JP5035380B2 - Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of performing formation of a resist pattern by a direct drawing exposure method with satisfactory sensitivity and resolution; a photosensitive element using the same; a method for forming the resist pattern; and a method for producing print wiring board. <P>SOLUTION: The photosensitive resin composition contains (A) a binder polymer, (B) a photopolymerizable compound having an ethylenic unsaturated bond and (C1) a compound represented by formula (1). Here, in the formula (1), at least one of the Rs represents an isopropyl group, and the sum of a, b and c is 1-6. When the sum of a, b and c is 2-6, a plurality of Rs in the same molecule can be the same or different. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element, a resist pattern forming method, and a printed wiring board manufacturing method.

  Microelectronic circuits such as printed wiring boards, plasma display wiring boards, liquid crystal display wiring boards, large-scale integrated circuits, thin transistors, and semiconductor packages are generally manufactured through a process of forming a resist pattern by so-called photolithography. Yes. In photolithography, for example, a photosensitive layer provided on a substrate is exposed by irradiating light such as ultraviolet rays through a mask film having a predetermined pattern, and then development with different solubility between an exposed portion and a non-exposed portion. A resist pattern is formed by developing with a liquid, and a conductive pattern is formed on the substrate by plating or etching the substrate using the resist pattern as a mask.

  In particular, in the field of surface mounting technology such as printed wiring boards and semiconductor packages, technological development for further increasing the density of electronic circuit wiring is being actively carried out, and the conductor pattern constituting the wiring is 10 μm. It is required to form with the following scale. For this reason, the photosensitive resin composition used for photolithography is required to have a resolution of 10 μm or less.

  Further, the photosensitive resin composition is required to have higher sensitivity. As the density of wiring increases, the problem of voltage drop due to the resistance of the power supply line tends to become obvious. For this problem, the conductors that make up the wiring are increased by increasing the film thickness of the resist pattern. It is effective to increase the thickness of the layer to about 10 μm or more. In order to form a thick resist pattern with high productivity, it is necessary to further increase the sensitivity of the photosensitive resin.

  On the other hand, as a method for forming a resist pattern, a so-called direct drawing exposure method in which a resist pattern is directly drawn without using a mask pattern has attracted attention. According to this direct drawing exposure method, it is considered possible to form a resist pattern with high productivity and high resolution. In recent years, a gallium nitride blue laser light source that oscillates laser light having a wavelength of 405 nm and has a long life and high output has become practically usable as a light source. By using such a short wavelength laser beam in the direct drawing exposure method, it is expected that a high-density resist pattern that has been difficult to manufacture can be formed. As such a direct drawing exposure method, a method using a DLP (Digital Light Processing) system proposed by Texas Instruments has been proposed by Ball Semiconductor, and an exposure apparatus using this method has already been put into practical use. It has begun.

  Furthermore, some photosensitive resin compositions intended to form a resist pattern by a direct drawing exposure method using a laser such as a blue laser as an actinic ray as described above have been proposed so far (for example, Patent Documents). (See 1 and 2)

JP 2002-296664 A JP 2004-45596 A

  However, in the case of the conventional photosensitive resin composition, when forming a high-density resist pattern by the direct drawing exposure method, it was not yet sufficient in terms of sensitivity and resolution.

  Accordingly, the present invention provides a photosensitive resin composition capable of performing resist pattern formation by a direct drawing exposure method with sufficient sensitivity and resolution, a photosensitive element using the same, a method for forming a resist pattern, and printing It aims at providing the manufacturing method of a wiring board.

ここで、式（１）中のＲは、少なくとも１つがイソプロピル基を示し、ａ、ｂ及びｃの総和は１〜６である。ａ、ｂ及びｃの総和が２〜６のとき、同一分子中の複数のＲはそれぞれ同一であっても異なっていてもよい。 In order to solve the above problems, the present invention contains (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C1) a compound represented by the following general formula (1). A photosensitive resin composition is provided.

Here, at least one R in the formula (1) represents an isopropyl group, and the sum of a, b and c is 1 to 6. When the sum of a, b and c is 2 to 6, a plurality of R in the same molecule may be the same or different.

  The photosensitive resin composition of the present invention can be formed with a sufficient sensitivity and resolution by forming a resist pattern by a direct drawing exposure method by combining the specific components as described above. The present inventors believe that by using a photopolymerization initiator containing a pyrazoline derivative having a specific substituent such as the component (C1), the effects of improving sensitivity and resolution as described above were obtained.

  Moreover, it is preferable that the total of a, b, and c of the compound represented by the said General formula (1) is 1-2 for the photosensitive resin composition of this invention.

  In the photosensitive resin composition of the present invention, the component (A) includes a monomer unit derived from acrylic acid and / or methacrylic acid, and a monomer unit derived from an alkyl ester of acrylic acid and / or an alkyl ester of methacrylic acid. It is preferable that the acrylic polymer which has as a structural unit is included. Thereby, the alkali developability and the peelability of the resist after light irradiation are further improved.

  In the photosensitive resin composition of the present invention, the blending amount of the component (B) is 20 to 80 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B), and the blending amount of the component (C1). Is preferably 0.001 to 5.0 parts by mass.

  The photosensitive resin composition of the present invention preferably further contains (C2) 2,4,5-triarylimidazole dimer or a derivative thereof in addition to the above components. This (C2) component also functions as a photopolymerization initiator in the same manner as the (C1) component. By using both the (C1) component and the (C2) component as a photopolymerization initiator, sensitivity and resolution are further improved. In addition to being enhanced synergistically, adhesion to the substrate is also enhanced.

  The photosensitive resin composition of the present invention is preferably used for forming a resist pattern by exposure to light having a maximum wavelength of 350 nm or more and less than 410 nm. According to the direct drawing exposure method using light having a maximum wavelength of 350 nm or more and less than 410 nm as an actinic ray, a high-density resist pattern can be easily formed. Therefore, the photosensitive resin composition of the present invention is particularly useful for the formation of a resist pattern with such a specific wavelength of light.

  The present invention provides a photosensitive element comprising a support and a photosensitive layer made of the photosensitive resin composition provided on the support. By providing the photosensitive element with the photosensitive layer of the photosensitive resin composition of the present invention, it is possible to form a resist pattern by a direct drawing exposure method with sufficient sensitivity and resolution. Therefore, the photosensitive element of the present invention can be suitably used for production of a printed wiring board having a high-density wiring pattern.

  The present invention includes a photosensitive layer forming step of forming a photosensitive layer comprising the photosensitive resin composition of the present invention on a substrate, an exposure step of exposing a predetermined portion of the photosensitive layer to light having a maximum wavelength of 350 nm or more and less than 410 nm, and exposure And a developing process for forming a resist pattern by developing the exposed photosensitive layer. Moreover, this invention provides the manufacturing method of a printed wiring board provided with the conductor pattern formation process which forms a conductor pattern on the said board | substrate based on the formed resist pattern in addition to the said process.

  According to the method for forming a resist pattern and the method for producing a printed wiring board, a high-density resist pattern or conductor pattern can be formed on a substrate with high productivity by using the photosensitive resin composition of the present invention. it can.

  According to the present invention, a photosensitive resin composition capable of performing resist pattern formation by a direct drawing exposure method with sufficient sensitivity and resolution, a photosensitive element using the same, a resist pattern forming method, and printing A method for manufacturing a wiring board can be provided.

It is a schematic cross section which shows one Embodiment of the photosensitive element by this invention. It is a figure which shows the UV absorption spectrum of the photosensitive layer which concerns on the reference example 1 and Example 1 of this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. In the present specification, “(meth) acrylic acid” means “acrylic acid” and “methacrylic acid” corresponding thereto, and “(meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto. “(Meth) acryloxy group” means “acryloxy group” and its corresponding “methacryloxy group”, and “(meth) acryloyl group” means “acryloyl group” and its corresponding “methacryloyl group”. means.

  The photosensitive resin composition of the present embodiment includes (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C1) a pyrazoline derivative represented by the general formula (1), and It contains.

  The binder polymer of component (A) is not particularly limited as long as it is a polymer that can uniformly dissolve or disperse other components in the resin composition. Examples of the component (A) include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. These may be used alone or in combination of two or more as the component (A). Among these, it is preferable that the acrylic polymer is contained in the component (A) from the viewpoint of excellent alkali developability and excellent peelability of the resist after light irradiation, and the acrylic polymer is acrylic acid and / or It is more preferable to have both monomer units derived from methacrylic acid and monomer units derived from an alkyl ester of acrylic acid and / or an alkyl ester of methacrylic acid as constituent units. Here, the “acrylic polymer” means a polymer mainly having monomer units derived from a polymerizable monomer having a (meth) acryl group.

  The acrylic polymer is produced by radical polymerization of a polymerizable monomer having a (meth) acryl group. Examples of the polymerizable monomer having a (meth) acryl group include acrylamide, acrylonitrile, alkyl (meth) acrylate, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, ( (Meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic Acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, and the like. These may be used alone or in combination of two or more. It can be used as a polymerizable monomer in combination. Of these, (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) acrylate. Hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and structural isomers thereof. These polymerizable monomers can be used individually by 1 type or in combination of 2 or more types.

  In addition to the polymerizable monomer having the (meth) acryl group as described above, the acrylic polymer includes styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, and the like. Polymerizable styrene derivatives, esters of vinyl alcohol such as vinyl-n-butyl ether, maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, silica One or two or more polymerizable monomers such as cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid may be copolymerized.

  The binder polymer preferably has a carboxyl group in order to make the alkali developability particularly excellent. Examples of the binder polymer having a carboxyl group include an acrylic polymer as described above, and a polymer having a polymerizable monomer having a carboxyl group (preferably methacrylic acid) as a monomer unit.

  Here, when the binder polymer has a carboxyl group, the acid value is preferably 30 to 200 mgKOH / g, and more preferably 45 to 150 mgKOH / g. When the acid value is less than 30 mgKOH / g, the development time tends to be long, and when it exceeds 200 mgKOH / g, the developer resistance of the photocured photosensitive layer tends to be lowered after exposure.

  Moreover, it is preferable that a binder polymer contains styrene or a styrene derivative as a monomer unit from the point which can make adhesiveness and peeling characteristics favorable. The binder polymer preferably contains 3 to 30% by mass of styrene or a styrene derivative, more preferably 4 to 28% by mass, and still more preferably 5 to 27% by mass based on the total amount. . If this content is less than 3% by mass, the adhesion tends to be inferior, and if it exceeds 30% by mass, the peel piece tends to be large and the peel time tends to be long. The binder polymer having styrene or a styrene derivative as a monomer unit is, for example, an acrylic polymer as described above, and a styrene or styrene derivative is copolymerized with a polymerizable monomer having a (meth) acryl group. Those are preferred.

  Furthermore, if necessary, the binder polymer may have a photosensitive group such as an ethylenically unsaturated bond.

  The binder polymer preferably has a dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 3.0, and more preferably 1.0 to 2.0. When the degree of dispersion exceeds 3.0, the adhesiveness and resolution tend to decrease. However, the weight average molecular weight and the number average molecular weight in this embodiment are values measured by gel permeation chromatography (GPC) and converted using standard polystyrene as a standard sample.

  The weight average molecular weight of the binder polymer (standard polystyrene conversion value measured by gel permeation chromatography (GPC)) is preferably 5,000 to 300,000, and more preferably 40000 to 150,000. When the weight average molecular weight is less than 5,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long.

  The binder polymer is composed of a single polymer or a combination of two or more polymers. When two or more types of polymers are combined, for example, combinations of two or more types of copolymers having different copolymerization components, two or more types of polymers having different weight average molecular weights, two or more types of polymers having different degrees of dispersion, etc. Can be mentioned. A polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used as a binder polymer.

  The blending ratio of the binder polymer of component (A) in the photosensitive resin composition is preferably 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B) described later, 30 It is more preferable in it being -70 mass parts. When the blending ratio is less than 20 parts by mass, the exposed and cured portion of the photosensitive resin composition layer made of the photosensitive resin composition becomes brittle compared to the case where the blending ratio is within the above range. It tends to be inferior in coating properties when used as a photosensitive element. When the blending ratio exceeds 80 parts by mass, the photosensitivity tends to be insufficient as compared with the case where the blending ratio is within the above range.

  As the photopolymerizable compound having an ethylenically unsaturated bond as the component (B), any compound having at least one ethylenically unsaturated bond may be used, and in particular, a monofunctional compound having one ethylenically unsaturated bond. It is preferable to use as a component (B) a combination of a polymerizable photopolymerizable compound and a polyfunctional photopolymerizable compound having two or more ethylenically unsaturated bonds.

  The ethylenically unsaturated bond of the component (B) is not particularly limited as long as it can be photopolymerized, and examples thereof include an α, β-unsaturated carbonyl group such as a (meth) acrylate group. Examples of the photopolymerizable compound having an α, β-unsaturated carbonyl group as an ethylenically unsaturated bond include α, β-unsaturated carboxylic acid ester of polyhydric alcohol, bisphenol A skeleton-containing (meth) acrylate compound, and glycidyl. Α, β-unsaturated carboxylic acid adducts of group-containing compounds, urethane bond-containing (meth) acrylate compounds, nonylphenoxypolyethyleneoxyacrylate, phthalic acid skeleton-containing (meth) acrylate compounds, (meth) acrylic acid alkyl esters, etc. It is done. These may be used alone or in combination of two or more. Among these, from the viewpoint of plating resistance and adhesion, a bisphenol A skeleton-containing (meth) acrylate compound and a urethane bond-containing (meth) acrylate compound are preferable, and a bisphenol A skeleton-containing (meth) acrylate compound is particularly preferable.

  Examples of the α, β-unsaturated carboxylic acid ester of a polyhydric alcohol include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and polypropylene glycol di (2 to 14) propylene groups ( (Meth) acrylate, polyethylene / polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, Tet Examples include lamethylol methane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more. In the above compound names, “EO modification” means having an ethylene oxide group block structure, and “PO modification” means having a propylene oxide group block structure. .

  The bisphenol A skeleton-containing (meth) acrylate compound contains a bisphenol skeleton (a structure obtained by removing a hydrogen atom from two phenolic hydroxyl groups of bisphenol A) and has at least one of a methacrylate group and an acrylate group. If there is no particular limitation. Specifically, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane and the like.

  2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane preferably has 4 to 20 ethylene oxide groups, and more preferably 8 to 15 ethylene oxide groups. Specifically, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-(( (Meth) acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl ) Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonato) C) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like.

  Among the above compounds, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as “BPE-500” (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). . 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as “BPE-1300” (manufactured by Shin-Nakamura Chemical Co., Ltd., product name).

  The number of ethylene oxide groups in one molecule of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane is preferably 4-20, and more preferably 8-15. . These are used alone or in combination of two or more.

  Examples of urethane bond-containing (meth) acrylate compounds include (meth) acrylic monomers having an OH group at the β-position and diisocyanate compounds (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6- Addition reaction products with hexamethylene diisocyanate, etc., tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, etc. . Examples of commercially available EO-modified urethane di (meth) acrylates include “UA-11” (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Moreover, as a commercial item of EO and PO modified urethane di (meth) acrylate, for example, “UA-13” (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) may be mentioned. These can be used alone or in combination of two or more.

  Nonylphenoxypolyethyleneoxyacrylate includes, for example, nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, nonylphenoxynonaethyleneoxy Examples include acrylate, nonylphenoxydecaethyleneoxyacrylate and nonylphenoxyundecaethyleneoxyacrylate. These can be used alone or in combination of two or more.

  As the phthalic acid skeleton-containing (meth) acrylate compound, a compound containing a phthalic acid skeleton (a structure obtained by removing a hydrogen atom from two carboxyl groups of phthalic acid) and having at least one of a methacrylate group and an acrylate group If there is no restriction in particular. Specific examples thereof include, for example, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloloxyalkyl-o-phthalate. Etc.

  The blending ratio of the photopolymerizable compound having an ethylenically unsaturated bond as the component (B) is 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). Preferably, it is 30-70 mass parts. When the blending ratio is less than 20 parts by mass, the photosensitivity tends to be insufficient as compared with the case where the blending ratio is within the above range. When the blending ratio exceeds 80 parts by mass, the blending ratio is Compared with the case where it is within the above range, the photocured portion tends to become brittle.

  The pyrazoline derivative as the component (C1) is not particularly limited as long as it is represented by the general formula (1). In general formula (1), there is no particular limitation as long as at least one of R is an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and the substituent may be linear. It may be branched.

  Moreover, from a viewpoint of improving the solubility to a solvent and a sensitivity, it is that in general formula (1), at least 1 is a C1-C10 alkoxy group or a C1-C3 alkyl group among R. A methoxy group or an isopropyl group is particularly preferable.

  Furthermore, as (C1) component of this invention, it is preferable that the sum total of a, b, and c in General formula (1) is 1-6, It is more preferable that it is 1-4, 1 or 2 It is particularly preferred.

  Specific examples of the (C1) component pyrazoline derivative include 1- (4-methoxyphenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4- Methoxyphenyl) -pyrazoline, 1,5-bis- (4-methoxyphenyl) -3- (4-methoxystyryl) -pyrazoline, 1- (4-isopropylphenyl) -3-styryl-5-phenyl-pyrazoline, 1 -Phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline, 1,5-bis- (4-isopropylphenyl) -3- (4-isopropylstyryl) -pyrazoline, 1- ( 4-methoxyphenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, -(4-tert-butyl-phenyl) -3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1- (4-isopropyl-phenyl) -3- (4-tert-butyl- Styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-isopropyl-styryl) -5- (4-isopropyl-phenyl) -pyrazoline 1- (4-methoxyphenyl) -3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline, 1- (4-isopropylphenyl) -3- (4-methoxystyryl) -5 -(4-Methoxyphenyl) -pyrazoline, 1-phenyl-3- (3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) Pyrazoline, 1-phenyl-3- (3,4-dimethoxystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,6-dimethoxystyryl) -5- (2, 6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,3-dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,4-dimethoxystyryl) -5- (2,4-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (3,4-dimetho Xystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (2,6-dimethoxystyryl) -5- (2,6-dimethoxyphenyl) -pyrazoline, 1 -(4-Methoxyphenyl) -3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (2,3-dimethoxystyryl) ) -5- (2,3-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (2,4-dimethoxystyryl) -5- (2,4-dimethoxyphenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pyrazoline, 1- (4-tert-butyl) Ru-phenyl) -3- (3,4-dimethoxystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (2,6-dimethoxystyryl) ) -5- (2,6-dimethoxyphenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxyphenyl) -pyrazoline 1- (4-tert-butyl-phenyl) -3- (2,3-dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3 -(2,4-dimethoxystyryl) -5- (2,4-dimethoxyphenyl) -pyrazoline, 1- (4-isopropyl-phenyl) -3- (3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pyrazoline, 1- (4-isopropyl-phenyl) -3- (3,4-dimethoxystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1- (4-Isopropyl-phenyl) -3- (2,6-dimethoxystyryl) -5- (2,6-dimethoxyphenyl) -pyrazoline, 1- (4-Isopropyl-phenyl) -3- (2,5-dimethoxy) Styryl) -5- (2,5-dimethoxyphenyl) -pyrazoline, 1- (4-isopropyl-phenyl) -3- (2,3-dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazoline, 1- (4-isopropyl-phenyl) -3- (2,4-dimethoxystyryl) -5- (2,4-dimethoxyphenyl) -pyrazoline, etc. . (C1) A component is used individually by 1 type or in combination of 2 or more types.

  Among the above components (C1), 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline is particularly preferable from the viewpoint of improving the ease of synthesis and sensitivity, and easy synthesis. From the viewpoint of improving the thickness and solubility, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline is particularly preferable.

  The pyrazoline derivative of the component (C1) according to the present invention can be synthesized by a known method. This pyrazoline derivative can be obtained, for example, by the synthesis method described in Japanese Patent No. 2931893 or a synthesis method based thereon. For example, first, a specific benzaldehyde and acetone or a specific acetophenone compound are condensed by a known condensation method, for example, in the presence of a basic substance in a water-alcohol mixed solvent. Alternatively, a specific benzaldehyde compound and a specific acetophenone compound are condensed in an organic solvent in the presence of a basic catalyst such as piperidine. Next, the chalcone compound obtained by the condensation and the specific hydrazine compound are condensed by a known method, for example, by reacting in acetic acid or alcohol, the pyrazoline derivative according to the present invention can be obtained.

  Commercially available products include 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline (manufactured by Nippon Chemical Industry Co., Ltd.), 1-phenyl-3- (4- And isopropylstyryl) -5- (4-isopropylphenyl) pyrazoline (manufactured by Nippon Chemical Industry Co., Ltd.).

  The compounding ratio of the compound represented by the general formula (1) as the component (C1) is 0.001 to 5.0 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is preferable that it is 0.05-3.0 mass parts, and it is still more preferable that it is 0.01-2.0 mass parts. When the blending ratio is out of the above range, it tends to be difficult to make both the photosensitivity and the resolution sufficient as compared with the case where the blending ratio is within the above range.

  As one of the main factors by which the photosensitive resin composition of the present embodiment can achieve sufficiently high sensitivity and resolution in the direct drawing exposure method, the present inventors have changed the pyrazoline derivative (C1) as another component. I think it can be mentioned that they are used together.

  The photosensitive resin composition of the present embodiment is a 2,4,5-triarylimidazole dimer of component (C2) in addition to component (C1) as a photopolymerization initiator in terms of adhesion and sensitivity. Or it is more preferable to contain the derivative further. By using the component (C2), the effects of high sensitivity and high resolution can be obtained.

  Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxy). Phenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- (Methoxyphenyl) -4,5-diphenylimidazole dimer and the like can be mentioned, and these can be used alone or in combination of two or more as the component (C2).

  The blending ratio of 2,4,5-triarylimidazole dimer or its derivative as component (C2) is 0.1-20 with respect to 100 parts by mass of the total amount of component (A) and component (B). It is preferable in it being a mass part, it is more preferable in it being 0.5-10 mass parts, and it is especially preferable in it being 1-5 mass parts. If the blending ratio is less than 0.1 parts by mass, the above effect due to the blending of the component (C2) tends to be insufficient, and if it exceeds 20 parts by mass, the effects exhibited by the other components are achieved. It tends to be disturbed.

  In addition to the components (C1) and (C2), a coumarin derivative, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl- N, N′-tetraalkyl-4,4′-diaminobenzophenone such as 4,4′-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- Aromatic ketones such as methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, quinones such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin , Benzyl derivatives such as benzyldimethyl ketal, 9-phenyla Photopolymerization initiators such as lysine, acridine derivatives such as 1,7-bis (9,9′-acridinyl) heptane, N-phenylglycine and N-phenylglycine derivatives may be further added to the photosensitive resin composition. .

  It is preferable that the photosensitive resin composition of this embodiment further contains leuco crystal violet in addition to the above-described components. Thereby, the photosensitive resin composition of the present embodiment can improve the photosensitivity and resolution in a more balanced manner. Leuco Crystal Violet has a property as a photochromic agent that absorbs light and develops a specific color, and it is considered that the above-described effects are exhibited due to the property.

  From the viewpoint of more effectively achieving this effect, the blending ratio of leuco crystal violet in the photosensitive resin composition of the present embodiment is 0.01 with respect to 100 parts by mass of the total amount of the component (A) and the component (B). -10 parts by mass, more preferably 0.05-5 parts by mass.

  In addition to the components described above, the photosensitive resin composition of the present embodiment includes a dye such as malachite green, a photochromic agent other than tribromophenyl sulfone, leuco crystal violet, and thermal coloring prevention, as necessary. Agents, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking You may contain about 0.01-20 mass parts of other additives, such as an agent, with respect to 100 mass parts of total amounts of (A) component and (B) component, respectively.

  The photosensitive resin composition of the present embodiment is preferably used for forming a resist pattern by exposure to light having a maximum wavelength of 350 nm or more and less than 410 nm (more preferably 335 to 365 nm or 405 nm).

  The light having a maximum wavelength of 350 nm or more and less than 410 nm may be a known light source such as a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp, an ultraviolet ray or visible light such as an Ar ion laser and a semiconductor laser. Those that radiate effectively are listed.

  Examples of a light source that is effectively used in the direct drawing method described later include an argon gas laser that oscillates 364 nm light, a solid-state UV laser that oscillates 355 nm light, and a gallium nitride blue laser that oscillates 405 nm light. . Among them, a gallium nitride blue laser is preferably used from the viewpoint of forming a resist pattern more easily. A digital direct exposure machine such as “DE-1AH” (trade name) manufactured by Hitachi Via Mechanics may also be used.

  The photosensitive resin composition as described above is coated on a metal surface such as copper, copper-based alloy, iron, iron-based alloy, etc. as a liquid resist, dried, and then covered with a protective film as necessary. Or used for photolithography in the form of a photosensitive element as described below.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present embodiment. The photosensitive element 1 shown in FIG. 1 includes a support 10 and a photosensitive layer 14 provided on the support 10. The photosensitive layer 14 consists of the photosensitive resin composition of this embodiment mentioned above.

  The thickness of the photosensitive layer 14 is not particularly limited, but is preferably about 1 to 100 μm. Further, the surface F1 opposite to the support 10 on the photosensitive layer 14 may be covered with a protective film. Examples of the protective film include films of polyethylene, polypropylene, and the like, and those having an adhesive force with the photosensitive layer 14 smaller than an adhesive force between the support 10 and the photosensitive layer 14 are preferable. The film is preferred.

  As the support 10, a film of polyethylene terephthalate, polypropylene, polyethylene, polyester or the like can be suitably used, and the thickness is preferably 1 to 100 μm.

  The photosensitive element 1 is further provided with an intermediate layer and a protective layer such as a cushion layer, an adhesive layer, a light absorbing layer, and a gas barrier layer in addition to the support 10, the photosensitive layer 14 and the protective film as described above. May be.

  The photosensitive element 1 can be obtained, for example, by applying a photosensitive resin composition on a support 10 and then drying to form a photosensitive layer 14. The coating can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater. Moreover, drying can be performed at 70-150 degreeC and about 5 to 30 minutes.

  When the photosensitive resin composition is applied onto the support 10, a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether is used as necessary. Or it is preferable to apply | coat the solution about 30-60 mass% of solid content which melt | dissolved the photosensitive resin composition in these mixed solvents. However, in this case, the amount of the remaining organic solvent in the photosensitive layer after drying is preferably 2% by mass or less in order to prevent the organic solvent from diffusing in the subsequent step.

  The obtained photosensitive element 1 is stored as it is or after further laminating the protective film on the photosensitive layer 14, and then wound around a cylindrical core. In addition, when winding up, it is preferable to wind up so that the support body 10 may become an outer side. As the winding core, those made of plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin acrylonitrile-butadiene-styrene copolymer) can be suitably used.

  It is preferable to install an end face separator on the end face of the photosensitive element roll wound up into a roll shape for protecting the end face, and it is preferable to install a moisture-proof end face separator from the viewpoint of edge fusion resistance. Moreover, it is preferable that the photosensitive element wound up in roll shape is wrapped and packed in a black sheet with low moisture permeability.

  The resist pattern forming method of the present embodiment includes a photosensitive layer forming step of forming a photosensitive layer comprising the photosensitive resin composition of the present embodiment on a substrate, and a predetermined portion of the photosensitive layer having a maximum wavelength of 350 nm or more and less than 410 nm. An exposure step for exposing to light and a development step for developing the exposed photosensitive layer to form a resist pattern.

  In the photosensitive layer forming step, the photosensitive element of the present embodiment can be suitably used. When the photosensitive element is used, when the photosensitive element has a protective film, the protective film is removed, and then the photosensitive layer is heated to about 70 to 130 ° C., under reduced pressure or normal pressure, and 0.1 to 1 MPa on the substrate. A photosensitive layer is formed on the substrate by pressing and laminating at a pressure of about 1 to 10 kgf / cm 2. As the substrate, for example, a copper clad laminate in which a copper foil is provided on one side or both sides of a layer made of an insulating material such as glass fiber reinforced epoxy resin is preferably used.

  In the exposure step, light (active light) is irradiated to a predetermined portion corresponding to a desired resist pattern in the photosensitive layer laminated on the substrate. The exposure can be performed by a mask exposure method performed through a mask pattern or a direct drawing exposure method such as a laser direct drawing exposure method and a DLP exposure method, but the direct drawing exposure method is preferable from the viewpoint of resolution and the like. As the active light source, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, an Ar ion laser, a semiconductor laser, or the like that effectively emits ultraviolet light, visible light, or the like is used. It is done.

  In this embodiment, the direct drawing method is preferably used from the viewpoint of high sensitivity and high resolution. Examples of the light source used in the direct drawing method include an argon gas laser that oscillates light of 364 nm, a solid-state UV laser that oscillates light of 355 nm, and a gallium nitride blue laser that oscillates light of 405 nm. Among them, a gallium nitride blue laser is preferably used from the viewpoint of forming a resist pattern more easily. A digital direct exposure machine such as “DE-1AH” (trade name) manufactured by Hitachi Via Mechanics may also be used.

  As the light, light from a light source that emits actinic rays having a maximum wavelength of 350 nm or more and less than 440 nm is used, or light adjusted so that the maximum wavelength is within the above range by spectroscopy using a filter or the like. Other details of the light source are the same as those described above in the description of the photosensitive resin composition.

  After exposure, if there is a support on the photosensitive layer, it is removed, and then the unexposed area is removed by wet development with a developing solution such as an alkaline aqueous solution, aqueous developer and organic solvent, or dry development. Development is performed to form a resist pattern. Although the development method is not particularly limited, for example, development can be performed by a method such as a dip method, a spray method, brushing, or slapping.

  As alkaline aqueous solution used for image development, 0.1-5 mass% sodium carbonate aqueous solution, 0.1-5 mass% potassium carbonate aqueous solution, 0.1-5 mass% sodium hydroxide aqueous solution etc. are mentioned, for example. Further, the pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature may be appropriately adjusted according to the solubility of the photosensitive layer. A surface active agent, an antifoaming agent, an organic solvent, and the like may be further added to the alkaline aqueous solution. After the development step, before forming the conductor pattern, the resin forming the resist pattern is further cured by heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm 2 as necessary. May be.

  In the printed wiring board manufacturing method of this embodiment, a printed wiring board is manufactured through a conductor pattern forming step of forming a conductor pattern on the substrate based on the resist pattern formed as described above. The conductive pattern is formed by treating the exposed copper foil portion without being masked with a developed resist pattern as a mask by a known method such as etching or plating. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating. Etching can be performed using, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or the like. By adopting these methods, a conductor layer can be selectively formed on a groove portion (exposed portion of the substrate) in the resist pattern, thereby forming a conductor pattern. Alternatively, conversely, a conductor layer may be selectively formed in a portion protected by a resin layer remaining after development.

  After the treatment by etching or plating, a predetermined conductor pattern was formed through a step of peeling the photosensitive layer forming the resist pattern using, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. A printed wiring board is obtained. As the strong alkaline aqueous solution, for example, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used. Examples of the method for peeling the photosensitive layer include an immersion method and a spray method.

  By adopting the manufacturing method as described above, a printed wiring board such as a multilayer printed wiring board having a small diameter through hole can be suitably manufactured.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
<Preparation of photosensitive resin composition solution>

  Each raw material shown in Table 1, (C1) component shown in Table 2, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline shown in Table 3 ( Table 3 shows “PYR-B”) and N, N′-tetraethyl-4,4′-diaminobenzophenone (shown as “EAB” in Table 3) uniformly in the amounts shown in each table. The solutions of the photosensitive resin compositions of Reference Examples 1 to 3, Examples 1 to 3, Comparative Examples 1 to 2 and Reference Example 4 were prepared. As the component (C1), 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline (shown as “PYR-M” in Table 2) and 1-phenyl-3 -(4-Isopropylstyryl) -5- (4-isopropylphenyl) pyrazoline (shown as "PYR-I" in Table 2) was used.

  From the viewpoint of improving both sensitivity and resolution in a balanced manner, it is preferable that the solubility of PYR-M, PYR-I, and PYR-B in the solvent is higher. Moreover, when solubility is high, preparation of the photosensitive resin composition solution will become easy, and it is excellent in the workability | operativity. Their solubility in 100 mL of toluene solvent at 23 ° C. is as shown in Table 4.

＜感光性エレメント＞

<Photosensitive element>

  The solutions of the photosensitive resin compositions of Reference Examples 1 to 3, Examples 1 to 3, Comparative Examples 1 to 2 and Reference Example 4 prepared as described above were uniformly applied on a 16 μm thick polyethylene terephthalate film, Photosensitivity in which a photosensitive layer comprising the above photosensitive resin composition is provided on one side of a polyethylene terephthalate film as a support by drying at 70 ° C. for 10 minutes and at 100 ° C. for 10 minutes using a hot air convection dryer. Got the element. The film thickness of the photosensitive layer was 25 μm.

The optical density (OD value) with respect to the exposure wavelength of the photosensitive layer was measured using a UV spectrophotometer (U-3310 spectrophotometer manufactured by Hitachi, Ltd.). The measurement is carried out by continuous measurement from 550 to 300 nm in the absorbance mode, using the same type of polyethylene terephthalate film as that used as the support as a reference, to obtain a UV absorption spectrum, and the absorbance values at 365 nm and 405 nm, O. at wavelength. D. Value. The UV absorption spectrum is shown in FIG. a1 is a UV absorption spectrum according to Reference Example 1, a2 is a UV absorption spectrum according to Example 1, and a3 is a UV absorption spectrum according to Reference Example 4. In FIG. 2, the spectra of a2 and a3 in the range of about 340 to 420 nm almost overlapped. The absorbances of Example 1 and Reference Example 4 were 0.48 and 0.44, respectively, when irradiated with 365 nm light, and 0.49 and 0.45, respectively, when irradiated with 405 nm light.
<Formation of resist pattern>

  The copper surface of a double-sided copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., “MCL-E-67” (product name)) in which copper foil (thickness 35 μm) is laminated on both sides of a glass fiber reinforced epoxy resin layer, Polishing was performed using a polishing machine (manufactured by Sankei Co., Ltd.) equipped with a brush equivalent to # 600, washed with water, and then dried with an air flow. Next, while heating the double-sided copper-clad laminate to 80 ° C., the photosensitive element obtained above was bonded so that the photosensitive layer side was in close contact with the copper foil surface and heated to 120 ° C. at 0.4 MPa. After pressurization, the laminate was cooled to 23 ° C. to obtain a laminate having a photosensitive layer provided on both sides of a double-sided copper-clad laminate.

  Subsequently, on the surface of the polyethylene terephthalate film located on the outermost layer of the laminate, each step (with a concentration region of 0.00 to 2.00, a concentration step of 0.05, and a tablet (rectangular) size of 20 mm × 187 mm) A photo tool having a 41-step tablet with a size of 3 mm × 12 mm and a photo having a wiring pattern with a line width / space width of 6/6 to 35/35 (unit: μm) as a negative for resolution evaluation Tools were stacked in order, and a spectral filter “HG0405” (product name) manufactured by Asahi Spectroscopy Co., Ltd., which is a hand-pass filter that splits light having a wavelength of 405 nm ± 30 nm, was placed thereon.

  In this state, using a parallel light exposure machine (“EXM-1201” (product name) manufactured by Oak Manufacturing Co., Ltd.) using a 5 kW short arc lamp as a light source, the number of remaining step stages after development of the 41-step tablet is 14, Exposure was performed with exposure amounts of 17 and 20 steps. At this time, the exposure amount at which the number of remaining step steps after development of the 41-step step tablet was 17 steps was defined as sensitivity. The illuminance of the light transmitted through the bandpass filter is determined by measuring the UV integrated light meter ("UIT-150-A" (product name), manufactured by Ushio Electric Co., Ltd., can also be used as an illuminometer) and "UVD" -S405 "(sensitivity wavelength range: 320 nm to 470 nm, absolute calibration wavelength: 405 nm), and the illuminance x exposure time was taken as the exposure amount.

  Next, the polyethylene terephthalate film was removed, and the exposed photosensitive layer was sprayed with a 1.0% by weight aqueous sodium carbonate solution at 30 ° C. for 24 seconds to remove unexposed portions, and development processing was performed. The minimum value of the space width between the line widths, in which the unexposed portions can be removed cleanly and the lines are generated without meandering or chipping, is defined as the resolution. Both the resolution and the sensitivity value are better as the numerical value is smaller.

  The results of the above evaluations performed on the photosensitive resin compositions of Reference Examples 1 to 3, Examples 1 to 3, Comparative Examples 1 to 2, and Reference Example 4 are summarized in Tables 2 and 3.

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 14 ... Photosensitive layer.

Claims (9)

(A) a binder polymer;
(B) a photopolymerizable compound having an ethylenically unsaturated bond;
(C1) a compound represented by the following general formula (1);
Containing a photosensitive resin composition.

[At least one R in the formula (1) represents an isopropyl group, and the sum of a, b and c is 1 to 6. When the sum of a, b and c is 2 to 6, a plurality of R in the same molecule may be the same or different. ]   The photosensitive resin composition of Claim 1 whose sum total of the said a, b, and c is 1-2.   The acrylic polymer in which the component (A) has a monomer unit derived from acrylic acid and / or methacrylic acid and a monomer unit derived from an alkyl ester of acrylic acid and / or an alkyl ester of methacrylic acid as constituent units. The photosensitive resin composition of Claim 1 or 2 containing this.   The blending amount of the component (B) is 20 to 80 parts by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B), and the blending amount of the component (C1) is 0.001 to 0.001. The photosensitive resin composition as described in any one of Claims 1-3 which is 5.0 mass parts.   (C2) The photosensitive resin composition as described in any one of Claims 1-4 which further contains a 2,4,5-triaryl imidazole dimer or its derivative (s) as a component.   The photosensitive resin composition as described in any one of Claims 1-5 used in order to expose to the light whose maximum wavelength is 350 nm or more and less than 410 nm, and to form a resist pattern.   A photosensitive element provided with a support body and the photosensitive layer which consists of the photosensitive resin composition as described in any one of Claims 1-6 provided on the said support body. A photosensitive layer forming step of forming a photosensitive layer comprising the photosensitive resin composition according to any one of claims 1 to 6 on a substrate;
An exposure step of exposing a predetermined portion of the photosensitive layer to light having a maximum wavelength of 350 nm or more and less than 410 nm;
A development step of developing the exposed photosensitive layer to form a resist pattern. A photosensitive layer forming step of forming a photosensitive layer comprising the photosensitive resin composition according to any one of claims 1 to 6 on a substrate;
An exposure step of exposing a predetermined portion of the photosensitive layer to light having a maximum wavelength of 350 nm or more and less than 410 nm;
A development step of developing the exposed photosensitive layer to form a resist pattern;
And a conductor pattern forming step of forming a conductor pattern on the substrate based on the resist pattern.

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