JP6569268B2 - Photosensitive resin composition, photosensitive element, resist pattern forming method, and semiconductor component manufacturing method - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a semiconductor component.

  In the field of manufacturing semiconductor components such as printed wiring boards and semiconductor elements, a layer formed using a photosensitive resin composition as a resist material used for etching or plating (hereinafter referred to as “photosensitive layer”). A photosensitive element (laminate) having a structure in which is formed on a support film and a protective film is disposed on a photosensitive layer is widely used.

  Conventionally, a printed wiring board is manufactured by the following procedure, for example, using the photosensitive element. That is, first, the photosensitive layer of the photosensitive element is laminated on a circuit forming substrate such as a copper-clad laminate. At this time, the surface (the “upper surface” of the photosensitive layer) opposite to the surface (the “lower surface” of the photosensitive layer) that is in contact with the support film of the photosensitive layer is in close contact with the surface on which the circuit of the circuit forming substrate is to be formed. Like that. Therefore, when the protective film is disposed on the upper surface of the photosensitive layer, this laminating operation is performed while peeling off the protective film. Next, the photosensitive layer is thermocompression bonded to the underlying circuit forming substrate.

  Next, pattern exposure is performed through a mask film or the like. At this time, the support film is peeled off at any timing before exposure or after exposure. Thereafter, the unexposed portion is dissolved or dispersed and removed with a developer. Next, an etching process or a plating process is performed to form a pattern, and finally the cured portion is peeled and removed.

  Here, the “etching process” is a method of removing a resist after etching away a metal surface not covered with a cured resist formed after development. On the other hand, “plating treatment” means that after a plating process such as copper or solder is applied to a metal surface not covered with a hardened resist formed after development, the resist is removed and the metal surface covered with the resist is etched. It is a method to do.

  Conventionally, in the above-described pattern exposure, exposure was performed through a photomask using a mercury lamp as a light source, but a direct drawing exposure method in which digital data of a pattern is directly drawn on a resist has been proposed. The direct drawing exposure method has been introduced for the production of a high-density package substrate because it has better alignment accuracy than exposure through a photomask and a fine pattern can be obtained. In the direct drawing exposure method, when a photosensitive element having the same sensitivity is used, generally, a lot of exposure time is required. For this purpose, it is necessary to increase the illuminance on the exposure apparatus side, increase the sensitivity of the resist, and the like. However, when the conventional photosensitive resin composition is applied to the direct drawing exposure method, the sensitivity, resolution, and resist stripping properties are not sufficient. In order to improve the sensitivity, resolution, and resist peeling characteristics, various studies have been made on binder resins, photopolymerization initiators, and the like (see, for example, Patent Documents 1 and 2 below).

JP 2006-234959 A JP 2005-122123 A

  However, in the method for manufacturing a semiconductor component using a resist pattern obtained by exposing and developing the photosensitive layer, even if the photosensitive resin composition described in Patent Documents 1 and 2 is used, the resolution is still high. Not enough. In addition, in this field, as the market for semiconductor package products that require resist patterns with excellent resolution has grown, the required characteristics for photosensitive resin compositions have also changed, making it more sensitive than contributing to mass production. There is also a tendency to focus on resolution that contributes to yield. Therefore, particularly in this field, there is a continuous need to improve the resolution even in units of 1 μm.

  An object of this invention is to provide the photosensitive resin composition which has the outstanding resolution. Another object of the present invention is to provide a photosensitive element, a resist pattern forming method, and a semiconductor component manufacturing method using the photosensitive resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have found a photosensitive resin composition having excellent resolution (resolution).

  That is, the photosensitive resin composition of the present invention comprises a step of forming a photosensitive layer on a substrate using the photosensitive resin composition, and exposing the predetermined portion by irradiating a predetermined portion of the photosensitive layer with actinic rays. And a step of performing post-exposure heat treatment, and removing a portion other than the predetermined portion of the photosensitive layer from the substrate, thereby forming a resist pattern containing a cured product of the photosensitive resin composition on the substrate. And a developing step formed as follows: (A) component: a resin having a phenolic hydroxyl group, and (B) component: two or more oxirane rings. An aliphatic or alicyclic epoxy compound, and (C) component: a photosensitive acid generator, and the content of the sensitizer is 1 part by mass with respect to 100 parts by mass of the component (A). It is as follows.

  According to the photosensitive resin composition of the present invention, excellent resolution can be obtained in a method for producing a semiconductor component using a resist pattern obtained by exposing and developing a photosensitive layer. According to such a photosensitive resin composition, a resist pattern having excellent resolution can be obtained.

  It is preferable that content of the said (B) component is 20-70 mass parts with respect to 100 mass parts of said (A) component.

  The component (B) preferably has two or more glycidyl ether groups, and more preferably has three or more glycidyl ether groups.

  In the photosensitive resin composition of the present invention, the method for manufacturing a semiconductor component may further include a step of etching or plating the base material on which the resist pattern is formed.

  In the photosensitive resin composition of the present invention, the method for manufacturing a semiconductor component may further include a step of peeling the resist pattern.

  The photosensitive element of this invention is equipped with the support body and the photosensitive layer provided on the said support body, and the said photosensitive layer contains the said photosensitive resin composition.

  The resist pattern forming method of the present invention includes a step of forming a photosensitive layer on a substrate using the photosensitive resin composition, and exposing the predetermined portion by irradiating a predetermined portion of the photosensitive layer with actinic rays. A step of performing post-exposure heat treatment (hereinafter, this heat treatment is also referred to as “post-exposure bake”), and removing portions other than the predetermined portion of the photosensitive layer from the substrate. And a development step of forming a resist pattern containing a cured product of the resin composition on the substrate.

  The method for manufacturing a semiconductor component of the present invention includes a step of etching or plating a base material on which a resist pattern is formed by the method for forming a resist pattern.

  The method for manufacturing a semiconductor component of the present invention may further include a step of peeling the resist pattern.

  According to the present invention, a photosensitive resin composition having excellent resolution can be provided. Moreover, according to this invention, the photosensitive element using the said photosensitive resin composition, the formation method of a resist pattern, and the manufacturing method of a semiconductor component can be provided.

It is a perspective view which shows typically an example of the manufacturing process of the printed wiring board by a semi-additive construction method.

  Hereinafter, although an embodiment of the present invention is described concretely, the present invention is not limited to this.

  In the present specification, “EO” represents an oxyethylene group, and “PO” represents an oxypropylene group. The term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when observed as a plan view. The term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. The content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. The term “Si—O bond” indicates a bond between a silicon atom and an oxygen atom.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment includes a step of forming a photosensitive layer on a substrate using the photosensitive resin composition, and irradiating the predetermined portion of the photosensitive layer with actinic rays to expose the predetermined portion. A resist pattern containing a cured product of the photosensitive resin composition is formed on the substrate by removing a portion other than the predetermined portion of the photosensitive layer from the substrate, and performing a post-exposure heat treatment step. And a developing step for forming the photosensitive resin composition. The photosensitive resin composition of the present embodiment includes (A) component: a resin having a phenolic hydroxyl group, (B) component: an aliphatic or alicyclic epoxy compound having two or more oxirane rings, and (C). Component: A photosensitive acid generator may be contained, and (D) component: A sensitizer may further be contained. In the photosensitive resin composition of this embodiment, content of (D) component is 1 mass part or less with respect to 100 mass parts of (A) component. Moreover, the photosensitive resin composition of this embodiment may contain (E) component: a crosslinking agent, (F) component: the compound which has Si-O bond, a photopolymerizable compound, etc. as needed. .

  The present inventors consider that the reason why excellent resolution can be obtained by the photosensitive resin composition of the present embodiment (for example, a resin pattern having a high aspect ratio can be formed) is as follows. First, in the unexposed area, the solubility of the component (A) in the developer is greatly improved by the addition of the component (B). Next, in the exposed area, the acid generated from the component (C) not only reacts and crosslinks two or more oxirane rings in the component (B), but also reacts with the phenolic hydroxyl group of the component (A), The solubility of the composition in the developer is greatly reduced. By this, when developing, the present inventors speculate that the difference in solubility between the unexposed part and the exposed part with respect to the developer becomes significant, and sufficient resolution is obtained. In addition, the present invention is such that a resin pattern having sufficient heat resistance can be obtained by further crosslinking of the component (B) and reaction of the component (A) and the component (B) by heat treatment of the pattern after development. They guess.

((A) component)
The photosensitive resin composition of this embodiment contains resin which has a phenolic hydroxyl group. Although it does not specifically limit as resin which has a phenolic hydroxyl group, Resin soluble in alkaline aqueous solution is preferable, and novolak resin is more preferable. Such a novolak resin can be obtained, 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-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 a copolymer thereof, a phenol-xylylene glycol condensed resin, a cresol-xylylene glycol condensed resin, and a phenol-dicyclopentadiene condensed resin.

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

  The weight average molecular weight of the component (A) is preferably 100000 or less, more preferably 1000 to 80000, still more preferably 2000 to 50000, from the viewpoint of further improving the resolution, developability, peelability, and the like of the resulting resin pattern. 2000 to 20000 is particularly preferable, and 5000 to 15000 is very preferable.

In addition, in this embodiment, the weight average molecular weight of each component can be measured on condition of the following by the gel permeation chromatography method (GPC) using a standard polystyrene calibration curve, for example.
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., trade name)
Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (above, manufactured by Hitachi Chemical Co., Ltd., trade name)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (trade name, manufactured by Hitachi, Ltd.)

  In the photosensitive resin composition of the present embodiment, the content of the component (A) is preferably 30 to 90 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition excluding the component (D). 80 parts by mass is more preferable. When the content of the component (A) is in the above range, the developability with an aqueous alkaline solution in a film formed using the photosensitive resin composition is further improved.

((B) component)
The photosensitive resin composition of the present embodiment contains an aliphatic or alicyclic epoxy compound having two or more oxirane rings. As the component (B), an epoxy compound having a molecular weight of 1000 or less is preferable. Further, the component (B) preferably has two or more glycidyl ether groups, and more preferably has three or more glycidyl ether groups. In the present specification, the “aliphatic or alicyclic epoxy compound” refers to a compound in which the main skeleton is an aliphatic skeleton and / or an alicyclic skeleton and does not include an aromatic ring or an aromatic heterocyclic ring.

  As component (B), 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 di Glycidyl ether, pentaerythritol tetraglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, glycerol propoxylate triglycidyl ether, dicyclopentadiene dioxide, 1,2,5,6-diepoxycyclooctane, 1 , 4-Cyclohexanedimethanol diglycidyl ether, diglycidyl 1,2-cyclohexanedi Rubokishireto, 3,4-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, cyclohexene oxide type epoxy resin or the like.

  Among the components (B), trimethylolethane triglycidyl ether or trimethylolpropane triglycidyl ether is preferable from the viewpoint of further excellent resolution.

  The component (B) 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, (Commercial name) is commercially available. (B) A component can be used individually by 1 type or in mixture of 2 or more types.

  In the photosensitive resin composition of the present embodiment, the content of the component (B) is preferably 20 to 70 parts by mass, more preferably 25 to 65 parts by mass, with respect to 100 parts by mass of the component (A). More preferred is 55 parts by weight. 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 further improved, and when it is 70 parts by mass or less, the photosensitive resin composition is placed on a desired support. Film formation can be facilitated, and the resolution tends not to decrease.

((C) component)
The photosensitive resin composition of this embodiment contains a photosensitive acid generator. Component (C) is a compound that generates an acid upon irradiation with actinic rays or the like, and not only the (B) component is cross-linked by the generated acid, but also the (B) component is a phenolic hydroxyl group of the (A) component. It reacts and the solubility of the composition in the developer is greatly reduced.

  The component (C) is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays, but onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, etc. Is mentioned. Among these, as the component (C), it is preferable to use an onium salt compound or a sulfonimide compound from the viewpoint of excellent availability. In particular, as the component (C), an onium salt compound is preferably used from the viewpoint of excellent solubility in a solvent. Specific examples of the component (C) are shown below.

[Onium salt compound]
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 diaryl iodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diaryliodonium salts such as diphenyliodonium tetrafluoroborate; triphenylsulfonium Triarylsulfonium salts such as trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate; 4-t-butylphenyl-diphenylsulfonium trifluoromethanesulfonate; 4-t-butylphenyl-diphenylsulfonium p- Toluenesulfonate; 4, 7 And di -n- butoxy naphthyl tetrahydrothiophenium trifluoromethanesulfonate, and the like.

[Halogen-containing compounds]
Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of preferred halogen-containing compounds include 1,10-dibromo-n-decane; 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane; phenyl-bis (trichloromethyl) -s-triazine. , S-triazine derivatives such as 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, and the like.

[Diazo ketone compounds]
Examples of the diazo ketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, and a diazonaphthoquinone compound. Specific examples include phenolic 1,2-naphthoquinonediazide-4-sulfonic acid ester compounds.

[Sulfone compound]
Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples include 4-tolylphenacylsulfone, mesitylphenacylsulfone, bis (phenacylsulfonyl) methane, and the like.

[Sulfonic acid compound]
Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred specific examples include benzoin p-toluenesulfonate, pyrogallol tris-trifluoromethanesulfonate, o-nitrobenzyl trifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate, and the like.

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

[Diazomethane compounds]
Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and the like.

  Component (C) is a compound having a tetrakis (pentafluorophenyl) borate group, a trifluoromethanesulfonate group, a hexafluoroantimonate group, a hexafluorophosphate group or a tetrafluoroborate group from the viewpoint of further improving the resolution. It is preferable that (C) A component can be used individually by 1 type or in mixture of 2 or more types.

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

((D) component)
The photosensitive resin composition of the present embodiment may or may not contain a sensitizer. When the photosensitive resin composition of this embodiment contains (D) component, the sensitivity of the photosensitive resin composition can be improved. Therefore, when manufacturing a mass-produced product or the like, the exposure amount may be small in order to form a fine resist pattern, and productivity is improved.

  Among the components (D), anthracene skeleton, pyrene skeleton, perylene skeleton, carbazole skeleton, phenothiazine skeleton, xanthone skeleton, thioxanthone skeleton, acridine skeleton, pyrazoline skeleton, distyrylbenzene skeleton from the viewpoint of further excellent resolution or solubility. And a compound having at least one skeleton selected from the group consisting of a distyrylpyridine skeleton, an anthracene skeleton, a pyrene skeleton, a perylene skeleton, a phenothiazine skeleton, a pyrazoline skeleton, a distyrylbenzene skeleton, and a distyrylpyridine skeleton A compound having at least one skeleton selected from the group consisting of is more preferable, a compound having an anthracene skeleton is more preferable, and 9,10-dibutoxyanthracene is particularly preferable. (D) A component can be used individually by 1 type or in mixture of 2 or more types.

  Examples of the compound having an anthracene skeleton include anthracene, 9-methylanthracene, 9-ethylanthracene, 9-propylanthracene, 9-butylanthracene, 9,10-dibutylanthracene, 2,3-dibutylanthracene, 9-hydroxyanthracene, 9 -Methoxyanthracene, 9-ethoxyanthracene, 9-propoxyanthracene, 9-butoxyanthracene, 9-hydroxymethylanthracene, 9- (2-hydroxyethyl) anthracene, 9-anthrylmethyl acrylate, 9-anthrylmethyl methacrylate , 9-anthracenecarboxylic acid, 2,3-dibutoxyanthracene, 9,10-hydroxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dip Poxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentanoxyanthracene, 9,10-dihexanoxyanthracene, 9,10-diheptanoxyanthracene, 9,10-dioctanoxyanthracene 9,10-dinonoxyanthracene, 9,10-didecanoxyanthracene, 9,10-bis (methoxycarbonyloxy) anthracene, 9,10-bis (ethoxycarbonyloxy) anthracene, 9,10-bis (propoxy) Carbonyloxy) anthracene, 9,10-bis (butoxycarbonyloxy) anthracene, 9,10-bis (pentanoxycarbonyloxy) anthracene, 9,10-bis (hexanoxycarbonyloxy) anthracene, 9,10-bis (Heptanoxycarbonylo C) Anthracene, 9,10-bis (octanoxycarbonyloxy) anthracene, 9,10-bis (nonanoxycarbonyloxy) anthracene, 9,10-bis (didecanoxycarbonyloxy) anthracene, 9,10-di Examples thereof include glycidyloxyanthracene. The compounds having an anthracene skeleton can be used singly or in combination of two or more.

  Examples of the compound having a pyrene skeleton include pyrene, 1-methylpyrene, 1-butylpyrene, 1- (hydroxymethyl) pyrene, 1-pyrenecarboxylic acid, 1-pyrenebutyric acid and the like. The compounds having a pyrene skeleton can be used singly or in combination of two or more.

  Examples of the compound having a perylene skeleton include perylene, 2,5,8,11-tetra-tert-butylperylene, N, N′-bis (2-ethylhexyl) -3,4,9,10-perylenetetracarboxylic acid diimide. N, N′-di-n-octyl-3,4,9,10-perylenetetracarboxylic acid diimide, N, N′-ditridecyl-3,4,9,10-perylenetetracarboxylic acid diimide, and the like. . The compounds having a perylene skeleton can be used singly or in combination of two or more.

  Examples of the compound having a carbazole skeleton include carbazole, 3-methyl-9H-carbazole, 3-ethyl-9H-carbazole, 3-propyl-9H-carbazole, 3-butyl-9H-carbazole, 3-methoxy-9H-carbazole, 3-ethoxy-9H-carbazole, 3-propoxy-9H-carbazole, 3-butoxy-9H-carbazole, 3-phenyl-9H-carbazole, 3,6-dimethyl-9H-carbazole, 3,6-diethyl-9H- Carbazole, 3,6-dipropyl-9H-carbazole, 3,6-dibutyl-9H-carbazole, 3,6-dimethoxy-9H-carbazole, 3,6-diethoxy-9H-carbazole, 3,6-dipropoxy-9H- Carbazole, 3,6-dibutoxy-9H-carbazo 3,6-diphenyl-9H-carbazole, 4-glycidyloxycarbazole, 9-methylcarbazole, 9-ethylcarbazole, 9-propylcarbazole, 9-butylcarbazole, 9- (2-ethylhexyl) carbazole, 9-vinyl Examples thereof include carbazole, 7H-dibenzo [c, g] carbazole, 3,3′-bicarbazole, 1,3-di-9-carbazolylbenzene and the like. The compounds having a carbazole skeleton can be used singly or in combination of two or more.

  Examples of the compound having a phenothiazine skeleton include phenothiazine, 2-chlorophenothiazine, 2-methoxyphenothiazine, 2-ethoxyphenothiazine, 2-propoxyphenothiazine, 2-butoxyphenothiazine, 10-methylphenothiazine, 10-ethylphenothiazine, 10-protylphenothiazine. Examples thereof include 10-butylphenothiazine, benzoylleucomethylene blue and the like. The compounds having a phenothiazine skeleton can be used singly or in combination of two or more.

  Compounds having a xanthone skeleton include xanthone, 3-hydroxyxanthen-9-one, 3-methoxyxanthen-9-one, 3-ethoxyxanthen-9-one, 3-propoxyxanthen-9-one, 2- (9 -Oxoxanthen-2-yl) propionic acid and the like. A compound having a xanthone skeleton can be used singly or in combination of two or more.

  Examples of the compound having a thioxanthone skeleton include thioxanthone, 2,4-diethylthioxanthen-9-one, 2-isopropylthioxanthone, and 2-chlorothioxanthone. The compounds having a thioxanthone skeleton can be used singly or in combination of two or more.

  Examples of the compound having an acridine skeleton include acridine, 9-methylacridine, 9-ethylacridine, 9-propylacridine, 9-butylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9-propoxyacridine, 9-butoxyacridine9. -Phenylacridine and the like. The compounds having an acridine skeleton can be used singly or in combination of two or more.

  Examples of the compound having a pyrazoline skeleton include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butylphenyl) -pyrazoline, 1-phenyl-3-biphenyl-5- (4- tert-butylphenyl) -pyrazoline, 1-phenyl-3- (4-methoxy-styryl) -5- (4-methoxyphenyl) -pyrazoline and the like. The compound having a pyrazoline skeleton can be used alone or in combination of two or more.

  Examples of the compound having a distyrylbenzene skeleton include 1,4-distyrylbenzene, 1,4-bis (2-methylstyryl) benzene, 1,4-bis (4-methylstyryl) benzene, 1,4-bis ( 2-methoxystyryl) benzene, 1,4-bis (4-methoxystyryl) benzene, 1,4-bis (2-diethylaminostyryl) benzene, 1,4-bis (4-diethylaminostyryl) benzene, 1,4- Dimethyl-2,5-distyrylbenzene, 1,4-distyryl-2,5-dimethylbenzene, 1,4-bis (4-methylstyryl) -2,5-dimethylbenzene, 1,4-bis (4- Methoxystyryl) -2,5-dimethylbenzene, 1,4-bis (4-diethylaminostyryl) -2,5-dimethylbenzene, 1,4-dimethoxy- , 5-distyrylbenzene, 1,4-distyryl-2,5-dimethoxybenzene, 1,4-bis (4-methylstyryl) -2,5-dimethoxybenzene, 1,4-bis (4-methoxystyryl) -2,5-dimethoxybenzene, 1,4-bis (4-diethylaminostyryl) -2,5-dimethoxybenzene, 4,4 '-(1,4-phenylenedivinyl) bis [N, N-di (p- Tolyl) aniline] and the like. The compounds having a distyrylbenzene skeleton can be used singly or in combination of two or more.

  Examples of the compound having a distyrylpyridine skeleton include 3,5-bis (2-methoxybenzylidenedicyclopentano [2,3-b, e]))-4- (2-methoxy) phenyl-pyridine, 3, 5-bis (3-methoxybenzylidenedicyclopentano [2,3-b, e]))-4- (3-methoxy) phenyl-pyridine, 3,5-bis (4-methoxybenzylidenedicyclopentano [ 2,3-b, e]))-4- (4-methoxy) phenyl-pyridine, 3,5-bis (2,4-dimethoxybenzylidenedicyclopentano [2,3-b, e]))- 4- (2,4-dimethoxy) phenyl-pyridine, 3,5-bis (3,4-dimethoxybenzylidenedicyclopentano [2,3-b, e]))-4- (3,4-dimethoxy) Phenyl-pyridine, 3, - bis (4,5-dimethoxy-benzylidene ethylidenedioxy cyclopentanoxime [2,3-b, e])) - 4- (4,5- dimethoxyphenyl) phenyl - pyridine, and the like. The compound having a distyrylpyridine skeleton can be used singly or in combination of two or more.

  The content of the component (D) is 1 part by mass or less with respect to 100 parts by mass of the component (A) from the viewpoint of obtaining excellent resolution. The component (D) is preferably 0.01 to 1 part by mass, and more preferably 0.05 to 0.75 part by mass. When the content of the component (D) is 0.01 parts by mass or more, the sensitivity of the photosensitive resin composition is likely to be improved. In addition, 0 mass part may be sufficient as content of (D) component with respect to 100 mass parts of (A) component.

((E) component)
The photosensitive resin composition of this embodiment may further contain a crosslinking agent as the component (E) as necessary. When the photosensitive resin composition of this embodiment contains the component (E), when the photosensitive layer is heated, the component (E) reacts with the component (A) to form a bridge structure, and the resin pattern Weakening and deformation of the resin pattern can be prevented.

  As the component (E), specifically, a compound having a phenolic hydroxyl group (however, the component (A) is not included) and a compound having a hydroxymethylamino group are preferable. (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) preferably further has a methylol group or an alkoxyalkyl group. The compound having a phenolic hydroxyl group as the component (E) can increase the dissolution rate of the unexposed area when developing with an alkaline aqueous solution, and can further improve the sensitivity. The compound having a phenolic hydroxyl group preferably has a weight average molecular weight of 2000 or less. The molecular weight of the compound having a phenolic hydroxyl group is preferably 94 to 2000, more preferably 108 to 2000, and more preferably 108 to 1500 in terms of weight average molecular weight in consideration of the balance with solubility in alkali aqueous solution, photosensitivity and mechanical properties. Further preferred. In addition, about the compound with a low molecular weight, when it is difficult to measure with the measuring method similar to the weight average molecular weight of the above-mentioned (A) component, molecular weight can be measured with another method and the average can also be calculated.

［一般式（１）中、Ｚは、単結合又は２価の有機基を示し、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又は１価の有機基を示し、Ｒ^３及びＲ^４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^１〜Ｒ^４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” used as the component (E), a conventionally known compound can be used, and the compound represented by the following general formula (1) has an effect of promoting dissolution of an unexposed portion, It is preferable because it is excellent in balance with the effect of preventing deformation of the resin pattern after curing by heating.

[In General Formula (1), Z represents a single bond or a divalent organic group, R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, and R ³ and R ⁴ represent Each independently represents a monovalent organic group, a and b each independently represent an integer of 1 to 3, and c and d each independently represent an integer of 0 to 3. 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; and 2 to 10 carbon atoms such as an ethenyl group. An alkenyl group; an aryl group having 6 to 30 carbon atoms, such as a phenyl group; and 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 ^{1 to} R ⁴ , they may be the same as or different from each other. ]

  In the general formula (1), the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. In addition, 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; and 2 to 10 carbon atoms such as an ethylidene group. An alkylidene group; an arylene group having 6 to 30 carbon atoms, such as a phenylene group; a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms; a sulfonyl group; a carbonyl group Ether bond; sulfide bond; amide bond and the like. Among these, Z is preferably a divalent organic group represented by the following general formula (2).

［一般式（２）中、Ｘは、単結合、アルキレン基（例えば、炭素原子数が１〜１０のアルキレン基）、アルキリデン基（例えば、炭素原子数が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^５は、水素原子、ヒドロキシル基、アルキル基又はハロアルキル基を示し、ｅは１〜１０の整数を示す。複数のＲ^５及びＸは互いに同一でも異なっていてもよい。］

[In general formula (2), X is a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), 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 ⁵ represents a hydrogen atom, a hydroxyl group, an alkyl group or a haloalkyl group, and e represents an integer of 1 to 10. A plurality of R ⁵ and X may be the same or different from each other. ]

  Examples of the compound having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N -Nitrogen-containing compounds obtained by alkyl etherifying all or part of methylol groups, such as -hydroxymethyl) urea. 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.

  In the photosensitive resin composition of this embodiment, 5-50 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (E) component, 5-30 mass parts is more preferable.

((F) component)
The photosensitive resin composition of this embodiment may contain a compound having a Si—O bond as the component (F). The component (F) is not particularly limited as long as it has a Si—O bond. For example, among inorganic fillers and silane compounds, a compound having a Si—O bond, and an alkoxy oligomer having a Si—O bond. Is mentioned. (F) A component can be used individually by 1 type or in mixture of 2 or more types.

  When an inorganic filler is used as the component (F), the inorganic filler is preferably silica such as fused spherical silica, fused pulverized silica, fumed silica, or sol-gel silica. Moreover, the inorganic filler may have a Si-O bond by processing an inorganic filler with a silane compound. Among inorganic fillers treated with a silane compound, as inorganic fillers other than silica, aluminum oxide, aluminum hydroxide, calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, or talc, Examples include inorganic fillers derived from mineral products such as mica.

  When a silane compound is used as the component (F), the silane compound is not particularly limited as long as the silane compound has a Si—O bond. Examples of the silane compound include alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acrylic silane, methacryl silane, mercapto silane, sulfide silane, isocyanate silane, sulfur silane, styryl silane, alkyl chlorosilane, and the like.

As a silane compound which is (F) component, the compound represented by following General formula (3) is preferable.
(R ¹⁰¹ O) _4-f -Si- (R ¹⁰² ) _f (3)

In General Formula (3), R ¹⁰¹ represents an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, or a propyl group, R ¹⁰² represents a monovalent organic group, and f represents An integer of 0 to 3 is shown. When f is 0, 1 or 2, the plurality of R ¹⁰¹ may be the same as or different from each other. When f is 2 or 3, the plurality of R ¹⁰² may be the same as or different from each other. R ¹⁰¹ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, from the viewpoint of further improving resolution. In order to improve the dispersibility of an inorganic filler, when processing with the compound represented by General formula (3), from the viewpoint of further improving the dispersibility of the inorganic filler, f is preferably 0 to 2, and 0 to 1 is preferable. More preferred.

  Specific examples of the silane compound as component (F) include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and diisopropyl. Dimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrieth Sisilane, 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- (triethoxy Silyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Tacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene ) -3-aminopropyltriethoxysilane and the like.

  As for content of (F) component, 1.8-420 mass parts is preferable with respect to 100 mass parts of (A) component, and 1.8-270 mass parts is more preferable.

(Photopolymerizable compound)
The photosensitive resin composition of the present embodiment is an aliphatic compound having two or more functional groups selected from the group consisting of an acryloyloxy group and a methacryloyloxy group from the viewpoint of improving the peelability after curing ( However, (B) component may not be included). In addition, the said compound may have 2 or more types of different functional groups one by one, and may have two or more single functional groups. The compound is preferably an aliphatic compound having at least three functional groups selected from the group consisting of an acryloyloxy group and a methacryloyloxy group. Moreover, 0-50 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of the said compound, 5-45 mass parts is more preferable, and 10-40 mass parts is still more preferable.

  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. The compounds having an acryloyloxy group can be used alone or in combination of two or more.

  Examples of the compound having a methacryloyloxy group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, and ditrimethylolpropane. Tetramethacrylate, EO-modified pentaerythritol tetramethacrylate, PO-modified pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, EO-modified pentaerythritol trimethacrylate, PO-modified pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, EO-modified trimethylolpropane methacrylate DOO, PO-modified trimethylolpropane dimethacrylate, trimethylolpropane dimethacrylate, EO modified glycerol trimethacrylate, PO-modified glycerol trimethacrylate, glycerine trimethacrylate and the like. The compound which has a methacryloyloxy group can be used individually by 1 type or in mixture of 2 or more types.

(Other ingredients)
The photosensitive resin composition of this embodiment may contain other components other than the above-mentioned components. Examples of other components include colorants, adhesion assistants, and leveling agents.

  In addition to the component (A), the photosensitive resin composition of the present embodiment may contain a phenolic low molecular compound having a molecular weight of less than 1000 (hereinafter referred to as “phenol compound (a)”). As the phenolic compound (a), 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, Tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl ] Benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- {1 -(4-Hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) Tan, and the like. Content of a phenol compound (a) is the range of 0-40 mass% (especially 0-30 mass%) with respect to 100 mass parts of (A) component.

[Photosensitive element]
Next, the photosensitive element (for example, photosensitive film) of this embodiment is demonstrated.

  The photosensitive element of this embodiment is equipped with the support body and the photosensitive layer provided on the said support body, and the said photosensitive layer contains the above-mentioned photosensitive resin composition. The photosensitive layer can be formed from the above-described photosensitive resin composition. The photosensitive element of this embodiment may further include a protective film that covers the photosensitive layer on the photosensitive layer.

  As the support, for example, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used. As for the thickness of the said support body (polymer film), 5-25 micrometers is preferable. In addition, you may use the said polymer film by laminating | stacking on the both surfaces of a photosensitive layer by using one as a support body and another as a protective film.

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

  The photosensitive layer 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 said photosensitive layer changes with uses, 10-100 micrometers is preferable after drying a photosensitive layer, 15-60 micrometers is more preferable, and 20-50 micrometers is still more preferable.

<Method for forming resist pattern>
Next, a resist pattern forming method of this embodiment will be described. The resist pattern forming method of the present embodiment includes a forming step (photosensitive layer forming step) in which a photosensitive layer is formed on a substrate using the photosensitive resin composition of the present embodiment, and active on a predetermined portion of the photosensitive layer. The photosensitive resin composition is cured by irradiating a light beam to expose the predetermined portion and performing a post-exposure heat treatment, and removing a portion other than the predetermined portion of the photosensitive layer from the substrate. And a developing step for forming a resist pattern including an object on the substrate. The photosensitive layer can include the photosensitive resin composition of the present embodiment. The said resist pattern consists of hardened | cured material of the said photosensitive resin composition, for example.

  In the method for forming a resist pattern of the present embodiment, for example, first, on a base material on which a resist pattern 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.) A photosensitive layer formed from the above-described photosensitive resin composition is formed. As the method for forming the photosensitive layer, the above-mentioned photosensitive resin composition is applied to a substrate (for example, coating), dried to volatilize a solvent or the like to form a coating film (photosensitive layer), or the above-described photosensitive layer. And a method of transferring the photosensitive layer in the conductive element onto the 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. Examples of the actinic rays used for exposure include g-line stepper rays; ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and i-line steppers; electron beams; The exposure amount is appropriately selected depending on the light source used, the thickness of the photosensitive layer, and the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, when the photosensitive layer thickness is 10 to 50 μm, about 1000 to 20000 J / m ^2. It is.

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

  Next, the post-exposure baked photosensitive layer is developed with an alkaline developer, and an unexposed area is dissolved and removed to obtain a desired resist pattern (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 about 1 to 10 minutes.

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

<Semiconductor parts>
The photosensitive resin composition of this embodiment can be used suitably for manufacture of semiconductor components (for example, wiring boards, such as a multilayer printed wiring board, a semiconductor element). A more preferred embodiment is application of the photosensitive resin composition to the production of a high-density package substrate, and application of the photosensitive resin composition to a semi-additive construction method.

  The manufacturing method of the semiconductor component of the present embodiment (for example, a wiring board such as a multilayer printed wiring board or a semiconductor element) is a step of forming a resist pattern by the resist pattern forming method of the present embodiment (the substrate on which the resist pattern is formed). A step of obtaining a material) and a step of etching or plating a base material (substrate or the like) on which a resist pattern is formed (an etching step or a plating step). The method for manufacturing a semiconductor component of this embodiment may further include a peeling process for peeling the resist pattern.

  Below, an example of the manufacturing process of the wiring board by a semi-additive construction method is demonstrated, referring FIG.

  In FIG. 1A, a base material (for example, a circuit forming substrate) in which a conductor layer 10 is formed on an insulating layer 15 is prepared. The conductor layer 10 is, for example, a metal copper layer. In FIG. 1B, the photosensitive layer 32 is formed on the conductive layer 10 of the substrate by the photosensitive layer forming step. In FIG. 1C, the mask 20 is disposed on the photosensitive layer 32, irradiated with an actinic ray 50, and a region other than the region where the mask 20 is disposed is exposed to form a photocured portion. In FIG.1 (d), the resist pattern 30 which is a photocuring part is formed on a base material by removing area | regions other than the photocuring part formed by the said exposure process from a base material by a image development process. In FIG. 1E, a plating layer 42 is formed on the conductor layer 10 by plating using the resist pattern 30 that is a photocured portion as a mask. In FIG. 1F, after the resist pattern 30 that is a photocured portion is peeled off with a strong alkaline aqueous solution, a part of the plating layer 42 and the conductor layer 10 masked by the resist pattern 30 are flash-etched. Then, the circuit pattern 40 is formed. The conductor layer 10 and the plating layer 42 may be made of the same material or different materials. When the conductor layer 10 and the plating layer 42 are the same material, the conductor layer 10 and the plating layer 42 may be integrated. Although the method for forming the resist pattern 30 using the mask 20 has been described with reference to FIG. 1, the resist pattern 30 may be formed by a direct drawing exposure method without using the mask 20.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples at all.

<Preparation of photosensitive resin composition>
(A) 100 parts by mass of novolak resin, (B) epoxy compound, (C) photosensitive acid generator, (D) sensitizer, (E) crosslinker, (F) silane compound, (H) light By mixing the polymerizable compound and the solvent in the blending amount (g) shown in Table 1, the photosensitive resin compositions (novolak resin-based photosensitive resin composition) of Examples 1 to 5 and Comparative Example 1 are obtained. It was. “-” Means not blended.

  Moreover, the solution of the photosensitive resin composition (acrylic resin-based photosensitive resin composition) of Comparative Examples 2 to 3 was prepared by mixing the components shown in Table 1 in the blending amounts (g) shown in Table 1. did. “-” Means not blended. The amount of component (H) shown in Table 1 is the mass (solid content) of the non-volatile content.

  Details of each component shown in Table 1 are as follows.

[(A) Novolac resin]
TR4020G (Asahi Organic Materials Co., Ltd., trade name): Cresol Novolac Resin TR4080G (Asahi Organic Materials Co., Ltd., trade name): Cresol Novolac Resin

[(B) Epoxy compound]
ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name, see formula (4) below): trimethylolpropane triglycidyl ether

[(C) Photosensitive acid generator]
CPI-310B (trade name, manufactured by San Apro Co., Ltd.): Triarylsulfonium salt

[(D) Sensitizer]
DBA (trade name, manufactured by Kawasaki Kasei Kogyo Co., Ltd.): 9,10-dibutoxyanthracene

[(E) Crosslinking agent]
MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.): 1,3,4,6-tetrakis (methoxymethyl) glycoluril

[(F) Silane compound]
KBM-403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.): 3-glycidoxypropyltrimethoxysilane

[(G) Binder polymer]
Binder polymers (G-1) and (G-2) described later

[(H) Photopolymerizable compound]
PET-30 (Nippon Kayaku Co., Ltd., trade name): Pentaerythritol triacrylate FA-321M (Hitachi Chemical Co., Ltd., trade name): 2,2-bis (4- (methacryloxypentaethoxy) phenyl ) Propane TMPT-21E (manufactured by Hitachi Chemical Co., Ltd., sample name): EO-modified trimethylolpropane trimethacrylate (average 21 mol of ethylene oxide adduct)
M-114 (trade name, manufactured by Toagosei Co., Ltd.): 4-normalnonylphenoxyoctaethylene glycol acrylate

[(I) Photopolymerization initiator]
B-CIM (trade name, manufactured by Hampford): 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole

[(J) amine compound]
LCV (trade name, manufactured by Yamada Chemical Co., Ltd.): Leuco Crystal Violet

[(K) dye]
MKG (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.): Malachite Green

(Synthesis of binder polymer (G-1))
A polymerizable monomer (monomer) of 150 g of methacrylic acid, 125 g of benzyl methacrylate, 25 g of methyl methacrylate and 200 g of styrene (mass ratio 30/25/5/40), and 9.0 g of azobisisobutyronitrile. The solution obtained by mixing was designated as “Solution a”.

  A solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 100 g of a mixed solution (mass ratio 3: 2) of 60 g of methyl cellosolve and 40 g of toluene was designated as “Solution b”.

  Into a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube, 450 g of a mixed solution of 270 g of methyl cellosolve and 180 g of toluene (mass ratio 3: 2) was charged, and nitrogen gas was introduced into the flask. The mixture was heated with stirring while being blown, and the temperature was raised to 80 ° C.

  The solution a was added dropwise to the mixed solution in the flask over 4 hours, and then kept at 80 ° C. for 2 hours with stirring. Next, the solution b was added dropwise to the solution in the flask over 10 minutes, and then the solution in the flask was kept at 80 ° C. for 3 hours while stirring. Further, the temperature of the solution in the flask was raised to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a binder polymer (G-1) solution.

  The non-volatile content (solid content) of the binder polymer (G-1) is 47.8% by mass, the weight average molecular weight is 40000, the number average molecular weight is 19000, the acid value is 196 mgKOH / g, and the degree of dispersion Was 2.1.

In addition, the weight average molecular weight and the number average molecular weight were measured by gel permeation chromatography (GPC), and were derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
{GPC condition}
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., trade name)
Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (above, manufactured by Hitachi Chemical Co., Ltd., trade name)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (trade name, manufactured by Hitachi, Ltd.)

The acid value was measured by the following procedure. About 1 g of the binder polymer synthesized in an Erlenmeyer flask is weighed, dissolved by adding a mixed solvent (mass ratio: toluene / methanol = 70/30), and then an appropriate amount of a phenolphthalein solution is added as an indicator, followed by 0.1N hydroxylation. The solution was titrated with an aqueous potassium solution, and the acid value was measured from the following formula.
x = 10 × Vf × 56.1 / (Wp × I)
In the formula, x represents an acid value (mgKOH / g), Vf represents a titration amount (mL) of a 0.1N KOH aqueous solution, Wp represents a mass (g) of the measured resin solution, and I Indicates the ratio (% by mass) of the non-volatile content in the measured resin solution.

(Synthesis of binder polymer (G-2))
As the polymerizable monomer (monomer), except that the materials shown in Table 2 were used at the mass ratio shown in Table 2, the binder polymer (G- A solution of 2) was obtained.

  The non-volatile content (solid content) of the binder polymer (G-2) is 42.3 mass%, the weight average molecular weight is 40000, the number average molecular weight is 19000, the acid value is 163 mgKOH / g, and the degree of dispersion Was 2.1.

  Table 2 shows the mass ratio, acid value, weight average molecular weight, and dispersity of the polymerizable monomers (monomers) in the binder polymers (G-1) and (G-2).

<Examples 1 to 5 and Comparative Example 1>
(Production of photosensitive element)
The photosensitive resin composition was applied onto a polyethylene terephthalate film (manufactured by Teijin DuPont Films, trade name: Purex A53) (support) so that the thickness of the photosensitive layer was uniform. It dried with the 110 degreeC hot-air convection dryer, and formed the photosensitive layer whose thickness of the photosensitive layer after drying is 25 micrometers. A polyethylene film (manufactured by Tamapoly Co., Ltd., trade name: NF-15) was bonded as a protective layer on the photosensitive layer to obtain a photosensitive element in which the support, the photosensitive layer, and the protective layer were sequentially laminated.

(Evaluation of resolution and sensitivity)
Copper-clad laminate (made by Hitachi Chemical Co., Ltd., trade name “MCL-E-679F”) made of glass epoxy material and copper foil (thickness 16 μm) formed on both sides thereof (hereinafter referred to as “substrate”) )), The photosensitive elements according to Examples and Comparative Examples were laminated on the copper surface of the substrate so that the photosensitive layer of each photosensitive element was in close contact with the copper surface of the substrate while removing the protective layer. To obtain a laminated substrate on which the photosensitive layer and the support were laminated. In addition, lamination uses a press-type vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd., trade name), press heat temperature 60 ° C., evacuation time 20 seconds, laminate press time 20 seconds, atmospheric pressure 4 kPa or less. The pressure was applied at a pressure of 0.4 MPa.

After peeling off the support from the laminated substrate thus produced to expose the photosensitive layer, i-line (projection exposure machine having a high-pressure mercury lamp (trade name: UX-2240SM-XJ01) made by Ushio Electric Co., Ltd.) 365 nm), the photosensitive layer was subjected to the same magnification projection exposure through a mask. 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. Further, the reduction projection exposure was performed while changing the exposure amount by 50 mJ / cm ^{2 in} the range of 100 to 500 mJ / cm ² .

Next, the exposed photosensitive layer is heated at 85 ° C. for 4 minutes (post-exposure bake), and a 2.38 mass% tetramethylammonium hydroxide aqueous solution is used for the shortest development time (the shortest time for removing the unexposed portion). Development was performed by immersing in a time corresponding to 8 times, and an unexposed portion was removed and development processing was performed. After the development treatment, the formed resist pattern was observed using a metal microscope. Among the patterns in which the space portion (unexposed portion) is neatly removed and the line portion (exposed portion) is formed without causing meandering or chipping, the smallest amount of exposure is within the range of 100 to 500 mJ / cm ^2. The width value was evaluated as resolution (minimum resolution). Moreover, the energy amount (mJ / cm < ² >) used for exposure at this time was made into the photosensitivity of each photosensitive resin composition. In the evaluation of sensitivity, the smaller this value, the higher the sensitivity. The results are shown in Table 1.

(Evaluation of resist shape)
The resist shape (cross-sectional shape of the resist pattern) obtained in the evaluation of the resolution was observed using a Hitachi scanning electron microscope S-500A. When the resist shape is trapezoidal or inverted trapezoidal, or when there is a skirting or cracking of the resist, there is a tendency that a short circuit or disconnection is likely to occur in a circuit formed by the subsequent etching process or plating process. Therefore, it is desirable that the resist shape is rectangular (rectangular) and there is no resist tailing or crack. The term “crack” means that a line portion (exposed portion) of the resist pattern has cracks or cracks, or accompanying this, the line portion is chipped or broken. The case where the resist shape is rectangular and there is no resist tailing or cracking is evaluated as “A”, and when the resist shape is trapezoidal or inverted trapezoidal, or when resist cracking or tailing is seen. B ”. The results are shown in Table 1.

(Evaluation of peelability)
The peelability was evaluated by the following method. First, a photosensitive layer was formed on a substrate, and each photosensitive layer was exposed, heated and developed to prepare a photocured film having a size of 40 mm × 50 mm. And the dry film peeling liquid (Mitsubishi Gas Chemical Co., Ltd. make, brand name: R-100S) heated to 50 degreeC and the peeling accelerator for R-100S (Mitsubishi Gas Chemical Co., Ltd. brand name: R-) 101) was peeled off using an aqueous solution containing 12% by volume and 4% by volume, respectively. Evaluation of peelability is “◯” when the photocuring film finishes peeling from the substrate within 5 minutes, “△” when it exceeds 5 minutes and within 15 minutes, “△”, and over 15 minutes As “×”. The results are shown in Table 1.

<Comparative Examples 2-3>
(Production of photosensitive element)
The same as that for obtaining the photosensitive elements of Examples 1 to 5 and Comparative Example 1, except that a polyethylene terephthalate film having a thickness of 16 μm (trade name “HTF-01” manufactured by Teijin Ltd.) (support) was used. Thus, a photosensitive element having a photosensitive layer thickness of 25 μm was obtained.

(Evaluation of resolution and sensitivity)
After heating the substrate to 80 ° C., the photosensitive elements according to Comparative Examples 2 to 3 were made to adhere to the copper surface of the substrate while removing the protective layer. Then, the substrate was laminated (laminated) on the copper surface to obtain a laminated substrate on which the photosensitive layer and the support were laminated. Lamination was performed under conditions of a temperature of 120 ° C. and a lamination pressure of 4 kgf / cm ² .

  When the obtained multilayer substrate is allowed to cool to 23 ° C., a direct drawing exposure apparatus using a semiconductor laser having a wavelength of 355 nm as a light source (trade name “Paragon-9000” manufactured by Nippon Orbotech Co., Ltd.) is used. The exposure was performed with a predetermined energy amount.

  After the exposure, the polyethylene terephthalate film was peeled off, and a 1.0% by mass sodium carbonate aqueous solution was sprayed at 30 ° C. for 50 seconds to remove the unexposed portion and development processing was performed. After the development treatment, the resist pattern formed using a metal microscope was observed, and the resolution and sensitivity were evaluated in the same manner as in Examples 1 to 5 and Comparative Example 1. The results are shown in Table 1.

(Evaluation of resist shape)
In the evaluation of the resolution, the resist shape was evaluated in the same manner as in Examples 1 to 5 and Comparative Example 1. The results are shown in Table 1.

(Evaluation of peelability)
The peelability was evaluated by the same method as in Examples 1 to 5 and Comparative Example 1 after forming the photosensitive layers according to Comparative Examples 2 and 3 on the substrate, exposing and developing each photosensitive layer. The results are shown in Table 1.

  As is clear from Table 1, Examples 1 to 5 showed higher resolution than Comparative Examples 1 to 3. Examples 1 to 2 and 5 showed equivalent peelability and high resolution as compared with Comparative Examples 2 and 3, which are conventional acrylic resin-based photosensitive resin compositions. In Examples 1 and 2, which do not contain a crosslinking agent and the content of the sensitizer is 0 to 1 part by mass, both the resolution and the peelability are good, and the content of the sensitizer is 0. In Example 2, which is a mass part, the resist shape was also good. Further, in Comparative Example 1 in which the sensitizer exceeds 1 part by mass, the resolution is lowered and the resist shape is an inverted trapezoid.

  The photosensitive resin composition of this invention is applicable as a material which forms the resist pattern for manufacturing semiconductor components (a printed wiring board, a semiconductor element, etc.). In particular, since the photosensitive resin composition of the present invention has high resolution, it manufactures semiconductor components (printed wiring boards, semiconductor elements, etc.) having thinned and densified wiring such as high-density package substrates. It is also suitably used for forming a resist pattern for this purpose.

  DESCRIPTION OF SYMBOLS 10 ... Conductive layer, 15 ... Insulating layer, 20 ... Mask, 30 ... Resist pattern, 32 ... Photosensitive layer, 40 ... Circuit pattern, 42 ... Plating layer, 50 ... Actinic ray.

Claims (10)

Forming a photosensitive layer on a substrate using the photosensitive resin composition;
Irradiating a predetermined part of the photosensitive layer with actinic rays to expose the predetermined part, and performing a post-exposure heat treatment;
A development step of forming a resist pattern including a cured product of the photosensitive resin composition on the substrate by removing portions other than the predetermined portion of the photosensitive layer from the substrate;
Etching or plating the substrate on which the resist pattern is formed, and used as the photosensitive resin composition in a method for manufacturing a semiconductor component,
(A) component: a resin having a phenolic hydroxyl group;
(B) component: an aliphatic or alicyclic epoxy compound having two or more oxirane rings,
(C) component: containing a photosensitive acid generator,
It is 0.01 to 1 part by mass relative to the content of the sensitizer is the component (A) 100 parts by weight, the photosensitive resin composition. Forming a photosensitive layer on a substrate using the photosensitive resin composition;
Irradiating a predetermined part of the photosensitive layer with actinic rays to expose the predetermined part, and performing a post-exposure heat treatment;
A development step of forming a resist pattern including a cured product of the photosensitive resin composition on the substrate by removing portions other than the predetermined portion of the photosensitive layer from the substrate;
A step of peeling the resist pattern, and used as the photosensitive resin composition in a method of manufacturing a semiconductor component,
(A) component: a resin having a phenolic hydroxyl group;
(B) component: an aliphatic or alicyclic epoxy compound having two or more oxirane rings,
(C) component: containing a photosensitive acid generator,
The photosensitive resin composition whose content of a sensitizer is 0.01-1 mass part with respect to 100 mass parts of said (A) component. The photosensitive resin composition of Claim 1 or 2 whose content of the said sensitizer is 0.71-1 mass part with respect to 100 mass parts of said (A) component. The photosensitive resin composition as described in any one of Claims 1-3 whose content of the said (B) component is 20-70 mass parts with respect to 100 mass parts of said (A) component. The photosensitive resin composition as described in any one of Claims 1-4 in which the said (B) component has a 2 or more glycidyl ether group. The photosensitive resin composition as described in any one of Claims 1-5 in which the said (B) component has a 3 or more glycidyl ether group. A support, and a photosensitive layer provided on the support,
The photosensitive element in which the said photosensitive layer contains the photosensitive resin composition as described in any one of Claims 1-6. Forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 6;
Irradiating a predetermined part of the photosensitive layer with actinic rays to expose the predetermined part, and performing a post-exposure heat treatment;
A development step of forming a resist pattern including a cured product of the photosensitive resin composition on the substrate by removing portions other than the predetermined portion of the photosensitive layer from the substrate. Pattern formation method.   The manufacturing method of a semiconductor component provided with the process of etching or plating the base material in which the resist pattern was formed by the method of Claim 8.   The method for manufacturing a semiconductor component according to claim 9, further comprising a step of peeling the resist pattern.

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