JP6136414B2 - Photosensitive resin composition, photosensitive element, method for manufacturing substrate with resist pattern, and method for manufacturing printed wiring board - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element, a method for producing a substrate with a resist pattern, and a method for producing a printed wiring board.

  In the field of manufacturing printed wiring boards, a photosensitive resin composition is widely used as a resist material used for etching treatment or plating treatment. A photosensitive resin composition includes a support film and a photosensitive element (laminated layer) including a layer formed on the support film using the photosensitive resin composition (hereinafter also referred to as “photosensitive resin composition layer”). Often used as a body).

  A printed wiring board is manufactured as follows, for example. First, the photosensitive resin composition layer of the photosensitive element is laminated (laminated) on the circuit forming substrate (lamination step). Next, a predetermined part of the photosensitive resin composition layer is irradiated with actinic rays to cure the exposed part (exposure process). Then, after peeling off and removing the support film, the unexposed portion is removed (developed) from the substrate, whereby a cured product of the photosensitive resin composition (hereinafter, “resist cured product”) is formed on the circuit forming substrate. A resist pattern is also formed (development process). The resulting resist pattern is etched or plated to form a circuit on the substrate (circuit formation process), and finally the resist is removed and removed (peeling process) to produce a printed wiring board. The

  As an exposure method, conventionally, a method of exposing via a photomask using a mercury lamp as a light source has been used. In recent years, a direct drawing exposure method called DLP (Digital Light Processing) or LDI (Laser Direct Imaging) for directly drawing a pattern on a photosensitive resin composition layer has been proposed. This direct drawing exposure method has been introduced for the production of a high-density package substrate because it has better alignment accuracy than the exposure method through a photomask and a high-definition pattern can be obtained.

  In general, in the exposure process, it is necessary to shorten the exposure time in order to improve production efficiency. However, in the above-described direct drawing exposure method, in addition to using monochromatic light such as a laser as a light source and irradiating a light beam while scanning the substrate, a long exposure time is required as compared with an exposure method using a conventional photomask. Tend. Therefore, in order to shorten the exposure time and increase the production efficiency, it is necessary to improve the sensitivity of the photosensitive resin composition than before.

  On the other hand, with the recent increase in the density of printed wiring boards, there is an increasing demand for a photosensitive resin composition capable of forming a resist pattern excellent in resolution (resolution) and adhesion. In particular, a photosensitive resin composition capable of forming a resist pattern having an L / S (line width / space width) of 10/10 (unit: μm) or less in package substrate production is required.

  Conventionally, various photosensitive resin compositions have been studied in response to these requirements. For example, Patent Document 1 discloses a photosensitive resin composition in which the above required characteristics are improved by using a styrylpyridine compound as a sensitizing dye. Patent Documents 2 and 3 disclose a photosensitive resin composition in which the above-described required properties are improved by using a specific binder polymer containing a structure derived from benzyl (meth) acrylate. .

Chinese Patent Application No. 101738861 JP 2006-234959 A International Publication No. 08/078483 Pamphlet

  However, the styrylpyridine compound disclosed in Patent Document 1 has a sufficiently high sensitivity compared with other sensitizing dyes often used at that time, but it is difficult to say that the resolution is high. there were. Therefore, a styrylpyridine compound has not been actively used from the viewpoint of increasing the resolution of the photosensitive resin composition.

  The present invention relates to a photosensitive resin composition capable of forming a resist pattern having excellent resolution and adhesion with excellent sensitivity, a photosensitive element using the photosensitive resin composition, a method for producing a substrate with a resist pattern, and printed wiring. It aims at providing the manufacturing method of a board.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a structural unit derived from a styrylpyridine compound represented by the general formula (1), (meth) acrylic acid and benzyl (meth) acrylate. Photosensitive resin composition capable of forming a resist pattern having excellent resolution and adhesion with excellent sensitivity by combining a binder polymer having a photopolymerizable compound having an ethylenically unsaturated bond group and a photopolymerization initiator The present inventors have found that a product can be obtained, and have completed the present invention.

  That is, the first aspect of the present invention is (A) a binder polymer having a structural unit derived from (meth) acrylic acid and benzyl (meth) acrylate, and (B) photopolymerization having an ethylenically unsaturated bond group. It is a photosensitive resin composition containing a functional compound, (C) a photopolymerization initiator, and (D) a styrylpyridine compound represented by the general formula (1).

In formula (1), R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, or an amino group. , An alkylamino group having 1 to 20 carbon atoms, a carboxyl group, a cyano group, a nitro group, an acetyl group or a (meth) acryl group, and a, b and c each independently represent an integer of 0 to 5. However, when a is 2 or more, a plurality of R ¹ may be the same or different, and when b is 2 or more, a plurality of R ² may be the same or different, and c is 2 or more. In the case, a plurality of R ³ may be the same or different.

  The said photosensitive resin composition can form the resist pattern which is excellent in the resolution and adhesiveness with the outstanding sensitivity by taking said aspect. According to the photosensitive resin composition, a resist pattern having L / S (line width / space width) of 10/10 (unit: μm) or less can be formed.

  From the point that the photosensitive resin composition further improves the sensitivity and the resolution and adhesion of the resist pattern to be formed, (C) the photopolymerization initiator is represented by the following general formula (2) 2, 4 It is preferable to contain at least one selected from the group consisting of, 5-triarylimidazole dimer and derivatives thereof.

In formula (2), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may each independently be substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy group. Represents an aryl group, X ¹ and X ² each independently represent a halogen atom, an alkyl group, an alkenyl group or an alkoxy group, and p and q each independently represents an integer of 1 to 5. However, when p is 2 or more, a plurality of X ¹ may be the same or different, and when q is 2 or more, a plurality of X ² may be the same or different.

  A second aspect of the present invention is a photosensitive element comprising: a support film; and a photosensitive resin composition layer that is a coating film of the photosensitive resin composition of the first aspect provided on the support film. It is. By using such a photosensitive element, in particular, a resist pattern excellent in resolution and adhesion can be efficiently formed with excellent sensitivity.

  According to a third aspect of the present invention, there is provided a lamination step of laminating a photosensitive resin composition layer, which is a coating film of the photosensitive resin composition of the first aspect, on a substrate, and the photosensitive resin composition layer. An exposure step of irradiating at least a part of the region with actinic rays and photocuring the region to form a cured product region; and regions other than the cured product region of the photosensitive resin composition layer from above the substrate And a developing process for forming a resist pattern comprising the cured product region on the substrate by removing the resist pattern. According to the above method for producing a substrate with a resist pattern, a resist pattern having excellent resolution and adhesion can be efficiently formed with excellent sensitivity.

  In the above method for producing a substrate with a resist pattern, the wavelength of the actinic ray to be irradiated is preferably in the range of 340 nm to 430 nm. Thereby, a resist pattern with better resolution and adhesion can be formed more efficiently with excellent sensitivity.

  The 4th aspect of this invention is a manufacturing method of a printed wiring board including the process of carrying out the etching process or the plating process of the board | substrate with which the resist pattern was formed by the manufacturing method of the said board | substrate with a resist pattern. According to this manufacturing method, a printed wiring board having high-density wiring such as a high-density package substrate can be efficiently manufactured with excellent accuracy and high productivity.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can form the resist pattern excellent in resolution and adhesiveness with the outstanding sensitivity, the photosensitive element using the same, the manufacturing method of a board | substrate with a resist pattern, and printed wiring board A manufacturing method can be provided.

It is a schematic cross section which shows one Embodiment of the photosensitive element of this invention. It is a perspective view which shows typically an example of the manufacturing process of the printed wiring board by a semi-additive construction method.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In this specification, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylate means acrylate or methacrylate, and (meth) acryloyloxy group means acryloyloxy group. Or means a methacryloyloxy group. (Poly) ethyleneoxy group means at least one ethyleneoxy group or polyethyleneoxy group in which two or more ethylene groups are linked by an ether bond. (Poly) propyleneoxy group means at least one propyleneoxy group or a polypropyleneoxy group in which two or more propylene groups are linked by an ether bond. Furthermore, “EO-modified” means a compound having a (poly) ethyleneoxy group, and “PO-modified” means a compound having a (poly) propyleneoxy group. “PO-modified” means a compound having both a (poly) ethyleneoxy group and a (poly) propyleneoxy group.

  In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. . Moreover, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. Furthermore, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

<Photosensitive resin composition>
The photosensitive resin composition of this embodiment comprises (A) component: a binder polymer having a structural unit derived from (meth) acrylic acid and a structural unit derived from benzyl (meth) acrylate, and (B) component: ethylene. A photopolymerizable compound having a polymerizable unsaturated bond group, (C) component: a photopolymerization initiator, and (D) a styrylpyridine compound represented by the general formula (1). The photosensitive resin composition may further contain other components as necessary.

  A binder polymer having a structural unit derived from (meth) acrylic acid and a structural unit derived from benzyl (meth) acrylate, a photopolymerizable compound having an ethylenically unsaturated bond group, a photopolymerization initiator, and a general formula By including the styrylpyridine compound represented by (1), a photosensitive resin composition capable of forming a resist pattern excellent in both resolution and adhesion with excellent sensitivity can be formed.

(A) Component: Binder Polymer The photosensitive resin composition is at least a binder polymer having a structural unit derived from (meth) acrylic acid and a structural unit derived from benzyl (meth) acrylate as the component (A). Contains one species.

  The binder polymer is, for example, as a polymerizable monomer (monomer), (meth) acrylic acid, benzyl (meth) acrylate, and other polymerizable monomers used as necessary in a radical manner. It is obtained by polymerizing.

Other polymerizable monomers can be polymerized with (meth) acrylic acid and benzyl (meth) acrylate, and may be different from (meth) acrylic acid and benzyl (meth) acrylate. There is no particular limitation. Other polymerizable monomers include (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid benzyl derivative, (meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofurfuryl. , Isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2 , 2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyloxy (meth) acrylate Ethyl, isobornyl (meth) acrylate Oxyethyl, cyclohexyloxyethyl (meth) acrylate, adamantyloxyethyl (meth) acrylate, dicyclopentenyloxypropyloxyethyl (meth) acrylate, dicyclopentanyloxypropyloxyethyl (meth) acrylate, (meth) (Meth) acrylic acid esters such as dicyclopentenyloxypropyloxyethyl acrylate, adamantyloxypropyloxyethyl (meth) acrylate; α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth) acrylic acid, (meth) acrylic acid derivatives such as β-styryl (meth) acrylic acid; polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, vinyltoluene, α-methylstyrene; diacetone acrylamide, etc. Acrylic Bromide; acrylonitrile; ether compound of vinyl alcohol and vinyl -n- butyl ether maleic acid; maleic anhydride; monomethyl maleate, monoethyl maleate, maleic acid monoesters such as maleic acid monoisopropyl; full circle acid, cinnamic And unsaturated carboxylic acid derivatives such as acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. These can be used individually by 1 type or in combination of 2 or more types.

  The content rate of the structural unit derived from (meth) acrylic acid in the binder polymer is a structural unit derived from the polymerizable monomer constituting the binder polymer from the viewpoint of effectively exhibiting developability and peeling properties. 1 mass% to 99 mass%, more preferably 5 mass% to 80 mass%, and more preferably 10 mass% to 60 mass%. More preferably, it is particularly preferably 15% by mass to 50% by mass.

  The content of the structural unit derived from benzyl (meth) acrylate in the binder polymer is the total mass of the structural unit derived from the polymerizable monomer constituting the binder polymer from the point of excellent resolution and peelability. As a reference (100% by mass, the same applies hereinafter), it is preferably 3% by mass to 85% by mass, more preferably 5% by mass to 75% by mass, and further more preferably 10% by mass to 70% by mass. The content is preferably 10% by mass to 50% by mass. From the viewpoint of excellent resolution, the content is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. Moreover, from the point which is excellent in peelability and adhesiveness, it is preferable that this content rate is 85 mass% or less, It is more preferable that it is 75 mass% or less, It is further more preferable that it is 70 mass% or less, 50 It is particularly preferable that the content is not more than mass%.

  Moreover, it is preferable that a binder polymer further has the structural unit derived from the (meth) acrylic-acid alkylester from a viewpoint of improving developability and a peeling characteristic.

  The (meth) acrylic acid alkyl ester is preferably a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms, more preferably a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms. preferable. Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic. Hexyl acid, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, (meth) An example is dodecyl acrylate. These can be used individually by 1 type or in combination of 2 or more types.

  When the binder polymer has a structural unit derived from an alkyl (meth) acrylate, the content is derived from the polymerizable monomer constituting the binder polymer in terms of excellent peelability, resolution and adhesion. It is preferably 1% by mass to 30% by mass based on the total mass (100% by mass) of the structural unit, more preferably 1% by mass to 20% by mass, and 2% by mass to 10% by mass. Is more preferable. In terms of excellent peelability, the content is preferably 1% by mass or more, and more preferably 2% by mass or more. In view of excellent resolution and adhesion, the content is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less.

  The acid value of the binder polymer is preferably 90 mgKOH / g to 250 mgKOH / g, more preferably 100 mgKOH / g to 240 mgKOH / g, and more preferably 120 mgKOH / g to 235 mgKOH / g in terms of excellent developability and adhesion. g is more preferable, and 130 mgKOH / g to 230 mgKOH / g is particularly preferable. From the viewpoint of shortening the development time, the acid value is preferably 90 mgKOH / g or more, more preferably 100 mgKOH / g or more, further preferably 120 mgKOH / g or more, and 130 mgKOH / g or more. It is particularly preferred. From the viewpoint of sufficiently achieving the adhesion of the cured product of the photosensitive resin composition, the acid value is preferably 250 mgKOH / g or less, more preferably 240 mgKOH / g or less, and 235 mgKOH / g or less. It is more preferable that it is 230 mgKOH / g or less.

  The weight average molecular weight (Mw) of the binder polymer is 10,000 to 200,000 in terms of excellent developability and adhesion when measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene). It is preferably 15000 to 100,000, more preferably 20000 to 80000, and particularly preferably 23,000 to 60000. In terms of excellent developability, it is preferably 200000 or less, more preferably 100000 or less, still more preferably 80000 or less, and particularly preferably 60000 or less. In terms of excellent adhesion, it is preferably 10,000 or more, more preferably 15,000 or more, further preferably 20,000 or more, and particularly preferably 23,000 or more.

The GPC calibration curve is approximated by a cubic equation using a standard polystyrene 5 sample set (PStQuick MP-H, PStQuick B [trade name, manufactured by Tosoh Corp.]). The GPC conditions are shown below.
Apparatus: (Pump: L-2130 type [manufactured by Hitachi High-Technologies Corporation]), (Detector: L-2490 type RI [manufactured by Hitachi High-Technologies Corporation]), (Column oven: L-2350 [( Made by Hitachi High-Technologies Corporation]])
Column: Gelpack GL-R440 + Gelpack GL-R450 + Gelpack GL-R400M (three in total) (trade name, manufactured by Hitachi Chemical Co., Ltd.)
Column size: 10.7 mmI. D. × 300mm
・ Eluent: Tetrahydrofuran ・ Sample concentration: 10 mg / 2 mL
・ Injection volume: 200 μL
・ Flow rate: 2.05 mL / min ・ Measurement temperature: 25 ° C.

  The degree of dispersion (weight average molecular weight / number average molecular weight) of the binder polymer is preferably 3.0 or less, more preferably 2.8 or less, and more preferably 2.5 or less in terms of excellent resolution and adhesion. More preferably.

  The binder polymer may have a characteristic group in its molecule that has photosensitivity to light having a wavelength in the range of 340 nm to 430 nm, if necessary. Examples of the characteristic group include a group constituted by removing at least one hydrogen atom from a sensitizing dye described later.

  As the component (A), one type of binder polymer may be used alone, or two or more types of binder polymers may be used in any combination.

  The content of the component (A) in the photosensitive resin composition is 30 parts by mass to 70 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B) in terms of excellent film formability, sensitivity, and resolution. The mass is preferably 35 parts by mass, more preferably 35 parts by mass to 65 parts by mass, and particularly preferably 40 parts by mass to 60 parts by mass. From the viewpoint of formability of the film (photosensitive resin composition layer), the content is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, and 40 parts by mass or more. Further preferred. Further, from the viewpoint of sufficiently obtaining sensitivity and resolution, the content is preferably 70 parts by mass or less, more preferably 65 parts by mass or less, and further preferably 60 parts by mass or less.

(B) Component: Photopolymerizable Compound Next, the photopolymerizable compound (hereinafter also referred to as “component (B)”) will be described. (B) The photopolymerizable compound which is a component contains at least 1 sort (s) of the photopolymerizable compound which has an ethylenically unsaturated bond group as an essential component.

  The said photosensitive resin composition contains the compound which has an ethylenically unsaturated bond group as (B) component. The compound having an ethylenically unsaturated bond group includes a compound having one ethylenically unsaturated bond group in the molecule, a compound having two ethylenically unsaturated bond groups in the molecule, and an ethylenically unsaturated bond in the molecule. Examples thereof include compounds having 3 or more groups.

  It is preferable that the said (B) component contains at least 1 sort (s) of the compound which has two ethylenically unsaturated bond groups in a molecule | numerator as a photopolymerizable compound. When the component (B) contains a compound having two ethylenically unsaturated bond groups in the molecule as the photopolymerizable compound, the content thereof is in 100 parts by mass of the total amount of the component (A) and the component (B). It is preferably 5 parts by mass to 70 parts by mass, more preferably 5 parts by mass to 65 parts by mass, and still more preferably 10 parts by mass to 60 parts by mass.

  Examples of the compound having two ethylenically unsaturated bond groups in the molecule include a bisphenol type di (meth) acrylate compound, a hydrogenated bisphenol A di (meth) acrylate compound, and a di (meta) having a urethane bond in the molecule. ) Acrylate compound, polyalkylene glycol di (meth) acrylate having both (poly) ethyleneoxy group and (poly) propyleneoxy group in the molecule, and trimethylolpropane di (meth) acrylate.

  The component (B) is a photopolymerizable compound, and from the viewpoint of improving resolution and peeling properties, a bisphenol-type di (meth) acrylate compound, a hydrogenated bisphenol A di (meth) acrylate compound, and (poly) ethylene in the molecule. It preferably contains at least one compound having two ethylenically unsaturated bond groups in the molecule selected from the group consisting of polyalkylene glycol di (meth) acrylates having an oxy group and a (poly) propyleneoxy group, More preferably, it contains at least one bisphenol-type di (meth) acrylate compound, has an ethyleneoxy group, and has at least one bisphenol-type di (meth) acrylate compound having 8 or less structural units of the ethyleneoxy group. More preferably, it contains a seed.

  Examples of the bisphenol di (meth) acrylate compound include compounds represented by the following general formula (3).

In the general formula (3), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group. XO and YO each independently represent an ethyleneoxy group or a propyleneoxy group. (XO) _m1 , (XO) _m2 , (YO) _n1 , and (YO) _n2 each represent a (poly) ethyleneoxy group or a (poly) propyleneoxy group. m1, m2, n1, and n2 each independently represent 0-40. m1, m2, n1, and n2 represent the number of structural units. Therefore, an integer value is shown in a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, the same applies to the number of structural units.

  When the compound has a propyleneoxy group, the total number of structural units of the propyleneoxy group in the compound is preferably 2 or more, more preferably 3 or more from the viewpoint of excellent resist resolution. . Moreover, it is preferable that it is 5 or less from a developable viewpoint.

  When the compound has an ethyleneoxy group, the total number of structural units of the ethyleneoxy group in the compound is preferably 4 or more, more preferably 6 or more, from the viewpoint of excellent developability. More preferably, it is 8 or more. Moreover, it is preferable that it is 16 or less from a viewpoint of resolution, and it is more preferable that it is 14 or less.

  Among the compounds represented by the general formula (3), 2,2-bis (4- (methacryloxide decaethoxytetrapropoxy) phenyl) propane is FA-3200MY (manufactured by Hitachi Chemical Co., Ltd., product name), 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane is commercially available as FA-324M (manufactured by Hitachi Chemical Co., Ltd., product name), and 2,2-bis (4- (Methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) or FA-321M (manufactured by Hitachi 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).These may be used alone or in any combination of two or more.

  When the photosensitive resin composition contains a bisphenol type di (meth) acrylate compound as the component (B), the content thereof is 1 part by mass in 100 parts by mass of the total amount of the component (A) and the component (B). It is preferably ~ 65 parts by mass, more preferably 5 parts by mass to 60 parts by mass, and still more preferably 10 parts by mass to 55 parts by mass.

  Examples of the hydrogenated bisphenol A di (meth) acrylate compound include 2,2-bis (4- (methacryloxypentaethoxy) cyclohexyl) propane. When the said photosensitive resin composition contains hydrogenated bisphenol A type | system | group di (meth) acrylate compound, as the content, 1 mass part-50 in 100 mass parts of total amounts of (A) component and (B) component. It is preferable that it is a mass part, and it is more preferable that it is 5 mass parts-40 mass parts.

  The component (B) preferably contains at least one polyalkylene glycol di (meth) acrylate as another photopolymerizable compound from the viewpoint of improving the flexibility of the resist pattern. When the photosensitive resin composition contains a polyalkylene glycol di (meth) acrylate, the content thereof is 5 to 30 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B). It is preferable that it is 10 mass parts-25 mass parts.

  As the polyalkylene glycol di (meth) acrylate compound, polyalkylene glycol di (meth) acrylate having both a (poly) ethyleneoxy group and a (poly) propyleneoxy group in the molecule is preferable. In the molecule of the polyalkylene glycol di (meth) acrylate, the (poly) ethyleneoxy group and the (poly) propyleneoxy group may be successively present in blocks or randomly. The propyleneoxy group in the (poly) propyleneoxy group may be either an n-propyleneoxy group or an isopropyleneoxy group. In the (poly) isopropyleneoxy group, the secondary carbon of the propylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.

  Polyalkylene glycol di (meth) acrylate is (poly) n-butyleneoxy group, (poly) isobutyleneoxy group, (poly) n-pentyleneoxy group, (poly) hexyleneoxy group, structural isomers thereof, etc. (Poly) alkyleneoxy group having about 4 to 6 carbon atoms and the like.

  The component (B) may contain at least one photopolymerizable compound having three or more ethylenically unsaturated bond groups in the molecule as the photopolymerizable compound.

  Examples of the compound having three or more ethylenically unsaturated bond groups include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate (one having 1 to 5 structural units of ethyleneoxy group) ), PO-modified trimethylolpropane tri (meth) acrylate, EO and PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate and tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) Examples include acrylate, ethoxylated pentaerythritol tetraacrylate, or dipentaerythritol hexa (meth) acrylate. These can be used alone or in combination of two or more.

  Tetramethylol methane triacrylate is A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name), and EO-modified trimethylol propane trimethacrylate is TMPT21E and TMPT30E (manufactured by Hitachi Chemical Co., Ltd., sample name). Pentaerythritol triacrylate is SR444 (product name, manufactured by Sartomer Co., Ltd.), and dipentaerythritol hexaacrylate is A-DPH (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethoxylated pentaerythritol. Tetraacrylate is commercially available as ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)).

  When the component (B) contains a photopolymerizable compound having three or more ethylenically unsaturated bond groups in the molecule as the photopolymerizable compound, the content thereof is resolution, adhesion, resist shape and after curing. From the viewpoint of improving the release properties in a well-balanced manner, the total amount of the component (A) and the component (B) is preferably 3 parts by mass to 30 parts by mass, and preferably 5 parts by mass to 25 parts by mass. It is more preferable that it is 5 to 20 parts by mass.

  The above component (B) is ethylenically unsaturated in the molecule as another photopolymerizable compound from the viewpoint of improving the resolution, adhesion, resist shape, and release properties after curing in a well-balanced manner, or suppressing the occurrence of scum. You may include the photopolymerizable compound which has one coupling group.

  Examples of the photopolymerizable compound having one ethylenically unsaturated bond group in the molecule include nonylphenoxypolyethyleneoxyacrylate, phthalic acid compound, and (meth) acrylic acid alkyl ester. Among the above, it is preferable that nonylphenoxypolyethyleneoxyacrylate or a phthalic acid compound is included from the viewpoint of improving the resolution, adhesion, resist shape, and release property after curing in a well-balanced manner.

  When the component (B) includes a photopolymerizable compound having one ethylenically unsaturated bond group in the molecule as the photopolymerizable compound, the content thereof is a total of 100 components (A) and (B). The mass part is preferably 1 part by mass to 20 parts by mass, more preferably 3 parts by mass to 15 parts by mass, and still more preferably 5 parts by mass to 12 parts by mass.

  The total content of the component (B) in the photosensitive resin composition is preferably 30 parts by mass to 70 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B), and 35 parts by mass. It is more preferable to set it as -65 mass parts, and it is especially preferable to set it as 35 mass parts-60 mass parts. When the content is 30 parts by mass or more, sufficient sensitivity and resolution tend to be easily obtained. When the content is 70 parts by mass or less, a film (photosensitive resin composition layer) tends to be easily formed, and a good resist shape tends to be easily obtained.

Component (C): Photopolymerization initiator The photosensitive resin composition contains at least one photopolymerization initiator as the component (C). Component (C) is at least one selected from the group consisting of 2,4,5-triarylimidazole dimer represented by the above general formula (2) and derivatives thereof from the viewpoint of improving sensitivity and adhesion. It is preferable to contain.

In formula (2), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may each independently be substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy group. Represents an aryl group, X ¹ and X ² each independently represent a halogen atom, an alkyl group, an alkenyl group or an alkoxy group, and p and q each independently represents an integer of 1 to 5. However, when p is 2 or more, a plurality of X ¹ may be the same or different, and when q is 2 or more, a plurality of X ² may be the same or different.

It is preferable that at least one of X ¹ and X ² is a chlorine atom.
When Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have the substituent, the number of substituents is preferably 1 to 5, more preferably 1 to 3, and more preferably 1. More preferably. Further, when Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have the substituent, the substitution position is not particularly limited, and is preferably the ortho position or the para position.
p and q are each independently an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1.

  Examples of the 2,4,5-triarylimidazole dimer represented by the general formula (2) or a derivative thereof include 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 -Diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer. In addition, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same to give the target compound, or differently give an asymmetric compound. These are used singly or in combination of two or more.

  As the photopolymerization initiator (C), other than the 2,4,5-triarylimidazole dimer represented by the general formula (2) or a derivative thereof, other photopolymerization initiators that are usually used. May be contained. Other photopolymerization initiators include benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2- Aromatic ketones such as 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- (2-chlorophenyl) ) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer such as 2- (2-fluorophenyl) -4,5-diphenylimidazole dimer; 9-phenylacridine, Acryl such as 1,7- (9,9′-acridinyl) heptane Emissions derivatives.

  The content of the component (C) in the photosensitive resin composition is preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is more preferably from 7 parts by mass to 7 parts by mass, further preferably from 2 parts by mass to 6 parts by mass, and particularly preferably from 3 parts by mass to 5 parts by mass. When the content of the component (C) is 0.1 parts by mass or more, good sensitivity, resolution, or adhesion tends to be obtained, and when it is 10 parts by mass or less, a good resist shape is easily obtained. Tend.

Component (D): Sensitizing dye In the photosensitive resin composition of the present embodiment, at least one styrylpyridine compound represented by the following general formula (1) is used as an essential component as the component (D). (D) The sensitizing dye which is a component can be used individually by 1 type or in combination of 2 or more types.

In formula (1), R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, or an amino group. , An alkylamino group having 1 to 20 carbon atoms, a carboxyl group, a cyano group, a nitro group, an acetyl group or a (meth) acryl group, and a, b and c each independently represent an integer of 0 to 5. However, when a is 2 or more, a plurality of R ¹ may be the same or different, and when b is 2 or more, a plurality of R ² may be the same or different, and c is 2 or more. In the case, a plurality of R ³ may be the same or different.

From the viewpoint of further improving the sensitivity, wherein ^{(1), R 1, R} 2 and ^{R 3} are independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, 1 to carbon atoms Preferably, it is a 6 alkyl ester group, an amino group, or an alkylamino group having 1 to 20 carbon atoms.
Moreover, a, b, and c show the integer of 0-5 each independently, the integer of 0-3 is preferable, and the integer of 0-2 is more preferable.

  Examples of the styrylpyridine compound represented by the general formula (1) include 3,5-dibenzylidenedicyclopentano [b, e] -4-phenylpyridine, 3,5-bis (4-methylbenzylidene diene). Cyclopentano [b, e])-4- (4-methylphenyl) pyridine, 3,5-bis (4-methoxybenzylidenedicyclopentano [b, e])-4- (4-methoxyphenyl) pyridine 3,5-bis (4-aminobenzylidenedicyclopentano [b, e])-4- (4-aminophenyl) pyridine, 3,5-bis (4-dimethylaminobenzylidenedicyclopentano [b, e])-4- (4-dimethylaminophenyl) pyridine, 3,5-bis (4-carboxybenzylidenedicyclopentano [b, e])-4- (4-carboxyphenyl) Lysine, 3,5-bis (4-acetylbenzylidenedicyclopentano [b, e])-4- (4-acetylphenyl) pyridine, 3,5-bis (4-cyanobenzylidenedicyclopentano [b, e])-4- (4-cyanophenyl) pyridine, 3,5-bis (4-nitrobenzylidenedicyclopentano [b, e])-4- (4-nitrophenyl) pyridine, 3,5-bis (4-acryloylbenzylidenedicyclopentano [b, e])-4- (4-acryloylphenyl) pyridine and 3,5-bis (2,4-dimethoxybenzylidenedicyclopentano [b, e])- 4- (2,4-dimethoxyphenyl) pyridine is mentioned.

  The styrylpyridine compound represented by the general formula (1) can be synthesized, for example, by a condensation reaction of a benzaldehyde derivative, a cyclic alkyl ketone, and ammonium acetate.

  The total content of the component (D) in the photosensitive resin composition is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is more preferable to set it as 0.05 mass part-5 mass parts, and it is still more preferable to set it as 0.1 mass part-3 mass parts. When the content is 0.01 parts by mass or more, sensitivity and resolution tend to be easily obtained. When the content is 10 parts by mass or less, a sufficiently good resist shape tends to be easily obtained.

(E) component: amine compound It is preferable that the said photosensitive resin composition contains at least 1 sort (s) of an amine compound as (E) component. Examples of the amine compound include bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leuco crystal violet. These can be used alone or in combination of two or more.

  When the photosensitive resin composition includes the component (E), the content is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass. If this content is 0.01 parts by mass or more, sufficient sensitivity tends to be obtained. If the content is 10 parts by mass or less, it is likely that excessive (E) component is prevented from being precipitated as a foreign substance after film formation.

(Other ingredients)
The above-mentioned photosensitive resin composition may contain, if necessary, 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, Victoria pure blue, Dye such as brilliant green and methyl violet, photochromic agent such as tribromophenylsulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline and 2-chloroaniline, thermochromic inhibitor, plasticizer such as 4-toluenesulfonamide , Pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, perfumes, imaging agents, thermal crosslinking agents, and the like. These are used individually by 1 type or in combination of 2 or more types. When the photosensitive resin composition contains other components, these contents are about 0.01 parts by mass to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B), respectively. It is preferable.

[Solution of photosensitive resin composition]
The photosensitive resin composition of this embodiment may further contain at least one organic solvent. Organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; N, N- And aprotic polar solvents such as dimethylformamide. These may be used alone or in combination of two or more. Content of the organic solvent contained in the said photosensitive resin composition can be suitably selected according to the objective etc. For example, it can be used as a solution having a solid content of about 30% by mass to 60% by mass. Hereinafter, the photosensitive resin composition containing the organic solvent is also referred to as “coating liquid”.

  The said coating liquid is apply | coated on surfaces, such as a support film mentioned later and a metal plate, and the photosensitive resin composition layer which is a coating film of the said photosensitive resin composition can be formed by making it dry. It does not restrict | limit especially as a metal plate, According to the objective etc., it can select suitably. Examples of the metal plate include metal plates such as copper, copper alloys, iron alloys such as nickel, chromium, iron, and stainless steel. As a metal plate, Preferably, metal plates, such as copper, a copper-type alloy, and an iron-type alloy, are mentioned.

  The thickness of the photosensitive resin composition layer to be formed is not particularly limited and can be appropriately selected depending on the application. For example, the thickness after drying is preferably about 1 μm to 100 μm. When the photosensitive resin composition layer is formed on the metal plate, the surface of the photosensitive resin composition layer may be covered with a protective film. Examples of the protective film include polymer films such as polyethylene and polypropylene.

  The said photosensitive resin composition is applicable to formation of the photosensitive resin composition layer of the photosensitive element mentioned later. That is, another embodiment of the present invention comprises (A) component: a binder polymer having a structural unit derived from (meth) acrylic acid and a structural unit derived from benzyl (meth) acrylate, and (B) component: ethylenic. A photosensitive resin composition comprising a photopolymerizable compound having an unsaturated bond group, (C) component: a photopolymerization initiator, and (D) component: a styrylpyridine compound represented by the general formula (1). Application to photosensitive elements. Moreover, the photosensitive resin composition of this embodiment can be used for the manufacturing method of the board | substrate with a resist pattern mentioned later. That is, another embodiment of the present invention comprises (A) component: a binder polymer having a structural unit derived from (meth) acrylic acid and a structural unit derived from benzyl (meth) acrylate, and (B) component: ethylenic. A photosensitive resin composition comprising a photopolymerizable compound having an unsaturated bond group, (C) component: a photopolymerization initiator, and (D) component: a styrylpyridine compound represented by the general formula (1). This is an application to a method for manufacturing a substrate with a resist pattern.

<Photosensitive element>
The photosensitive element of this invention is equipped with the support film and the photosensitive resin composition layer which is a coating film of the said photosensitive resin composition provided on this support film. The coating film is one in which the photosensitive resin composition is in an uncured state. The said photosensitive element may have other layers, such as a protective film, as needed.

  FIG. 1 shows an embodiment of the photosensitive element. In the photosensitive element 1 shown in FIG. 1, a support film 2, a photosensitive resin composition layer 3 that is a coating film of the photosensitive resin composition, and a protective film 4 are laminated in this order. The photosensitive element 1 can be obtained as follows, for example. On the support film 2, the coating liquid which is the said photosensitive resin composition containing an organic solvent is apply | coated, an application layer is formed, and the photosensitive resin composition layer 3 is formed by drying this. Next, the surface of the photosensitive resin composition layer 3 opposite to the support film 2 is covered with a protective film 4, thereby supporting the support film 2 and the photosensitive resin composition layer 3 laminated on the support film 2. And the photosensitive element 1 of this embodiment provided with the protective film 4 laminated | stacked on this photosensitive resin composition layer 3 is obtained. The photosensitive element 1 does not necessarily have to include the protective film 4.

  As the support film 2, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used.

  The thickness of the support film (polymer film) 2 is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, and still more preferably 5 μm to 30 μm. When the thickness of the support film 2 is 1 μm or more, the support film 2 can be prevented from being broken when the support film 2 is peeled off. Moreover, the fall of the resolution is suppressed because the thickness of the support film 2 is 100 micrometers or less.

  The protective film 4 preferably has a smaller adhesive force to the photosensitive resin composition layer 3 than the adhesive force of the support film 2 to the photosensitive resin composition layer 3. A low fisheye film is preferred. Here, “fish eye” means that when a material is heat-melted, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are present in the film. It means what was taken in. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.

  Specifically, as the protective film 4, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polyolefin such as polypropylene and polyethylene can be used. Examples of commercially available products include polypropylene films such as Alphan MA-410 and E-200 manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and PS series polyethylene terephthalate films such as PS-25 manufactured by Teijin Limited. It is done. The protective film 4 may be the same as the support film 2.

  The thickness of the protective film 4 is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, still more preferably 5 μm to 30 μm, and particularly preferably 15 μm to 30 μm. When the thickness of the protective film 4 is 1 μm or more, the protective film 4 can be prevented from being broken when the photosensitive resin composition layer 3 and the support film 2 are laminated on the substrate while peeling off the protective film 4. When the thickness of the protective film 4 is 100 μm or less, it is excellent in handleability and inexpensiveness.

  Specifically, the photosensitive element of this embodiment can be manufactured as follows, for example. (A) component: binder polymer, (B) component: photopolymerizable compound, (C) photopolymerization initiator, and (D) component: a coating solution prepared by dissolving a sensitizing dye in the organic solvent. And a step of forming the coating layer by applying the coating solution on the support film 2 and a step of forming the photosensitive resin composition layer 3 by drying the coating layer. can do.

  Application of the photosensitive resin composition solution onto the support film 2 can be performed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating.

  The drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. It is preferable to carry out at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin composition layer 3 is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

  The thickness of the photosensitive resin composition layer 3 in the photosensitive element can be appropriately selected depending on the application. The thickness after drying is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, and still more preferably 5 μm to 40 μm. Industrial coating becomes easy because the thickness of the photosensitive resin composition layer 3 is 1 μm or more. When the thickness of the photosensitive resin composition layer 3 is 100 μm or less, adhesion and resolution tend to be sufficiently obtained.

The transmittance of the photosensitive resin composition layer 3 with respect to ultraviolet rays is preferably 5% to 75%, more preferably 10% to 65%, with respect to ultraviolet rays having a wavelength in the range of 350 nm to 420 nm. % To 55% is particularly preferable. When the transmittance is 5% or more, sufficient adhesion tends to be obtained. When this transmittance is 75% or less, sufficient resolution tends to be easily obtained. The transmittance can be measured with a UV spectrometer.
An example of the UV spectrometer is a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

  The photosensitive element may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. As these intermediate layers, for example, the intermediate layers described in JP-A-2006-098982 can also be applied in the present invention.

  The form of the obtained photosensitive element is not particularly limited. For example, it may be in the form of a sheet, or may be in the form of a roll wound around a core. When winding in roll form, it is preferable to wind up so that the support film 2 may become an outer side. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). From the viewpoint of end face protection, it is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll thus obtained, and it is preferable to install a moisture-proof end face separator from the standpoint of edge fusion resistance. As a packaging method, it is preferable to wrap and package in a black sheet with low moisture permeability.

  The photosensitive element of this embodiment can be used suitably for the manufacturing method of the board | substrate with a resist pattern mentioned later, for example.

<Method for manufacturing substrate with resist pattern>
A substrate with a resist pattern can be produced using the photosensitive resin composition. The method for producing a substrate with a resist pattern according to this embodiment includes (i) a lamination step of laminating a photosensitive resin composition layer, which is a coating film of the photosensitive resin composition, on the substrate, and (ii) the photosensitive resin. An exposure step of irradiating at least a part of the composition layer with actinic rays to expose the region to form a cured product region; and (iii) other than the cured product region of the photosensitive resin composition layer. A development step of removing the region from the substrate and forming a resist pattern comprising the cured product region on the substrate. The manufacturing method of the said board | substrate with a resist pattern may have another process further as needed.

(I) Lamination process First, the photosensitive resin composition layer 3 which is a coating film of the said photosensitive resin composition is laminated | stacked on a board | substrate. As the substrate, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used.

  For example, when the photosensitive element has the protective film 4, the photosensitive resin composition layer 3 is laminated on the substrate after the protective film 4 is removed and then the photosensitive resin composition of the photosensitive element. This is performed by pressing the physical layer 3 to the substrate while heating. Thereby, the laminated body by which the board | substrate, the photosensitive resin composition layer 3, and the support film 2 were laminated | stacked in this order is obtained.

This lamination step is preferably performed under reduced pressure from the viewpoint of adhesion and followability. Heating at least one of the photosensitive resin composition layer 3 and the substrate at the time of pressure bonding is preferably performed at a temperature of 70 ° C. to 130 ° C., and about 0.1 MPa to 1.0 MPa (1 kgf / cm ^{2 to} 10 kgf / cm). It is preferable to perform pressure bonding at a pressure of about ² ). These conditions are not particularly limited, and are appropriately selected as necessary. In addition, if the photosensitive resin composition layer 3 is heated to 70 ° C. to 130 ° C., it is not necessary to pre-heat the substrate in advance. Adhesion and follow-up can be further improved by pre-heat treatment of the circuit forming substrate.

(Ii) Exposure Step In the exposure step, an exposed portion irradiated with actinic rays by irradiating at least a part of the photosensitive resin composition layer 3 formed on the substrate as described above with actinic rays. Is photocured to form a latent image. Under the present circumstances, when the support film 2 which exists on the photosensitive resin composition layer 3 is transparent with respect to actinic light, it can irradiate actinic light through the support film 2. FIG. On the other hand, when the support film 2 shows a light-shielding property against actinic rays, the photosensitive resin composition layer 3 is irradiated with actinic rays after the support film 2 is removed.

  Examples of the exposure method include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork (mask exposure method). Alternatively, a method of irradiating actinic rays in an image form by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.

  The light source for actinic rays is not particularly limited, and a known light source can be used. For example, carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, solid-state lasers such as YAG lasers, ultraviolet rays such as semiconductor lasers and gallium nitride blue-violet lasers, and visible light are effectively emitted. What to do is used.

  The wavelength of the actinic ray (exposure wavelength) is preferably in the range of 340 nm to 430 nm, more preferably in the range of 350 nm to 420 nm, from the viewpoint of obtaining the effects of the present invention more reliably.

(Iii) Development step In the development step, the uncured portion of the photosensitive resin composition layer 3 is removed from the circuit forming substrate by a development treatment, whereby the cured product obtained by photo-curing the photosensitive resin composition layer 3. A resist pattern is formed on the substrate. When the support film 2 exists on the photosensitive resin composition layer 3, the support film 2 is removed, and then the unexposed portion is removed (development). Development processing includes wet development and dry development, and wet development is widely used.

In the case of wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. As a developing method, dipping method, Pa Torr method, spraying method, brushing, slapping, scratcher bi ring, include methods using reciprocal dipping, etc., from the viewpoint of improved resolution, high-pressure spray system is most suitable Yes. You may develop by combining these 2 or more types of methods.

  The developer is appropriately selected according to the configuration of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution, an aqueous developer, an organic solvent developer, and the like.

  The alkaline aqueous solution is safe and stable when used as a developer, and has good operability. 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, sodium phosphate, and the like. Alkali metal phosphates; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used.

  Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1% by mass to 5% by mass of sodium carbonate, a dilute solution of 0.1% by mass to 5% by mass of potassium carbonate, and 0.1% by mass to 5% by mass of sodium hydroxide. A dilute solution of 0.1 mass% to 5 mass% of sodium tetraborate is preferred. The pH of the alkaline aqueous solution is preferably in the range of 9-11. The temperature is adjusted in accordance with the alkali developability of the photosensitive resin composition layer 3. The alkaline aqueous solution may contain a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like.

  The aqueous developer is, for example, 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, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3 -Propanediol, 1,3-diamino-2-propanol, morpholine and the like. The pH of the aqueous developer is preferably as low as possible within a range where development is sufficiently performed, preferably 8 to 12, and more preferably 9 to 10.

  Examples of the organic solvent used in the aqueous developer 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. Etc. These are used individually by 1 type or in combination of 2 or more types. The content of the organic solvent in the aqueous developer is usually preferably 2% by mass to 90% by mass. Moreover, the temperature can be adjusted according to alkali developability. A small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.

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

The resist in the patterned substrate manufacturing method, by performing after the removal of the unexposed portions, the order of 60 ° C. to 250 DEG ° C. heating or 0.2J ^/ cm ² ~10J ^/ cm 2 about exposure as necessary, A step of further curing the resist pattern may be further included.

<Method for manufacturing printed wiring board>
The method for producing a printed wiring board of the present invention includes a step of forming a conductor pattern by etching or plating the substrate on which the resist pattern is formed by the method for producing a substrate with a resist pattern. As the substrate, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer is preferably used. The manufacturing method of a printed wiring board may include other processes, such as a resist removal process, as needed. Etching or plating of the substrate is performed on the conductor layer of the substrate using the formed resist pattern as a mask.

  In the etching process, using the resist pattern (cured resist) formed on the substrate as a mask, the conductor layer of the circuit forming substrate not covered with the cured resist is removed by etching to form a conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. Examples of the etching solution include cupric chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide etching solution and the like. Among these, it is preferable to use a ferric chloride solution because it has a good etch factor.

  On the other hand, in the plating process, copper, solder, or the like is plated on the conductor layer of the circuit forming substrate that is not covered with the cured resist, using the resist pattern (cured resist) formed on the substrate as a mask. After the plating treatment, the hardened resist is removed, and the conductor layer covered with the hardened resist is etched to form a conductor pattern. The method of plating treatment may be electrolytic plating treatment or electroless plating treatment. The plating treatment includes copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, hard gold plating, and soft plating. Examples thereof include gold plating such as gold plating.

  After the etching process and the plating process, the resist pattern on the substrate is removed (peeled). The resist pattern can be removed using, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step. As this strongly alkaline aqueous solution, a 1% by mass to 10% by mass sodium hydroxide aqueous solution, a 1% by mass to 10% by mass potassium hydroxide aqueous solution and the like are used. Among them, it is preferable to use a 1% by mass to 10% by mass sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution, and it is more preferable to use a 1% by mass to 5% by mass sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution. Examples of the application method of the alkaline aqueous solution include a dipping method and a spray method, and these may be used alone or in combination.

  When the resist pattern is removed after the plating process, a desired printed wiring board can be manufactured by further removing the conductor layer covered with the cured resist by the etching process and forming the conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. For example, the above-described etching solution can be applied.

  The printed wiring board manufacturing method of the present invention can be applied not only to a single-layer printed wiring board but also to a multilayer printed wiring board, and also to a printed wiring board having a small-diameter through hole. .

  The photosensitive resin composition of this embodiment can be used suitably for manufacture of a wiring board. That is, one of the preferred embodiments of the present invention includes (A) component: a binder polymer having a structural unit derived from (meth) acrylic acid and a structural unit derived from benzyl (meth) acrylate, and (B) Component: a photopolymerizable compound having an ethylenically unsaturated bond group; (C) component: a photopolymerization initiator; and (D) component: a styrylpyridine compound represented by the general formula (1). This is an application of the resin composition to the production of a printed wiring board. A more preferred embodiment is application of the photosensitive resin composition to the production of a high-density package substrate, and application of the photosensitive resin composition to a semi-additive construction method. Below, an example of the manufacturing process of the wiring board by a semi-additive construction method is demonstrated, referring drawings.

  In FIG. 2A, a substrate (circuit forming substrate) in which the conductor layer 10 is formed on the insulating layer 15 is prepared. The conductor layer 10 is, for example, a metal copper layer. In FIG.2 (b), the photosensitive resin composition layer 32 is laminated | stacked on the conductor layer 10 of a board | substrate by the said lamination process. In FIG.2 (c), the mask 20 is laminated | stacked on the photosensitive resin composition layer 32, actinic light 50 is irradiated, area | regions other than the area | region where the mask 20 was laminated | stacked are exposed, and a photocuring part is formed. . In FIG. 2D, the resist pattern 30 which is a photocuring part is formed on a board | substrate by removing areas other than the photocuring part formed by the said exposure process from a board | substrate by a image development process. In FIG. 2E, a plating layer 42 is formed on the conductor layer 10 by plating using the resist pattern 30 that is a photocured portion as a mask. In FIG. 2F, after the resist pattern 30 which is a photocured portion is peeled off with a strong alkaline aqueous solution, a part of the plating layer 42 and the conductor layer 10 masked by the resist pattern 30 are removed by flash etching. The circuit pattern 40 is formed by removing. Although the method of forming the resist pattern 30 using the mask 20 has been described with reference to FIG. 2, the resist pattern 30 may be formed by direct drawing exposure without using the mask 20.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
(Preparation of solution of photosensitive resin composition)
By mixing the components (A) to (E) shown in Tables 2 and 3 with 9 g of acetone, 5 g of toluene and 5 g of methanol in the blending amounts (g units) shown in the same table, Examples 1 to 3 and Comparative Example Solutions of 1 to 4 photosensitive resin compositions were respectively prepared. The blending amount of the component (A) shown in Tables 2 and 3 is the mass (solid content) of the nonvolatile content. Details of each component shown in Tables 2 and 3 are as follows. “-” Means not blended.

(A) Binder polymer [synthesis of binder polymer (A-1)]
90 g of methacrylic acid which is a polymerizable monomer (monomer), 6 g of methyl methacrylate, styrene 150 and 54 g of benzyl methacrylate (mass ratio 30/2/50/18) and 1.5 g of azobisisobutyronitrile. The solution obtained by mixing was designated as “Solution a”.

  A solution obtained by dissolving 0.5 g of azobisisobutyronitrile in 100 g of a mixed solution (mass ratio 3: 2) of 60 g of methyl cellosolve and 40 g of toluene was designated as “Solution b”.

  A flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube was charged with 300 g of a mixture of 180 g of methyl cellosolve and 120 g of toluene (mass ratio 3: 2), and nitrogen gas was introduced into the flask. The mixture was heated with stirring while being blown, and the temperature was raised to 80 ° C.

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

  The binder polymer (A-1) had a non-volatile content (solid content) of 47.4% by mass, a weight average molecular weight of 44,000, an acid value of 196 mgKOH / g, and a dispersity of 1.6.

  The weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.

GPC conditions Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: 3 in total, column specifications: 10.7 mmφ x 300 mm
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M (Hitachi Chemical Co., Ltd., trade name) Eluent: Tetrahydrofuran (THF)
Sample concentration: 120 mg of a resin solution having a solid content of 40% was collected and dissolved in 5 mL of THF to prepare a sample.
Measurement temperature: 40 ° C
Injection volume: 200 μL
Pressure: 49Kgf / cm ² (4.8MPa)
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

[Synthesis of Binder Polymers (A-2) to (A-4)]
As the polymerizable monomer (monomer), the binder polymer (A-2) was obtained in the same manner as the solution of the binder polymer (A-1) except that the materials shown in Table 1 were used in the mass ratio shown in the same table. ) To (A-4) were obtained.

  Table 1 shows the mass ratio (%), acid value, weight average molecular weight, and degree of dispersion of the polymerizable monomers (monomers) for the binder polymers (A-1) to (A-4). “-” Means not blended.

(B) Photopolymerizable compound FA-321M (manufactured by Hitachi Chemical Co., Ltd., trade name): 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane FA-324M (manufactured by Hitachi Chemical Co., Ltd., Product name): 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane FA-3200MY (trade name, manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis (4- (methacryloxyethoxypropoxy) Phenyl) propane (ethylene oxide average 12 mol and propylene oxide average 4 mol adduct)

(C) Photopolymerization initiator B-CIM (product name, manufactured by Hampford): 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole [2- ( 2-chlorophenyl) -4,5-diphenylimidazole dimer]

(D) Sensitizing dye 2,4-DMOP-DSP (synthetic sample name): 3,5-bis (2,4-dimethoxybenzylidenedicyclopentano [b, e])-4- (2,4- Dimethoxyphenyl) pyridine • PYR-1 (manufactured by Nippon Chemical Industry Co., Ltd.): 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline • EAB (manufactured by Hodogaya Chemical Co., Ltd.) Name): 4,4′-diethylaminobenzophenone H-MOP-DSP (synthetic sample name): 4,6-bis (4-methoxybenzylidenedicyclohexano [b, e])-5- (4-methoxyphenyl) Pyridine

(E) Amine compound LCV (manufactured by Yamada Chemical Co., Ltd., product name): Leuco Crystal Violet

Dye ・ MKG (Osaka Organic Chemical Co., Ltd., product name): Malachite Green

<Production of photosensitive element>
The photosensitive resin composition solution obtained above was applied onto a polyethylene terephthalate film having a thickness of 16 μm (product name “FB-40” manufactured by Toray Industries, Inc.), and hot air convection at 70 ° C. and 110 ° C. A photosensitive resin composition layer having a dried film thickness of 25 μm was formed by sequentially drying with a type dryer. A protective film (manufactured by Oji Paper Co., Ltd., product name “E-200K”) is bonded onto the photosensitive resin composition layer, and a polyethylene terephthalate film (support film), the photosensitive resin composition layer, and the protective film are bonded. A photosensitive element in which and were sequentially laminated was obtained.

<Production of laminated substrate>
Copper-clad laminate (product name “MCL-E-679F” manufactured by Hitachi Chemical Co., Ltd.) (hereinafter referred to as “substrate”) made of glass epoxy material and copper foil (thickness 16 μm) formed on both surfaces thereof. ) Was heated to 80 ° C., and the photosensitive elements according to Examples 1 to 3 and Comparative Examples 1 to 4 were laminated (laminated) on the copper surface of the substrate. Lamination is performed under conditions of a temperature of 120 ° C. and a lamination pressure of 4 kgf / cm ² (0.4 MPa) so that the photosensitive resin composition layer of each photosensitive element is in close contact with the copper surface of the substrate while removing the protective film. Went under. Thus, the laminated substrate by which the photosensitive resin composition layer and the polyethylene terephthalate film were laminated | stacked on the copper surface of the board | substrate was obtained.

The obtained laminated substrate was allowed to cool and when the temperature reached 23 ° C., on the polyethylene terephthalate film of the laminated substrate, a concentration region of 0.00 to 2.00, a concentration step of 0.05, and a tablet size of 20 mm × 187 mm. A photo tool having a 41-step tablet having a size of 3 mm × 12 mm for each step was brought into close contact. Using a direct drawing exposure machine “Paragon 9000M” (product name) manufactured by Orbotech using a semiconductor laser having a wavelength of 355 nm as a light source, with a photo tool and a polyethylene terephthalate film at an energy amount (exposure amount) of 100 mJ / cm ² Exposure was performed with respect to the photosensitive resin composition layer.

<Evaluation of sensitivity>
After the exposure, the polyethylene terephthalate film was peeled from the laminated substrate, the photosensitive resin composition layer was exposed, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 60 seconds to remove unexposed portions. Thus, the resist pattern which consists of hardened | cured material of the photosensitive resin composition was formed on the copper surface of a board | substrate. The sensitivity of the photosensitive resin composition was evaluated by measuring the number of remaining steps (step number) of the step tablet obtained as a resist pattern (cured film). Sensitivity is indicated by the amount of energy (unit: mJ / cm ² ) at which the number of step steps is 23, and the lower this value, the better the sensitivity. The results are shown in Tables 4 and 5.

<Evaluation of resolution and adhesion>
The remaining 41-step tablet using a drawing pattern having a line width (L) / space width (S) (hereinafter referred to as “L / S”) of 3/3 to 30/30 (unit: μm) Exposure (drawing) was performed on the photosensitive resin composition layer of the laminated substrate with an energy amount of 23 steps. After the exposure, the same development processing as in the sensitivity evaluation was performed.

  After development, the space portion (unexposed portion) is removed without residue, and the line portion (exposed portion) is formed with the minimum value of the line width / space width values in the resist pattern formed without meandering and chipping. The resolution and adhesion were evaluated. A smaller value means better resolution and adhesion. The results are shown in Tables 4 and 5.

  As is clear from Tables 4 and 5, a binder polymer having (meth) acrylic acid and benzyl (meth) acrylate, a photopolymerizable compound having an ethylenically unsaturated bond group, a photopolymerization initiator, The resist pattern formed from the photosensitive resin composition containing the styrylpyridine compound represented by the formula (1) was excellent in all of sensitivity, resolution, and adhesion.

DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 2 ... Support film, 3 ... Photosensitive resin composition layer, 4 ... Protective film, 10 ... Conductive layer, 15 ... Insulating layer, 20 ... Mask, 30 ... Resist pattern, 32 ... Photosensitive resin composition Material layer, 40 ... circuit pattern, 42 ... plating layer

Claims (6)

(A) a binder polymer having a structural unit derived from (meth) acrylic acid and benzyl (meth) acrylate;
(B) a photopolymerizable compound having an ethylenically unsaturated bond group;
(C) a photopolymerization initiator;
(D) A photosensitive resin composition containing a styrylpyridine compound represented by the following general formula (1).

Wherein ^{(1), R 1, R} 2 and ^{R 3} are independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, amino Group, a C1-C20 alkylamino group, a carboxyl group, a cyano group, a nitro group, an acetyl group or a (meth) acryl group, a, b and c each independently represents an integer of 0 to 5. However, when a is 2 or more, a plurality of R ¹ may be the same or different, and when b is 2 or more, a plurality of R ² may be the same or different, and c is 2 or more. In the case, a plurality of R ³ may be the same or different. ] (C) The photopolymerization initiator contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers represented by the following general formula (2) and derivatives thereof. The photosensitive resin composition as described in 2.

[In Formula (2), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may each independently be substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group and an alkoxy group. A good aryl group, X ¹ and X ² each independently represent a halogen atom, an alkyl group, an alkenyl group or an alkoxy group; p and q each independently represent an integer of 1 to 5; However, when p is 2 or more, a plurality of X ¹ may be the same or different, and when q is 2 or more, a plurality of X ² may be the same or different. ]   A photosensitive element comprising: a support film; and a photosensitive resin composition layer that is a coating film of the photosensitive resin composition according to claim 1 or 2 provided on the support film. A laminating step of laminating a photosensitive resin composition layer which is a coating film of the photosensitive resin composition according to claim 1 or 2 on a substrate;
An exposure step of irradiating at least a part of the photosensitive resin composition layer with actinic rays and photocuring the region to form a cured product region;
A development step of removing a region other than the cured product region of the photosensitive resin composition layer from the substrate and forming a resist pattern including the cured product region on the substrate;
The manufacturing method of the board | substrate with a resist pattern which has this.   The method for producing a substrate with a resist pattern according to claim 4, wherein the wavelength of the active light is in a range of 340 nm to 430 nm.   A method for producing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method for producing a substrate with a resist pattern according to claim 4 or 5.