‧‧Soldering agent

Fig. 1 is a schematic cross-sectional view showing a photosensitive element according to an embodiment of the present disclosure. Fig. 2 is a schematic cross-sectional view showing a photosensitive element according to another embodiment of the present disclosure. 3(a) to 3(f) are schematic views showing a method of manufacturing the multilayer printed wiring board of the embodiment.

no

Claims (15)

A photosensitive resin composition comprising: (A) component: a resin having a phenolic hydroxyl group; (B) component: having two or more selected from the group consisting of an acryloxy group, a methacryloxy group, a glycidoxy group, and An aliphatic compound having one or more functional groups in a hydroxyl group; (C) component: a photo-sensitive acid generator; and (D) component: an inorganic filler having an average particle diameter of 100 nm or less and surface-treated with a decane coupling agent . The photosensitive resin composition according to claim 1, wherein the decane coupling agent has an alkoxy group and has a phenyl group, a vinyl group, an epoxy group, a methacryl fluorenyl group, an amine group, and a ureido group. , mercapto, isocyanate, or acrylonitrile. The photosensitive resin composition according to claim 1 or 2, wherein the decane coupling agent is selected from the group consisting of phenyltrimethoxydecane, vinyltrimethoxydecane, and epoxytrimethoxydecane. And at least one of methacryl decyl trimethoxy decane, aminotrimethoxy decane, ureido trimethoxy decane, decyl trimethoxy decane, isocyanate decane, and acrylonitrile trimethoxy decane. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (D) component has a maximum particle diameter of less than 1000 nm. The photosensitive resin composition according to any one of the items 1 to 4, wherein the component (B) has three or more selected from the group consisting of an acryloxy group and a methacryloxy group. An aliphatic compound having one or more functional groups of a glycidoxy group and a hydroxyl group. The photosensitive resin composition according to any one of claims 1 to 5, further comprising (E) a component having a group selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring. At least one compound having a methylol or alkoxyalkyl group. The photosensitive resin composition according to any one of the above-mentioned items (A), which contains 20 parts by mass to 70 parts by mass of the component (B), based on 100 parts by mass of the component (A). . The photosensitive resin composition according to any one of claims 1 to 7, wherein the component (D) is cerium oxide. A photosensitive member comprising a support and a photosensitive layer provided on the support, and the photosensitive layer is a photosensitive resin according to any one of claims 1 to 8. Formed by the composition. The photosensitive element according to claim 9, further comprising an fluorenone resin layer or an alkyd resin layer between the support and the photosensitive layer. The photosensitive member according to claim 9 or 10, wherein the photosensitive layer has a thickness of less than 50 μm. A cured product which is a cured product of the photosensitive resin composition according to any one of claims 1 to 8. A cured product obtained by using a photosensitive layer in the photosensitive element according to any one of the items 9 to 11 of the patent application. A method of forming a resist pattern, comprising: applying a photosensitive resin composition according to any one of claims 1 to 8 to a substrate, and applying the photosensitive resin a step of drying the composition to form a photosensitive layer; exposing the photosensitive layer to a predetermined pattern, and performing a heat treatment after exposure; and developing the photosensitive layer after the heat treatment, and obtaining the resin The pattern is subjected to a heat treatment step. A method of forming a resist pattern, comprising: forming a photosensitive layer on a substrate by using the photosensitive element according to any one of claims 9 to 11; a step of exposing to a predetermined pattern and performing heat treatment after exposure; and developing the photosensitive layer after the heat treatment and subjecting the obtained resin pattern to heat treatment.