JP2017167396A - Photosensitive resin composition, photosensitive element, method for producing substrate with resist pattern, and method for manufacturing printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having excellent chemical solution resistance, a photosensitive element, and a method for manufacturing a printed wiring board.SOLUTION: A photosensitive resin composition comprises a (meth) acrylic acid binder polymer, a urethane (meth) acrylate, a photopolymerization initiator and a compound represented by formula (1).SELECTED DRAWING: None

Description

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

  In the field of manufacturing printed wiring boards, a photosensitive resin composition is widely used as a resist material used when etching or plating is performed on a circuit forming substrate. A photosensitive resin composition includes a support and a layer (hereinafter also referred to as “photosensitive layer”) using the photosensitive resin composition provided on the support. ) Is often used.

  A printed wiring board is manufactured as follows, for example. First, a photosensitive layer is formed on a circuit forming substrate using a photosensitive element (photosensitive layer forming step). Next, the exposed portion is cured by irradiating a predetermined portion of the photosensitive layer with actinic rays (exposure step). Then, after peeling off and removing the support, a resist pattern made of a cured product of the photosensitive resin composition is formed on the circuit forming substrate by removing (developing) the unexposed portion of the photosensitive layer from the substrate. (Development process). After the conductor pattern (circuit) is formed on the substrate by performing etching or plating on the substrate using the formed resist pattern as a resist (circuit formation process), the resist pattern is finally peeled off and removed. (Peeling step) to produce a printed wiring board.

  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 layer has been proposed. This direct drawing exposure method has been introduced for manufacturing a high-density package substrate because it has better alignment accuracy than a photomask-based exposure method and can provide a high-definition pattern.

  In general, in the exposure process, it is desired 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. There is a tendency. 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, it is difficult to form a resist pattern having an L / S (line width / space width) of 10/10 (unit: μm) or less in package substrate fabrication. Therefore, it is strongly required to improve the resolution (resolution) and adhesion of the resist pattern in units of 1 μm.

  Conventionally, various photosensitive resin compositions have been studied in response to these requirements. For example, Patent Document 1 proposes a photosensitive resin composition that improves the above-described required characteristics by using a styrylpyridine compound as a sensitizing dye. Patent Documents 2 to 5 disclose a photosensitive resin composition that improves the above-described required characteristics by using a specific binder polymer, photopolymerizable compound, photopolymerization initiator, and sensitizing dye. Proposed.

Chinese Patent Application No. 101738861 JP 2005-122123 A JP 2007-114452 A International Publication No. 10/098183 International Publication No. 12/067107

  By the way, it is preferable that the resist pattern formed by the photosensitive resin composition is excellent in chemical resistance. When a plating process is performed on a substrate using a resist pattern having poor chemical resistance as a resist, plating dipping may occur. Here, “plating dive” means a phenomenon in which a plating solution enters between the resist pattern and the substrate. In particular, since the printed wiring board has been densified in recent years, there is a possibility that the conductor pattern is connected and short-circuited when plating submergence occurs.

  However, although the photosensitive resin compositions described in Patent Documents 1 to 5 have relatively high sensitivity, there is still room for improvement in chemical resistance of the resist pattern to be formed.

  The present disclosure relates to a photosensitive resin composition capable of forming a resist pattern excellent in chemical resistance with excellent sensitivity, a photosensitive element using the photosensitive resin composition, a method for manufacturing a substrate with a resist pattern, and a printed wiring board. It is an object to provide a manufacturing method.

Specific means for solving the above problems include the following embodiments.
<1> (A) a binder polymer having a structural unit derived from (meth) acrylic acid;
(B) a photopolymerizable compound containing (meth) acrylate having a urethane bond;
(C) a photopolymerization initiator;
(D) The photosensitive resin composition containing the styryl pyridine compound shown by following 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, An amino group, an alkylamino group having 1 to 20 carbon atoms, a carboxy group, a cyano group, a nitro group, an acetyl group, or a (meth) acryloyl group; a, b, and c each independently represent 0 to 5; Indicates an integer. ]

<2> The (meth) acrylate having a urethane bond includes at least one compound selected from the group consisting of a compound represented by the following formula (2) and a compound represented by the following formula (3). > Photosensitive resin composition.

[In Formula (2), Q represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a phenylene group, and R ⁴ and R ⁵ are each independently a hydrogen atom or methyl. L ¹ represents an ethylene group, L ² represents a propylene group, L ³ represents a butylene group, r 1 and r 2 each independently represent a number of 1 to 40, s 1, s2, t1, and t2 each independently represents a number from 0 to 40. ]

[In the formula (3), R ⁶ , R ⁷ and R ⁸ each independently represents an alkylene group having 1 to 20 carbon atoms, and R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom. Or a methyl group, L ¹ represents an ethylene group, L ² represents a propylene group, L ³ represents a butylene group, and r ³ , r 4, and r 5 are each independently a number of 1 to 40. S3, s4, s5, t3, t4, and t5 each independently represents a number from 0 to 40. ]

<3> The photosensitive resin composition according to <1> or <2>, wherein the (C) photopolymerization initiator includes a 2,4,5-triarylimidazole dimer represented by the following formula (4): object.

[In Formula (4), Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group, and an alkoxy 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. Show. ]

A photosensitive element provided with a <4> support body and the photosensitive layer which uses the photosensitive resin composition of any one of <1>-<3> provided on the said support body.

<5> forming a photosensitive layer using the photosensitive resin composition according to any one of <1> to <3> on a substrate;
Irradiating at least a part of the photosensitive layer with actinic rays to photocuring the region to form a cured product region;
Removing at least a portion of the photosensitive layer other than the cured product region from the substrate, and forming a resist pattern on the substrate.

<6> The method for producing a substrate with a resist pattern according to <5>, wherein the wavelength of the actinic ray is within a range of 340 to 430 nm.

<7> A printed wiring board having a step of performing at least one of an etching process and a plating process on a substrate on which a resist pattern is formed by the method for producing a substrate with a resist pattern according to <5> or <6> Production method.

  According to the present disclosure, a photosensitive resin composition capable of forming a resist pattern with excellent chemical resistance with excellent sensitivity, a photosensitive element using the photosensitive resin composition, a method for producing a substrate with a resist pattern, and a print A method for manufacturing a wiring board can be provided.

It is a schematic cross section which shows an example of the photosensitive element. 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 of the present invention will be described. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and the present invention is not limited thereto.

  In this specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acryloyl” means acryloyl. Or methacryloyl. The “(poly) ethyleneoxy group” means at least one of an ethyleneoxy group (hereinafter also referred to as “EO group”) or a polyethyleneoxy group in which two or more ethylene groups are connected by an ether bond. The “(poly) propyleneoxy group” means at least one of a propyleneoxy group (hereinafter also referred to as “PO group”) or a polypropyleneoxy group in which two or more propylene groups are connected by an ether bond. The “(poly) butyleneoxy group” means at least one kind of butyleneoxy group (hereinafter also referred to as “BO group”) or a polybutyleneoxy group in which two or more butylene groups are connected by an ether bond. “EO-modified” means a compound having a (poly) ethyleneoxy group, “PO-modified” means a compound having a (poly) propyleneoxy group, and “BO-modified” The term “(poly) butyleneoxy group” means a compound having a (poly) butyleneoxy group. “EO / PO modified” means a compound having both (poly) ethyleneoxy group and (poly) propyleneoxy group, and “EO / BO modified” means (poly) ethyleneoxy group and It means that the compound has both (poly) butyleneoxy groups, and “EO / PO / BO modified” means (poly) ethyleneoxy groups, (poly) propyleneoxy groups, and (poly) butyleneoxy groups. It means that it is a compound having these three.

In this specification, the term “layer” is formed only in a part of the region in addition to the case where the layer is formed over the entire region when the region in which the layer is present is observed. Cases are also included. The term “stacked” indicates that the layers are stacked, and two or more layers may be bonded, or two or more layers may be detachable.
In addition, in this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term is used as long as the intended purpose of the process is achieved. include.
In the present specification, numerical ranges indicated using “to” indicate ranges including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. Good. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
In addition, in the present specification, the content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, the plurality of kinds present in the composition unless otherwise specified. It means the total amount of substance.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment comprises (A) component: a binder polymer having a structural unit derived from (meth) acrylic acid, and (B) component: photopolymerizability containing (meth) acrylate having a urethane bond. A compound, (C) component: a photoinitiator, and (D) component: the styrylpyridine compound shown by Formula (1). The said photosensitive resin composition may contain the other component as needed.

  A binder polymer having a structural unit derived from (meth) acrylic acid, a photopolymerizable compound containing a (meth) acrylate having a urethane bond, a photopolymerization initiator, and a styrylpyridine compound represented by the formula (1) By containing, the photosensitive resin composition which can form the resist pattern excellent in chemical | medical solution tolerance (especially tolerance with respect to plating solution) with the outstanding sensitivity can be comprised. Although the detailed reason which produces the said effect is not necessarily clear, the present inventors guess as follows. By using in combination with a (meth) acrylate having a urethane bond effective in adhesion and a styrylpyridine compound excellent in photosensitization, the reaction rate is increased while having high adhesion to the substrate, A resist pattern can be formed. This presumes that the cross-linking network in the resist pattern is further densified and the chemical resistance is improved.

(A) component: Binder polymer The said photosensitive resin composition contains the binder polymer (henceforth a "specific binder polymer") which has a structural unit derived from (meth) acrylic acid as (A) component. The component (A) may further contain a binder polymer other than the specific binder polymer as necessary.

  The content of the structural unit derived from (meth) acrylic acid is based on the total mass of the polymerizable monomer constituting the specific binder polymer (100% by mass) from the viewpoint of excellent balance between developability and resist pattern adhesion. The same applies hereinafter), 15 to 40% by mass, 18 to 38% by mass, or 20 to 35% by mass. From the viewpoint of further improving developability, the content may be 15% by mass or more, 18% by mass or more, or 20% by mass or more. Further, from the viewpoint of further improving the adhesion of the resist pattern, the content may be 40% by mass or less, 38% by mass or less, or 35% by mass or less.

  The specific binder polymer may further have a structural unit derived from styrene or α-methylstyrene. When the specific binder polymer further has a structural unit derived from styrene or α-methylstyrene, the content of the structural unit derived from styrene or α-methylstyrene is from the viewpoint of further improving the adhesion and peelability of the resist pattern. , Based on the total mass of the polymerizable monomers constituting the specific binder polymer, it may be 10 to 70% by mass, 15 to 60% by mass, or 20 to 55% by mass. Good. From the viewpoint of further improving the adhesiveness of the resist pattern, the content may be 10% by mass or more, 15% by mass or more, or 20% by mass or more. Further, from the viewpoint of further improving the releasability of the resist pattern, the content may be 70% by mass or less, 60% by mass or less, or 55% by mass or less.

  The specific binder polymer may have other structural units other than the above structural units. Examples of the other structural units include structural units derived from the following other polymerizable monomers.

  Other polymerizable monomers are polymerizable monomers that can be polymerized with (meth) acrylic acid, styrene, or α-methylstyrene, and are different from (meth) acrylic acid, styrene, and α-methylstyrene. If so, there is no particular limitation. Other polymerizable monomers include (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid benzyl, (meth) acrylic acid furfuryl, Tetrahydrofurfuryl (meth) acrylate, 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, (meta ) Dicyclopentanyl acrylate Cyethyl, isobornyloxyethyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, adamantyloxyethyl (meth) acrylate, dicyclopentenyloxypropyloxyethyl (meth) acrylate, dimethacrylate (meth) acrylate (Meth) acrylic esters such as cyclopentanyloxypropyloxyethyl, dicyclopentenyloxypropyloxyethyl (meth) acrylate, adamantyloxypropyloxyethyl (meth) acrylate; α-bromoacrylic acid, α-chloroacrylic (Meth) acrylic acid derivatives such as acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid; polymerizable styrene derivatives substituted in the aromatic ring; acrylamide such as diacetone acrylamide; acryloni Tolyl; ether compounds of vinyl alcohol such as vinyl-n-butyl ether; maleic acid; maleic anhydride; maleic monoesters such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate; fumaric acid, cinnamic acid, α -Unsaturated carboxylic acid derivatives such as cyanocinnamic acid, itaconic acid, crotonic acid and propiolic acid. These polymerizable monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the specific binder polymer has other structural units, the content of the other structural units is the total mass of the polymerizable monomer constituting the specific binder polymer from the viewpoint of further improving the resolution and releasability of the resist pattern. As a reference | standard, 3-85 mass% may be sufficient, 5-75 mass% may be sufficient, 10-70 mass% may be sufficient, and 10-50 mass% may be sufficient.

  The specific binder polymer is, for example, (meth) acrylic acid as a polymerizable monomer (monomer), styrene or α-methylstyrene and other polymerizable monomers used as necessary, by a conventional method. It can be obtained by radical polymerization.

  (A) As a component, a specific binder polymer may be used individually by 1 type, and 2 or more types of specific binder polymers may be used in arbitrary combinations. Moreover, you may use other binder polymers other than a specific binder polymer with a specific binder polymer.

  The acid value of the specific binder polymer may be 90 to 250 mgKOH / g, 100 to 240 mgKOH / g, or 120 to 235 mgKOH / g from the viewpoint of good balance between developability and resist pattern adhesion. It may be 130-230 mgKOH / g. From the viewpoint of further shortening the development time, the acid value may be 90 mgKOH / g or more, 100 mgKOH / g or more, 120 mgKOH / g or more, or 130 mgKOH / g or more. May be. From the viewpoint of further improving the adhesion of the resist pattern, the acid value may be 250 mgKOH / g or less, 240 mgKOH / g or less, 235 mgKOH / g or less, or 230 mgKOH. / G or less.

  When the weight average molecular weight (Mw) of the specific binder polymer is measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene), it is excellent in balance between developability and resist pattern adhesion. 10,000 to 200,000, 15,000 to 100,000, 20,000 to 80,000, or 23,000 to 60,000. From the viewpoint of further shortening the development time, the weight average molecular weight may be 200000 or less, 100000 or less, 80000 or less, or 60000 or less. From the viewpoint of further improving the adhesion of the resist pattern, the weight average molecular weight may be 10,000 or more, 15000 or more, 20000 or more, 23000 or more, 25000 It may be the above.

  The degree of dispersion (weight average molecular weight / number average molecular weight) of the specific binder polymer may be 3.0 or less or 2.8 or less from the viewpoint of further improving the resolution and adhesion of the resist pattern. 2.5 or less.

  The specific binder polymer may have, in the molecule, a characteristic group having photosensitivity to light having a wavelength in the range of 340 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 such as component (D) described later.

  The content of the component (A) in the photosensitive resin composition is 100 parts by mass of the total amount of the component (A) and the component (B) from the viewpoint of further improving the formability of the photosensitive layer, the sensitivity, and the resolution of the resist pattern. On the other hand, it may be 30 to 70 parts by mass, 35 to 65 parts by mass, or 40 to 60 parts by mass. From the viewpoint of further improving the formability of the photosensitive layer, the content may be 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more. Further, from the viewpoint of improving sensitivity and resolution of the resist pattern, the content may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less.

(B) Component: Photopolymerizable Compound The photosensitive resin composition is also referred to as a (meth) acrylate having a urethane bond (hereinafter referred to as “specific photopolymerizable compound”) as the photopolymerizable compound as component (B). ). The component (B) may further contain a photopolymerizable compound other than the specific photopolymerizable compound as necessary.

  The number of urethane bonds present in the molecule of the specific photopolymerizable compound is not particularly limited, and may be one, two, or three or more. Further, the number of (meth) acryloyl groups present in the molecule of the specific photopolymerizable compound is not particularly limited, and may be one, two, or three or more.

  The specific photopolymerizable compound may have a (poly) alkyleneoxy group in the molecule. Examples of (poly) alkyleneoxy groups include (poly) ethyleneoxy groups, (poly) propyleneoxy groups, and (poly) butyleneoxy groups.

  Specific photopolymerizable compounds include, for example, EO-modified urethane di (meth) acrylate, PO-modified urethane di (meth) acrylate, BO-modified urethane di (meth) acrylate, EO / PO-modified urethane di (meth) acrylate, and EO / BO-modified urethane di ( (Meth) acrylate, EO / PO / BO modified urethane di (meth) acrylate, EO modified isocyanurate derived tri (meth) acrylate, PO modified isocyanurate derived tri (meth) acrylate, BO modified isocyanurate derived tri (meth) acrylate, EO -PO-modified isocyanurate-derived tri (meth) acrylate, EO / BO-modified isocyanurate-derived tri (meth) acrylate, and EO / PO / BO-modified isocyanurate-derived tri (meth) acrylate.

  The specific photopolymerizable compound is selected from the group consisting of a compound represented by the following formula (2) and a compound represented by the following formula (3) from the viewpoint of further improving the resolution, adhesion, and chemical resistance of the resist pattern. It may contain at least one compound. The compound represented by the formula (2) and the compound represented by the formula (3) may be used singly or in combination of two or more.

In formula (2), Q represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a phenylene group, and R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group. L ¹ represents an ethylene group, L ² represents a propylene group, L ³ represents a butylene group, r 1 and r 2 each independently represents a number of 1 to 40, s 1, s 2 , T1, and t2 each independently represents a number from 0 to 40. When r1, r2, s1, s2, t1, or t2 is 2 or more, a plurality of the structural units represented by -L ¹ O-, -L ² O-, or -L ³ O- are present randomly. Alternatively, a block may be formed. r1, r2, s1, s2, t1, and t2 indicate the number of structural units. Therefore, an integer value is shown for a single molecule. Hereinafter, the same applies to the number of structural units.

In Formula (3), R ⁶ , R ⁷ , and R ⁸ each independently represent an alkylene group having 1 to 20 carbon atoms, and R ⁹ , R ¹⁰ , and R ¹¹ are each independently a hydrogen atom or A methyl group, L ¹ represents an ethylene group, L ² represents a propylene group, L ³ represents a butylene group, and r ³ , r 4, and r 5 each independently represents a number of 1 to 40. S3, s4, s5, t3, t4, and t5 each independently represents a number from 0 to 40. When r3, r4, r5, s3, s4, s5, t3, t4, or t5 is 2 or more, a plurality of the structural units represented by -L ¹ O-, -L ² O,-, or -L ³ O- May be present at random or may form a block. r3, r4, r5, s3, s4, s5, t3, t4, and t5 indicate the number of structural units.

  In Formula (2), Q may be an alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, or a phenylene group from the viewpoint of further improving the resolution of the resist pattern. It may be an alkylene group having 1 to 15 carbon atoms, a cycloalkylene group having 3 to 7 carbon atoms, or a phenylene group, and may be an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, or a phenylene group. May be.

  In the formula (2), r1 and r2 may each independently be a number of 1 to 35 or a number of 1 to 30 from the viewpoint of further improving the developability and the releasability of the resist pattern. The number of 1-25 may be sufficient. From the viewpoint of further improving the resolution of the resist pattern, s1 and s2 may be independently a number of 0 to 30, a number of 0 to 25, or a number of 0 to 20. Also good. From the viewpoint of further improving the resolution of the resist pattern, t1 and t2 may each independently be a number from 0 to 25, a number from 0 to 20, or a number from 0 to 15. Also good.

  As a commercial item of the compound represented by the formula (2), for example, an EO-modified urethane dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., UA-11) represented by the following formula (5) and the following formula (6) EO / PO-modified urethane dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., UA-13).

In the formula (3), R ⁶ , R ⁷ and R ⁸ may be an alkylene group having 1 to 18 carbon atoms or an alkylene group having 1 to 15 carbon atoms from the viewpoint of further improving the resolution of the resist pattern. Or an alkylene group having 1 to 10 carbon atoms.

  In the formula (3), r3, r4, and r5 may each independently be a number of 1 to 35 from the viewpoint of further improving the developability and the releasability of the resist pattern. Number may be sufficient and the number of 1-25 may be sufficient. From the viewpoint of further improving the resolution of the resist pattern, s3, s4, and s5 may each independently be a number from 0 to 30, may be a number from 0 to 25, and may be a number from 0 to 20. It may be. From the viewpoint of further improving the resolution of the resist pattern, t3, t4, and t5 may each independently be a number from 0 to 25, a number from 0 to 20, or a number from 0 to 15 It may be.

  As a commercial item of the compound represented by the formula (3), for example, an EO-modified isocyanurate-derived trimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., UA-7100) represented by the following formula (7) and the following formula (8) And EO-modified isocyanurate-derived trimethacrylate (made by Shin-Nakamura Chemical Co., Ltd., UA-21).

  The content of the specific photopolymerizable compound in the photosensitive resin composition is such that (A) component and (B) from the viewpoint of suppressing swelling by suppressing molecular motion in the crosslinked network after photocuring and improving chemical resistance. 1-60 mass parts may be sufficient with respect to 100 mass parts of total amounts of a component, 4-50 mass parts may be sufficient, and 8-40 mass parts may be sufficient.

  The said photosensitive resin composition may contain other photopolymerizable compounds other than a specific photopolymerizable compound as (B) component. Other photopolymerizable compounds are not particularly limited as long as photopolymerization is possible. The other photopolymerizable compound may be a compound having an ethylenically unsaturated bond group. 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.

  When the component (B) contains other photopolymerizable compound, the content of the specific photopolymerizable compound is improved from the viewpoint of improving the adhesion to the base material and improving chemical resistance, and the total amount of the component (B) is 100. 1-60 mass parts may be sufficient with respect to a mass part, 6-50 mass parts may be sufficient, and 10-40 mass parts may be sufficient.

  The component (B) may contain at least one compound having two ethylenically unsaturated bond groups in the molecule as the other photopolymerizable compound. When the component (B) includes a compound having two ethylenically unsaturated bond groups in the molecule as the other photopolymerizable compound, the content is 100 parts by mass of the total amount of the component (A) and the component (B). 5-60 mass parts may be sufficient with respect to this, 5-55 mass parts may be sufficient, and 10-50 mass parts may be sufficient.

  Examples of the compound having two ethylenically unsaturated bond groups in the molecule include bisphenol A type di (meth) acrylate, hydrogenated bisphenol A type di (meth) acrylate, polyalkylene glycol di (meth) acrylate, and tri Examples include methylolpropane di (meth) acrylate.

  Component (B) is a bisphenol A-type di (meth) acrylate, a hydrogenated bisphenol A-type di (meth) acrylate, and a polyalkylene as other photopolymerizable compounds from the viewpoint of improving the resolution and peeling characteristics of the resist pattern. You may contain at least 1 sort (s) of the compound which has two ethylenically unsaturated bond groups in the molecule | numerator selected from the group which consists of glycol di (meth) acrylate.

  Examples of the bisphenol A type di (meth) acrylate include compounds represented by the following formula (9).

In formula (9), R ¹² and R ¹³ each independently represent a hydrogen atom or a methyl group. XO and YO each independently represent an EO group or a PO 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 represents a number from 0 to 40. m1, m2, n1, and n2 represent the number of structural units.

  When the compound represented by the formula (9) has a PO group, the total number of structural units of the PO group in the compound may be 2 or more, or 3 or more from the viewpoint of improving the resolution of the resist pattern. Also good. Further, the total number of PO group structural units in the compound may be 5 or less from the viewpoint of improving developability.

  When the compound represented by the formula (9) has an EO group, the total number of structural units of the EO group in the compound may be 4 or more, or 6 or more from the viewpoint of improving developability. 8 or more. The total number of structural units of the EO group in the compound may be 16 or less or 14 or less from the viewpoint of improving the resolution of the resist pattern.

  Among the compounds represented by the formula (9), 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane (EO group: 12 mol (average value), PO group: 4 mol (average value)) is FA -3200MY (manufactured by Hitachi Chemical Co., Ltd., product name), 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane is used as FA-324M (manufactured by Hitachi Chemical Co., Ltd., product name). 2-Bis (4- (methacryloxypentaethoxy) phenyl) propane is 2,2 as BPE-500 (Shin-Nakamura Chemical Co., Ltd., product name) or FA-321M (Hitachi Chemical Co., Ltd., product name). 2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name), respectively. It is a work available. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the component (B) contains bisphenol A type di (meth) acrylate, the content thereof may be 1 to 65 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). 5 to 60 parts by mass, or 10 to 55 parts by mass.

Examples of the hydrogenated bisphenol A type di (meth) acrylate include 2,2-bis (4- (methacryloxypentaethoxy) cyclohexyl) propane.
In the case where the component (B) contains hydrogenated bisphenol A type di (meth) acrylate, the content thereof is suppressed from the viewpoint of suppressing swelling by suppressing molecular motion in the crosslinked network after curing, and improving chemical resistance (A ) Component and (B) component may be 1 to 50 parts by mass or 5 to 40 parts by mass with respect to 100 parts by mass in total.

  Component (B) may contain at least one polyalkylene glycol di (meth) acrylate as another photopolymerizable compound from the viewpoint of improving the flexibility, resolution, and adhesion of the resist pattern in a balanced manner. Good. When the component (B) contains polyalkylene glycol di (meth) acrylate, the content thereof is based on 100 parts by mass of the total amount of the component (A) and the component (B) from the viewpoint of the resolution and flexibility of the resist pattern. 1-30 mass parts may be sufficient, and 5-25 mass parts may be sufficient.

  The polyalkylene glycol di (meth) acrylate may be a polyalkylene glycol di (meth) acrylate having both a (poly) ethyleneoxy group and a (poly) propyleneoxy group in the molecule. 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 PO 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 other photopolymerizable compound.

  Examples of the compound having three or more ethylenically unsaturated bond groups include trimethylolpropane tri (meth) acrylate and EO-modified trimethylolpropane tri (meth) acrylate (one having 1 to 5 structural units of EO group). , PO-modified trimethylolpropane tri (meth) acrylate, EO / PO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetraacrylate, and di An example is pentaerythritol hexa (meth) acrylate. These compounds may be used alone or in combination of two or more.

  Among the compounds having three or more ethylenically unsaturated bond groups, EO-modified trimethylolpropane trimethacrylate is TMPT21E and TMPT30E (manufactured by Hitachi Chemical Co., Ltd., sample name), and pentaerythritol triacrylate is SR444 (Sartomer Co., Ltd.). Dipentaerythritol hexaacrylate as A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) and ethoxy as A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Pentaerythritol tetraacrylate is commercially available as ATM-35E (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

  When the component (B) contains a photopolymerizable compound having three or more ethylenically unsaturated bond groups in the molecule, the content of the resist pattern shape and the resolution, adhesion and peelability of the resist pattern are balanced. From a viewpoint of improving, 3-30 mass parts may be sufficient with respect to 100 mass parts of total amounts of (A) component and (B) component, 5-25 mass parts may be sufficient, and 5-20 mass parts It may be.

  From the viewpoint of improving the resist pattern shape and the resolution, adhesion and peelability of the resist pattern in a well-balanced manner, or from the viewpoint of suppressing scum generation, the component (B) is an ethylenic compound in the molecule as another photopolymerizable compound. A photopolymerizable compound having one unsaturated bond group may be included.

  Examples of the photopolymerizable compound having one ethylenically unsaturated bond group in the molecule include nonylphenoxypolyethyleneoxy (meth) acrylate, phthalic acid compound, and (meth) acrylic acid alkyl ester. Among these, nonylphenoxypolyethyleneoxy (meth) acrylate or a phthalic acid compound may be included from the viewpoint of improving the resist pattern shape and the resolution, adhesion, and peelability of the resist pattern in a well-balanced manner.

  When (B) component contains the photopolymerizable compound which has one ethylenically unsaturated bond group in a molecule | numerator, the content is 1 with respect to 100 mass parts of total amounts of (A) component and (B) component. -20 mass parts may be sufficient, 3-15 mass parts may be sufficient, and 5-12 mass parts may be sufficient.

  The content of the component (B) in the photosensitive resin composition may be 30 to 70 parts by mass, or 35 to 65 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It may be. When the content of the component (B) is 30 parts by mass or more, the sensitivity and the resolution of the resist pattern tend to be improved. When the content of the component (B) is 70 parts by mass or less, a photosensitive layer is easily formed, and a good resist pattern 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 a 2,4,5-triarylimidazole compound represented by the following formula (4) from the viewpoint of improving sensitivity and resolution and adhesion of the resist pattern while maintaining the chemical resistance of the resist pattern. It may contain a mer.

In Formula (4), Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group, and an alkoxy 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 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.

X ¹ and X ² are each independently a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It may be an alkoxy group. It is preferable that at least one of X ¹ and X ² is a chlorine atom.
The substitution position of X ¹ and X ² is not particularly limited, and is preferably an ortho position or a para position.
p and q are each independently an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1.

Examples of the aryl group represented by Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ include a phenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is preferable.
As the substituent that Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ may have, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkoxy having 1 to 6 carbon atoms And at least one substituent selected from the group consisting of groups. When Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ each independently have the above substituents, the number of substituents is preferably 1 to 5, more preferably 1 to 3, and More preferably it is. Further, when Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ each independently have the above substituent, the substitution position is not particularly limited, and is preferably the ortho position or the para position. Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are preferably all unsubstituted.

  Examples of the 2,4,5-triarylimidazole dimer represented by the formula (4) include 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2-chlorophenyl)- 4,5-di (methoxyphenyl) imidazole dimer, 2- (2-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2-methoxyphenyl) -4,5-diphenylimidazole dimer And 2- (4-methoxyphenyl) -4,5-diphenylimidazole dimer. In addition, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may give the same target compound or differently give asymmetric compounds. The 2,4,5-triarylimidazole dimer represented by the formula (4) may be used alone or in combination of two or more.

  (C) When a component contains the 2,4,5-triarylimidazole dimer shown by Formula (4), the content is 25 mass parts with respect to 100 mass parts of total amounts of (C) component. The above may be sufficient, 50 mass parts or more may be sufficient, and 75 mass parts or more may be sufficient.

  As the photopolymerization initiator (C), in addition to the 2,4,5-triarylimidazole dimer represented by the formula (4), other photopolymerization initiators that are usually used may be included. Good. 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; quinone compounds such as alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoins; benzyl derivatives such as benzyldimethyl ketal; 9-phenylacridine, 1 , 7- (9,9′-acridinyl) heptane and the like.

  Content of (C) component in the said photosensitive resin composition may be 0.1-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and 1-7 It may be part by mass, 2 to 6 parts by mass, or 3 to 5 parts by mass. When the content of the component (C) is 0.1 parts by mass or more, the sensitivity, the resolution of the resist pattern, and the adhesiveness tend to be improved. When the content of the component (C) is 10 parts by mass or less, a good resist pattern shape tends to be easily obtained.

Component (D): styrylpyridine compound represented by formula (1) The photosensitive resin composition contains at least one styrylpyridine compound represented by the following formula (1) as the component (D). (D) A component may be used individually by 1 type and may be used in combination of 2 or more type.

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, amino Group, a C1-C20 alkylamino group, a carboxy group, a cyano group, a nitro group, an acetyl group, or a (meth) acryloyl group, a, b, and c are each independently an integer of 0 to 5 Indicates. 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.
In addition, carbon number of an alkyl ester group means carbon number of an alkyl part.

From the viewpoint of further improving the sensitivity, 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, or 1 carbon atom. The alkyl ester group of -6, an amino group, or a C1-C20 alkylamino group may be sufficient.
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 formula (1) include 3,5-dibenzylidenedicyclopentano [b, e] -4-phenylpyridine, 3,5-bis (4-methylbenzylidenedicyclopentano). [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-carboxybenzylidene dicyclopentano [b, e])-4- (4-carboxyphenyl) pyridine 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, 3,5-bis (4- (methoxycarbonyl) benzylidenedicyclopentano [b, e])-4- (4- (methoxycarbonyl) phenyl) pyridine and 3,5-bis (2,4-dimethoxybenzylidenedicyclopentano [b, e])-4- (2,4-dimethoxyphene Le) pyridine, and the like.

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

  Content of (D) component in the said photosensitive resin composition may be 0.01-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, 0.05 -5 mass parts may be sufficient, and 0.08-3 mass parts may be sufficient. When the content of the component (D) is 0.01 parts by mass or more, the sensitivity and the resolution of the resist pattern are improved, and a resist pattern excellent in chemical resistance tends to be obtained. When the content of the component (D) is 10 parts by mass or less, a good resist pattern shape tends to be obtained.

(E) component: amine compound The said photosensitive resin composition may contain 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 amine compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the said photosensitive resin composition contains (E) component, the content may be 0.01-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. It may be 0.05 to 5 parts by mass or 0.1 to 2 parts by mass. When the content of component (E) is 0.01 parts by mass or more, sufficient sensitivity tends to be obtained. When the content of the component (E) is 10 parts by mass or less, it tends to be suppressed that the excessive component (E) is deposited as a foreign substance after the formation of the photosensitive layer.

(Other ingredients)
The photosensitive resin composition may be used in addition to a photopolymerizable compound (oxetane compound, etc.) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, and a component (D) as necessary. Sensitizing dyes, dyes such as malachite green, Victoria pure blue, brilliant green and methyl violet, photochromic agents such as tribromophenylsulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline and 2-chloroaniline, thermal coloring Inhibitors, plasticizers such as 4-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, heat Other components such as a crosslinking agent may be contained. These other components may be used alone or in combination of two or more for each component.

  When the said photosensitive resin composition contains these other components, these content is about 0.01-20 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, respectively. It may be.

[Solution of photosensitive resin composition]
The photosensitive resin composition 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 organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type. Content of the organic solvent contained in the said photosensitive resin composition can be suitably selected according to the objective etc. For example, an organic solvent can be contained in the photosensitive resin composition and used as a solution having a solid content of about 30 to 60% by mass. Hereinafter, the photosensitive resin composition containing an organic solvent is also referred to as “coating liquid”.

  A coating layer of the photosensitive resin composition can be formed by applying the coating solution on the surface of a support, a metal plate or the like described later and drying it. 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 layer to be formed is not particularly limited and can be appropriately selected depending on the application. For example, the thickness after drying may be about 1 to 100 μm. When the photosensitive layer is formed on the metal plate, the surface of the photosensitive layer may be covered with a protective layer. Examples of the protective layer include polymer films such as polyethylene and polypropylene.

The said photosensitive resin composition can be applied to formation of the photosensitive layer of the photosensitive element mentioned later. That is, another embodiment of the present disclosure is a photopolymerizable composition including (A) component: a binder polymer having a structural unit derived from (meth) acrylic acid, and (B) component: (meth) acrylate having a urethane bond. This is an application to a photosensitive element of a photosensitive resin composition containing a compound, (C) component: a photopolymerization initiator, and (D) component: a styrylpyridine compound represented by the formula (1).
Moreover, the said photosensitive resin composition can be used for the manufacturing method of the board | substrate with a resist pattern mentioned later. That is, another embodiment of the present disclosure is a photopolymerizable composition including (A) component: a binder polymer having a structural unit derived from (meth) acrylic acid, and (B) component: (meth) acrylate having a urethane bond. Application of photosensitive resin composition containing compound, (C) component: photopolymerization initiator, and (D) component: styrylpyridine compound represented by formula (1) to a method for producing a substrate with a resist pattern It is.

<Photosensitive element>
The photosensitive element of this embodiment is equipped with a support body and the photosensitive layer which uses the said photosensitive resin composition provided on this support body. In addition, a photosensitive layer is a coating film formed using the said photosensitive resin composition, Comprising: The said photosensitive resin composition is a thing of an unhardened state. The photosensitive element may have other layers, such as a protective layer, as needed.

  FIG. 1 shows an example of a photosensitive element. In the photosensitive element 1 shown in FIG. 1, the support body 2, the photosensitive layer 3, and the protective layer 4 are laminated | stacked in this order. The photosensitive element 1 can be obtained as follows, for example. On the support 2, a coating solution, which is the photosensitive resin composition containing an organic solvent, is applied to form a coating layer, which is dried to form the photosensitive layer 3. Next, the surface of the photosensitive layer 3 opposite to the support 2 is covered with a protective layer 4, thereby laminating the support 2, the photosensitive layer 3 formed on the support 2, and the photosensitive layer 3. The photosensitive element 1 provided with the protective layer 4 obtained is obtained. The photosensitive element 1 does not necessarily have to include the protective layer 4.

  As the support 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 2 may be 1 to 100 μm, 5 to 50 μm, or 5 to 30 μm. When the thickness of the support 2 is 1 μm or more, the support 2 tends to be prevented from being broken when the support 2 is peeled off. Moreover, it exists in the tendency for the fall of the resolution to be suppressed as the thickness of the support body 2 is 100 micrometers or less.

  The protective layer 4 is preferably such that the adhesive force of the photosensitive layer 3 to the protective layer 4 is smaller than the adhesive force of the photosensitive layer 3 to the support 2. Also, a low fish eye 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 layer 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. Commercially available products include Alfane MA-410 and E-200 manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and PS series polyethylene terephthalate films such as PS-25 manufactured by Teijin Limited. It is done. The protective layer 4 may be the same as the support 2.

  The thickness of the protective layer 4 may be 1 to 100 μm, 5 to 50 μm, 5 to 30 μm, or 15 to 30 μm. When the thickness of the protective layer 4 is 1 μm or more, the protective layer 4 tends to be prevented from being broken when the photosensitive layer 3 and the support 2 are laminated on the substrate while peeling off the protective layer 4. When the thickness of the protective layer 4 is 100 μm or less, the handling property and the inexpensiveness tend to be excellent.

  Specifically, the photosensitive element can be produced, for example, as follows. (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: styrylpyridine compound represented by formula (1) A step of preparing a coating solution dissolved in an organic solvent, a step of coating the coating solution on the support 2 to form a coating layer, and a step of drying the coating layer to form a photosensitive layer 3. A photosensitive element can be manufactured with the manufacturing method including.

  Application of the coating solution onto the support 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. The coating layer is preferably dried at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive layer 3 may be 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step.

  The thickness of the photosensitive layer 3 in the photosensitive element can be appropriately selected depending on the application. The thickness of the photosensitive layer 3 after drying may be 1 to 100 μm, 1 to 50 μm, or 5 to 40 μm. When the thickness of the photosensitive layer 3 is 1 μm or more, industrial coating tends to be facilitated. When the thickness of the photosensitive layer 3 is 100 μm or less, sufficient adhesion and resolution of the resist pattern tend to be obtained.

  The transmittance of the photosensitive layer 3 with respect to ultraviolet rays may be 5 to 75%, 10 to 65%, or 15 to 55% with respect to ultraviolet rays in the wavelength range of 350 to 420 nm. Good. When the transmittance is 5% or more, the resist pattern tends to have sufficient adhesion. If the transmittance is 75% or less, the resolution of the resist pattern tends to be sufficiently obtained. The transmittance can be measured with an ultraviolet spectrometer. Examples of the ultraviolet spectrometer include 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, an intermediate layer described in JP-A-2006-098982 can be applied to this embodiment.

  The form of the obtained photosensitive element is not particularly limited. For example, the photosensitive element 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 body 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 said photosensitive element 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 manufacturing a substrate with a resist pattern according to this embodiment includes (i) a step of forming a photosensitive layer using the photosensitive resin composition on the substrate (photosensitive layer forming step), and (ii) the photosensitive layer. Irradiating at least a part of the actinic ray to photocuring the region to form a cured product region (exposure step); and (iii) at least a part of the photosensitive layer other than the cured product region. Is removed from the substrate and a resist pattern is formed on the substrate (development step). The manufacturing method of the said board | substrate with a resist pattern may have another process further as needed.

(I) Photosensitive layer formation process First, the photosensitive layer 3 is formed on a board | substrate using the said photosensitive resin composition. As the substrate, for example, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used. As an insulating layer, a glass epoxy material is mentioned, for example. An example of the conductor layer is copper foil.

  For example, when the photosensitive element has the protective layer 4, the photosensitive layer 3 is formed on the substrate by removing the protective layer 4 and then heating the photosensitive layer 3 of the photosensitive element. This is done by pressure bonding to the substrate. Thereby, a laminate in which the substrate, the photosensitive layer 3 and the support 2 are laminated in this order is obtained.

This photosensitive layer forming step is preferably performed under reduced pressure from the viewpoint of adhesion and followability. Heating to at least one of the photosensitive layer 3 and the substrate during the pressure bonding is preferably performed at a temperature of 70 to 130 ° C., and the pressure bonding is performed at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). It is preferable. These conditions are not particularly limited, and are appropriately selected as necessary. If the photosensitive layer 3 is heated to 70 to 130 ° C., the substrate need not be preheated. Adhesion and follow-up can be further improved by pre-heating the substrate.

(Ii) Exposure Step In the exposure step, the exposed portion irradiated with the actinic ray is photocured by irradiating at least a part of the photosensitive layer 3 formed on the substrate as described above with the actinic ray. Thus, a latent image is formed. At this time, when the support 2 existing on the photosensitive layer 3 is transparent to the active light, the active light can be irradiated through the support 2. On the other hand, when the support 2 shows a light-shielding property against actinic rays, the photosensitive layer 3 is irradiated with actinic rays after the support 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. Specifically, 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, visible light, etc. What emits effectively is used.

  The wavelength of the actinic ray (exposure wavelength) may be in the range of 340 to 430 nm, or may be in the range of 350 to 420 nm. By setting the wavelength of the actinic ray within the range of 340 to 430 nm, a resist pattern excellent in chemical resistance tends to be formed more efficiently with excellent sensitivity.

(Iii) Development Step In the development step, the uncured portion of the photosensitive layer 3 is removed from the substrate by development processing, whereby a resist pattern, which is a cured product obtained by photocuring the photosensitive layer 3, is formed on the substrate. . When the support 2 is present on the photosensitive layer 3, the support 2 is removed, and then the unexposed portion is removed (developed). 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. Examples of the developing method include a method using a dipping method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like. From the viewpoint of improving resolution, the high pressure spray method is most suitable. 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 and an organic solvent developer.

  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 Alkali metal phosphates such as sodium pyrophosphate and potassium pyrophosphate, borax (sodium tetraborate), sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2 -Amino-2-hydroxymethyl-1,3-propanediol, 1,3-diamino-2-propanol, morpholine and the like are used.

  Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, a dilute solution of 0.1 to 5% by mass of sodium hydroxide, A dilute solution of 1 to 5 mass% sodium tetraborate is preferred. The pH of the alkaline aqueous solution is preferably in the range of 9-11. The temperature is adjusted according to the alkali developability of the photosensitive 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 alkaline aqueous solution may contain one or more organic solvents. Examples of the organic solvent to be used 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. These are used alone or in combination of two or more. When the alkaline aqueous solution contains an organic solvent, the content of the organic solvent is preferably 2 to 90% by mass based on the total amount of the alkaline aqueous solution.

  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. In order to prevent flammability, it is preferable to add water in the range of 1 to 20% by mass to these organic solvents to obtain an organic solvent developer.

The above-described method for producing a substrate with a resist pattern includes removing a non-exposed portion, and then performing heating at 60 to 250 ° C. or exposure with an energy amount of 0.2 to 10 J / cm ² as necessary. You may have further the process of further hardening.

<Method for manufacturing printed wiring board>
The method for manufacturing a printed wiring board according to the present embodiment includes a step of performing at least one of an etching process and a plating process on a substrate on which a resist pattern is formed by the method for manufacturing a substrate with a resist pattern. As the substrate, for example, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer is preferably used. The method for manufacturing a printed wiring board may have other steps such as a resist removal step as necessary. The etching process and the plating process of the substrate are 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 a cupric chloride aqueous solution, a ferric chloride aqueous solution, an alkali etching solution, and a hydrogen peroxide etching solution. Among these, it is preferable to use a ferric chloride aqueous 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 removal of the resist pattern can be performed, for example, using a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step. As this strongly alkaline aqueous solution, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used. Among them, it is preferable to use a 1 to 10% by mass aqueous sodium hydroxide solution or a 1 to 10% by mass potassium hydroxide aqueous solution, and more preferably to use a 1 to 5% by mass sodium hydroxide aqueous solution or a 1 to 5% by mass potassium hydroxide aqueous solution. preferable. Examples of a method for applying a strong alkaline aqueous solution to a resist pattern include an immersion method and a spray method, and these may be used alone or in combination of two or more.

  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 method for manufacturing a printed wiring board 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 said photosensitive resin composition can be used conveniently for manufacture of a printed wiring board. That is, one of the preferred embodiments is a photopolymerizability containing (A) component: a binder polymer having a structural unit derived from (meth) acrylic acid, and (B) component: (meth) acrylate having a urethane bond. This is an application to the production of a printed wiring board of a photosensitive resin composition containing a compound, (C) component: photopolymerization initiator, and (D) component: a styrylpyridine compound represented by formula (1). .
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 FIG. The size of the members in FIG. 2 is conceptual, and the relative relationship between the sizes of the members is not limited to this.

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. 2B, the photosensitive layer 32 is formed on the conductor layer 10 of the substrate by the photosensitive layer forming step. In FIG.2 (c), the mask 20 is arrange | positioned on the photosensitive layer 32, an active ray 50 is irradiated to the photosensitive layer 32 by the said exposure process, and areas other than the area | region where the mask 20 is arrange | positioned are exposed, A photocured portion is formed on the photosensitive layer 32. In FIG. 2D, a region other than the photocured portion in the photosensitive layer 32 is removed from the substrate by a developing process, thereby forming a resist pattern 30 as a photocured portion on the substrate. 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. The conductor layer 10 and the plating layer 42 may be made of the same material or different materials.
Although the method for 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 a direct drawing exposure method without using the mask 20.

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

(Examples 1-6 and Comparative Examples 1-4)
<Preparation of solution of photosensitive resin composition>
By mixing each component shown in Table 2 and Table 3 with 9 g of acetone, 5 g of toluene and 5 g of methanol in the blending amount (unit: g) shown in the same table, Examples 1 to 6 and Comparative Examples 1 to 4 Each solution of the photosensitive resin composition was 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)]
A polymerizable monomer (monomer) 81 g of methacrylic acid, 135 g of styrene, 69 g of benzyl methacrylate, and 15 g of methyl methacrylate (mass ratio: 27/45/23/5) and 1.5 g of azobisisobutyronitrile A solution obtained by mixing the above 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 inlet tube was charged with 300 g of a mixed solution of 180 g of methyl cellosolve and 120 g of toluene (mass ratio: 3: 2), and nitrogen was introduced into the flask. The mixture was heated with stirring while blowing gas, 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 41.5% by mass, a weight average molecular weight of 44000, an acid value of 176 mgKOH / g, and a dispersity of 2.2.

  The weight average molecular weight was measured by a gel permeation chromatography (GPC) method and was 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 (above, manufactured by Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran (THF)
Sample concentration: 120 mg of a resin solution having a solid content of 40% by mass was sampled and dissolved in 5 mL of THF to prepare a sample.
Measurement temperature: 40 ° C
Injection volume: 200 μL
Pressure: 49 kgf / cm ² (4.8 MPa)
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

[Synthesis of Binder Polymer (A-2)]
A polymerizable monomer (monomer) 81 g of methacrylic acid, 9 g of 2-hydroxyethyl methacrylate, 141 g of styrene, 69 g of benzyl methacrylate (mass ratio: 27/3/47/23), and azobisisobutyronitrile The solution obtained by mixing 2.4 g was referred to as “solution c”, and the solution of the binder polymer (A-1) was obtained in the same manner as in the case of obtaining the solution of the binder polymer (A-1) except that the solution c was used instead of the solution a. A solution of binder polymer (A-2) was obtained.
The binder polymer (A-2) had a nonvolatile content (solid content) of 41.7% by mass, a weight average molecular weight of 38000, an acid value of 176 mgKOH / g, and a dispersity of 1.8.

  Table 1 shows the mass ratio (%) of the polymerizable monomer (monomer), the acid value, the weight average molecular weight, and the degree of dispersion of the binder polymers (A-1) and (A-2). “-” Means not blended.

(B) Photopolymerizable compound FA-321M (manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (EO group: 10 mol (average value))
UA-11 (manufactured by Shin-Nakamura Chemical Co., Ltd.): (EO) modified urethane dimethacrylate (EO group: 10 mol (average value))
UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd.): (EO) (PO) modified urethane dimethacrylate (EO group: 2 mol (average value), PO group: 18 mol (average value))
UA-7100 (manufactured by Shin-Nakamura Chemical Co., Ltd.): (EO) modified isocyanurate-derived trimethacrylate (EO group: 27 mol (average value))
UA-21 (manufactured by Shin-Nakamura Chemical Co., Ltd.): (EO) modified isocyanurate-derived trimethacrylate (EO group: 12 mol (average value))
FA-3200MY (manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane (EO group: 12 mol (average value), PO group: 4 mol (average value))
FA-024M (manufactured by Hitachi Chemical Co., Ltd.): (PO) (EO) (PO) modified polypropylene glycol # 700 dimethacrylate

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

(D) A styrylpyridine compound represented by the formula (1): 2,4-DMOP-DSP: 3,5-bis (2,4-dimethoxybenzylidenedicyclopentano [b, e])-4- (2, 4-Dimethoxyphenyl) pyridine

(D) Other sensitizing dyes other than component PYR-1 (manufactured by Nippon Chemical Industry Co., Ltd.): 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline EAB ( Hodogaya Chemical Co., Ltd.): 4,4'-diethylaminobenzophenone H-MOP-DSP: 4,6-bis (4-methoxybenzylidene dicyclohexano [b, e])-5- (4-methoxyphenyl) ) Pyridine

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

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

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

<Production of laminated substrate>
A copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., “MCL-E-679F”) (hereinafter referred to as “substrate”) composed of a glass epoxy material and copper foil (thickness: 16 μm) formed on both surfaces thereof. After heating to 80 ° C., the photosensitive elements according to Examples 1 to 6 and Comparative Examples 1 to 4 were laminated (laminated) on the copper surface of the substrate. Lamination was performed under conditions of a temperature of 110 ° C. and a lamination pressure of 4 kgf / cm ² (0.4 MPa) so that the photosensitive layer of each photosensitive element was in close contact with the copper surface of the substrate while removing the protective layer. . In this way, a laminated substrate in which the photosensitive layer and the support were laminated on the copper surface of the substrate was obtained. The obtained laminated substrate was allowed to cool to 23 ° C.

<Evaluation of sensitivity>
On the support of the laminated substrate, there is a 41 step tablet having a density region of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm × 187 mm, and a size of each step of 3 mm × 12 mm. A photo tool was placed. Using a direct drawing exposure machine ("DE-1UH" manufactured by Via Mechanics Co., Ltd.) using a blue-violet laser diode having a wavelength of 405 nm as a light source, with a predetermined energy amount (exposure amount) through a photo tool and a support The photosensitive layer was exposed. For measurement of illuminance, an ultraviolet illuminance meter (Ushio Electric Co., Ltd., “UIT-150”) to which a 405 nm probe was applied was used.

After exposure, the support was peeled from the laminated substrate to expose the photosensitive layer, 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 above step number when exposed at 100 mJ / cm ² , and the higher 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) The photosensitive layer of the laminated substrate was exposed (drawn) with an energy amount of 14 steps. After the exposure, the same development processing as in the sensitivity evaluation was performed.

  After development, the space portion (unexposed portion) is removed cleanly, and the line portion (exposed portion) is the minimum of the line width / space width values in the resist pattern formed without causing meandering, chipping, or other defects. The resolution and adhesion were evaluated based on the values. The smaller this value, the better the resolution and adhesion of the resist pattern. The obtained resist pattern was observed with an optical microscope at a magnification of 1000 times to confirm the presence or absence of defects. The results are shown in Tables 4 and 5.

<Evaluation of reaction rate>
The photosensitive layer of the photosensitive element was exposed with an energy amount such that the remaining number of stages of the 41-step tablet was 14 to obtain a photocured product. Before and after exposure, FT-IR measurement of the photosensitive layer or its photocured product was performed using a Fourier transform infrared spectroscopy (FT-IR) apparatus (“VERTEX70” manufactured by Bruker Optics, Inc.). And the peak derived from the aromatic in 1570cm < ^-1 > was made into an internal standard, and the reaction rate (%) was computed from the peak derived from the vinyl group observed at 1637cm < ^-1 > according to the following formula | equation. The results are shown in Tables 4 and 5.
Reaction rate (%) = (1−I / I ₀ ) × 100
I: Peak intensity after exposure I ₀ : Peak intensity before exposure

<Evaluation of plating solution resistance (chemical solution resistance)>
After heating the copper clad laminated board for flexible printed wiring boards (the Nikkan Kogyo Co., Ltd. make, "F30VC1") to 80 degreeC, the photosensitive element which concerns on Examples 1-6 and Comparative Examples 1-4 was used. The laminate was laminated on the copper surface of the substrate. Lamination was performed under conditions of a temperature of 110 ° C. and a lamination pressure of 4 kgf / cm ² (0.4 MPa) so that the photosensitive layer of each photosensitive element was in close contact with the copper surface of the substrate while removing the protective layer. . In this way, an evaluation laminate in which the photosensitive layer and the support were laminated on the copper surface of the substrate was obtained. The obtained laminate for evaluation was allowed to cool to 23 ° C.

  A glass phototool having a wiring pattern with L / S of 5/5, 8/8, 10/10, and 15/15 (unit: μm) is brought into close contact with the support of the evaluation laminate and developed. The exposure was performed with an energy amount that resulted in 14 remaining steps. Next, the support was peeled off, and an unexposed portion was removed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. to obtain a substrate for evaluation. The development time was a time corresponding to twice the shortest development time (the shortest time for removing the unexposed area).

The substrate for evaluation was immersed in a degreasing solution (Meltex Co., Ltd., “PC-455”, 25 mass%) for 5 minutes, washed with water, immersed in a soft etch solution (ammonium persulfate 150 g / L) for 2 minutes, washed with water. Pretreatment was sequentially performed in the order of immersion in 10% by mass sulfuric acid for 1 minute. And it puts into a copper sulfate plating solution (copper sulfate 75 g / L, sulfuric acid 190 g / L, chloride ion 50 mass ppm, made by Meltex Co., Ltd., “Capper Grime PCM”, 5 mL / L) under the condition of 1 A / dm ² . Copper plating treatment was performed until the plating thickness reached 12 μm.

  The substrate for evaluation after the copper plating treatment was washed with water and dried, and then the resist pattern was peeled off by dipping in a 50 ° C. stripping solution (Mitsubishi Gas Chemical Co., Ltd., “R-100”, 0.2% by volume). The base copper was etched with an aqueous solution containing 0.1% by mass sulfuric acid and 0.1% by mass hydrogen peroxide. Thereafter, the plating latent was confirmed from above using an optical microscope, and “A (excellent)” was evaluated when the plating latent was not generated, and “C (defect)” was evaluated when the plating latent was generated. In addition, when plating submergence arises, the metal copper which precipitated by copper plating in the area | region masked with the resist pattern is observed. The results are shown in Tables 4 and 5.

  As is clear from Tables 4 and 5, a binder polymer having a structural unit derived from (meth) acrylic acid, a photopolymerizable compound containing a (meth) acrylate having a urethane bond, a photopolymerization initiator, a formula Examples 1 to 6 using the photosensitive resin composition containing the styrylpyridine compound represented by (1) are sensitive to the sensitivity of the photosensitive resin composition, as well as the resist pattern resolution, adhesion, and chemical resistance. Both were excellent.

On the other hand, Comparative Example 1 using a photosensitive resin composition not containing a (meth) acrylate having a urethane bond was excellent in the sensitivity of the photosensitive resin composition, but had a resist pattern resolution, adhesion, and chemical solution. Resistance was inferior to Examples 1-6.
Moreover, Comparative Examples 2-4 using the photosensitive resin composition which does not contain the styryl pyridine compound shown by Formula (1) are the sensitivity of the photosensitive resin composition, the resolution of a resist pattern, adhesiveness, and chemical | medical solution tolerance. However, it was inferior to Examples 1-6.

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 2 ... Support body, 3 ... Photosensitive layer, 4 ... Protective layer, 10 ... Conductive layer, 15 ... Insulating layer, 20 ... Mask, 30 ... Resist pattern, 32 ... Photosensitive layer, 40 ... Conductor pattern, 42 ... Plating layer

Claims (7)

(A) a binder polymer having a structural unit derived from (meth) acrylic acid;
(B) a photopolymerizable compound containing (meth) acrylate having a urethane bond;
(C) a photopolymerization initiator;
(D) The photosensitive resin composition containing the styryl pyridine compound shown by following 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, An amino group, an alkylamino group having 1 to 20 carbon atoms, a carboxy group, a cyano group, a nitro group, an acetyl group, or a (meth) acryloyl group; a, b, and c each independently represent 0 to 5; Indicates an integer. ] The (meth) acrylate having a urethane bond includes at least one compound selected from the group consisting of a compound represented by the following formula (2) and a compound represented by the following formula (3). Photosensitive resin composition.

[In Formula (2), Q represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a phenylene group, and R ⁴ and R ⁵ are each independently a hydrogen atom or methyl. L ¹ represents an ethylene group, L ² represents a propylene group, L ³ represents a butylene group, r 1 and r 2 each independently represent a number of 1 to 40, s 1, s2, t1, and t2 each independently represents a number from 0 to 40. ]

[In the formula (3), R ⁶ , R ⁷ and R ⁸ each independently represents an alkylene group having 1 to 20 carbon atoms, and R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom. Or a methyl group, L ¹ represents an ethylene group, L ² represents a propylene group, L ³ represents a butylene group, and r ³ , r 4, and r 5 are each independently a number of 1 to 40. S3, s4, s5, t3, t4, and t5 each independently represents a number from 0 to 40. ] The photosensitive resin composition according to claim 1, wherein the (C) photopolymerization initiator includes a 2,4,5-triarylimidazole dimer represented by the following formula (4).

[In Formula (4), Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group, and an alkoxy 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. Show. ]   A photosensitive element provided with a support body and the photosensitive layer which uses the photosensitive resin composition of any one of Claims 1-3 provided on the said support body. Forming a photosensitive layer using the photosensitive resin composition according to any one of claims 1 to 3 on a substrate;
Irradiating at least a part of the photosensitive layer with actinic rays to photocuring the region to form a cured product region;
Removing at least a portion of the photosensitive layer other than the cured product region from the substrate, and forming a resist pattern on the substrate.   The manufacturing method of the board | substrate with a resist pattern of Claim 5 whose wavelengths of the said actinic light are in the range of 340-430 nm.   The manufacturing method of a printed wiring board which has the process of performing at least one process of an etching process and a plating process with respect to the board | substrate with which the resist pattern was formed by the manufacturing method of the board | substrate with a resist pattern of Claim 5 or Claim 6.