KR101350547B1 - Photosensitive resin composition, photosensitive element utilizing the composition method for formation of resist pattern, and process for production of printed circuit board - Google Patents

Abstract

[화학식 2]

[화학식 3]

[식 (1)~(3) 중, R¹~R1²는 각각 독립적으로 알킬기, 시클로 알킬기, 페닐기, 나프틸기 또는 복소환식기를 포함하는 1가의 유기기를 나타내고, R¹과 R², R³ 와 R⁴, R⁵와 R⁶, R⁷과 R⁸, R⁹와 R¹⁰, R¹¹과 R¹²는, 서로 결합하여 피라진 골격의 2개의 탄소 원자와 함께 환을 형성하고 있어도 된다. 식 (2), 중 X 및 Y는, 각각 독립적으로 피라진 골격의 2개의 탄소와 함께 형성된 단환구조 또는 축합다환구조의 방향족환을 구성하는 원자군을 나타니고, 식 (3) 중, Z는, 피라진 골격의 4개의 탄소와 함께 형성된, 단환구조 혹은 축합다환구조의 방향족환, 또는, 복소환을 구성하는 원자군을 나타낸다.]It contains a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and at least one pyrazine compound selected from the group consisting of a compound having a structure represented by the following formula (1), (2), or (3): The photosensitive resin composition.
[Chemical Formula 1]

(2)

(3)

[In formula (1)-(3), R < ¹ > -R < ¹² > respectively independently represents the monovalent organic group containing an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group, or a heterocyclic group, and R <^1> , R <^2> , R <^3> And R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² may be bonded to each other to form a ring together with two carbon atoms of a pyrazine skeleton. In the formula (2), X and Y each independently represent an atomic group constituting an aromatic ring of a monocyclic structure or a condensed polycyclic structure formed with two carbons of a pyrazine skeleton, and in formula (3), Z is A group of atoms constituting an aromatic ring having a monocyclic structure or a condensed polycyclic structure formed with four carbons of the pyrazine skeleton, or a heterocyclic ring.]

Description

PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE ELEMENT UTILIZING THE COMPOSITION METHOD FOR FORMATION OF RESIST PATTERN, AND PROCESS FOR PRODUCTION OF PRINTED CIRCUIT BOARD}

This invention relates to the photosensitive resin composition, the photosensitive element using this, the formation method of a resist pattern, and the manufacturing method of a printed wiring board.

In the manufacturing fields of microelectronic circuits such as printed wiring boards, wiring boards for plasma displays, wiring boards for liquid crystal displays, large-scale integrated circuits, thin transistors, and semiconductor packages, photosensitive resin compositions and photosensitive elements (such as lamination materials) are used as resist materials used for etching and plating. Sieve) is widely used.

A fine electronic circuit is manufactured as follows, for example. First, the photosensitive resin composition layer of the photosensitive element is laminated (laminated) on the circuit forming substrate. Next, after peeling and removing a support film, actinic light is irradiated to the predetermined part of the photosensitive resin composition layer, and an exposure part is hardened. Thereafter, by removing (developing) the unexposed portion from the substrate, a resist pattern made of a cured product of the photosensitive resin composition is formed on the substrate. An etching process or plating process is performed with respect to the obtained resist pattern, and a circuit is formed on a board | substrate, and finally, a resist is peeled off and a fine electronic circuit is manufactured.

As the method of exposure, the method of exposing through a photomask using the mercury lamp centering on wavelength 365nm as a light source is used conventionally. Moreover, in recent years, the direct drawing exposure method which draws the digital data of a pattern directly on the photosensitive resin composition layer using the long lifetime and high output gallium nitride system blue semiconductor laser of wavelength 405nm or the solid-state laser of wavelength 355nm has been proposed ( For example, see Nonpatent Literature 1). These direct drawing exposure methods, called DLP (Digital Light Processing) or LDI (Laser Direct Imaging), have higher alignment accuracy than the exposure method via a photomask, and can obtain a high-precision pattern. It is introduced for production.

Moreover, examination is also made about the photosensitive material suitable for laser exposure. For example, as a photosensitive material used when using a semiconductor blue violet laser as a light source, Patent Documents 1 and 2 disclose a photosensitive resin composition using a specific initiator.

Patent Document 1: Japanese Patent Publication No. 2002-296764 Patent Document 2: Japanese Patent Publication No. 2004-45596

Non-Patent Document 1: Electronics Packaging Technology June 2002 Issue (p.74-79)

By the way, in an exposure process, it is necessary to shorten an exposure time as much as possible 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 a substrate, a large exposure time is required as compared with the exposure method via a conventional photomask. Tend to. Therefore, it is necessary to improve the sensitivity of the photosensitive resin composition conventionally.

On the other hand, with the recent increase in the density of printed wiring boards, the demand for high resolution and high adhesiveness for photosensitive resin compositions is also increasing. In addition to the miniaturization of wiring, the problem of voltage drop due to the resistance of the power supply line is also surfaced, and the formation of a plating layer (conductor layer) having a thickness of 10 µm or more has been a problem. In order to form a plating layer having a thickness of 10 μm or more, the resist requires a film thickness of 15 μm or more, but in general, when the film thickness of the photosensitive layer becomes thick, resolution tends to decrease. Therefore, the photosensitive resin composition which can satisfy | fill both the characteristics of a film thickness and resolution is calculated | required.

Moreover, it is also important that the photosensitive resin composition is low in contamination with plating. When the photosensitive resin composition contaminates a plating bath, there exists a problem of discoloration in the external appearance of the board | substrate to which the plating process was applied, or a fall of plating formability and a cause of disconnection.

Moreover, the photosensitive resin composition is calculated | required to be excellent in the peeling characteristic of the resist after plating. When the peeling characteristic is insufficient, in the resist peeling step after the plating treatment, it is difficult to peel the resist between fine wirings, and the peeling time increases, and the production efficiency decreases. Moreover, there exists a problem of peeling residue which arises between wirings, and a yield falls.

Therefore, the present invention is excellent in sensitivity, resolution, adhesion, peeling property, and plating formability to light having a wavelength of 350 to 410 nm, and has a low staining resistance to plating, forming a photosensitive element and a resist pattern using the same. It aims at providing the method and the manufacturing method of a printed wiring board.

The present invention is at least one pyrazine selected from the group consisting of a photopolymerizable compound having a binder polymer and an ethylenically unsaturated bond and a compound having a structure represented by the following formula (1), (2), or (3): It provides the photosensitive resin composition containing a compound.

[Formula 1]

In formula (1), R <^1> , R <^2> , R <^3> and R <^4> respectively independently represent the monovalent organic group containing an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group, or a heterocyclic group, and R <^1> , R <^2> , Alternatively, R ³ and R ⁴ may be bonded to each other to form a ring together with two carbon atoms of a pyrazine skeleton.

(2)

In formula (2), R <^5> , R <^6> , R <^7> and R <^8> respectively independently represent the monovalent organic group containing an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group, or a heterocyclic group, and R <^5> , R <^6> , Alternatively, R ⁷ and R ⁸ may be bonded to each other to form a ring together with two carbon atoms of a pyrazine skeleton. X and Y respectively independently represent the atomic group which comprises the aromatic ring of the monocyclic structure or condensed polycyclic structure formed with two carbons of a pyrazine skeleton.

(3)

In formula (3), R <^9> , R <^10> , R <^11> and R <^12> represent a monovalent organic group containing an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group, or a heterocyclic group each independently, and R <^9> and R <^10> , or , R ¹¹ and R ¹² may be bonded to each other to form a ring together with two carbon atoms of a pyrazine skeleton. Z represents the atomic group which comprises the aromatic ring of monocyclic structure or condensed polycyclic structure, or heterocyclic ring formed with four carbons of a pyrazine skeleton.

Since the said pyrazine compound has comparatively strong absorption with respect to the light of wavelength 350-410 nm, the photosensitive resin composition of this invention can obtain favorable sensitivity with respect to the light of wavelength 350-410 nm. Moreover, the photosensitive resin composition of this invention containing the said pyrazine compound is excellent in resolving property, adhesiveness, peeling property (peeling characteristic) of the photosensitive resin composition after hardening, and plating formation property, and also becomes low in contamination with plating.

Moreover, it is preferable that the said pyrazine compound is a compound which has a structure represented by said Formula (1).

Moreover, in the photosensitive resin composition of this invention, it is preferable that the maximum absorption wavelength of a pyrazine compound exists in the range of 350-410 nm. Thereby, while the favorable sensitivity can be acquired with respect to the light of wavelength 350-410 nm, absorption in the long wavelength side of wavelength 500nm or more becomes small, and stability under yellow light becomes favorable.

Moreover, in the photosensitive resin composition of this invention, it is preferable that a binder polymer contains (meth) acrylic acid and styrene or a styrene derivative as a copolymerization component. Thereby, alkali developability, resolution, and adhesiveness of the photosensitive resin composition further improve.

Moreover, it is preferable that the photosensitive resin composition of this invention contains the compound represented by following formula (4). Thereby, there exists a tendency for a sensitivity and imaging property (color development property of a resist) to improve, maintaining the resolution and adhesiveness of the photosensitive resin composition.

[Chemical Formula 4]

In formula (4), X represents a carbon atom or a nitrogen atom, R <^13> , R <^14> and R <^15> represent a halogen atom or a C1-C5 alkyl group each independently, At least in R <^13> , R <^14> and R <^15> . One represents a halogen atom. R <^16> represents a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group, and l shows the integer of 0-4. When l is 2-4, some R <^16> may be same or different.

Moreover, it is preferable that the photosensitive resin composition of this invention contains a hydrogen donor compound further. Thereby, the sensitivity of the photosensitive resin composition improves.

Moreover, in the photosensitive resin composition of this invention, it is preferable that a hydrogen donor compound contains the compound represented by following formula (5). There exists a tendency for the sensitivity of the photosensitive resin composition to improve further by this.

[Chemical Formula 5]

Equation (5) of, R ¹⁷ represents an alkyl group, an alkoxy group or an ester group, a hydroxyl group, or a halogen atom having 1 to 6 carbon atoms. n is an integer of 0-5, and when n is 2-5, some R <^17> may be same or different.

Moreover, this invention provides the photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the said photosensitive resin composition formed on this support body. By using such a photosensitive element, the resist pattern which is excellent in a sensitivity, resolution, adhesiveness, peeling characteristic, and plating formation property, and is low in contamination with plating can be formed efficiently.

Moreover, this invention is the lamination process of laminating | stacking the photosensitive resin composition layer which consists of said photosensitive resin composition on a board | substrate, the exposure process which irradiates a predetermined part of the photosensitive resin composition layer, and the said predetermined | prescribed of the photosensitive resin composition layer. By removing parts other than a part from a board | substrate, the formation method of the resist pattern including the image development process of forming the resist pattern which consists of hardened | cured material of the photosensitive resin composition on a board | substrate is provided. According to the above method, a resist pattern excellent in sensitivity, resolution, adhesion, peeling property, and plating formability and low in contamination with plating can be efficiently formed.

In the formation method of the said resist pattern, it is preferable that the wavelength of an actinic light is 390-410 nm. Thereby, the resist pattern which is further excellent in a sensitivity, resolution, adhesiveness, peeling characteristic, and plating formation property can be formed.

Moreover, this invention provides the manufacturing method of the printed wiring board containing the process of etching or plating the board | substrate with which the resist pattern was formed by the said method. According to this manufacturing method, the printed wiring board which has high density wiring like the high density package board | substrate can be manufactured efficiently.

According to the present invention, a photosensitive resin composition having excellent sensitivity to light having a wavelength of 350 to 410 nm, resolution, adhesiveness, peeling property, and plating formability, and low pollution to plating, a photosensitive element using the same, and a method of forming a resist pattern And a manufacturing method of a printed wiring board can be provided.

1: is a schematic cross section which shows an example of the photosensitive element.
2 is a 1 H-NMR spectrum of (C-1) according to the present example.
3 is a 13C-NMR spectrum of (C-1) related to the present example.
4 is ultraviolet visible absorption spectra of (C-1) and (C-3) according to the present embodiment.
5 is an ultraviolet visible absorption spectrum of (C-1) and (C-2) according to the present embodiment.

EMBODIMENT OF THE INVENTION Hereinafter, the best form for implementing this invention is demonstrated in detail. However, the present invention is not limited to the following embodiments. In addition, in this specification, (meth) acrylic acid means acrylic acid or methacrylic acid, a (meth) acrylate means an acrylate or methacrylate, and a (meth) acryloyl group is an acryl diary Or methacryloyl group. In addition, a (poly) oxyethylene chain means an oxy ethylene group or a polyoxy ethylene chain, and a (poly) oxypropylene chain means an oxypropylene group or a polyoxypropylene chain. In addition, "EO modification" means that it is a compound which has a (poly) oxyethylene chain, "PO modification" means that it is a compound which has a (poly) oxypropylene chain, and "EO-PO modification" is ( It means a compound having both poly) oxyethylene chain and (poly) oxy propylene chain.

(Photosensitive resin composition)

First, the photosensitive resin composition which concerns on this embodiment is demonstrated. The photosensitive resin composition of this embodiment contains (A) binder polymer, (B) photopolymerizable compound, and (C) photoinitiator.

First, the binder polymer which is (A) component is demonstrated. Examples of the (A) binder polymer include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. In view of alkali developability, acrylic resins are preferred. These can be used individually by 1 type or in combination of 2 or more type.

(A) A binder polymer can be manufactured by radically polymerizing a polymerizable monomer, for example. Examples of the polymerizable monomer include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene, acrylamide, acrylonitrile, vinyl-n-butyl ether, and the like. Esters of vinyl alcohol, (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid furfuryl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) Dimethylaminoethyl acrylate, diethylaminoethyl ester (meth) acrylate, glycidyl ester (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetra Fluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-cro (meth) acrylic acid, β-pril (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid , Maleic acid Maleic acid monoesters such as anhydride, monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like. These are used individually by 1 type or in combination of 2 or more types.

As said (meth) acrylic-acid alkylester, For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) T-butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and structural isomers thereof. These can be used individually by 1 type or in combination of 2 or more type.

(A) It is preferable to contain a carboxyl group from a viewpoint of alkali developability, and (A) binder polymer can be manufactured by radically polymerizing the polymerizable monomer which has a carboxyl group, and another polymerizable monomer, for example. As a polymerizable monomer which has the said carboxyl group, (meth) acrylic acid is preferable.

(A) It is preferable to contain a styrene or a styrene derivative as a copolymerization component from a viewpoint of adhesive improvement. When the said styrene or a styrene derivative is included as a copolymerization component, it is preferable that the content contains 5 to 70 weight% with respect to the whole non volatile matter of (A) component from a viewpoint of improving the adhesiveness and peeling characteristic balance well, It is more preferable to contain 10 to 65 weight%, and it is especially preferable to contain 15 to 60 weight%. When content is less than 5 weight%, there exists a tendency for adhesiveness to be inferior, and when it exceeds 70 weight%, peeling time becomes long and there exists a tendency which the peeling residue after plating tends to produce.

Moreover, it is preferable that (A) binder polymer contains (meth) acrylic-acid benzyl ester as a copolymerization component. When (meth) acrylic-acid benzyl ester is included as a copolymerization component, it is preferable that the content contains 5 to 70 weight% with respect to the whole non volatile matter of (A) component from a viewpoint of balancingly improving resolution and peeling characteristics. It is more preferable to contain 10 to 65 weight%, and it is especially preferable to contain 15 to 60 weight%. When content is less than 5 weight%, there exists a tendency for the resolution to be inferior, and when it exceeds 70 weight%, peeling time becomes long and there exists a tendency which the peeling residue after plating tends to produce.

However, the weight average molecular weight and number average molecular weight in this invention are measured by gel permeation chromatography (GPC), and the value converted into standard polystyrene is used.

It is preferable that the weight average molecular weights of (A) binder polymer are 5000-300000, It is more preferable that it is 10000-150000, It is still more preferable that it is 20000-80000, It is especially preferable that it is 30000-70000. If the weight average molecular weight is less than 5000, the developer resistance tends to be lowered. If the weight average molecular weight is more than 300000, the development time is prolonged, the resolution is high, and the peeling property tends to be lowered.

It is preferable that it is 50-250 mgKOH / g, as for the acid value of (A) component, it is more preferable that it is 10-230 mgKOH / g, and it is more preferable that it is 130-200 mgKOH / g. If the acid value is less than 50 mgKOH / g, the developing time tends to be long, and if it exceeds 250 mgKOH / g, the developer resistance (adhesiveness) of the photocured resist tends to decrease. In addition, when using an organic solvent developing solution as a developing process, it is preferable to prepare the polymerizable monomer which has a carboxyl group in small quantities.

(A) It is preferable that dispersion degree (weight average molecular weight / number average molecular weight) is 1.0-3.0, and, as for a binder polymer, it is more preferable that it is 1.0-2.0. When dispersion degree exceeds 3.0, there exists a tendency for adhesiveness and resolution to fall.

(A) A binder polymer is used individually by 1 type or in combination of 2 or more types. As a binder polymer in the case of using in combination of 2 or more types, for example, two or more types of binder polymers which consist of another copolymerization component, two or more types of binder polymers of different weight average molecular weight, two or more types of binder polymers of different dispersion degrees, etc. Can be mentioned. Moreover, the polymer which has the multi-mode molecular weight distribution of Unexamined-Japanese-Patent No. 11-327137 can also be used.

In addition, the (A) binder polymer may have a photosensitive group as needed.

Next, the photopolymerizable compound which has an ethylenically unsaturated bond which is (B) component is demonstrated.

(B) There is no restriction | limiting in particular as long as it has at least 1 ethylenically unsaturated bond in a molecule | numerator as a photopolymerizable compound, For example, the bisphenol-A (meth) acrylate compound and the (alpha), (beta)-unsaturated carboxylic acid in polyhydric alcohol A urethane monomer such as a (meth) acrylate compound having a urethane bond in the molecule, a nonyl phenoxy polyethyleneoxy acrylate, a phthalic acid compound, a (meth) acrylic acid alkyl ester, a glycidyl group-containing compound, The compound etc. which are obtained by making (beta)-unsaturated carboxylic acid react are mentioned. These are used individually by 1 type or in combination of 2 or more types.

(B) It is preferable that a photopolymerizable compound contains a bisphenol-A (meth) acrylate compound from a viewpoint of improving resolution and peeling characteristics. It is more preferable that these contain 20 to 80 weight% with respect to the total amount of the whole (B) component, It is further more preferable to contain 30 to 70 weight%.

As a bisphenol A type (meth) acrylate compound, 2, 2-bis (4- ((meth) acryloxy polyethoxy) phenyl) propane, 2, 2-bis (4- ((meth) acryloxy polypropoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) Propane etc. are mentioned, Especially, 2, 2-bis (4-((meth) acryloxy polyethoxy) phenyl) propane is preferable from a viewpoint of further improving resolution and peeling characteristics.

As 2, 2-bis (4- ((meth) acryloxy polyethoxy) phenyl) propane, 2, 2-bis (4- ((meth) acryloyl ethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) Phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxynonaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxyundecethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxytridecaethoxy) phenyl ) Propane, 2,2-bis (4-((meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2 And 2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl) propane and the like.

As 2, 2-bis (4- ((meth) acryloxy polypropoxy) phenyl) propane, 2, 2-bis (4- ((meth) acryloxy dipropoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaprop Foxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis (4- ( (Meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic Roxy hexadecapropoxy) phenyl) propane etc. are mentioned. These are used individually by 1 type or in combination of 2 or more types.

Among them, 2,2-bis (4- (methacryloylethoxy) phenyl) propane is commercially available as BPE-100 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) or FA-321M (manufactured by Hitachi Kasei Co., Ltd., It is commercially available as a product name), and 2, 2-bis (4- (methacryloxy pentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (made by Shin-Nakamura Chemical Co., Ltd., product name). It is possible. From the viewpoint of flexibility, resolution and adhesion of the cured product, the number of ethylene oxide groups in 1 molecule of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane is preferably 4-20. It is more preferable that it is 8-15. In addition, from the viewpoint of further improving the peelability, resolution and adhesion, the number of ethylene oxide groups in 1 molecule of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane is 1 It is preferable that it is -3, and it is especially preferable to use together the compound whose number of ethylene oxide groups in 1 molecule is 4-20, and the compound which is 1-3.

As 2, 2-bis (4- ((meth) acryloxy polyethoxy polypropoxy) phenyl) propane, 2, 2-bis (4- ((meth) acryloxy diethoxy octapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane Can be mentioned.

As a compound obtained by making (alpha), (beta)-unsaturated carboxylic acid react with a polyhydric alcohol, the polyethyleneglycol di (meth) acrylate whose number of ethylene groups is 2-14, and the polypropylene glycol di (meth) whose number of propylene groups is 2-14. Acrylate, trimethylolpropanedi (meth) acrylate, trimethylolpropanetri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO, PO Modified trimethylolpropane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate etc. are mentioned. These are used individually by 1 type or in combination of 2 or more types.

Among these, tetramethylol methane triacrylate is A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and EO-modified trimethylolpropane trimethacrylate is TMPT21E or TMPT30E (Hitachi Kasei Co., Ltd.). Available from Kyobo Industries Ltd., sample name).

(B) The photopolymerizable compound is trimethylolpropane tree (meth) having a (poly) oxyethylene chain or a (poly) oxypropylene chain in a molecule from the viewpoint of improving alkali developability, resolution, adhesiveness, or peeling characteristics. It is preferable to contain an acrylate compound, and it is more preferable to contain the trimethylol propane tri (meth) acrylate compound which has a (poly) oxyethylene chain in a molecule | numerator. It is more preferable that these contain 5-50 weight% with respect to the total amount of the whole (B) component, It is further more preferable that 10-40 weight% is included.

In addition, the (B) photopolymerizable compound is a polyalkyl having both a (poly) oxy ethylene chain and a (poly) oxy propylene chain in a molecule from the viewpoint of improving the flexibility of the cured product (cured film) of the photosensitive resin composition. It is preferable to contain lenglycol di (meth) acrylate. It is more preferable to contain 5-50 weight% with respect to the total amount of the whole (B) component, and, as for these, it is still more preferable to contain 10-40 weight%.

As said polyalkylene glycol di (meth) acrylate, it is a (poly) oxyalkylene chain in a molecule | numerator (poly) oxyethylene chain, and (poly) oxypropylene chain ((poly) oxy-n-propylene) chain or (poly) ) Oxyisopropylene chain). In addition, the polyalkylene glycol di (meth) acrylate is further a (poly) oxy-n-butylene chain, a (poly) oxy-n-pentylene chain, a (poly) oxy-n-hexylene chain, You may have a (poly) oxyalkylene chain of about 4-6 carbon atoms which is these structural isomers.

In the molecule | numerator of polyalkylene glycol di (meth) acrylate, (poly) oxyethylene chain and a (poly) oxypropylene chain may exist respectively continuously in block form or may exist in random. In addition, in the (poly) oxyisopropylene chain, the secondary carbon of the propylene group may be bonded to the oxygen atom, and the primary carbon may be bonded to the oxygen atom.

As polyalkylene glycol di (meth) acrylate, the compound especially represented by following formula (6), (7) or (8) is preferable. These are used individually by 1 type or in combination of 2 or more types.

[Chemical Formula 6]

[Formula 7]

[Formula 8]

In said Formula (6), (7), and (8), R <^18> -R <^23> represents a hydrogen atom or a methyl group each independently, EO represents an oxyethylene group, PO represents an oxypropylene group. m <^1> , m <^2> , m <^3> and m <^4> show the repeating number of the structural unit which consists of an oxyethylene group, n <^1> , n <^2> , n <^3> and n <^4> show the repeating number of the structural unit which consists of an oxypropylene group, The repeating total number of groups m ¹ + m ² , m ³ and m ⁴ (average value) each independently represent an integer of 1 to 30, and the repeating total number n ¹ , n ² + n ³ and n ⁴ (average value) of the oxypropylene group are respectively Independently, the integer of 1-30 is represented.

In the compound represented by the formula (6), (7) or (8), the repeating total number m ¹ + m ² , m ³ and m ⁴ of the oxyethylene group is an integer of 1 to 30, preferably 1 to 10. It is an integer of, More preferably, it is an integer of 4-9, Especially preferably, it is an integer of 5-8. When the total number of this repeating number exceeds 30, resolution and adhesiveness will worsen, and it will become difficult to obtain a favorable resist shape.

Further, the repeating total number n ¹ , n ² + n ³ and n ⁴ of the oxypropylene group is an integer of 1 to 30, preferably an integer of 5 to 20, more preferably an integer of 8 to 16, and particularly preferably Is an integer from 10 to 14. When the total number of the repetition numbers exceeds 30, it becomes difficult to obtain sufficient resolution, and sludge tends to be easily generated.

Examples of the compound represented by the formula (6) include a vinyl compound (manufactured by Hitachi Chemical Co., Ltd.), wherein R ¹⁸ and R ¹⁹ = methyl group, m ¹ + m ² = 6 (average), and n ¹ = 12 (average). : FA-023M). Examples of the compound represented by the formula (7) include a vinyl compound (manufactured by Hitachi Chemical Co., Ltd.), wherein R ²⁰ and R ²¹ = methyl group, m ³ = 6 (average), n ² + n ³ = 12 (average) FA-024M) etc. can be mentioned. Examples of the compound represented by the formula (8) include a vinyl compound (manufactured by Shin-Nakamura Chemical Co., Ltd.), sample name of R ²² and R ²³ = hydrogen atom, m ⁴ = 1 (average), n ⁴ = 9 (average) : NK ester HEMA-9P), etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

As a (meth) acrylate compound which has a urethane bond in the said molecule | numerator, the (meth) acryl monomer and diisocyanate compound (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluenedi) which have a (meth) acryl monomer which has an OH group in (beta) position Addition reactant with isocyanate, 1,6-hexamethylene diisocyanate, etc.), tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified Urethane di (meth) acrylate etc. are mentioned. Examples of EO-modified urethane di (meth) acrylate include UA-11 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Examples of EO and PO-modified urethane di (meth) acrylates include UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). These are used individually by 1 type or in combination of 2 or more types.

As said nonylphenoxy polyethylene oxyacrylate, nonyl phenoxy tetraethylene oxy acrylate, nonyl phenoxy pentaethylene oxy acrylate, nonyl phenoxy hexaethylene oxy acrylate, nonyl phenoxy hepta ethylene oxy acrylate, Nonyl phenoxy octaethylene oxyacrylate, nonyl phenoxy nona ethylene oxy acrylate, nonyl phenoxy deca ethylene oxy acrylate, and nonyl phenoxy undeca ethylene oxy acrylate are mentioned. These are used individually by 1 type or in combination of 2 or more types.

As said phthalic acid type compound, (gamma) -chloro- (beta) -hydroxypropyl- (beta) '-(meth) acryloyloxyethyl-o-phthalate, (beta) -hydroxyalkyl- (beta)'-(meth) acryloyloxyalkyl- o-phthalate, and the like. These are used individually by 1 type or in combination of 2 or more types.

Moreover, it is preferable that the (B) photopolymerizable compound contains the photopolymerizable compound which has one ethylenically unsaturated bond in a molecule | numerator from a viewpoint of improving the peeling characteristic of the hardened | cured material (cured film) of the photosensitive resin composition, It is more preferable to contain 3-30 weight% with respect to the total amount of the whole (B) component, and, as for content, it is still more preferable to contain 5-20 weight%.

The content of the component (B) is preferably 30 to 70 parts by weight, more preferably 35 to 65 parts by weight, more preferably 40 to 60 parts by weight based on 100 parts by weight of the total amount of the component (A) and the component (B). It is especially preferable to make it rich. When this content is less than 30 weight part, it will become difficult to obtain sufficient sensitivity and resolution, and when it exceeds 70 weight part, it will become difficult to form a film, and also it will become difficult to obtain a favorable resist shape.

Next, the photoinitiator which is (C) component is demonstrated.

The photoinitiator which is (C) component is (C1) the pyrazine compound which has a structure represented by following formula (1) (henceforth called "(C1) component"), (C2) by following formula (2) Pyrazine compound (hereinafter, sometimes referred to as "(C2) component") having a structure represented and (C3) Pyrazine compound (hereinafter, sometimes referred to as "(C3) component) which has a structure represented by following formula (3) At least one pyrazine compound selected from the group consisting of &quot;

[Chemical Formula 9]

In formula (1), R <^1> , R <^2> , R <^3> and R <^4> respectively independently represent the monovalent organic group containing an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group, or a heterocyclic group, and R <^1> , R <^2> , Alternatively, R ³ and R ⁴ may be bonded to each other to form a ring together with two carbon atoms of a pyrazine skeleton.

[Formula 10]

In formula (2), R <^5> , R <^6> , R <^7> and R <^8> respectively independently represent the monovalent organic group containing an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group, or a heterocyclic group, and R <^5> , R <^6> , Alternatively, R ⁷ and R ⁸ may be bonded to each other to form a ring together with two carbon atoms of a pyrazine skeleton. X and Y each independently represent an atomic group constituting an aromatic ring of a monocyclic structure or a condensed polycyclic structure formed with two carbons of a pyrazine skeleton, and the two aromatic rings are bonded by a single bond between predetermined constituent atoms, have.

[Formula 11]

In formula (3), R <^9> , R <^10> , R <^11> and R <^12> respectively independently represent the monovalent organic group containing an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group, or a heterocyclic group, and R <^9> , R <^10> , Alternatively, R ¹¹ and R ¹² may be bonded to each other to form a ring together with two carbon atoms of a pyrazine skeleton. Z represents the atomic group which comprises the aromatic ring of monocyclic structure or condensed polycyclic structure, or heterocyclic ring formed with four carbons of a pyrazine skeleton.

As a pyrazine compound, (C1) component can be used from a viewpoint of improving the sensitivity of the photosensitive resin composition among (C1) component, (C2) component, and (C3) component.

As said alkyl group in said Formula (1)-(3), a C1-C10 linear or branched alkyl group is preferable, For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and hep Tyl group, octyl group, nonyl group, decyl group, and these structural isomers are mentioned. As a cycloalkyl group, a C4-C10 cycloalkyl group is preferable, and a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclo octyl group, a cyclo nonyl group, and a cyclodecyl group are mentioned. Moreover, the thing by which the hydrogen atom of the cycloalkyl group was substituted by arbitrary substituents is mentioned. As a heterocyclic group, a furanyl group, thienyl group, imidazolyl group, an oxazolyl group, a pyridinyl group, etc. are mentioned, for example. In addition, the hydrogen atom of a phenyl group, a naphthyl group, and a heterocyclic group may be substituted by arbitrary substituents.

As said arbitrary substituent, For example, a C1-C10 linear or branched alkyl group, C1-C10 linear or branched alkoxy group, C1-C10 ester group, C1-C10 alkylamino group Etc. can be mentioned.

When R ¹ to R ⁴ , R ⁵ to R ^8, or R ⁹ to R ¹² are monovalent organic groups containing a phenyl group, a naphthyl group, or a heterocyclic group, solubility is improved and the light absorption wavelength of the compound At least one of R ¹ to R ⁴ , at least one of R ⁵ to R ⁸ , or at least one of R ⁹ to R ¹² is a linear or branched alkoxy having 1 to 10 carbon atoms. It is preferable to include a group.

Examples of the aromatic ring having a monocyclic structure or a condensed polycyclic structure include benzene, naphthalene, anthracene, tetracene, pentacene, phenanthrene, triphenylene, pyrene and those in which the hydrogen atoms of these aromatic rings are substituted with arbitrary substituents. These are mentioned, It is preferable that they are benzene or naphthalene from a viewpoint of price or the solubility at the time of synthesis.

Examples of the heterocycle include pyridine, pyrimidine, pyrazine, pyrrole, furan, thiophene, and those in which the hydrogen atoms of these heterocycles are substituted with arbitrary substituents. desirable.

In addition, R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² combine with each other to form two carbons of a pyrazine skeleton In the case of forming a ring together, the ring formed may be either an aliphatic ring or an aromatic ring, and is preferably an aromatic ring from the viewpoint of improving solubility and adjusting the light absorption wavelength of the compound to the visible portion (near 405 nm). As an aromatic ring, it is more preferable that it is a benzene ring or a naphthalene ring.

In the pyrazine compound represented by the formula (1), when R ³ and R ⁴ are bonded to each other to form a ring together with two carbons of the pyrazine skeleton, the ring formed is preferably an aromatic ring, and more preferably a naphthalene ring. . Moreover, it is preferable that R <^1> and R <^2> is a phenyl group, and it is more preferable that the hydrogen atom of a phenyl group is substituted by the C1-C10 linear or branched alkoxy group. In addition, the position of a substituent is arbitrary. As a pyrazine compound represented by said Formula (1), the compound etc. which are represented by following formula (9), (10), (11), (12) are mentioned, for example.

[Chemical Formula 12]

[Chemical Formula 13]

[Formula 14]

[Formula 15]

Moreover, as a pyrazine compound represented by said Formula (2), the compound etc. which are represented by following formula (13), (14) are mentioned, for example.

[Chemical Formula 16]

[Chemical Formula 17]

Moreover, as a pyrazine compound represented by said Formula (3), the compound etc. which are represented by following formula (15), (16) are mentioned, for example.

[Chemical Formula 18]

[Chemical Formula 19]

Moreover, in this photosensitive resin composition, it is preferable that the maximum absorption wavelength of (C1), (C2), and (C3) component exists in the range of 350-410 nm. Thereby, while being able to acquire favorable sensitivity with respect to the light of wavelength 350-410 nm, absorption in the long wavelength side of wavelength 500nm or more becomes small, and stability under yellow light becomes favorable.

When using the direct drawing exposure apparatus of wavelength 405nm which has several exposure heads especially, it is preferable that the maximum absorption wavelength of (C1), (C2), and (C3) components exists in the range of 380-410 nm. When the maximum absorption wavelength is in the range of 380 to 410 nm, even if the light emission wavelength dispersion is slightly different in the light source of each exposure head, the amount of light absorption near the wavelength of 405 nm becomes substantially constant. As a result, the possibility that a difference arises in a sensitivity for every exposure head can be reduced. Moreover, since high sensitivity is obtained stably, it becomes possible to reduce the addition amount of a photoinitiator.

It is preferable that content of said (C1), (C2) and (C3) component is 50-100 weight% with respect to the total amount of the whole (C) component, It is more preferable that it is 70-100 weight%, 80-100 It is more preferable that it is weight%. When this content is less than 50 weight%, there exists a tendency for a sensitivity and resolution to fall. In addition, the "content" here means content of those sum totals, when two or more types are included in (C1), (C2), and (C3) component.

(C) Photoinitiator may contain the other photoinitiator so that the effect by (C1), (C2), and (C3) component is not impaired. As another photoinitiator, it is benzophenone, 2-benzyl-2- dimethyl amino-1- (4-morpholinophenyl) -butanone- 1, 2-methyl-1- [4- (methylthio, for example). ) Phenyl] -2-morpholinopropanone-1, such as aromatic ketones, quinones, such as alkyl anthraquinone, benzoin ether compounds, such as benzoin alkyl ether, benzoin compounds, such as benzoin and alkyl benzoin, benzyl Benzyl derivatives such as dimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, etc. And acridine derivatives such as 2,4,5-triarylimidazole dimer, 9-phenylacridine, and 1,7- (9,9'-acridinyl) heptane. These can be used individually by 1 type or in combination of 2 or more types.

In addition, the substituent of the aryl group of said two 2,4,5-triarylimidazole may be same or different. These are used individually or in combination of 2 or more types.

Moreover, as another photoinitiator, the compound represented by following formula (4) is mentioned.

[Chemical Formula 20]

In formula (4), X represents a carbon atom or a nitrogen atom, R <^13> , R <^14> and R <^15> represent a halogen atom or a C1-C5 alkyl group each independently, At least in R <^13> , R <^14> and R <^15> . One represents a halogen atom. R <^16> represents a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group, and l shows the integer of 0-4. When l is 2-4, some R <^16> may be same or different.

In the photosensitive resin composition of this invention, by using the compound represented by the said Formula (4) and (C1) component or (C2) component as a (C) photoinitiator, it is a sensitivity and maintains resolution and adhesiveness, There exists a tendency for the imaging property (color development property of a resist) to improve.

As content of the photoinitiator of (C) component, it is preferable to set it as 0.01-10 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, It is more preferable to set it as 0.05-6 weight part, 0.1 ~ It is especially preferable to set it as 4 weight part. When this content is less than 0.01 weight part, there exists a tendency for favorable sensitivity and resolution not to be obtained, and when it exceeds 10 weight part, there exists a tendency for a favorable shape to not be obtained.

Moreover, it is preferable that the photosensitive resin composition of this invention contains the (D) hydrogen donor compound further. As the hydrogen donating compound, for example, bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, leuco crystal violet, 2-mercaptobenzoxazole, the following formula ( The compound represented by 5), etc. are mentioned, A sensitivity can be improved more. It is more preferable to include the compound represented by following formula (5) from a viewpoint of improving a sensitivity further. As a compound represented by Formula (5), N-phenylglycine etc. are mentioned, for example.

[Chemical Formula 21]

In formula (5), R <^17> represents a C1-C6 alkyl group, an alkoxy group or ester group, a hydroxyl group, or a halogen atom. n is an integer of 0-5, and when n is 2-5, some R <^17> may be same or different. R <^17> represents a C1-C6 alkyl group, an alkoxy group or ester group, a hydroxyl group, or a halogen atom. n is an integer of 0-5, and when n is 2-5, some R <^17> may be same or different. In the photosensitive resin composition of this invention, there exists a tendency for the sensitivity with respect to the light of wavelength 350-410nm to improve by using combining the compound represented by the said Formula (5), (C1) component or (C2) component.

(D) It is preferable to make content with a hydrogen donor compound into 0.01-10 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, It is more preferable to set it as 0.05-5 weight part, 0.1 ~ It is especially preferable to set it as 2 weight part. When this compounding quantity is less than 0.01 weight part, there exists a tendency for favorable sensitivity not to be obtained, and when it exceeds 10 weight part, it will tend to precipitate as a foreign material after film formation. These are used individually by 1 type or in combination of 2 or more types.

Moreover, for the purpose of making sensitivity higher, you may further include the (E) sensitizing dye. Although a sensitizing dye can select what has the absorption wavelength according to the wavelength of the actinic light to be used, The compound whose maximum absorption wavelength is 370 nm-420 nm is preferable. By using such a sensitizing dye, especially the exposure light of the direct drawing exposure method of wavelength 405nm, the photosensitive resin composition will have a sufficiently high sensitivity. When the maximum absorption wavelength of a sensitizing dye is less than 370 nm, there exists a tendency for the sensitivity to direct drawing exposure light to fall, and when it is 420 nm or more, there exists a tendency for stability under yellow light to fall.

(E) As a sensitizing dye, for example, dialkylaminobenzophenones, pyrazolines, anthracenes, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, Triazines, thiophenes, naphthalimides, triarylamines, etc. are mentioned. A sensitizing dye is used individually by 1 type or in combination of 2 or more types.

In particular, when exposing the photosensitive resin composition layer using 390-420 nm actinic light, from the viewpoint of sensitivity and adhesiveness, the (E) sensitizing dye is pyrazoline, anthracene, coumarin and triarylamines. It is preferable to include at least 1 sort (s) chosen from the group which consists of, and it is more preferable to contain pyrazoline, anthracene, or triarylamine especially.

It is preferable to make content of (E) sensitizing dye into 0.01-10 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, It is more preferable to set it as 0.05-5 weight part, 0.1-2 weight It is especially preferable to make it rich. If this blending amount is less than 0.01 part by weight, there is a tendency that good sensitivity and resolution are not obtained, and if it exceeds 10 parts by weight, there is a tendency that a good shape cannot be obtained.

The photosensitive resin composition which concerns on this embodiment is a photopolymerizable compound (oxetane compound etc.) which has at least 1 cation-polymerizable cyclic ether in a molecule | numerator as needed, dyes, such as a cationic polymerization initiator and malachite green, leuco crystal violet Photochromic agents, exothermic color inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion imparting agents, leveling agents, peeling accelerators, antioxidants, flavoring agents, imaging agents, thermal crosslinking agents, and the like. You may contain it. These are used individually by 1 type or in combination of 2 or more types. It is preferable to make these content into about 0.01-20 weight part with respect to 100 weight part of total amounts of (A) component (binder polymer) and (B) component (photopolymerizable compound), respectively.

The photosensitive resin composition which concerns on this embodiment mentioned above is melt | dissolved in the organic solvent, and is apply | coated on the surface, such as a metal plate, as a solution (coating liquid) of the photosensitive resin composition of about 30 to 60 weight% of solid content, for example. And drying, the photosensitive resin composition layer which consists of the photosensitive resin composition of this embodiment can be formed. Examples of the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. Moreover, as a metal plate, iron-based alloys, such as copper, a copper alloy, nickel, chromium, iron, stainless steel, Preferably copper, a copper alloy, an iron alloy is mentioned.

Although the thickness of the photosensitive resin composition layer changes with the uses, it is preferable that it is about 1-100 micrometers in the thickness after drying. The surface of the photosensitive resin composition layer opposite to the metal plate may be coated with a protective film. As a protective film, aggregate films, such as polyethylene and a polypropylene, etc. are mentioned.

(Photosensitive element)

Next, the photosensitive resin composition layer and the photosensitive element which concern on this embodiment are demonstrated. 1: is a schematic cross section which shows an example of the photosensitive element. The photosensitive element 1 is a laminated body in which the support film 2, the photosensitive resin composition layer 3, and the protective film 4 were laminated | stacked in this order in some cases.

As the support film 2, the aggregate film which has heat resistance and solvent resistance, such as polyester, such as polyethylene terephthalate, polypropylene, and polyethylene, can be used. It is preferable that it is 1-100 micrometers, as for the thickness of a support film (assembly film), it is more preferable that it is 5-50 micrometers, and it is still more preferable that it is 5-30 micrometers. When this thickness is less than 1 micrometer, when a peeling of a support film, a support film tends to be torn easily, and when it exceeds 100 micrometers, there exists a tendency which resolution becomes difficult to be obtained sufficiently.

The photosensitive resin composition layer 3 which consists of said photosensitive resin composition is formed on the support film 2 by apply | coating the solution of the photosensitive resin composition concerning this embodiment mentioned above on the support film 2, and drying it. Can be.

Application | coating on the support film 2 of the solution of the photosensitive resin composition can be performed by well-known methods, such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die cocker, a bar coater.

It is preferable to perform drying of the solution of the photosensitive resin composition at 70-150 degreeC for about 5 to 30 minutes. After drying, it is preferable to make the amount of the residual organic solvent in the photosensitive resin composition layer 3 into 2 weight% or less from a viewpoint of preventing the diffusion of the organic solvent in a later process.

Although the thickness of the photosensitive resin composition layer 3 in the photosensitive element 1 changes with a use, it is preferable that it is 1-100 micrometers in thickness after drying, It is more preferable that it is 1-50 micrometers, 5-50 It is more preferable that it is micrometer, and it is especially preferable that it is 10-40 micrometers. When this thickness is less than 1 micrometer, there exists a tendency for industrial coating to become difficult, and when it exceeds 100 micrometers, there exists a tendency for adhesiveness and resolution to become difficult to fully acquire.

As for the transmittance | permeability of the ultraviolet-ray to the photosensitive resin composition layer 3, it is preferable that it is 5-75% in the ultraviolet-ray of wavelength 405 nm, It is more preferable that it is 10-65%, It is especially preferable that it is 15-55%. When this transmittance | permeability is less than 5%, it will become difficult to obtain sufficient adhesiveness, and when it exceeds 75%, it will tend to become difficult to obtain sufficient resolution. The transmittance can be measured by a UV spectrometer. As a UV spectrometer, the Hitachi, Ltd. type 228A W-beam spectrophotometer is mentioned.

The photosensitive element 1 may be equipped with the protective film 4 which coat | covers the surface on the opposite side to the support film 2 of the photosensitive resin composition layer 3 as needed.

As the protective film 4, it is preferable that the adhesive force with respect to the photosensitive resin composition layer 3 is smaller than the adhesive force with respect to the photosensitive resin composition layer of the support film 2, and the film of the low fisheye is preferable. Here, "fisheye" means that foreign materials, undissolved matters, oxidative degradation materials, etc. of materials are contained in the film when the material is thermally dissolved and kneaded, extruded, biaxially stretched, cast or the like. . That is, "low fisheye" means that the said foreign material in a film is few.

Specifically, as the protective film 4, an aggregate film having heat resistance and solvent resistance, such as polyester, such as polyethylene terephthalate, polypropylene, and polyethylene, can be used. Commercially available examples include polyethylene terephthalate films such as polypropylene films such as Arpan MA-410, E-200C manufactured by Oji Paper Co., Ltd., and PS series such as PS-25 manufactured by Teijin Co., Ltd. . In addition, the protective film 4 may be the same as that of a support film.

It is preferable that the thickness of the protective film 4 is 1-100 micrometers, It is more preferable that it is 5-50 micrometers, It is further more preferable that it is 5-30 micrometers, It is especially preferable that it is 15-30 micrometers. When this thickness is less than 1 micrometer, when laminating (laminating) the photosensitive resin composition layer 2 and the protective film 4 on a board | substrate, there exists a tendency for the protective film 4 to tear easily, and when it exceeds 100 micrometers It tends to be insufficient in terms of inexpensiveness.

The photosensitive element may further have intermediate | middle layers, such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.

The obtained photosensitive element 1 can be wound and stored in a sheet form or a core in roll shape. When winding in roll shape, it is preferable to wind so that the support film 2 may become an outer side. Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). In the end face of the roll-shaped photosensitive element obtained in this way, it is preferable to provide a cross-sectional separator from the standpoint of end surface protection, and it is preferable to provide a moisture proof cross-section separator from the standpoint of edge fusion. As a packing method, it is preferable to wrap in a black sheet with small moisture permeability, and to package.

(Method of forming resist pattern)

A resist pattern can be formed using the said photosensitive resin composition. The method of forming a resist pattern according to the present embodiment includes (i) a lamination step of laminating a photosensitive resin composition layer made of the photosensitive resin composition on a substrate, and (ii) actinic light on a predetermined portion of the photosensitive resin composition layer. It has an exposure process to irradiate, and (iii) developing process which forms the resist pattern which consists of hardened | cured material of the photosensitive resin composition on a board | substrate by removing parts other than the said predetermined part of the photosensitive resin composition layer from a board | substrate.

(i) a laminating step

First, the photosensitive resin composition layer which consists of a photosensitive resin composition is laminated | stacked on a board | substrate. As a board | substrate, the board | substrate (circuit formation board | substrate) provided with the insulating layer and the conductor layer formed on this insulating layer can be used.

Lamination | stacking on the board | substrate of the photosensitive resin composition layer is performed by crimping | bonding to the said board | substrate, heating the photosensitive resin composition layer of the photosensitive element, for example after removing the protective film of the said photosensitive element. Thereby, the laminated body which consists of a board | substrate, the photosensitive resin composition layer, and a support film and these laminated | stacked in order is obtained.

This lamination operation is preferably carried out under reduced pressure in view of adhesion and followability. There is no restriction | limiting in particular in the conditions, such as the heating temperature and pressure with respect to the photosensitive resin composition layer and / or board | substrate at the time of crimping | bonding, It is preferable to carry out at the temperature of 70-130 degreeC, and about 0.1-1.OMPa (1-10 kgf / compression to a pressure of about ² cm). In addition, when the photosensitive resin composition layer is heated to 70-130 degreeC, it is not necessary to preheat-process a board | substrate previously, In order to further improve lamination property, you may perform a preheating process of a board | substrate.

(ii) exposure step

Next, actinic light is irradiated to the predetermined part of the photosensitive resin composition layer on a board | substrate, it is exposed to the predetermined part, and it hardens. At this time, when the support film existing on the photosensitive resin composition layer has transparency to actinic light, actinic light can be irradiated through the support film, but when the support film has light shielding property to actinic light, After removing a support film, actinic light is irradiated to the photosensitive resin composition layer.

As an exposure method, the method (mask exposure method) which irradiates an actinic light to an image image through the negative or positive mask pattern called artwork is mentioned. Moreover, you may employ | adopt the method which irradiates an actinic light on an image by direct drawing exposure methods, such as LDI (Laser Direct Imaging) exposure method and DLP (Digital Light Processing) exposure method.

As a light source of active light, a well-known light source can be used, For example, a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp, a gas laser, such as an argon laser, a solid laser, such as a YAG laser, a semiconductor laser, etc. Effectively emitting ultraviolet rays, visible light, and the like.

As a wavelength (exposure wavelength) of an actinic light, it is preferable to carry out in the range of 350-410 nm from a viewpoint of obtaining the effect of this invention more reliably, and it is more preferable to carry out in the range of 390-410 nm.

(iii) development process

Moreover, the resist pattern which consists of hardened | cured material of the photosensitive resin composition is formed on a board | substrate by removing parts other than the said predetermined part of the photosensitive resin composition layer from a board | substrate. When the support film exists on the photosensitive resin composition layer, after removing a support film, parts (unexposed part) other than the said predetermined part (exposed part) are removed (developed). The developing method includes a wet phenomenon and a dry phenomenon, but a wet phenomenon is widely used.

In the case of wet development, development is carried out by a known development method using a developer corresponding to the photosensitive resin composition. As the developing method, a method using a dip method, a battle method, a spray method, blushing, slapping, scraping, oscillation dipping and the like can be cited. In view of improving resolution, a high pressure spray method is most suitable. These may develop in combination of 2 or more types of methods.

As a developing solution, alkaline aqueous solution, an aqueous developing solution, an organic solvent developing solution, etc. are mentioned.

When used as a developing solution, alkaline aqueous solution is safe and stable, and its operativity is favorable. As a base of alkaline aqueous solution, Alkali metal hydroxides, such as hydroxide of lithium, sodium, or potassium; Carbonates or bicarbonates of lithium, sodium, potassium or ammonium; Alkali metal phosphates such as potassium phosphate and sodium phosphate; Alkali metal pyrophosphate such as sodium pyrophosphate, potassium pyrophosphate and the like are used.

As the alkaline aqueous solution, a lean solution of 0.1-5% by weight sodium carbonate, a lean solution of 0.1-5% by weight potassium carbonate, a lean solution of 0.1-5% by weight sodium hydroxide, a lean solution of 0.1-5% by weight sodium tetraborate is preferable. Do. It is preferable to make pH of alkaline aqueous solution into the range of 9-11, and the temperature is adjusted according to the alkali developability of the photosensitive resin composition layer.

In alkaline aqueous solution, you may mix surface active agent, an antifoamer, a small amount of organic solvents for promoting image development, etc ..

An aqueous developing solution is a developing solution which consists of water or alkaline aqueous solution, and 1 or more types of organic solvents, for example. Here, as the base of the alkaline aqueous solution, in addition to the substances described above, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl- 1,3-propanediol, morpholine, etc. are mentioned. It is preferable to make pH of an aqueous developing solution as small as possible in the range in which image development is fully performed, It is preferable to set it as pH8-12, and it is more preferable to set it as pH9-10.

As an organic solvent used for an aqueous developing solution, acetone, ethyl acetate, the alkoxy ethanol which has a C1-C4 alkoxy group, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether and the like. These are used individually by 1 type or in combination of 2 or more types. It is preferable to make the density | concentration of the organic solvent in an aqueous developing solution normally 2 to 90 weight%, and the temperature can be adjusted according to alkali developability. In the aqueous developer, a small amount of a surfactant, an antifoaming agent, or the like may be mixed.

As the organic solvent developer, organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone and γ-butyl olactone are used. Can be mentioned. It is preferable to add water to these organic solvents in the range of 1-20 weight% in order to prevent flammability.

After removing an unexposed part, you may harden a resist pattern further by heating about 60-250 degreeC or exposing about 02-10 J / cm <^2> as needed.

(Manufacturing method of printed wiring board)

A printed wiring board can be produced by etching or plating a substrate on which a resist pattern is formed by the above method. Etching or plating of the substrate is performed on the conductor layer or the like of the substrate using the formed resist pattern as a mask.

Examples of the etching solution in the case of etching include a cupric chloride solution, a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide etching solution. Among them, a ferric chloride solution is used because the etching factor is good. It is preferable.

As the plating method for plating, copper plating such as copper sulfate plating, copper plating such as pyrophosphate copper plating, solder plating such as high draw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard gold plating And gold plating such as soft gold plating.

After completion of etching or plating, the resist pattern can be peeled off by, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. As this strongly alkaline aqueous solution, 1-10 weight% sodium hydroxide aqueous solution, 1-10 weight% potassium hydroxide aqueous solution, etc. are used, for example. Especially, it is preferable to use the 1-10 weight% sodium hydroxide aqueous solution or the potassium hydroxide aqueous solution, and it is more preferable to use the 1-5 weight% sodium hydroxide aqueous solution or the potassium hydroxide aqueous solution.

As a peeling method of a resist pattern, an immersion system, a spray system, etc. are mentioned, These may be used independently or may be used together. Moreover, a multilayer printed wiring board may be sufficient as the printed wiring board with which the resist pattern was formed, and may have a through hole with a small diameter.

As mentioned above, although the very suitable embodiment of this invention was described, this invention is not limited to the said embodiment at all.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Examples 1-13 and Comparative Example 1>

[Preparation of solution of photosensitive resin composition]

The solution of the photosensitive resin composition of Examples 1-13 and the comparative example 1 was prepared by mixing the component shown in following Table 1 and Table by the compounding quantity shown in the same table. In addition, the compounding quantity of (A) component shown in Table 1 and Table 2 is the mass (solid amount) of a non volatile matter. About the detail of each component shown in following Table 1 and Table 2, it is as follows.

&Lt; (A) Binder polymer &

[Synthesis of binder polymer (A-1)]

150 g of methacrylic acid as polymerizable monomer (monomer), 125 g of methacrylic acid benzyl ester, 25 g of methyl methacrylate and 200 g of styrene (weight ratio 30/25/5/40) and 9.Og of azobisisobutylonitrile The obtained solution was called "solution a."

The solution obtained by melt | dissolving 1.2 g of azobisisobutylonitrile in the liquid mixture (mass ratio 3: 2) of 60 g of methyl cellosolves and 40 g of toluene was called "solution b."

To a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping lot, and a nitrogen gas introduction tube, a mixed solution (mass ratio 3: 2) of 270 g of methyl cellosolve and 180 g of toluene was introduced, and mixed while blowing nitrogen gas into the flask. Heated and heated up to ° C.

The solution a was added dropwise to the mixed solution in the flask over 4 hours, and then the mixture was 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 with stirring. Furthermore, the solution in a flask was heated up to 90 degreeC over 30 minutes, it was kept at 90 degreeC for 2 hours, and it cooled, and obtained the liquid containing binder polymer (A-1).

The nonvolatile matter (solid content) of the binder polymer (A-1) was 47.8 wt%, the weight average molecular weight was 30,000, and the acid value was 196 mgKOH / g. In addition, the weight average molecular weight was measured by gel permeation chromatography method (GPC), and it derived by converting using the analytical curve of standard polystyrene. The conditions of GPC are shown below.

(GPC conditions)

Pump: Hitachi L-6000 type [made by Hitachi, Ltd.]

Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (three in total) (above, Hitachi Kasei Co., Ltd., brand name)

Eluent: tetrahydrofuran

Measuring temperature: 40 ° C

Flow rate: 2.05 mL / min

Detector: Hitachi L-3300 type RI [made by Hitachi, Ltd.]

<B) Photopolymerizable Compound>

MPT21E: trimethylolpropane polyoxyethylene ether trimethacrylate (manufactured by Hitachi Chemical Co., Ltd., brand name)

FA-321M: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane) (product made by Hitachi Kasei Co., Ltd., brand name)

FA-024M: In the compound represented by the formula (6), R ²⁰ and R ²¹ = methyl group, m ³ = 6 (average), n ² + n ³ = 12 (average)) (Hitachi Kasei Kogyo Co., Ltd.) Shikiisha, brand name)

M-114: 4-normal nonyl phenoxy octaethylene glycol acrylate (Toa synthetic Co., Ltd. product, brand name)

BPE-100: 2,2-bis (4- (methacryloxypolyethoxy) phenyl) propane) (an average of ethylene oxide chains contained in 1 molecule is 2.6 mol) (manufactured by Shin-Nakamura Chemical Co., Ltd., brand name)

<Photoinitiator (C)>

[Synthesis of Photoinitiator (C-1)]

20 mL of ethanol, 2 mmol of 3,3 ', 4,4'-biphenyltetraamine and 4 mmol of 3,3'-dimethoxybenzyl were added to the flask, mixed, nitrogen-substituted air in the flask, and the mixture was stirred at 80 ° C. It was refluxed for time. After cooling to room temperature and adding 200 mL of water, the product (C-1) was obtained by filtration under reduced pressure.

It was confirmed that product (C-1) is a compound of the structure shown by following formula (13) from the 1H-NMR spectrum shown in FIG. 2, and the 13C-NMR spectrum shown in FIG.

[Chemical Formula 22]

[Synthesis of Photoinitiator (C-2)]

A compound of the structure represented by the following formula (14) was obtained in the same manner as in (C-1) except that 4,4'-dimethoxybenzyl was used instead of 3,3'-dimethoxybenzyl.

(23)

[Synthesis of Photoinitiator (C-3)]

Instead of using 2 mmol of 3,3 ', 4,4'-biphenyltetraamine and 4 mmol of 3,3'-dimethoxybenzyl, 2 mmol of 2,3-diaminonaphthalene and 2 mmol of 3,3'-dimethoxybenzyl In the same manner as in the above (C-1), a compound having a structure represented by the following formula (11) was obtained.

&Lt; EMI ID =

[Synthesis of Photoinitiator (C-4)]

Instead of using 2 mmol of 3,3 ', 4,4'-biphenyltetraamine and 4 mmol of 3,3'-dimethoxybenzyl, other than using 2 mmol of 2,3-diaminonaphthalene and 2 mmol of 4,4'-dimethoxybenzyl In the same manner as in the above (C-1), a compound having a structure represented by the following formula (12) was obtained.

(25)

[Other photopolymerization initiators]

Photoinitiators other than (C-1), (C-2), (C-3), and (C-4) are shown below.

BCIM: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole (made by Hampford, brand name)

TPS: α, α, α-tribromomethylphenylsulfone

(Measurement of absorption spectrum)

The ultraviolet-visible absorption spectra of the products (C-1), (C-2) and (C-3) were measured as follows.

Using the film containing the product (C-1) produced in Example 1, and the film containing the product (C-3) produced in Example 8, each sample was made using the ultraviolet visible spectrophotometer UV2550 by Shimadzu Corporation. The ultraviolet visible absorption spectrum of the film was measured. The obtained result is shown in FIG.

In addition, the products (C-1) and (C-2) were chamfered to 1 × 10 ⁻⁵ mol / L in chloroform and placed in a quartz cell using an ultraviolet visible spectrophotometer UV2550 manufactured by Shimadzu Corporation. The ultraviolet visible absorption spectrum of each sample solution was measured. The obtained result is shown in FIG.

4 and 5 showed that the products (C-1), (C-2), and (C-3) had maximum absorption wavelengths in the range of 350 to 410 nm.

<(D) hydrogen donor compound>

LCV: Loikaw Crystal Violet

NPG: N-phenylglycine (R ¹⁷ = hydrogen atom)

(D-1): 2-mercaptobenzoxazole

<(E) sensitizing dye>

Nikka flow MC: 7-diethylamino-4-methylcoumarin (made by Nippon Chemical Co., Ltd., brand name)

DBA: 9,10-dibutoxy anthracene (made by Kawasaki Kasei Co., Ltd., brand name)

(E-1): 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) pyrazoline (made by Nippon Chemical Co., Ltd.)

[Table 1]

[Table 2]

(Photosensitive element)

The solution of the photosensitive resin composition of the said Examples 1-13 and Comparative Example 1 was apply | coated uniformly on the polyethylene terephthalate film (Teijin Co., Ltd. product name "HTF-01") of thickness each 16 micrometers, respectively, 70 It dried with the hot air convection type dryer of 110 degreeC and 110 degreeC, and formed the photosensitive resin composition layer whose film thickness after drying is 40 micrometers. A protective film (Tamapoly Co., Ltd. product name "NF-15") is bonded together on this photosensitive resin composition layer, and a polyethylene terephthalate film (support film), the photosensitive resin composition layer, and a protective film are laminated in order. The obtained photosensitive elements of Examples 1-13 and Comparative Example 1 were obtained.

(Laminated substrate)

A polishing machine having a blush equivalent of # 600 on the copper surface of a copper clad laminate (made by Hitachi Chemical Co., Ltd., product name MCL-E-67) made of a glass epoxy material and copper foil (35 µm thick) formed on both sides thereof. (Made by Sanke), and after washing with water, it was dried by air. After heating this copper clad laminated board and heating up at 80 degreeC, the photosensitive element of Examples 1-13 and Comparative Example 1 was laminated (laminated) on the copper surface of a board | substrate. Lamination was performed under the conditions of the temperature of 120 degreeC, and the lamination pressure of 4 kgf / cm <^2> , making the photosensitive resin composition layer of each photosensitive element adhere to the copper surface of a board | substrate, removing a protective film. Thus, the laminated substrate by which the photosensitive resin composition layer and the polyethylene terephthalate film were laminated | stacked on the copper surface of the board | substrate was obtained.

(Evaluation of sensitivity)

When the obtained laminated substrate was left to cool and it became 23 degreeC, on the polyethylene terephthalate film of a laminated substrate, concentration area 0.00-2.00, concentration step 0.05, tablet size 20mm * 187mm, and the size of each step is 3mm * 12mm. Photo tool having 41 steps of step tablets was stuck. Photosensitive resin through a phototool and a polyethylene terephthalate film with a predetermined amount of energy (exposure amount) using a weaving machine "DE-1AH" (trade name) made by Hitachi Via Mechanics Co., Ltd. using a blue violet laser diode having a wavelength of 405 nm as a light source. The composition layer was exposed. In addition, the measurement of illuminance was performed using the ultraviolet illuminometer (The Ushio Denki Corporation make, brand name "UIT-150") to which the 405 nm corresponding probe was applied.

After exposure, the polyethylene terephthalate film was peeled off from the laminated substrate, the photosensitive resin composition layer was exposed, and the unexposed portion was removed by spraying a 1% by weight aqueous sodium carbonate solution at 30 ° C. for 60 seconds. In this way, the cured film 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 the exposure amount (mJ / cm <^2> ) when the remaining stage of the step tablet obtained as a cured film became 20 steps. Smaller value means better sensitivity. The results are shown in Table 3 and Table 4.

(Evaluation of resolution and adhesion)

Remaining 41-step step tablet using a drawing pattern having a line width L / space width S (hereinafter referred to as "L / S") of 5/5 to 30/30 (unit: µm) Exposure (drawing) was performed with respect to the photosensitive resin composition layer of the said laminated | multilayer board | substrate with the energy amount used as 20 steps of stages. After the exposure, the same development treatment as that for evaluation of the sensitivity was performed.

After the development, the space portion (unexposed portion) is neatly removed, and the resolution and the line width / space width are reduced by the smallest line width / space width value among the resist patterns formed without causing the line portion (exposed portion) to bend or lose. Adhesiveness was evaluated. The smaller this value means, the better both the resolution and the adhesion. The results are shown in Table 3 and Table 4.

(Evaluation of peeling property)

The laminated substrate on which the resist pattern obtained by the said resolution and adhesiveness evaluation was formed was immersed in the plating liquid of copper sulfate / sulfuric acid aqueous solution, and electrolytic copper plating was performed for 15 minutes by 2 A of total electric current values. The obtained plated copper thickness was about 15 micrometers. 50 degreeC 3 weight% sodium hydroxide aqueous solution was sprayed on the laminated board | substrate after plating, and the resist was peeled off from the board | substrate. The laminated substrate after peeling was observed using the optical microscope, and the presence or absence of the peeling remainder of the cured film between plating patterns (copper wiring) was investigated. The results are shown in Table 3 and Table 4.

(Evaluation of Plating Formability)

The laminated board | substrate after peeling obtained by evaluation of the said peeling characteristic was observed using the optical microscope, and plating formation property was evaluated by the smallest plating width formed without the disconnection or short circuit of the plating pattern. Smaller value means better plating formability. The results are shown in Table 3 and Table 4.

(Evaluation of prevention of contamination to plating)

Each photosensitive element was cut into the size of 40 cm x 50 cm, the protective film was removed, it exposed to the photosensitive resin composition layer at the exposure amount which becomes a step tablet of 20 steps, the polyethylene terephthalate film was peeled off, and the cured film was obtained. This cured film was immersed in 1 L of plating liquid of copper sulfate / sulfuric acid aqueous solution for 3 days. The copper clad laminate (substrate) was subjected to electrolytic copper plating for 15 minutes at a total current value of 2 A using a Halssel test bath (manufactured by Yamamoto Plating Test Co., Ltd.).

The appearance of the plating in the case of using the plating solution in which the cured film was immersed was visually observed using the plating in the case of using the plating solution in which the cured film was not immersed. Compared with the reference, there was no change in the appearance of the plating, and there was no contamination, change in discoloration, and the like was determined as being polluted. The results are shown in Table 3 and Table 4.

[Table 3]

[Table 4]

The photosensitive resin composition of Examples 1-15 was high sensitivity with respect to the direct drawing exposure of wavelength 405nm compared with the comparative example 1, and also the resolution, adhesiveness, and plating formation property were favorable. Moreover, the peeling characteristic of resist and the prevention of the contamination with respect to plating were also maintained favorably. In particular, Examples 2 and 8 using the (C1) component or (C2) component as a photoinitiator, and using only N-phenylglycine represented by said Formula (5) as a hydrogen donating compound improved the sensitivity. In addition, the (C1) component or the (C2) component was used independently by using together the (C1) component or the (C2) component with the (alpha), (alpha), (alpha)-tribromomethylphenyl sulfone shown by said Formula (4). Sensitivity was improved than ever. In addition, when using together the (alpha), (alpha), (alpha)-tribromomethylphenyl sulfone represented by said Formula (4), Example 15 using the (C1) component represented by Formula (C-4) is Formula (C-) Sensitivity was improved compared with Example 14 using the (C1) component represented by 3), and Example 9 using the (C2) component represented by Formula (C-1).

As mentioned above, it became clear that the photosensitive resin composition and the photosensitive element which are excellent in a sensitivity, resolution, adhesiveness, peeling characteristic, and plating formation, and are low in contamination with plating are obtained.

One … Photosensitive element, 2... Support film, 3... Photosensitive resin composition, 4... Protective film.

Claims (11)

It contains a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and at least one pyrazine compound selected from the group consisting of a compound having a structure represented by the following formula (1), (2), or (3): As a photosensitive resin composition to say,
The photosensitive resin composition in which the said binder polymer contains (meth) acrylic acid and styrene or a styrene derivative as a copolymerization component.
[Chemical Formula 1]

[In formula (1), R <^1> , R <^2> , R <^3> and R <^4> respectively independently represent the monovalent organic group containing an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group, or a heterocyclic group, and R <^1> and R <^2> Alternatively, R ³ and R ⁴ may be bonded to each other to form a ring together with two carbon atoms of a pyrazine skeleton.]
(2)

[In formula (2), R <^5> , R <^6> , R <^7> and R <^8> respectively independently represent the monovalent organic group containing an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group, or a heterocyclic group, and R <^5> and R <^6> Alternatively, R ⁷ and R ⁸ may be bonded to each other to form a ring together with two carbon atoms of a pyrazine skeleton. X and Y each independently represent an atomic group constituting an aromatic ring of a monocyclic structure or a condensed polycyclic structure formed with two carbons of a pyrazine skeleton.]
(3)

[In formula (3), R <^9> , R <^10> , R <^11> , and R <^12> respectively independently represents the monovalent organic group containing an alkyl group, a cycloalkyl group, a phenyl group, a naphthyl group, or a heterocyclic group, and R <^9> , R <^10> , Alternatively, R ¹¹ and R ¹² may be bonded to each other to form a ring together with two carbon atoms of a pyrazine skeleton. Z represents an atomic group constituting an aromatic ring of a monocyclic structure or a condensed polycyclic structure, or a heterocycle, formed together with four carbons of a pyrazine skeleton.] The method of claim 1,
The photosensitive resin composition whose said pyrazine compound is a compound which has a structure represented by said Formula (1). 3. The method according to claim 1 or 2,
The photosensitive resin composition whose maximum absorption wavelength of the said pyrazine compound exists in the range of 350-410 nm. delete 3. The method according to claim 1 or 2,
The photosensitive resin composition containing the compound represented by following formula (4).
[Chemical Formula 4]

[In Formula (4), X represents a carbon atom or a nitrogen atom, R <^13> , R <^14> and R <^15> represent a halogen atom or a C1-C5 alkyl group each independently, and in R <^13> , R <^14> and R <^15> At least one represents a halogen atom. R <^16> represents a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group, and l shows the integer of 0-4. When l is 2-4, some R <^16> may be same or different.] 3. The method according to claim 1 or 2,
The photosensitive resin composition containing a hydrogen donor compound further. The method according to claim 6,
The photosensitive resin composition in which the said hydrogen donor compound contains the compound represented by following formula (5).
[Chemical Formula 5]

[In formula (5), R <^17> represents a C1-C6 alkyl group, an alkoxy group or ester group, a hydroxyl group, or a halogen atom. n is an integer of 0-5, and when n is 2-5, some R <^17> may be same or different.] The photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the photosensitive resin composition of Claim 1 or 2 formed on this support body. A lamination step of laminating the photosensitive resin composition layer made of the photosensitive resin composition according to claim 1 on a substrate;
An exposure step of irradiating active light to a predetermined portion of the photosensitive resin composition layer;
And a developing step of forming a resist pattern made of a cured product of the photosensitive resin composition on the substrate by removing portions other than the predetermined portion of the photosensitive resin composition layer from the substrate. 10. The method of claim 9,
The wavelength of the said actinic light is 390-410 nm, The formation method of the resist pattern. The manufacturing method of the printed wiring board containing the process of etching or plating the board | substrate with which the resist pattern was formed by the method of Claim 9 or 10.

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