JPWO2007034610A1 - Photosensitive resin composition, photosensitive element, resist pattern forming method, printed wiring board manufacturing method, and plasma display partition forming method - Google Patents

Abstract

The photosensitive resin composition comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) An amine compound represented by the formula (1) and (E) a sensitizing dye are included. In the general formula (1), R1 to R4 each independently represents an alkyl group having 1 to 6 carbon atoms.

Description

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

  In the field of manufacturing printed wiring boards, as a resist material used for etching and plating, a photosensitive resin composition and a layer made of this photosensitive resin composition (hereinafter referred to as “photosensitive resin composition layer”) are used. A photosensitive element (laminate) formed on a support film and having a structure in which a protective film is disposed on a photosensitive resin composition layer is widely used (see, for example, Patent Document 1).

  The printed wiring board is manufactured by the following procedure, for example, using the photosensitive element. That is, first, the photosensitive resin composition layer of the photosensitive element is laminated on a circuit forming substrate such as a copper-clad laminate. At this time, the surface opposite to the surface of the photosensitive resin composition layer in contact with the support film (hereinafter referred to as the “lower surface” of the photosensitive resin composition layer) (hereinafter referred to as the “upper surface of the photosensitive resin composition layer”). ") In close contact with the surface of the circuit forming substrate on which the circuit is to be formed. Therefore, when the protective film is arrange | positioned on the upper surface of the photosensitive resin composition layer, this lamination operation is performed while peeling off the protective film. Next, the photosensitive resin composition layer is thermocompression bonded to the underlying circuit forming substrate (normal pressure laminating method).

  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 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 treatment 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, the plating process is a method in which a metal surface not covered with a hardened resist formed after development is subjected to a plating process such as copper and solder and then the resist is removed and the metal surface covered with the resist is etched. .

  On the other hand, in the field of flat panel display (FDP), the plasma display panel (PDP) has advantages such as being capable of displaying at a higher speed than a liquid crystal panel and being easy to enlarge. It is used as a display device such as OA equipment and public information display device. Recently, progress in PDP is also expected in the field of high-definition television.

  In a PDP, plasma discharge is generated between electrodes in a discharge space provided between a front glass substrate and a back glass substrate, and ultraviolet rays generated from a gas sealed in the discharge space are converted into phosphors in the discharge space. The display is performed by hitting to. The discharge space is usually secured by a partition formed on the back glass substrate. The barrier ribs have a width of about 20 to 80 μm and a height of about 60 to 200 μm in order to suppress the spread of the discharge in the discharge space to a certain region and perform display in a prescribed cell, and at the same time to secure a uniform discharge space. It has the shape of

  As a method for forming the partition wall, a sand blast method, a screen printing method, a photosensitive paste method, a photo embedding method, a mold transfer method and the like are mainly known. In some of these methods, photosensitive elements are utilized. For example, in the sandblast method, a photosensitive element is used to form a resist pattern. In the photo embedding method, a photosensitive element is used to create a resin pattern for forming a groove for embedding.

  By the way, for the pattern exposure of the photosensitive resin composition layer, conventionally, a method of exposing via a photomask using a mercury lamp as a light source has been used, but recently, as a new exposure technique, DLP (Digital Light Processing) directly. A drawing method has been proposed (see, for example, Non-Patent Document 1). This direct drawing method is expected as a method suitable for small-volume, multi-product use, large-scale board production, short delivery time, etc. in that it does not require a photomask because the pattern digital data is drawn directly on the photosensitive resin composition layer. Yes.

JP 11-327137 A Electronics Packaging Technology June 2002 p. 74-79

  However, the conventional photosensitive element using the photosensitive resin composition has a low throughput due to insufficient sensitivity in the direct drawing method, and has sufficient resolution and good resist while ensuring high productivity for the following reasons. The shape could not be obtained.

  For example, in order to improve the sensitivity of the photosensitive resin composition layer, a method of adding a color former such as leuco crystal violet is known, but according to the study by the present inventors, the amount of leuco crystal violet added is increased. It has been found that if the amount is increased and the sensitivity in the direct drawing method is sufficiently secured, the resolution decreases. For this reason, it has been difficult to sufficiently shorten the exposure time.

  The present invention has been made in view of the above problems, and a photosensitive resin composition capable of forming a resist pattern by a direct drawing method with sufficient sensitivity and resolution, and photosensitivity using the same. It is an object of the present invention to provide an element, a resist pattern forming method, a printed wiring board manufacturing method, and a plasma display partition forming method.

  As a result of intensive studies, the present inventors have found that a photosensitive resin composition comprising a specific composition containing a specific amine compound is sufficiently sensitive to the wavelength of light used in the direct drawing method. The present inventors have found that a resist pattern having a good resist shape can be formed with high resolution, and the present invention has been completed.

一般式（１）中、Ｒ^１〜Ｒ^４はそれぞれ独立に、炭素数１〜６個のアルキル基を示す。The photosensitive resin composition of the present invention comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D ) It contains an amine compound represented by the following general formula (1) and (E) a sensitizing dye.

In general formula (1), R < ¹ > -R < ⁴ > shows a C1-C6 alkyl group each independently.

  According to the photosensitive resin composition of the present invention, it becomes possible to form a resist pattern by a direct drawing method with sufficient sensitivity and resolution. As a result, the exposure time can be sufficiently shortened, and even a small amount of various types of printed wiring boards or large printed wiring boards can be manufactured with high productivity. In addition, according to the photosensitive resin composition of the present invention, it is possible to form a resist pattern and a resin pattern for forming a partition wall of a plasma display at a high speed and with a sufficient resolution, thereby improving the productivity of the PDP. it can.

  By the way, when the amount of color former such as leuco crystal violet is increased in the conventional photosensitive resin composition, one of the factors that lowers the resolution is that the solubility of the color former is low, so that the photosensitive resin composition layer is removed from the coating solution. The present inventors consider that this is because foreign matters are deposited when forming the film. Then, due to the occurrence of this foreign matter, the adhesion of the cured resist is reduced, or residues are deposited on the unexposed areas that should be dissolved by development, making it difficult to form a high-resolution resist pattern. It is assumed that On the other hand, the photosensitive resin composition of the present invention is a foreign substance even when the photosensitive resin composition layer is formed from the coating liquid because the amine compound is sufficiently excellent in solubility in a solvent. It is possible to increase the compounding amount of the amine compound while sufficiently suppressing the precipitation of. For these reasons as well, it is considered that the formation of the resist pattern by the direct drawing method has been achieved with sufficient sensitivity and resolution by the photosensitive resin composition of the present invention.

  In the photosensitive resin composition of the present invention, the (C) photopolymerization initiator is preferably a hexaarylbiimidazole derivative. By combining such a photopolymerization initiator and the amine compound, sensitivity and resolution can be achieved at a higher level.

  Moreover, it is preferable that the photosensitive resin composition of this invention is used in order to form a resist pattern by exposing to the light which has a peak in the wavelength range of 350 nm or more and less than 440 nm. According to the direct drawing exposure method using light having a peak within a wavelength range of 350 nm or more and less than 440 nm as an actinic ray, a high-density resist pattern can be easily formed. The resin composition is particularly useful for forming a resist pattern with light having such a specific wavelength. Here, “having a peak” means that the intensity of light shows a maximum value within a predetermined wavelength range.

  The present invention provides a photosensitive element comprising a support film and a photosensitive resin composition layer made of the photosensitive resin composition of the present invention formed on the support film. By providing the photosensitive resin composition of the present invention as a photosensitive layer, this photosensitive element can form a resist pattern by a direct drawing method with sufficient sensitivity and resolution, and has a high-density wiring pattern. It can use suitably for manufacture of the printed wiring board which has this. And according to the photosensitive element of this invention, even if it is a small quantity many kinds printed wiring board, a large sized printed wiring board, etc., it becomes possible to manufacture with high productivity. Further, according to the photosensitive element of the present invention, the resist pattern and the resin pattern for forming the partition of the plasma display can be formed at a high speed and with sufficient resolution, so that the productivity of the PDP can be improved.

  In the present invention, a photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention is laminated on a circuit forming substrate, and exposure is performed by irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray. A method of forming a resist pattern is provided in which a portion is photocured and then a portion other than the exposed portion is removed.

  In the present invention, a photosensitive resin composition layer of the photosensitive element of the present invention is laminated on a circuit forming substrate, and a predetermined portion of the photosensitive resin composition layer is irradiated with actinic rays to illuminate an exposed portion. There is provided a method for forming a resist pattern which is cured and then removed except for the exposed portion.

  This invention provides the manufacturing method of the printed wiring board which etches or plates the board | substrate for circuit formation in which the resist pattern was formed by the formation method of the resist pattern of the said invention.

  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.

  In the present invention, a photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention is laminated on a partition wall material layer provided on a plasma display substrate, and the photosensitive resin composition layer A step of irradiating a predetermined portion with actinic rays to photocure the exposed portion, and then removing a portion other than the exposed portion to form a resist pattern, and a step of etching the partition material layer on which the resist pattern is formed A method for forming a partition wall of a plasma display is provided.

  In the present invention, the photosensitive resin composition layer of the photosensitive element of the present invention is laminated on the partition wall material layer provided on the plasma display substrate, and a predetermined portion of the photosensitive resin composition layer is formed. Irradiating actinic rays to photocuring the exposed portion, and then removing the portions other than the exposed portion to form a resist pattern and etching the partition wall material layer on which the resist pattern is formed. The present invention provides a method for forming a partition wall of a plasma display.

  According to the method for forming a partition of a plasma display of the present invention, a resist pattern can be formed on the partition material layer at high speed and with sufficient resolution by using the photosensitive resin composition or photosensitive element of the present invention. Therefore, a partition having a good shape with high productivity can be formed. Thereby, the productivity of PDP can be improved.

  In addition, according to the method for forming a partition of a plasma display of the present invention, the productivity of a color PDP having a fine and many display cells can be improved, and the production cost of a high-definition television PDP can be reduced more effectively. It becomes feasible.

  According to the present invention, a photosensitive resin composition capable of forming a resist pattern by a direct drawing method with sufficient sensitivity and resolution, a photosensitive element using the same, a method for forming a resist pattern, and a printed wiring board And a method for forming a partition of a plasma display. Therefore, according to the printed wiring board manufacturing method of the present invention, it is possible to manufacture even a small quantity of various types of printed wiring boards or large printed wiring boards with high productivity. In addition, according to the method for forming a partition of a plasma display of the present invention, a partition having a good shape can be formed on a substrate with high productivity, and the productivity of PDP can be improved.

It is a schematic cross section which shows one Embodiment of the photosensitive element of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support film, 14 ... Photosensitive resin composition layer.

  Hereinafter, embodiments of the present invention will be described in detail. In the present invention, “(meth) acrylic acid” means “acrylic acid” or “methacrylic acid”, “(meth) acrylate” means “acrylate” or “methacrylate” corresponding thereto, The “(meth) acryloyl group” means “acryloyl group” or “methacryloyl group”.

上記式（１）中、Ｒ^１〜Ｒ^４はそれぞれ独立に、炭素数１〜６個のアルキル基を示す。(Photosensitive resin composition)
The photosensitive resin composition of the present invention comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D ) It contains an amine compound represented by the following general formula (1) and (E) a sensitizing dye.

In said formula (1), R < ¹ > -R < ⁴ > shows a C1-C6 alkyl group each independently.

  Examples of the (A) component binder polymer include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. From the viewpoint of alkali developability, an acrylic resin is preferable. These can be used alone or in combination of two or more.

  The (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, vinyltoluene, and α-methylstyrene as a copolymer component. Other components include acrylamide such as diacetone acrylamide, esters of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether, alkyl (meth) acrylate, tetrahydrofurfuryl ester (meth) acrylate, dimethyl (meth) acrylate Aminoethyl 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, maleic acid, maleic anhydride , Monomethyl maleate, Ynoic acid monoethyl maleate monoesters such as maleic acid monoisopropyl, fumaric acid, cinnamic acid, alpha-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid. These may be used alone or in any combination of two or more.

As said (meth) acrylic-acid alkylester, the compound etc. which the hydroxyl group, the epoxy group, the halogen group, etc. substituted the compound represented by following General formula (2) and the alkyl group of these compounds etc. are mentioned, for example.
^{_{CH 2 = C (R 5)}} -COOR 6 ... (2)
In the general formula (2), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 1 to 12 carbon atoms.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁶ in the general formula (2) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Nonyl group, decyl group, undecyl group, dodecyl group and structural isomers thereof can be mentioned. Examples of the monomer represented by the general formula (2) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (Meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, Examples include (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, and (meth) acrylic acid dodecyl ester. These may be used alone or in any combination of two or more.

  Moreover, it is preferable that the (A) binder polymer used by this invention consists of 1 type (s) or 2 or more types of the polymer which has a carboxyl group from the viewpoint of the developability at the time of performing alkali image development using an alkaline solution. Such a (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer.

  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 mg KOH / g, the development time tends to be long, and when it exceeds 200 mg KOH / g, the developer resistance of the photocured resist tends to be lowered. Moreover, when performing solvent image development as a image development process, it is preferable to prepare the polymerizable monomer which has a carboxyl group in a small quantity.

  Further, from the viewpoints of adhesion and peeling properties, the (A) binder polymer preferably contains methacrylic acid as a monomer unit in the molecule.

  In addition, from the viewpoint of improving both the adhesion and release characteristics of the photosensitive resin composition layer comprising the photosensitive resin composition as a constituent material to the circuit forming substrate, (A) the binder polymer contains styrene or It is preferable to contain a styrene derivative as a monomer unit. Furthermore, the binder polymer preferably contains 3 to 30% by mass of styrene or a styrene derivative based on the total weight of the molecule, more preferably 4 to 28% by mass, and particularly preferably 5 to 27% by mass. preferable. If this content is less than 3% by mass, the above-mentioned adhesion tends to be inferior. If this content exceeds 30% by mass, the peel piece tends to be large and the peel time tends to be long. In the present invention, the “styrene derivative” refers to a compound in which a hydrogen atom in styrene is substituted with a substituent (an organic group such as an alkyl group or a halogen atom). The binder polymer containing 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. Is preferred.

  Moreover, (A) binder polymer may have a characteristic group having photosensitivity to light having a wavelength of 340 to 440 nm in its molecule, if necessary. Examples of such a characteristic group include those having a basic skeleton of (E) sensitizing dye described later as a substituent.

  (A) The weight average molecular weight Mw (standard polystyrene conversion value measured by gel permeation chromatography (GPC)) of the binder polymer is preferably 5000 to 300000, more preferably 20000 to 150,000, and 25000. Even more preferably, it is ˜60000. When the weight average molecular weight Mw 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 (A) preferably has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.0 to 3.0, more preferably 1.0 to 2.0. When the degree of dispersion exceeds 3.0, the adhesion and resolution tend to decrease. The number average molecular weight Mn of the binder polymer means a standard polystyrene equivalent value measured by gel permeation chromatography (GPC).

  (A) The binder polymer is composed of one kind of polymer alone or in combination of two or more kinds of 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-11-327137 can also be used as a binder polymer.

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

  (B) The photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond (hereinafter referred to as “photopolymerizable compound”) may be any one having at least one ethylenically unsaturated bond. In particular, as a component (B), a monofunctional photopolymerizable compound having one ethylenically unsaturated bond and a polyfunctional photopolymerizable compound having two or more ethylenically unsaturated bonds are combined. It is preferable to use from the viewpoint of obtaining the effect of the present invention more reliably.

  (B) As the photopolymerizable compound, for example, a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol, a bisphenol A-based (meth) acrylate compound, a glycidyl group-containing compound with α, β- Compounds obtained by reacting unsaturated carboxylic acids, urethane monomers such as (meth) acrylate compounds having a urethane bond in the molecule, nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, (meth) acrylic acid alkyl esters, etc. It is done. These may be used alone or in combination of two or more. From the viewpoint of plating resistance and adhesion, it is preferable that a bisphenol A-based (meth) acrylate compound or a (meth) acrylate compound having a urethane bond in the molecule is contained as a component of the compound.

  Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups. Polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO, PO modified trimethylolpropane tri (meth) acrylate, tetramethylol methanetri (meth) A Examples thereof include acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more. Here, “EO” represents ethylene oxide, and an EO-modified compound represents one having a block structure of an ethylene oxide group. “PO” represents propylene oxide, and a PO-modified compound has a propylene oxide group block structure.

  Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 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. . Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 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) acryloxy nonaethoxy) ) 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) acryloxyhexa) Decaethoxy) phenyl) propane and the like.

  2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name), and 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 may be used alone or in any combination of two or more.

  As the (meth) acrylate compound having a urethane bond in the molecule, for example, a (meth) acryl monomer having an OH group at the β-position and a diisocyanate compound (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.) addition reaction product, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, etc. Is mentioned. Examples of the EO-modified urethane di (meth) acrylate include UA-11 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Examples of the EO and PO-modified urethane di (meth) acrylate include UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). These may 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 may be used alone or in any combination of two or more.

  Examples of the phthalic acid compounds include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloloxyalkyl-o-phthalate, and the like. Is mentioned. These may be used alone or in any combination of two or more.

  (B) It is preferable that the content rate of a photopolymerizable compound is 20-80 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and is 30-70 mass parts. Is more preferable. When the content ratio is less than 20 parts by mass, the photosensitivity tends to be insufficient as compared with the case where the content ratio is within the above range. When the content ratio exceeds 80 parts by mass, the content ratio is Compared with the case where it is within the above range, the photocured portion tends to become brittle.

  (C) As a photoinitiator, for example, benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] Aromatic ketones such as 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, 2- ( o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5- Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5 2,4,5-triarylimidazole dimer such as diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis ( And acridine derivatives such as (9,9'-acridinyl) heptane.

  The two substituents of the aryl group of the 2,4,5-triarylimidazole may be the same and give the target compound, or differently give the asymmetric compound. Further, from the viewpoint of adhesion and sensitivity, a hexaarylbiimidazole derivative is preferable, and a 2,4,5-triarylimidazole dimer is more preferable. These are used alone or in combination of two or more.

  (C) It is preferable that the content rate of a photoinitiator is 0.1-20 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, 0.5-10 mass parts Part is more preferable, 1 to 5 parts by mass is further preferable, and 3 to 4.5 parts by mass is particularly preferable. When the content 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 content ratio is within the above range.

  (D) Examples of the amine compound represented by the general formula (1) include bis [4- (dimethylamino) phenyl] methane and bis [4- (diethylamino) phenyl] methane. These are used alone or in combination of two or more. In the present invention, commercially available compounds can be used. Specifically, for example, amine compounds obtained from Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd., Kanto Chemical Co., Ltd. and the like can be used.

  The content ratio of the component (D) is preferably 0.01 to 10 parts by weight, and 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). More preferably, it is 0.2-2 parts by weight. When the content ratio is less than 0.01 parts by mass, good sensitivity tends to be difficult to obtain. When the content ratio exceeds 10 parts by mass, a film-like photosensitive resin composition layer is formed from the coating liquid. It tends to be deposited as foreign matter.

  (E) Examples of the sensitizing dye include pyrazolines, anthracenes, coumarins, chitosans, thioxanthones, 4,4′-bis (dialkylamino) benzophenones, oxazoles, benzoxazoles, thiazoles, benzoates Examples include thiazoles, triazoles, stilbenes, triazines, thiophenes, and naphthalimides. These are used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, although depending on the light source used, it is preferable to use a sensitizing dye having an absorption wavelength (λ) in the range of 340 to 440 nm, and in the range of 350 to 420 nm. It is more preferable to use a sensitizing dye. By using a sensitizing dye having an absorption wavelength (λ) in such a range, good sensitivity and resolution can be easily obtained. Further, from the viewpoint of more reliably obtaining good sensitivity and resolution, the sensitizing dye preferably has an absorption maximum in the range of 340 to 440 nm, and has an absorption maximum in the range of 350 to 420 nm. It is more preferable to have it. From the same viewpoint, it is preferable to use a sensitizing dye having a maximum absorption wavelength (λ _max ) in the range of 340 to 440 nm, and more preferably in the range of 350 to 420 nm. . The absorption wavelength (λ), absorption maximum wavelength (λ _n ), and maximum absorption wavelength (λ _max ) of the sensitizing dye can be measured and confirmed with a UV spectrophotometer or the like.

  (E) It is preferable that the content rate of a component shall be 0.01-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and shall be 0.05-5 mass parts. Is more preferable, and 0.1 to 2 parts by mass is particularly preferable. If this content is less than 0.01 parts by mass, good sensitivity and resolution tend to be difficult to obtain, and if it exceeds 10 parts by mass, a good resist shape tends to be difficult to obtain. Moreover, when this content rate exceeds 10 mass parts, when it forms a film-like photosensitive resin composition layer from a coating liquid, it exists in the tendency which is easy to precipitate as a foreign material.

  In addition, the photosensitive resin composition of the present invention includes a photopolymerizable compound (such as an oxetane compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, malachite green, if necessary. Dyes such as tribromophenyl sulfone, leuco crystal violet, photochromic agents such as leuco crystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion Additives such as an imparting agent, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, and a thermal crosslinking agent can be contained alone or in combination of two or more. The content of these additives is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B).

  The photosensitive resin composition of the present invention is dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. It is good also as a solution about 30-60 mass% of solid content.

  The above coating solution may be used to form a photosensitive resin composition layer of a photosensitive element by coating and drying on a support film described later. For example, the surface of a metal plate, preferably copper , Copper alloys, nickel alloys, chromium alloys, iron alloys such as stainless steel, more preferably copper, copper alloys, iron alloys on the surface as a liquid resist, after drying, if necessary You may coat and use a protective film. Examples of the protective film include polymer films such as polyethylene and polypropylene.

  The layer thickness of the formed photosensitive resin composition layer is preferably about 1 to 100 μm as the thickness after drying.

  The photosensitive resin composition of the present invention is preferably used for forming a resist pattern by exposure to light having a peak in a wavelength range of 350 nm or more and less than 440 nm. According to the direct drawing exposure method using light having a peak within a wavelength range of 350 nm or more and less than 440 nm as an actinic ray, a high-density resist pattern can be easily formed. The resin composition is particularly useful for forming a resist pattern with light having such a specific wavelength.

  Examples of the light source used include a UV 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. In particular, it is preferable to use a gallium nitride blue laser as a light source because it is easy to form a resist pattern by a direct drawing method. Further, a digital direct exposure machine such as “DE-1AH” (trade name) manufactured by Hitachi Via Mechanics may be used.

(Photosensitive element)
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. The photosensitive element 1 shown in FIG. 1 includes a support film 10 and a photosensitive resin composition layer 14 provided on the support film 10. The photosensitive resin composition layer 14 is composed of the above-described photosensitive resin composition of the present invention.

  Examples of the support film 10 include polymer films having heat resistance and solvent resistance, such as polyethylene terephthalate, polypropylene, polyethylene, and polyester. The thickness of the support film is preferably 1 to 100 μm, more preferably 5 to 40 μm, and particularly preferably 10 to 30 μm. When the thickness of the support film is less than 1 μm, the mechanical strength decreases, and the support film tends to be broken when the support film is peeled off before development, whereas when it exceeds 100 μm, the resolution decreases. Tend.

  The photosensitive resin composition layer 14 can be formed, for example, by applying the photosensitive resin composition of the present invention on the support 10 and then drying it. 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.

  Although the thickness of the photosensitive resin composition layer 14 changes with uses, it is preferable that it is 1-100 micrometers in thickness after drying, and it is more preferable that it is 1-50 micrometers. If the thickness is less than 1 μm, it tends to be difficult to apply industrially, and if it exceeds 100 μm, the adhesive force and resolution tend to decrease, and the effects of the present invention are not sufficiently obtained.

  Further, the photosensitive resin composition layer 14 preferably has a transmittance of 5 to 75%, more preferably 7 to 60%, and more preferably 10 to 40% with respect to ultraviolet rays having a wavelength of 365 nm and / or 405 nm. It is particularly preferred. If the transmittance is less than 5%, the adhesion tends to be inferior, and if it exceeds 75%, the resolution tends to be inferior. The transmittance can be measured by a UV spectrometer, and examples of the UV spectrometer include a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

  In the photosensitive element 1, it is preferable to cover the surface F1 opposite to the support film side of the photosensitive resin composition layer 14 with a protective film (not shown) as necessary. The adhesive force between the protective film and the photosensitive resin composition layer 14 is such that the protective film is easily peeled off from the photosensitive resin composition layer 14 so that the protective film is peeled off from the photosensitive resin composition layer 14 and the support 10. It is preferable that it is smaller than the adhesive force.

  As the protective film, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. Examples of commercially available products include, for example, polyethylene such as “Alphan MA-410” and “E-200C” manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and “PS-25” manufactured by Teijin Limited. Although a terephthalate film etc. are mentioned, it is not restricted to this.

  In the photosensitive element 1, you may use the polymer film similar to the above-mentioned support film as a protective film.

  The protective film is preferably a low fish eye film. "Fish eye" means that when a material is melted by heat, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidized degradation products, etc. It is taken in.

  The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, still more preferably 5 to 30 μm, and particularly preferably 15 to 30 μm. When the thickness is less than 1 μm, the protective film tends to be easily broken during lamination, and when it exceeds 100 μm, the cost tends to be inferior.

  The photosensitive element 1 may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.

  The photosensitive element 1 is, for example, in the form of a flat plate as it is, or by laminating a protective film on one surface of the photosensitive resin composition layer (on the surface that is not protected and exposed) to form a cylindrical shape or the like. It can be wound around a core and stored in roll form. In addition, it is preferable to wind up in this case so that a support film may become the outermost side.

  The core is not particularly limited as long as it is conventionally used. For example, plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), etc. Etc. Moreover, it is preferable to install an end face separator from the viewpoint of protecting the end face on the end face of the photosensitive element (photosensitive element roll) wound up in a roll shape, and in addition, a moisture-proof end face separator is installed from the viewpoint of edge fusion resistance. It is preferable to do. Moreover, when packaging the photosensitive element 1, it is preferable to wrap it in a black sheet with low moisture permeability.

(Method for forming resist pattern)
The first resist pattern forming method of the present invention comprises a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention or a photosensitive resin composition of the photosensitive element of the present invention on a circuit forming substrate. A physical layer is laminated | stacked, actinic light is irradiated to the predetermined part of the photosensitive resin composition layer, an exposed part is photocured, and then parts other than an exposed part are removed. The “circuit forming substrate” refers to a substrate including an insulating layer and a conductor layer formed on the insulating layer.

  In the first resist pattern forming method of the present invention, when the photosensitive element 1 having a protective film is used, the protective film of the photosensitive element 1 is gradually peeled off from the photosensitive resin composition layer 14 and simultaneously with this. The portion of the surface of the photosensitive resin composition layer 14 that is gradually exposed is brought into close contact with the surface of the circuit forming substrate on which the circuit is to be formed, whereby the photosensitive resin composition layer 14 is formed on the circuit forming substrate. A first step of laminating, a second step of irradiating a predetermined portion of the photosensitive resin composition layer 14 to be exposed with actinic rays to form an exposed portion, and then removing an unexposed portion other than the exposed portion. A resist pattern is formed by a method including three steps.

As a method of laminating the photosensitive resin composition layer on the circuit forming substrate in the first step, after removing the protective film, the photosensitive resin composition layer is used for circuit formation while heating the photosensitive resin composition layer. The method of laminating | stacking by crimping | bonding to a board | substrate is mentioned. In addition, it is preferable to laminate | stack this operation under pressure reduction from the viewpoint of adhesiveness and followability. In the lamination of the photosensitive element, the photosensitive resin composition layer and / or the circuit forming substrate is preferably heated to 70 to 130 ° C., and the pressure bonding pressure is about 0.1 to 1.0 MPa (1 to 10 kgf / cm). it is preferably about ^2), but not particularly limited to these conditions. Further, if the photosensitive resin composition layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the circuit forming substrate in advance, but in order to further improve the laminating property, Pre-heat treatment of the substrate can also be performed.

  Examples of the method for forming the exposed portion in the second step include a method of irradiating an image with active light through a negative or positive mask pattern called an artwork (mask exposure method). At this time, when the support film present on the photosensitive resin composition layer is transparent to the active light, the active light can be irradiated through the support film, and when the support film is light-shielding After removing the support film, the photosensitive resin composition layer is irradiated with actinic rays. Further, a method of irradiating actinic rays in an image form by a direct drawing method using a laser exposure method or the like may be employed.

  As a light source of actinic light, a known 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, effectively emits ultraviolet light, visible light, or the like. Things are used.

  In the first resist pattern forming method of the present invention, the photosensitive resin composition of the present invention is applied to a direct drawing method requiring high sensitivity and high resolution, that is, a method of forming an exposed portion is directly used. A drawing method is preferred. Examples of the light source used in the direct drawing method include a UV 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. In particular, it is preferable to use a gallium nitride blue laser as a light source because it is easy to form a resist pattern by a direct drawing method. Further, a digital direct exposure machine such as “DE-1AH” (trade name) manufactured by Hitachi Via Mechanics may be used.

  As a method for removing portions other than the exposed portion in the third step, when a support film is present on the photosensitive resin composition layer, the support film is first removed, and then wet development, dry development, etc. And a method of developing by removing portions other than the exposed portion. Thereby, a resist pattern is formed.

  In the case of wet development, for example, using a developer corresponding to the photosensitive resin composition such as an alkaline aqueous solution, an aqueous developer, an organic solvent developer, for example, spraying, rocking immersion, brushing, scraping, etc. Development is performed by a known method.

  As the developing solution, a safe and stable solution having good operability such as an alkaline aqueous solution is used. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate, potassium phosphate, and phosphoric acid. Alkali metal phosphates such as sodium and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used.

  Moreover, as alkaline aqueous solution used for image development, 0.1-5 mass% dilute solution of sodium carbonate, 0.1-5 mass% dilute solution of potassium carbonate, 0.1-5 mass% dilute solution of sodium hydroxide, A dilute solution of 0.1 to 5% by mass sodium tetraborate is preferred. Moreover, it is preferable to make pH of the alkaline aqueous solution used for image development into the range of 9-11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.

  Examples of the aqueous developer include a developer composed of water or an alkaline aqueous solution and one or more organic solvents. Here, as the base of the alkaline aqueous solution, in addition to the substances described above, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1, 3 -Propanediol, 1,3-diaminopropanol-2, morpholine and the like. The pH of the developer is preferably as low as possible within a range where the resist can be sufficiently developed, preferably pH 8-12, more preferably pH 9-10.

  Examples of the organic solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like. It is done. These are used alone or in combination of two or more. The concentration of the organic solvent is usually preferably 2 to 90% by mass, and the temperature can be adjusted according to the developability. Further, a small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.

  Examples of the organic solvent developer using an organic solvent alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. It is preferable to add water to these organic solvents in the range of 1 to 20% by mass in order to prevent ignition.

  Two or more of the above developing solutions may be used in combination as required.

  Examples of the development method include a dip method, a spray method, brushing, and slapping. Among these, it is preferable to use a high-pressure spray system from the viewpoint of improving resolution.

In the method for forming a resist pattern of the present invention, as a treatment after development, the resist pattern is further cured by performing heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ² as necessary. May be.

  Further, as a treatment after development, the metal surface can be etched using, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or the like.

  Next, the second resist pattern forming method of the present invention will be described.

  In the second resist pattern forming method of the present invention, instead of the circuit forming substrate in the first resist pattern forming method of the present invention, the partition material layer provided on the plasma display substrate is formed on the partition material layer. Except for laminating the photosensitive resin composition layer comprising the photosensitive resin composition of the present invention or the photosensitive resin composition layer of the photosensitive element of the present invention, it is the same as the first resist pattern forming method. .

  Examples of the plasma display substrate include a glass substrate on which a partition material (rib material) for forming a partition is applied as a paste.

(Printed wiring board manufacturing method)
The method for producing a printed wiring board of the present invention is a method characterized by etching or plating a circuit forming substrate on which a resist pattern is formed by the first resist pattern forming method of the present invention.

  Etching and plating of the circuit forming substrate is performed on a conductor layer or the like of the circuit forming substrate using the formed resist pattern as a mask. Examples of the etching solution include cupric chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide-based etching solution, etc. Among these, ferric chloride has a good etch factor. It is preferable to use a solution. The types of plating used for plating include copper sulfate plating, copper pyrophosphate plating, etc., solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel sulfamate plating, etc. Examples thereof include gold plating such as nickel plating, hard gold plating, and soft gold plating.

  After the etching or plating is completed, the resist pattern can be peeled off with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example. Examples of the strong alkaline aqueous solution include an aqueous solution of 0.1 to 10% by mass sodium hydroxide, an aqueous solution of 0.1 to 10% by mass potassium hydroxide, and the like. Examples of the peeling method include an immersion method and a spray method. These peeling methods may be used alone or in combination.

  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.

(Plasma display panel partition formation method)
The method for forming a partition of a plasma display panel according to the present invention comprises the step of forming a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention on a partition material layer provided on a substrate for a plasma display or the above-described photosensitive of the present invention. By laminating the photosensitive resin composition layer of the photosensitive element, irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays to photocure the exposed portion, and then removing the portion other than the exposed portion A step of forming a resist pattern, and a step of etching the partition wall material layer on which the resist pattern is formed.

  As the plasma display substrate and the partition wall material layer, the same ones as those used in the above-described second resist pattern forming method of the present invention are used.

  Examples of the method for etching the partition wall material layer include a sand blast method and a wet etching process method. In the case of the sandblast method, the partition wall material is etched by spraying cutting particles such as silica and alumina directly on the substrate. In the case of the wet etching process method, the partition wall material is etched with an acid solution such as nitric acid.

  Through the above etching process, partition walls (ribs) having a predetermined shape are formed on the plasma display substrate. The resist pattern can be peeled off after the etching according to the method used in the printed wiring board manufacturing method described above.

  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.

(Examples 1-8 and Comparative Examples 1-3)
(Preparation of photosensitive resin composition)
First, the components shown in Table 1 were mixed in the amounts (g) shown in the same table to obtain a solution.

＊１：下記一般式（３）で示されるＥＯ変性ビスフェノールＡジメタクリレート（日立化成工業社製、製品名「ＦＡ−３２１Ｍ」）。下記一般式（３）において、ｍ＋ｎ＝１０（平均値）である。

* 1: EO-modified bisphenol A dimethacrylate represented by the following general formula (3) (manufactured by Hitachi Chemical Co., Ltd., product name “FA-321M”). In the following general formula (3), m + n = 10 (average value).

  Next, in the obtained solution, the amine compound (D) component shown in Table 2, the sensitizing dye (E) component, and leuco crystal violet (color former) in the amount (g) shown in the same table. It was made to melt | dissolve and the solution of the photosensitive resin composition was obtained.

＊２：ビス［４−（ジメチルアミノ）フェニル］メタン （ＭＤＰ、和光純薬工業（株）製）。
＊３：７−ジエチルアミノ−４−メチルクマリン （Ｃ１、（株）日本化学工業所製、最大吸収波長［λ_ｍａｘ］＝３７４ｎｍ）。
＊４：９−メチルジュロリジノ［９，１０−ｅ］−１１Ｈ−ピラン−１１−オン （Ｃ１０２、（株）日本化学工業所製、最大吸収波長［λ_ｍａｘ］＝３９０ｎｍ）。
＊５：９，１０−ジブトキシアントラセン （ＤＢＡ、川崎化成（株）製、吸収極大を示す波長［λ_ｎ］＝３６８ｎｍ、３８８ｎｍ、４１０ｎｍ）。
＊６：１−フェニル−３−（４−ｔ−ブチルスチリル）−５−（４−ｔ−ブチルフェ
ニル）−ピラゾリン （ＰＹＲ１、（株）日本化学工業所製、最大吸収波長［λ_ｍａｘ］＝３８７ｎｍ）。
＊７：４，４’−ビス（ジエチルアミノ）ベンゾフェノン（ＥＡＢ、保土ヶ谷化学（株）製、最大吸収波長［λ_ｍａｘ］＝３６５ｎｍ）
＊８：２，４−ジエチルチオキサントン（ＤＥＴＸ、日本化薬（株）製、最大吸収波長［λ_ｍａｘ］＝３７５ｎｍ）

* 2: Bis [4- (dimethylamino) phenyl] methane (MDP, manufactured by Wako Pure Chemical Industries, Ltd.).
* 3: 7-diethylamino-4-methylcoumarin (C1, manufactured by Nippon Chemical Industry Co., Ltd., maximum absorption wavelength [λ _max ] = 374 nm).
* 4: 9-methyljulolidino [9,10-e] -11H-pyran-11-one (C102, manufactured by Nippon Chemical Industry Co., Ltd., maximum absorption wavelength [λ _max ] = 390 nm).
* 5: 9,10-dibutoxyanthracene (DBA, manufactured by Kawasaki Kasei Co., Ltd., wavelength [λ _n ] = 368 nm, 388 nm, 410 nm).
* 6: 1-phenyl-3- (4-t-butylstyryl) -5- (4-t-butylphenyl) -pyrazoline (PYR1, manufactured by Nippon Chemical Industry Co., Ltd., maximum absorption wavelength [λ _max ] = 387 nm).
* 7: 4,4′-bis (diethylamino) benzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd., maximum absorption wavelength [λ _max ] = 365 nm)
* 8: 2,4-diethylthioxanthone (DETX, manufactured by Nippon Kayaku Co., Ltd., maximum absorption wavelength [λ _max ] = 375 nm)

(Production of photosensitive element)
The obtained photosensitive resin composition solution was uniformly applied onto a 16 μm-thick polyethylene terephthalate film (product name: “HTF01”, manufactured by Teijin Limited) as a support, and hot air convection drying at 70 ° C. and 100 ° C. A photosensitive element was obtained by drying for 1 minute at a speed of 4 m / min. The film thickness after drying of the photosensitive resin composition layer was 25 μm.

<Solubility>
To a mixed solvent of 9 g of acetone, 5 g of toluene and 5 g of methanol, the amount (g) shown in Table 2 was added to the components (D), (E) and leucocrystal violet shown in Table 2. (D) Component, (E) component, and each liquid mixture to which leuco crystal violet is added (Note that (D) component is not included for those corresponding to Comparative Examples 1 and 2, and those corresponding to Comparative Example 3) (E) does not contain component) for 15 minutes, and then examined for the presence of foreign matter. The results are shown in Table 3 as “good” when no foreign matter precipitation was observed and “foreign matter precipitation” when foreign matter precipitation was observed.

<Absorbance test>
The optical density (OD value) with respect to the exposure wavelength of the photosensitive resin composition layer was measured using a UV spectrophotometer (manufactured by Hitachi, Ltd., product name “U-3310 spectrophotometer”). The measurement is based on a polyethylene terephthalate film of the same type as that used as the support film, and a UV absorption spectrum is obtained by performing continuous measurement with light having a wavelength of 600 to 300 nm in the absorbance mode, in which the absorbance value at 405 nm is obtained. O. D. Value. The measurement results are shown in Table 3.

(Formation of resist pattern)
About each obtained photosensitive element, the photosensitive resin composition layer was laminated | stacked on the copper clad laminated board with the following method, and the laminated body was obtained. That is, the copper surface of a copper-clad laminate (made by Hitachi Chemical Co., Ltd., product name “MCL-E-67”), which is a glass epoxy material in which copper foil (thickness 35 mm) is laminated on both sides, is equivalent to # 600. Polishing was performed using a polishing machine having a brush (manufactured by Sankei Co., Ltd.), washed with water, and then dried with an air flow. The obtained copper clad laminate was heated to 80 ° C., and the photosensitive resin composition layer was peeled off at 120 ° C. under a pressure of 4 kgf / cm ² while peeling the protective film of the photosensitive element on the copper clad laminate. By laminating below, a laminate was obtained.

<Photosensitivity and resolution adhesion test>
Subsequently, the laminate is cooled to 23 ° C., and on the surface of the polyethylene terephthalate film located in the outermost layer of the laminate, a concentration region of 0.00 to 2.00, a concentration step of 0.05, a tablet ( (Rectangle) is 20mm x 187mm and each step (Rectangle) is 3mm x 12mm and has a 41-step tablet and a line width / space width of 6/6 ~ A phototool having a wiring pattern of 35/35 (unit: mm) was sequentially laminated. Further, a sharp cut filter SCF-100S-39L (product name) manufactured by Sigma Koki Co., Ltd. for exposure at a wavelength of 405 nm was disposed thereon.

  In this state, exposure using a parallel light exposure machine (product name “EXM-1201”, manufactured by Oak Manufacturing Co., Ltd.) using a 5 kW short arc lamp as a light source, the number of remaining steps after development of a 41-step tablet is 17 steps. The exposure was carried out in a quantity, and this exposure quantity was taken as the sensitivity. The illuminance is measured using an ultraviolet illuminometer (product name “UIT-150” + light receiving unit “UVD-S405” manufactured by USHIO INC.) With a 405 nm probe applied to the light transmitted through the sharp cut filter. The product of illuminance and exposure time was taken as the exposure amount. The results are shown in Table 3.

  Next, the polyethylene terephthalate film was peeled off, and a 1% by mass sodium carbonate aqueous solution was sprayed at 30 ° C. for 24 seconds to remove unexposed portions. The resolution adhesion was evaluated based on the smallest value of the space width between the line widths in which the unexposed portions could be removed cleanly by the development process, and the lines were generated without snakes and chips. The lower the numerical value, the better the sensitivity (exposure amount at which the number of remaining step steps becomes 17 by exposure at a wavelength of 405 nm) and the resolution adhesion degree. The results are shown in Table 3.

  The resist shape after development was observed using a Hitachi scanning electron microscope S-500A. The results are shown in Table 3. The resist shape is preferably close to a rectangle.

<Peelability>
First, the laminated body was produced like the said Examples 1-8 and Comparative Examples 1-3. Next, a resist pattern with a pitch of 40 microns (L / S = 20/20 μm) is formed on these laminates, and electrolytic copper plating is performed under the conditions shown in Table 4 to form a plating layer with a copper thickness of 20 μm. did. Then, peeling was performed on the conditions shown in Table 4 using 3.0 mass% sodium hydroxide aqueous solution as peeling liquid. The laminated board after peeling was observed with a metal microscope, and the resist peeling residue was evaluated based on the following evaluation criteria. The results are shown in Table 3.
OK: No peeling residue is observed.
NG: Peeling residue of 40 μm pitch pattern is observed.

  As shown in Table 3, it was confirmed that the photosensitive elements of Examples 1 to 8 had sufficiently high sensitivity and good resolution adhesiveness of 18 μm or less. On the other hand, the sensitivity of the photosensitive element of Comparative Example 1 was insufficient, and the photosensitive element of Comparative Example 2 had insufficient foreign matter deposited on the photosensitive resin composition layer, resulting in insufficient resolution adhesion. In addition, it is thought that precipitation of the foreign material in Comparative Example 2 is due to the fact that the color former was not sufficiently dissolved during the preparation of the solution of the photosensitive resin composition. Further, the photosensitive element of Comparative Example 3 had insufficient sensitivity and resolution adhesion, and the resist shape was not preferable as an inverted trapezoid.

  The reason why the photosensitive elements of Examples 1 to 8 have sufficiently high sensitivity is not necessarily clear, but the present inventors speculate as follows. That is, the present inventors consider that in the photosensitive elements of Examples 1 to 8, highly reactive radicals generated by hydrogen abstraction between molecules work as starting species for the polymerization reaction. More specifically, first, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5 ′, which is a photopolymerization initiator, is irradiated by light irradiation to the photosensitive resin composition layer of the photosensitive element. -It is thought that tetraphenylbisimidazole is excited to generate a lophyll radical. Then, it is considered that this lophyl radical extracts a hydrogen atom from the compound represented by the general formula (1), thereby generating a radical in which the hydrogen atom is extracted from the compound represented by the general formula (1). It is considered that the radical generated by such an intermolecular hydrogen abstraction type radical generation mechanism has high reactivity capable of sufficiently promoting the polymerization reaction of the component (B). Furthermore, the photopolymerization initiator is efficiently excited when exposed to predetermined light (light having a peak in the wavelength range of 350 nm or more and less than 440 nm) by the presence of the sensitizing dye as component (E). It is presumed that high sensitivity has been sufficiently achieved by increasing the concentration of the radical derived from the compound represented by the general formula (1).

  On the other hand, the photosensitive element of Comparative Example 2 shows sufficient sensitivity even though it does not contain the compound represented by the general formula (1). This is because the leuco crystal violet exhibits the general formula (1). The present inventors speculate that this is because the compound functions in the same manner as the above compound. However, in order to obtain equivalent sensitivity using leuco crystal violet instead of the compound represented by the general formula (1), it is necessary to increase the amount of leuco crystal violet added. In this case, the adhesion of the cured resist is reduced due to the precipitation of foreign matters, or a residue is deposited on an unexposed portion that should be dissolved by development, so that a high-resolution resist pattern cannot be formed. In addition, the photosensitive element of Comparative Example 1 in which the amount of leuco crystal violet added is small is considered that sufficient sensitivity was not obtained because an amount of starting species that sufficiently accelerates the polymerization reaction of component (B) was not generated. It is done.

(Examples 9-11, Comparative Examples 4 and 5)
(Preparation of photosensitive resin composition)
First, various components shown in Table 5 were mixed in the amounts shown in the same table to obtain a solution.

＊１：表１における「ＦＡ−３２１Ｍ」と同じ化合物である。

* 1: The same compound as “FA-321M” in Table 1.

  Next, in the obtained solution, the amine compound as component (D) shown in Table 6, the sensitizing dye as component (E), and leuco crystal violet as the color former in the amount (g) shown in the same table. It was made to melt | dissolve and the solution of the photosensitive resin composition was obtained.

表６中の＊２〜＊８は、表２における＊２〜＊８と同じである。

* 2 to * 8 in Table 6 are the same as * 2 to * 8 in Table 2.

(Production of photosensitive element)
The obtained photosensitive resin composition solution was uniformly applied onto a 16 μm-thick polyethylene terephthalate film (product name: “HTF01”, manufactured by Teijin Limited) as a support, and hot air convection drying at 70 ° C. and 100 ° C. The photosensitive elements of Examples 8 to 11 and Comparative Examples 4 and 5 were obtained by drying for 1 minute at a speed of 4 m / min. The film thickness after drying of the photosensitive resin composition layer was 25 μm.

<Solubility>
To a mixed solvent of 9 g of acetone, 5 g of toluene and 5 g of methanol, the amount (g) shown in Table 6 was added to the (D) component, (E) component and leuco crystal violet shown in Table 6. (D) Component, (E) component, and each liquid mixture with which leuco crystal violet was added (In addition, (D) component is not included about the thing corresponding to Comparative Examples 4 and 5), 15 minutes was stirred, The presence or absence of foreign matters was examined. The results are shown in Table 7 as “good” when no foreign matter precipitation was observed and “foreign matter precipitation” when foreign matter precipitation was observed.

<Absorbance test>
The optical density (OD value) with respect to the exposure wavelength of the photosensitive resin composition layer was measured using a UV spectrophotometer (manufactured by Hitachi, Ltd., product name “U-3310 spectrophotometer”). The measurement is based on a polyethylene terephthalate film of the same type as that used as the support film, and a UV absorption spectrum is obtained by performing continuous measurement with light having a wavelength of 600 to 300 nm in the absorbance mode, in which the absorbance value at 405 nm is obtained. O. D. Value. The measurement results are shown in Table 7.

(Formation of resist pattern)
For each of the obtained photosensitive elements, a photosensitive resin is peeled while peeling the protective film of the photosensitive element on a PDP rib substrate for evaluation (a glass substrate coated with a rib paste, manufactured by Asahi Glass Co., Ltd., trade name: PD-200). A laminate was obtained by laminating the composition layer at 120 ° C. under a pressure of 4 kgf / cm ² .

<Photosensitivity and resolution adhesion test>
Subsequently, the laminate is cooled to 23 ° C., and on the surface of the polyethylene terephthalate film located in the outermost layer of the laminate, a concentration region of 0.00 to 2.00, a concentration step of 0.05, a tablet ( (Rectangle) is 20mm x 187mm and each step (Rectangle) is 3mm x 12mm and has a 41-step tablet and a line width / space width of 6/6 ~ A phototool having a wiring pattern of 35/35 (unit: mm) was sequentially laminated. Further, a sharp cut filter SCF-100S-39L (product name) manufactured by Sigma Koki Co., Ltd. for exposure at a wavelength of 405 nm was disposed thereon.

  In this state, exposure using a parallel light exposure machine (product name “EXM-1201”, manufactured by Oak Manufacturing Co., Ltd.) using a 5 kW short arc lamp as a light source, the number of remaining steps after development of a 41-step tablet is 17 steps. The exposure was carried out in a quantity, and this exposure quantity was taken as the sensitivity. The illuminance is measured using an ultraviolet illuminometer (product name “UIT-150” + light receiving unit “UVD-S405” manufactured by USHIO INC.) With a 405 nm probe applied to the light transmitted through the sharp cut filter. The product of illuminance and exposure time was taken as the exposure amount. The results are shown in Table 7.

  Next, the polyethylene terephthalate film was peeled off, and a 1% by mass sodium carbonate aqueous solution was sprayed at 30 ° C. for 24 seconds to remove unexposed portions. The resolution adhesion was evaluated based on the smallest value of the space width between the line widths in which the unexposed portions could be removed cleanly by the development process, and the lines were generated without snakes and chips. The lower the numerical value, the better the sensitivity (exposure amount at which the number of remaining step steps becomes 17 by exposure at a wavelength of 405 nm) and the resolution adhesion degree. The results are shown in Table 7.

  The resist shape after development was observed using a Hitachi scanning electron microscope S-500A. The results are shown in Table 7. The resist shape is preferably close to a rectangle.

<Peelability>
First, laminates were produced in the same manner as in Examples 9 to 11 and Comparative Examples 4 and 5. Next, a resist pattern of 40 mm × 60 mm was formed on these laminates. Thereafter, a 3.0% by mass aqueous sodium hydroxide solution was used as the stripping solution, and stripping was performed under the conditions of the stripping solution temperature: 50 ° C. and the spray pressure: 0.20 MPa. By observing the peeled laminate with a metal microscope, the peeling time required until no peeling residue was observed was measured, and the peelability of the resist was evaluated based on the following evaluation criteria. The results are shown in Table 7.
OK: The peeling time until no peeling residue is observed is within 30 seconds.
NG: The peeling time until no peeling residue is observed exceeds 30 seconds.

＊９：「すそ食われ」とは、現像後のレジストパターンの厚み方向での断面において、リブ基板との界面付近のレジスト側面が削られたようなレジスト形状をいう。

* 9: “Sweeping” refers to a resist shape in which the resist side surface near the interface with the rib substrate is cut off in the cross section in the thickness direction of the resist pattern after development.

  According to the present invention, a photosensitive resin composition capable of forming a resist pattern by a direct drawing method with sufficient sensitivity and resolution, a photosensitive element using the same, a method for forming a resist pattern, and a printed wiring board And a method for forming a partition of a plasma display. Therefore, according to the printed wiring board manufacturing method of the present invention, it is possible to manufacture even a small quantity of various types of printed wiring boards or large printed wiring boards with high productivity. In addition, according to the method for forming a partition of a plasma display of the present invention, a partition having a good shape can be formed on a substrate with high productivity, and the productivity of PDP can be improved.

Claims (9)

(A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) represented by the following general formula (1) A photosensitive resin composition comprising an amine compound and (E) a sensitizing dye.

[However, R < ¹ > -R < ⁴ > shows a C1-C6 alkyl group each independently. ] The photosensitive resin composition according to claim 1, wherein the (C) photopolymerization initiator is a hexaarylbiimidazole derivative. 3. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is used for forming a resist pattern by exposure to light having a peak in a wavelength range of 350 nm or more and less than 440 nm. A photosensitive element comprising: a support film; and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 3 formed on the support film. . The photosensitive resin composition layer which consists of the photosensitive resin composition of any one of Claims 1-3 is laminated | stacked on the circuit formation board | substrate, and actinic light is applied to the predetermined part of this photosensitive resin composition layer. Is used to photo-cure the exposed portion, and then the portions other than the exposed portion are removed. A photosensitive resin composition layer of the photosensitive element according to claim 4 is laminated on a circuit forming substrate, and a predetermined portion of the photosensitive resin composition layer is irradiated with actinic rays to photocure the exposed portion. Then, a method for forming a resist pattern, wherein a portion other than the exposed portion is removed. A method for manufacturing a printed wiring board, comprising etching or plating a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern according to claim 5. A photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 3 is laminated on a partition wall material layer provided on a plasma display substrate, and the photosensitive resin composition Irradiating a predetermined portion of the physical layer with actinic rays to photocure the exposed portion, and then forming a resist pattern by removing portions other than the exposed portion; and
Etching the partition material layer on which the resist pattern is formed;
A partition forming method for a plasma display, comprising: A photosensitive resin composition layer of the photosensitive element according to claim 4 is laminated on a partition wall material layer provided on a plasma display substrate, and a predetermined portion of the photosensitive resin composition layer is irradiated with actinic rays. Photocuring the exposed portion, and then forming a resist pattern by removing portions other than the exposed portion; and
Etching the partition material layer on which the resist pattern is formed;
A partition forming method for a plasma display, comprising:

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