JP2016105117A - Photosensitive resin composition, photosensitive element, manufacturing method of substrate with resist pattern and manufacturing method of print circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of forming a resit pattern even with low exposure amount and excellent in tent reliability, resolution property and adhesiveness of a formed cured film.SOLUTION: The photosensitive resin composition contains (A) component: a binder polymer, (B) component: a photopolymerizable compound, (C) component: a photoinitiator and (D) component: a compound having (poly)ethylene oxide as a constitutional unit. The (A) component: binder polymer has (A1) a structural unit derived from at least one kind selected from a group consisting of styrene or styrene derivative and benzyl (meth)acrylate or benzyl (meth)acrylate derivative and percentage content of the structural unit in the binder polymer is 10 mass% to 60 mass%. Percentage content of the structural unit of (poly)ethylene oxide to the solid content total amount of the (A) component and the (B) component is 25 mass% or more.SELECTED DRAWING: None

Description

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

  Conventionally, in the field of manufacturing printed wiring boards, a photosensitive resin composition as a resist material used for etching treatment or plating treatment, and a photosensitive resin layer, a support, and a protective film obtained using the photosensitive resin composition, Photosensitive elements having the following are widely used.

  A printed wiring board is formed by laminating the photosensitive element on a circuit-forming substrate, exposing the photosensitive resin layer in a pattern, and then removing the unexposed portion with a developer to form a resist pattern, followed by an etching process. Alternatively, after the plating process is performed to form a circuit on the substrate, the cured portion that is the exposed portion is removed from the substrate and removed.

  As the developer, an alkaline developer such as an aqueous sodium carbonate solution or an aqueous sodium hydrogen carbonate solution is mainly used from the viewpoint of environmental performance and safety. The unexposed portion of the photosensitive resin layer is removed from the substrate by the development pressure with these developers and the spray pressure of water washing. Therefore, the photosensitive resin composition is required to be capable of forming a cured film (resist pattern) having excellent tent reliability (tenting property) that is not damaged by the spray pressure of development and washing after exposure. . Further, it is necessary to improve the adhesion so that the cured film does not peel from the substrate due to the spray pressure of development and washing with water.

  In order to have excellent tent reliability, it is effective to increase the flexibility of the cured film formed from the photosensitive resin composition. However, when the flexibility of the cured film is increased, there is a problem that the alkali resistance of the cured film is lowered and the resolution is lowered.

  In particular, recently, a laser direct imaging (LDI) method has been adopted as a method for directly drawing a pattern produced by CAD (computer-aided design) without using a mask and using laser light. However, from the viewpoint of throughput, the resist material used in the LDI method, which is required to be used with a smaller exposure amount, requires alkali resistance at a low exposure amount and a low degree of cure. Often used. However, since a compound having a rigid skeleton deteriorates the tenting property, a resist having high throughput, high resolution and high tenting property by the LDI method has not been developed so far. For example, even when the photosensitive resin compositions described in Patent Documents 1 to 5 were used, there was room for improvement.

JP 2006-234959 A JP 2007-1222028 A International Publication No. 2008/078483 Pamphlet JP 2009-69465 A International Publication No. 2010/103918 Pamphlet

  Therefore, the present invention has an object to provide a photosensitive resin composition that can form a resist pattern even at a low exposure amount and is excellent in tent reliability, resolution, and adhesion of a formed cured film. To do. Moreover, it aims at providing the manufacturing method of the photosensitive element using the said photosensitive resin composition, the board | substrate with a resist pattern, and a printed wiring board.

Specific means for solving the above problems are as follows.
<1> (A) component: a binder polymer,
(B) component: a photopolymerizable compound;
(C) component: a photopolymerization initiator,
(D) component: (poly) ethylene oxide [-(C ₂ H ₄ O) _n- : n is 1 or more] as a structural unit,
Component (A): The binder polymer has a structural unit derived from at least one selected from the group consisting of (A1) styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative, and a binder The content of the structural unit in the total solid content of the polymer is 10% by mass to 60% by mass,
The content of the structural unit of the (poly) ethylene oxide [— (C ₂ H ₄ O) _n —] relative to the total solid content of the component (A) and the component (B) is 25% by mass or more. Photosensitive resin composition.

<2> The photosensitive resin according to <1>, wherein the (A) binder polymer contains a structural unit derived from (A2) alkyl (meth) acrylate (the alkyl group has 1 to 20 carbon atoms). Composition.

<3> a support film;
A photosensitive resin layer which is a coating film of the photosensitive resin composition according to <1> or <2> provided on the support film;
A photosensitive element.

<4> A laminating step of laminating a photosensitive resin layer formed using the photosensitive resin composition according to <1> or <2> on a substrate;
An exposure step of irradiating at least a part of the photosensitive resin layer with actinic rays to cure the region;
A developing step of forming a resist pattern composed of a cured product of the photosensitive resin composition on the substrate by removing an unexposed portion other than the region of the photosensitive resin layer from the substrate,
A method for manufacturing a substrate with a resist pattern having

<5> A method for producing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method according to <4>.

  According to the present invention, it is possible to form a resist pattern even at a low exposure amount, and it is possible to provide a photosensitive resin composition excellent in tent reliability, resolution, and adhesion of a formed cured film. It becomes. Moreover, it becomes possible to provide the photosensitive element using the said photosensitive resin composition, the manufacturing method of a board | substrate with a resist pattern, and the manufacturing method of a printed wiring board.

It is an end view which shows one Embodiment of the photosensitive element of this invention. It is process drawing which illustrates the specification location of the photosensitive element of this invention. It is a top view of the hole tearing number measuring substrate used for evaluation of tent reliability.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

In this specification, “(meth) acrylic acid” means at least one of “acrylic acid” and “methacrylic acid”, and “(meth) acrylate” means at least one of “acrylate” and “methacrylate” corresponding thereto. The “(meth) acryloyl group” means at least one of “acryloyl group” and “methacryloyl group”.
Further, “(poly) ethylene oxide” or “(poly) oxyethylene” means at least one kind of polyoxyethylene group in which an oxyethylene group and two or more ethylene groups are connected by an ether bond, and “(poly) ") Propylene oxide" or "(poly) oxypropylene" means at least one polyoxypropylene group in which an oxypropylene group and two or more propylene groups are linked by an ether bond.

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

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment comprises (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: (poly). And a compound having ethylene oxide [— (C ₂ H ₄ O) _n —: n is 1 or more] as a structural unit (hereinafter sometimes referred to as “(poly) ethylene oxide compound”). Component (A): a structural unit derived from at least one selected from the group consisting of (A1) styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative (hereinafter referred to as “structural unit”) The content of the structural unit in the total solid content of the binder polymer is 10% by mass to 60% by mass. Then, to the solid content total amount of the (A) wherein the component (B) component, the (poly) ethylene oxide _{[- (C 2 H 4 O)} n - ] content of the structural units is 25% by weight or more is there.

  However, the component (D): (poly) ethylene oxide compound may also serve as the component (A), the component (B) or the component (C), and is contained as a component other than the components (A) to (C). May be. The said photosensitive resin composition may further contain another component as needed.

By using a binder polymer containing 10% by mass to 60% by mass of the structural unit (A1) and adjusting the content of the structural unit of (poly) ethylene oxide to 25% by mass or more, a resist pattern can be formed even at a low exposure amount. The photosensitive resin composition can be formed and has excellent tent reliability, resolution and adhesion of the cured film to be formed.
Below, each component is demonstrated in detail.

[(A) component: binder polymer]
The photosensitive resin composition contains at least one binder polymer as the component (A). The binder polymer has a structural unit (A1) derived from at least one selected from the group consisting of styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative, and has a binder polymer solid content. The content rate of the structural unit (A1) in the total amount is 10% by mass to 60% by mass. By including the specific amount of the structural unit (A1) in the total amount of the binder polymer solid content, the adhesiveness when cured is excellent while maintaining the flexibility of the binder polymer.

・ Structural unit (A1)
At least one of the binder polymers has a structural unit (A1) derived from at least one selected from the group consisting of styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative. Among these, it is preferable to have a structural unit derived from at least one selected from styrene and styrene derivatives.

  The content of the structural unit (A1) in the binder polymer is 10% by mass to 60% by mass, and 13% by mass to 40% by mass in the total solid content of the binder polymer from the viewpoint of improving both adhesion and peeling properties. %, And more preferably 15% by mass to 25% by mass. When the content is 10% by mass or more, the adhesion tends to be improved. When the content is 60% by mass or less, the peeling piece can be prevented from becoming large, and the peeling time can be prevented from becoming long. Tending to be improved. The peeling piece refers to a piece generated when peeling a resist pattern composed of a cured product of the photosensitive resin composition.

Specific examples of the styrene derivative include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as α-methylstyrene, vinyltoluene, and p-chlorostyrene.
Specific examples of the benzyl (meth) acrylate derivative include 4-methylbenzyl (meth) acrylate, 4-ethylbenzyl (meth) acrylate, 4-t-butylbenzyl (meth) acrylate, 4-methoxybenzyl (meth) acrylate, Examples include 4-ethoxybenzyl (meth) acrylate, 4-hydroxybenzyl (meth) acrylate, and 4-chlorobenzyl (meth) acrylate.

・ Structural unit (A2)
At least one of the (A) binder polymer preferably has a structural unit derived from (A2) alkyl (meth) acrylate (hereinafter sometimes referred to as “structural unit (A2)”). The alkyl group in the alkyl (meth) acrylate may be linear or branched. Examples of the alkyl (meth) acrylate include compounds represented by the following general formula (I).

^{_{CH 2 = C (R 3)}} -COOR 4 (I)

In general formula (I), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 1 to 20 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁴ in the general formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Group, decyl group, undecyl group, dodecyl group and structural isomers thereof. The alkyl group having 1 to 20 carbon atoms represented by R ⁴ may have a substituent. Examples of the substituent include a hydroxyl group, an epoxy group, and a halogen group. When the alkyl group having 1 to 20 carbon atoms represented by R ⁴ has a substituent, the number of substituents and the substitution position are not particularly limited.

  The alkyl group in the alkyl (meth) acrylate preferably has 1 to 20 carbon atoms, more preferably 5 to 20 carbon atoms from the viewpoint of further improving tenting properties, and 8 carbon atoms. More preferably, it is -14.

  Examples of the compound represented by the general formula (I) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Nonyl acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

  When the binder polymer includes the structural unit (A2), the content of the structural unit (A2) in the total mass of the binder polymer is 1% by mass to 70% by mass from the viewpoints of adhesion, resolution, and developability. It is preferably 30% by mass to 65% by mass, and more preferably 45% by mass to 60% by mass. By setting the content to 1% by mass or more, the tenting property of the cured film is further improved, and by setting the content to 80% by mass or less, the resolution and adhesion are further improved.

・ Structural unit (A3)
At least one of the binder polymers preferably has a carboxy group from the viewpoint of alkali developability. The binder polymer containing a carboxy group can be produced, for example, by radical polymerization using a polymerizable monomer having a carboxy group. Hereinafter, a structural unit derived from a polymerizable monomer having a carboxy group may be referred to as “structural unit (A3)”. Examples of the polymerizable monomer having a carboxy group include (meth) acrylic acid; α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, and the like. (Meth) acrylic acid derivatives; maleic acid; maleic acid derivatives such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, etc. (Meth) acrylic acid is preferable, and methacrylic acid is more preferable.

  When the binder polymer contains the structural unit (A3), the content of the structural unit (A3) is 12% by mass to 50% by mass in the total mass of the binder polymer from the viewpoint of the balance between alkali developability and developer resistance. In view of superior alkali developability, the content is preferably 15% by mass to 35% by mass, and more preferably 15% by mass to 30% by mass.

-Other structural unit The binder polymer may contain other structural units other than said (A1)-(A3). The other structural unit may be a structural unit derived from the following polymerizable monomer. Examples of the polymerizable monomer include acrylamide such as diacetone acrylamide; acrylonitrile; ethers of vinyl alcohol such as vinyl-n-butyl ether; and organic acid derivatives such as maleic anhydride. These can be used alone or in combination of two or more.

The content of other structural units in the total mass of the binder polymer is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoints of adhesion, resolution, and developability. It is more preferable not to contain (0.5 mass% or less).
That is, the content of the total amount of the structural units (A1), (A2), and (A3) in the total solid content of the binder polymer is preferably 90% by mass or more, and preferably 95% by mass or more. More preferably, it is more preferably 99.5% by mass or more.

-Binder polymer A binder polymer is obtained by polymerizing the monomer corresponding to each structural unit. Examples of the polymerization method include radical polymerization.
In the copolymer thus obtained, each structural unit may be randomly contained in the copolymer such as a so-called random copolymer, or some specific unit such as a block copolymer. It may be a copolymer in which structural units exist in a localized manner. Each structural unit may be a single type or a plurality of types.

  Furthermore, in addition to the binder polymer containing the structural unit (A1) and the binder polymer containing (A2) or (A3), another binder polymer may be used in combination. Other binder polymers are not particularly limited as long as they are soluble in an alkaline aqueous solution and can form a film. For example, acrylic resins (however, those not including the structural unit (A1), (A2) or (A3)), epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins are listed. It is done. Of these, acrylic resins are preferred from the viewpoint of alkali developability. These can be used alone or in combination of two or more.

  Even when other binder polymer is used, the content of the structural unit (A1) in the total amount of the binder polymer solid content is preferably 10% by mass to 60% by mass, and more preferably 13% by mass to 40% by mass. Preferably, it is 15 mass%-25 mass%. Moreover, when using another binder polymer, it is preferable that the content rate of the other binder polymer in binder polymer solid content total amount is 10 mass% or less, and it is more preferable that it is 5 mass% or less. It is more preferable that other binder polymers are not substantially contained, and it is particularly preferable that other binder polymers are not contained.

The weight average molecular weight of the binder polymer is preferably 20,000 to 300,000, more preferably 30,000 to 200,000, from the viewpoint of the balance between developer resistance and alkali developability. More preferably, it is from 1,000 to 100,000.
In addition, the weight average molecular weight in this specification is a value measured by a gel permeation chromatography method and converted by a calibration curve prepared using standard polystyrene, and the measurement conditions are the same as in the examples.

  The acid value of the binder polymer is preferably 120 mgKOH / g to 200 mgKOH / g, and more preferably 150 mgKOH / g to 170 mgKOH / g.

  The binder polymer as the component (A) can be used alone or in combination of two or more. As a binder polymer in the case of using two or more types in combination, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, two or more types of binder polymers having different degrees of dispersion, etc. Is mentioned. The degree of dispersion of the binder polymer is obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).

  The content of the binder polymer as the component (A) is preferably 30 parts by mass to 80 parts by mass with respect to 100 parts by mass of the total solid content of the component (A) and the component (B), and 40 parts by mass to 75 parts by mass. It is more preferable to set it as a mass part, and it is still more preferable to set it as 50 mass parts-70 mass parts. When the content of the component (A) is within this range, the coating property of the photosensitive resin composition and the strength of the photocured product become better.

[(B) component: photopolymerizable compound]
The photosensitive resin composition contains at least one photopolymerizable compound as the component (B). The photopolymerizable compound as component (B) is not particularly limited, and can be appropriately selected from commonly used photopolymerizable compounds. Examples of the photopolymerizable compound include compounds having a photopolymerizable unsaturated double bond.

  Specifically, examples of the photopolymerizable compound include polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polyethylene polypropylene glycol di (meth) acrylate; trimethylolpropane tri Multifunctional (meth) acrylates such as (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) Bisphenol A-based (meth) acrylate compounds such as propane and 2,2-bis (4-((meth) acryloxypolyethyleneoxypolypropyleneoxy) phenyl) propane; γ-chloro-β-hydroxy Cypropyl-β '-(meth) acryloyloxyethylene-o-phthalate, β-hydroxyethyl-β'-(meth) acryloyloxyethylene-o-phthalate, β-hydroxypropyl-β '-(meth) acryloyloxyethylene- phthalic acid derivatives such as o-phthalate; alkyl (meth) acrylate; and the like.

  Among these, from the viewpoint of adhesion and resolution, the photopolymerizable compound includes at least one selected from the group consisting of bisphenol A (meth) acrylate compounds and polyalkylene glycol poly (meth) acrylates. It is more preferable to use at least one bisphenol A-based (meth) acrylate compound and at least one polyalkylene glycol poly (meth) acrylate in combination, and 2,2-bis (4-((meth) acryloxy) More preferably, at least one of polyethyleneoxy) phenyl) propane and at least one of polyethylene glycol poly (meth) acrylate are used in combination.

  Examples of 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethyleneoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxypentaethyleneoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethyleneoxy) phenyl) propane, and the like can be given.

  2,2-bis (4- (methacryloxypentaethyleneoxy) phenyl) propane is commercially available as BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). 4- (Methacryloxypentadecaethyleneoxy) phenyl) propane is commercially available as BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). These can be used alone or in combination of two or more.

  When a plurality of photopolymerizable compounds as component (B) are used in combination, a compound having two or more unsaturated double bonds capable of photopolymerization in one molecule in the total solid content of component (B) is 75 It is preferable that it is at least mass%. (B) Tenting property and resolution / adhesiveness when the compound having two or more photopolymerizable unsaturated double bonds in one molecule is 75% by mass or more in the total solid content of component (B) Tend to improve.

  (B) component in the said photosensitive resin composition: Content of a photopolymerizable compound shall be 20 mass parts-70 mass parts in 100 mass parts of solid content of (A) component and (B) component. preferable. In terms of further improving the tent reliability and resolution, the content of the component (B) is preferably 20 parts by mass or more, and 25 parts by mass in 100 parts by mass of the solid content of the component (A) and the component (B). Part or more is more preferable, and 30 parts by mass or more is still more preferable. In terms of imparting film properties and excellent resist shape after curing, the content of component (B) is 70 parts by mass or less in 100 parts by mass of the total solid content of component (A) and component (B). Preferably, 60 parts by mass or less is more preferable, 55 parts by mass or less is more preferable, and 50 parts by mass or less is particularly preferable.

[(C) component: photopolymerization initiator]
The said photosensitive resin composition contains at least 1 sort (s) of a photoinitiator as (C) component. There is no restriction | limiting in particular as a photoinitiator, It can select from the photoinitiator used normally and can use it suitably. Among these, the component (C) preferably contains an acridine compound having one or two acridinyl groups in one molecule. That is, the component (C) is composed of an acridine compound having two acridinyl groups (hereinafter also referred to as “(C1) compound”) and an acridine compound having one acridinyl group (hereinafter also referred to as “(C2) compound”). It is preferable that at least one compound selected from the group consisting of:

  Examples of the compound (C1) include acridine compounds represented by the following general formula (II).

In the formula (II), R ³ represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms. R ³ is preferably an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 4 to 14 carbon atoms, from the viewpoint of more reliably obtaining the effect exhibited by the photosensitive resin composition.

  Examples of the compound represented by the general formula (II) include 1,2-di (9-acridinyl) ethane, 1,3-di (9-acridinyl) propane, 1,4-di (9-acridinyl). Butane, 1,5-di (9-acridinyl) pentane, 1,6-di (9-acridinyl) hexane, 1,7-di (9-acridinyl) heptane, 1,8-di (9-acridinyl) octane, 1,9-di (9-acridinyl) nonane, 1,10-di (9-acridinyl) decane, 1,11-di (9-acridinyl) undecane, 1,12-di (9-acridinyl) dodecane, 1, 14-di (9-acridinyl) tetradecane, 1,16-di (9-acridinyl) hexadecane, 1,18-di (9-acridinyl) octadecane, 1,20-di (9-acridinyl) Ai Di (9-acridinyl) alkanes such as San; 1,3-di (9-acridinyl) -2-oxapropane; 1,5-di (9-acridinyl) -3-oxapentane; 1,3-di (9 -Acridinyl) -2-thiapropane; 1,5-di (9-acridinyl) -3-thiapentane; and the like. These are used individually by 1 type or in combination of 2 or more types.

From the standpoint of improving photosensitivity and resolution, as the (C1) compound, an acridine compound in which R ³ in the formula (II) is a heptylene group (for example, product name “N-1717” manufactured by ADEKA Corporation) ) Is preferably included.

  When the photosensitive resin composition contains the compound (C1) as a photopolymerization initiator, the content of the compound (C1) is from the viewpoint of sensitivity, resolution, and adhesion, and the components (A) and (B) The total solid content of 100 parts by mass is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, and 1 part by mass to 5 parts by mass. It is still more preferable and it is especially preferable that it is 1 mass part-3 mass parts. There exists a tendency for a more favorable sensitivity, resolution, or adhesiveness to be acquired as this content is 0.1 mass part or more. When the amount is 10 parts by mass or less, a better resist shape tends to be obtained.

  Examples of the compound (C2) include acridine compounds represented by the following general formula (III).

In formula (III), R ⁴ represents a halogen atom, an amino group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkylamino group having 1 to 6 carbon atoms. m shows the integer of 0-5.

  Examples of the acridine compound represented by the general formula (III) include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine, 9- (p-chlorophenyl) acridine. , 9- (m-chlorophenyl) acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylaminoacridine and 9-pentylaminoacridine. These are used individually by 1 type or in combination of 2 or more types.

  When the photosensitive resin composition contains the (C2) compound as a photopolymerization initiator, the content of the (C2) compound is (A) and (B) from the viewpoint of sensitivity, resolution and adhesion. It is preferable that it is 0.1 mass part-10 mass parts with respect to 100 mass parts of solid content total amount of a component, It is more preferable that it is 0.5 mass part-5 mass parts, 1 mass part-5 mass parts More preferably, it is more preferably 1 part by mass to 3 parts by mass. There exists a tendency for a more favorable sensitivity, resolution, or adhesiveness to be acquired as this content is 0.1 mass part or more. When the amount is 10 parts by mass or less, a better resist shape tends to be obtained.

  The said photosensitive resin composition may contain photoinitiators other than the said (C1) compound and (C2) compound as (C) component.

Examples of photopolymerization initiators other than the (C1) compound and the (C2) compound include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4 ′. -Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl Aromatic ketone compounds such as 2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2 -Phenylanthraquinone, 2,3-diphenylanthraquinone, -Quinone compounds such as chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl 1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin methyl ether, benzoin ethyl ether And benzoin ether compounds such as benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin, and ethyl benzoin; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) ) 2,4,5-triarylimidazole dimers such as 4,5-diphenylimidazole dimer; benzyl derivatives such as benzyldimethyl ketal; 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9 , 10-dipropoxyanthracene, 9,10-dibutoxyanthracene, substituted anthracene compounds such as 9,10-dipentoxyanthracene; coumarin compounds; oxazole compounds; pyrazoline compounds; triarylamine compounds;
These are used individually by 1 type or in combination of 2 or more types. Moreover, it is good also as a photoinitiator combining a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and a dimethylamino benzoic acid.

  The 2,4,5-triarylimidazole dimer is a symmetric compound in which the substituents of the aryl groups of two 2,4,5-triarylimidazoles constituting the dimer are the same. They may be different or asymmetrical compounds.

  When the photosensitive resin composition contains a photopolymerization initiator other than the (C1) compound and the (C2) compound as the component (C), the content is (A) from the viewpoint of sensitivity and internal photocurability. It is preferable that it is 0.01 mass part-10 mass parts with respect to 100 mass parts of solid content total amount of a component and (B) component, It is more preferable that it is 0.1 mass part-7 mass parts. It is particularly preferably 2 to 5 parts by mass.

  (C) Content of a component is 0.01 mass part-20 with respect to a solid content 100 mass part of (A) component and (B) component from a viewpoint of a sensitivity, adhesiveness, and internal photocurability. It is preferable that it is a mass part, It is more preferable that it is 0.05 mass part-10 mass parts, It is especially preferable that it is 0.1 mass part-5 mass parts.

[(D) component: (poly) ethylene oxide compound]
The photosensitive resin composition, (D) component as (poly) ethylene oxide _{[- (C 2 H 4 O)} n -: n is 1 or more] comprising at least one compound having a structural unit. The (poly) ethylene oxide compound as component (D) may be used alone or in combination of two or more. Component (D): The (poly) ethylene oxide compound may also serve as the component (A), component (B) or component (C), and is contained as a component other than the components (A) to (C). May be.

In the case where the (poly) ethylene oxide compound also serves as the component (A): binder polymer, examples include those containing structural units derived from (poly) ethylene oxide mono (meth) acrylate or derivatives thereof.
When the (poly) ethylene oxide compound also serves as the component (B): photopolymerizable compound, for example, 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) propane, polyethylene glycol poly ( And (meth) acrylate.

The (poly) ethylene oxide compound preferably has a ratio (EO content) of 60% or more of (poly) ethylene oxide [— (C ₂ H ₄ O) _n —] structural unit in one molecule. % To 90% is more preferable.

As the (poly) ethylene oxide compound, trimethylolpropane polyethylene ether tri (meth) acrylate, pentaerythritol propane polyethylene ether tetra (meth) acrylate and the like are preferable. More preferably, trimethylolpropane polyethylene ether tri (meth) acrylate, pentaerythritol propane polyethylene ether tetra (meth) acrylate, etc., which is a structural unit of (poly) ethylene oxide [— (C ₂ H ₄ O) _n —] Is a compound having a ratio (EO content) of 70% to 90% in one molecule. The photosensitive resin composition using this compound further improves the resolution and tenting properties of the cured film.

The content of the structural unit of the (poly) ethylene oxide [— (C ₂ H ₄ O) _n —] with respect to the total solid content of the component (A) and the component (B) is 25% by mass or more, It is preferable that it is 25 mass%-40 mass%. By setting the content of the (poly) ethylene oxide compound to 25% by mass or more, the cured film becomes flexible and has excellent tenting properties. Moreover, the peeling time becomes short by setting it as 40 mass% or less.
From the viewpoint of more excellent resolution and shortening the peeling time, the content of the (poly) ethylene oxide compound may be 25% by mass to 35% by mass in the total solid content of the photosensitive resin composition. More preferably, it is more preferably 25% by mass to 30% by mass.

[Other ingredients]
In addition, the photosensitive resin composition of the present embodiment, if necessary, a dye such as malachite green, Victoria pure blue, brilliant green, methyl violet; leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, Photochromic agent such as o-chloroaniline; Thermochromic inhibitor; Plasticizer such as p-toluenesulfonamide; Pigment; Filler; Antifoaming agent; Flame retardant; Adhesiveness imparting agent; Leveling agent; Other additives such as an inhibitor, a polymerization inhibitor, a fragrance, an imaging agent, and a thermal crosslinking agent may be further included.

  When the said photosensitive resin composition contains another additive, the content can be suitably selected according to the objective etc. For example, it can be contained in an amount of about 0.01 to 20 parts by mass per 100 parts by mass of the total solid content of the component (A) and the component (B). These can be used individually by 1 type or in combination of 2 or more types.

Moreover, 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 may be used alone or in combination of two or more.
Content of the organic solvent contained in the said photosensitive resin composition can be suitably selected according to the objective etc. For example, it can be used as a solution having a solid content of about 30% by mass to 60% by mass (hereinafter, a photosensitive resin composition containing an organic solvent is also referred to as “coating liquid”).

  The said photosensitive resin composition can be used for formation of the photosensitive resin layer of the photosensitive element mentioned later. That is, another embodiment of the present invention is the use of the photosensitive resin composition for a photosensitive element. Moreover, the said photosensitive resin composition can be used for the manufacturing method of the board | substrate with a resist pattern mentioned later and the manufacturing method of a printed wiring board.

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

  FIG. 1 shows an embodiment of the photosensitive element of the present invention. In the photosensitive element 10 shown in FIG. 1, the support film 2, the photosensitive resin layer 4 which is the coating film of the said photosensitive resin composition, and the protective film 6 are laminated | stacked in this order. The photosensitive element 10 can be obtained as follows, for example. On the support film 2, the coating liquid which is the said photosensitive resin composition containing an organic solvent is apply | coated, an application layer is formed, and the photosensitive resin layer 4 is formed by drying this. Next, the surface of the photosensitive resin layer 4 opposite to the supporting film 2 is covered with a protective film 6, thereby supporting the supporting film 2, the photosensitive resin layer 4 laminated on the supporting film 2, and the photosensitive film. The photosensitive element 10 of this embodiment provided with the protective film 6 laminated | stacked on the photosensitive resin layer 4 is obtained. The photosensitive element 10 does not necessarily include the protective film 6.

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

  The thickness of the support film 2 (polymer film) is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, and still more preferably 1 μm to 30 μm. When the thickness of the support film 2 is 1 μm or more, the support film 2 can be prevented from being broken when the support film 2 is peeled from the photosensitive resin layer 4. Moreover, the fall of the resolution is suppressed because it is 100 micrometers or less.

  The protective film 6 preferably has a smaller adhesive force to the photosensitive resin layer 4 than the adhesive force of the support film 2 to the photosensitive resin layer 4. A low fisheye film is preferred. Here, “fish eye” means that when a material is heat-melted, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are present in the film. It means what was taken in. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.

  Specifically, as the protective film 6, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used. Examples of commercially available products include polypropylene films such as Alphan MA-410 and E-200C manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and polyethylene terephthalate films such as PS series such as PS-25 manufactured by Teijin Limited. The protective film 6 may be the same as the support film 2.

  The thickness of the protective film 6 is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, and still more preferably 1 μm to 30 μm. When the thickness of the protective film 6 is 1 μm or more, the protective film 6 can be prevented from being broken when the photosensitive resin layer 4 and the support film 2 are laminated on the substrate while peeling off the protective film 6. When it is 100 μm or less, it is excellent in handleability and inexpensiveness.

  Specifically, the photosensitive element of this embodiment can be manufactured as follows, for example. Coating solution prepared by dissolving at least (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) photopolymerization initiator, and (D) component: (poly) ethylene oxide compound in the organic solvent. And a step of forming a coating layer by applying the coating liquid on the support film 2 and a step of forming a photosensitive resin layer by drying the coating layer. be able to.

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

  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. For example, it is preferable to carry out at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin layer is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

  The thickness of the photosensitive resin layer 4 in the photosensitive element 10 can be appropriately selected depending on the intended use. The thickness after drying is preferably 1 μm to 200 μm, more preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm. More preferably. When the thickness is 1 μm or more, industrial coating becomes easy. When the thickness is 200 μm or less, the sensitivity and the photocurability of the resist bottom tend to be sufficiently obtained.

  The photosensitive element 10 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, the intermediate layers described in JP-A-2006-089882 and the like can also be applied in the present invention.

  The form of the obtained photosensitive element 10 is not particularly limited. For example, it may be in the form of a sheet, or may be in the form of a roll wound around a core. When winding in roll form, it is preferable to wind up so that the support film 2 may become an outer side. Examples of the core material include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). From the viewpoint of end face protection, it is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll thus obtained, and it is preferable to install a moisture-proof end face separator from the standpoint of edge fusion resistance. As a packaging method, it is preferable to wrap and package in a black sheet with low moisture permeability.

  The photosensitive element 10 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 resist pattern can be formed on a substrate using the photosensitive resin composition. The manufacturing method of the board | substrate with a resist pattern of this embodiment consists of (i) the lamination process which laminates | stacks the photosensitive resin layer which is a coating film of the said photosensitive resin composition on a board | substrate, (ii) of the said photosensitive resin layer. An exposure step of irradiating at least a portion of the region with actinic rays to cure the region; and (iii) removing an unexposed portion other than the region of the photosensitive resin layer from the substrate. And a developing step for forming a resist pattern composed of a cured product of the photosensitive resin composition. The manufacturing method of the said board | substrate with a resist pattern may have another process further as needed.

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

  For example, when the photosensitive element 10 has the protective film 6, the photosensitive resin layer 4 is laminated on the substrate after the protective film 6 is removed and then the photosensitive resin layer 4 of the photosensitive element 10. This is performed by pressure-bonding to the substrate while heating. Thereby, the laminated body provided with the board | substrate, the photosensitive resin layer 4, and the support film 2 in this order is obtained.

This lamination operation is preferably performed under reduced pressure from the viewpoint of adhesion and followability. It is preferable to heat the photosensitive resin layer and / or the substrate at the time of pressure bonding at a temperature of 70 ° C to 130 ° C. The crimping is preferably performed at a pressure of about ^{0.1MPa~1.0MPa (1kgf / cm 2 ~10kgf /} cm 2 or so). These conditions are appropriately selected as necessary. In addition, if the photosensitive resin layer is heated to 70 ° C. to 130 ° C., it is not necessary to pre-heat the substrate in advance, but the adhesion and followability are further improved by performing the pre-heating of the circuit forming substrate. be able to.

(Ii) Exposure Step In the exposure step, at least a part of the photosensitive resin layer 4 formed on the substrate as described above is irradiated with actinic rays, so that the exposed portion irradiated with actinic rays is light. Curing forms a latent image. Examples of the actinic ray irradiation include a method of irradiating actinic rays in an image form through a negative or positive mask pattern. At this time, when the support film 2 existing on the photosensitive resin layer 4 is transparent to the active light, the active light can be irradiated through the support film 2, and the support film 2 can be applied to the active light. When light-shielding properties are exhibited, the photosensitive resin layer 4 is irradiated with actinic rays after the support film 2 is removed.

  The light source of actinic light is not particularly limited, and conventionally known light sources such as carbon arc lamps, mercury vapor arc lamps, ultrahigh pressure mercury lamps, high pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, solid state lasers such as YAG lasers, A semiconductor laser, a gallium nitride blue-violet laser, or the like that effectively emits ultraviolet light, visible light, or the like is used. Further, a laser direct drawing exposure method may be used.

The photosensitive resin composition of this embodiment can be used suitably for a direct drawing exposure method.
That is, one preferred embodiment of the present invention is an application of the photosensitive resin composition to a direct drawing exposure method.

(Iii) Development Step In the development step, the uncured portion of the photosensitive resin layer 4 is removed from the circuit-forming substrate by development, so that the photosensitive resin layer 4 is a cured product obtained by photocuring. A pattern is formed on the substrate. When the support film 2 exists on the photosensitive resin layer 4, the support film 2 is removed, and then the unexposed portion is removed (development). Development methods include 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 development methods include dip method, battle method, spray method, brushing, slapping, scrapping, rocking immersion, etc., and high-pressure spray method is most suitable from the viewpoint of improving resolution. Yes. You may develop by combining these 2 or more types of methods.

  The configuration of the developer is appropriately selected according to the configuration of the photosensitive resin composition. For example, alkaline aqueous solution, aqueous developer, organic solvent developer and the like can be mentioned.

  The alkaline aqueous solution is safe and stable when used as a developer, and has good operability. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate; potassium phosphate, sodium phosphate, and the like. Alkali metal phosphates; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate;

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

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

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

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

Wherein in the developing step, after removing the unexposed portion, by performing about 60 ° C. to 250 DEG ° C. heating or 0.2J ^/ cm ² ~10J ^/ cm 2 about exposure as necessary, further a resist pattern You may further include the process to harden | cure.

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

  In the etching process, using the resist pattern formed on the substrate as a mask, the conductor layer of the circuit forming substrate not covered with the resist is removed by etching to form a conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. Etching solutions include cupric chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide etching solution, etc. Among these, ferric chloride solution is used from the viewpoint of good etch factor. It is preferable.

  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 resist, using the resist pattern formed on the substrate as a mask. After the plating process, the cured resist is removed, and the conductor layer covered with the resist is etched to form a conductor pattern. The method of plating treatment may be electrolytic plating treatment or electroless plating treatment. Examples of the plating treatment include 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, Examples thereof include gold plating such as soft gold plating.

  After the etching process and the plating process, the resist pattern on the substrate is removed. The resist pattern can be removed using, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step. As this strongly alkaline aqueous solution, for example, a 1% by mass to 10% by mass sodium hydroxide aqueous solution, a 1% by mass to 10% by mass potassium hydroxide aqueous solution and the like are used. Especially, it is preferable to use 1 mass%-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, and it is more preferable to use 1 mass%-5 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.

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

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

  FIG. 2 is a diagram illustrating a conventional method for manufacturing a multilayer printed wiring board. A multilayer printed wiring board 100A shown in FIG. 2F has a wiring pattern on the surface and inside. The multilayer printed wiring board 100A is obtained by laminating a copper clad laminate, an interlayer insulating material, a metal foil, and the like, and appropriately forming a wiring pattern by an etching method, a semi-additive method, or the like.

  First, an interlayer insulating layer 103 is formed on both surfaces of a copper clad laminate 101 having a wiring pattern 102 on the surface (see FIG. 2A). The interlayer insulating layer 103 may be printed with a thermosetting composition using a screen printer or a roll coater, or a film made of the thermosetting composition is prepared in advance, and this film is printed using a laminator. It can also be attached to the surface of the wiring board. Next, an opening 104 is formed using a YAG laser or a carbon dioxide gas laser at a portion that needs to be electrically connected to the outside, and smear (residue) around the opening 104 is removed by a desmear process (FIG. 2B). )reference). Next, a seed layer 105 is formed by an electroless plating method (see FIG. 2C). A photosensitive resin composition is laminated on the seed layer 105, and a predetermined portion is exposed and developed to form a resist pattern 106 (see FIG. 2D). Next, a wiring pattern 107 is formed by electrolytic plating, the resist pattern 106 is removed by a stripping solution, and then the seed layer 105 is removed by etching (see FIG. 2E). By repeating the above and forming the solder resist 108 on the outermost surface, the multilayer printed wiring board 100A can be manufactured (see FIG. 2F).

  The photosensitive resin composition of this embodiment can be used suitably for manufacture of a printed wiring board. That is, one of the preferred embodiments of the present invention is application of the photosensitive resin composition to the production of a printed wiring board.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

[(A) component: binder polymer]
[Synthesis Method of (P-1)]
(Preparation of solution a-1)
Dissolve 2.0 g of azobisisobutyronitrile, which is a radical reaction initiator, in a mixed solution of polymerizable monomers (copolymerization monomers, monomers) shown in Table 1 to obtain “Solution a-1”. Prepared.

(Radical polymerization reaction)
Into a flask equipped with a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas introduction tube, 400 g of a mixed solution of 240 g of methyl cellosolve and 160 g of toluene (mass ratio 3: 2) was charged. While the nitrogen gas was blown into the flask, the mixture was heated while stirring to raise the temperature to 80 ° C.

  After “solution a-1” was dropped into the above mixed solution in the flask over 4 hours, the solution in the flask was kept at 80 ° C. for 2 hours while stirring. Next, a solution obtained by further dissolving 1 g of azobisisobutyronitrile in 100 g of “solution a-1” was dropped into the solution in the flask over 10 minutes, and then the solution in the flask was stirred at 80 ° C. for 3 minutes. Keep warm for hours. Furthermore, the solution in the flask was heated to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a solution of the binder polymer as the component (A-1).

  Acetone was added to this binder polymer solution to prepare a non-volatile component (solid content) of 50% by mass. The weight average molecular weight of the binder polymer was 55000. The weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The conditions for GPC are as follows.

-GPC conditions-
Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.)
Column: The following three total Gelpack GL-R420
Gelpack GL-R430
Gelpack GL-R440
(The above is a product name manufactured by Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran Measurement temperature: 25 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

[Synthesis Method of (P-2)]
(Preparation of solution a-2)
Dissolve 1.0 g of azobisisobutyronitrile, which is a radical reaction initiator, in a mixture of polymerizable monomers (copolymerization monomers, monomers) shown in Table 2, and add “Solution a-2”. Prepared.

  Thereafter, a radical polymerization reaction was performed in the same manner as the component (A1). The weight average molecular weight was 100,000.

[Preparation of photosensitive resin composition]
By blending the components (B) and (C), 8 g of acetone, 8 g of toluene and 8 g of methanol in the binder polymer solution obtained above in the blending amounts (g) shown in the following table, Examples 1 to 6 And the solution of the photosensitive resin composition of Comparative Examples 1-14 was prepared, respectively. In addition, the compounding quantity of the binder polymer shown in Table 3 is the mass (solid content) of a non-volatile component.

Details of the materials shown in Table 3 are as follows.
P-1: Binder polymer prepared above: copolymer of methacrylic acid / methyl methacrylate / styrene (25/50/25 (mass ratio)), weight average molecular weight 55000, acid value 163 mg KOH / g, solid content 50 Mass% methyl cellosolve / toluene = 6/4 (mass ratio) solution. Including structural units (A1), (A2) and (A3).

  P-2: Binder polymer prepared above: copolymer of methacrylic acid / methyl methacrylate / octyl acrylate (25/50/25 (mass ratio)), weight average molecular weight 100,000, acid value 163 mg KOH / g, solid 50% by weight methyl cellosolve / toluene = 6/4 (mass ratio) solution. Including structural units (A2) and (A3).

  -P-3: a copolymer of methacrylic acid / benzyl methacrylate / methyl methacrylate / styrene (30/25/5/40 (mass ratio)), weight average molecular weight 30000, acid value 196 mgKOH / g, solid content 50 mass % Methyl cellosolve / toluene = 6/4 (mass ratio) solution. Including structural units (A1), (A2) and (A3).

  FA-321M: Bisphenol A polyoxyethylene dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Corresponds to component (B) and also applies to component (D).

BPE-100: EO-modified bisphenol A dimethacrylate (the total number of repeating oxyethylene groups is 2.6). Corresponds to component (B) and also applies to component (D).
FA-137M: trimethylolpropane polyethylene oxide trimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Corresponds to component (B) and also applies to component (D).
A-TMPT-3EO: modified trimethylolpropane triacrylate (the total number of repeating oxyethylene groups is 3). Corresponds to component (B) and also applies to component (D).
UA-HCY-19: Urethane reaction product of hexamethylene diisocyanate trimer and polyethylene oxide methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Corresponds to component (B) and also applies to component (D).
PDE-400: Polyethylene glycol # 400 dimethacrylate (manufactured by NOF Corporation, product name, average value of the total number of oxyethylene groups is 9). Corresponds to component (B) and also applies to component (D).

FA-314A: nonylphenoxypolyethylene glycol acrylate (average number of oxyethylene groups is 4) (product name, manufactured by Hitachi Chemical Co., Ltd.). Corresponds to component (B) and also applies to component (D).
M-114: Nonylphenoxy polyethylene glycol acrylate (average value of the total number of oxyethylene groups is 8). Corresponds to component (B) and also applies to component (D).
FA-MECH: (2-hydroxy-3-chloro) propyl-2-methacryloyloxyethyl phthalate. Corresponds to component (B).
UA-13: Urethane reaction product of hexamethylene diisocyanate and polypropylene oxide (poly) ethylene oxide methacrylate (product name, manufactured by Hitachi Chemical Co., Ltd.). Corresponds to component (B) and also applies to component (D).

FA-023M: Polypropylene oxide polyethylene oxide dimethacrylate (dipolymethacrylate of (poly) ethylene oxide- (poly) propylene oxide- (poly) ethylene oxide block copolymer) (product name, manufactured by Hitachi Chemical Co., Ltd.). Corresponds to component (B) and also applies to component (D).
FA-024M: Polypropylene oxide polyethylene oxide dimethacrylate (dipolymethacrylate of (poly) propylene oxide- (poly) ethylene oxide- (poly) propylene oxide block copolymer) (product name, manufactured by Hitachi Chemical Co., Ltd.). Corresponds to component (B) and also applies to component (D).
APG-400: Polypropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Corresponds to component (B).

N-1717: 1,7-di (9-acridinyl) heptane (manufactured by ADEKA, product name). Corresponds to component (C).
LCV: Leuco Crystal Violet (Yamada Chemicals, product name)
・ MKG: Malachite Green (product name, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

  In Table 3, “structural unit (A1) content” is a structure derived from at least one selected from the group consisting of styrene or a styrene derivative and benzyl (meth) acrylate or benzyl (meth) acrylate derivative in the binder polymer. Represents the unit content. “Styrene content” represents the content of structural units derived from at least one selected from the group consisting of styrene and styrene derivatives in the total solid content of the photosensitive resin composition. “BzMA content” refers to the content of structural units derived from at least one selected from the group consisting of benzyl (meth) acrylate and benzyl (meth) acrylate derivatives in the total solid content of the photosensitive resin composition. Represent.

The “EO content” in the upper column of Table 3 represents the content of the structural unit of (poly) ethylene oxide [— (C ₂ H ₄ O) _n —] in each component. The "EO content" on the left bottom column, to the solid content total amount of the components (A) and component (B), (poly) ethylene oxide structural units _{[- - (C 2 H 4 O} ) n ] Represents content.

[Production of photosensitive element]
The photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 14 were each applied onto a polyethylene terephthalate film (trade name “G2-16” manufactured by Teijin Limited) having a thickness of 16 μm, and hot air at 100 ° C. It dried for 10 minutes with the convection type dryer, and formed the photosensitive resin layer whose film thickness after drying is 30 micrometers. By laminating a protective film (trade name “NF-13”, manufactured by Tamapoly Co., Ltd.) on the photosensitive resin layer by roll pressurization, a polyethylene terephthalate film (support film), a photosensitive resin layer, and a protection The photosensitive element concerning Examples 1-6 and Comparative Examples 1-14 with which the film was laminated | stacked in this order was obtained, respectively.

[Preparation of laminated substrate for evaluation]
Subsequently, a 1.6 mm thick copper clad laminate (made by Hitachi Chemical Co., Ltd., trade name “MCL-E-67”) composed of a glass epoxy material and copper foil (thickness 35 μm) formed on both surfaces thereof. The copper surface was polished using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, washed with water, and then dried with an air stream. After heating this copper clad laminated board (henceforth a "board | substrate") and heating up to 80 degreeC, the photosensitive element concerning Examples 1-6 and Comparative Examples 1-14 was made into the copper surface of the both sides of a board | substrate. The laminated substrates for evaluation were respectively prepared by laminating (lamination). Lamination is performed at a speed of 1.5 m / min so that the photosensitive resin layer of each photosensitive element adheres to each copper surface of the substrate while removing the protective film using a 110 ° C. heat roll. It was. Moreover, the heat roll pressure at the time of lamination was 0.4 Mpa.

[Evaluation of sensitivity]
The obtained multilayer substrate for evaluation was allowed to cool, and when the temperature reached 23 ° C., a phototool having a step tablet was brought into close contact with the polyethylene terephthalate film (support film) on the surface of the multilayer substrate for evaluation. As the step tablet, a 41-step 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 each step size of 3 mm × 12 mm was used. . The photosensitive resin layer was exposed through a phototool having such a step tablet and a polyethylene terephthalate film. The exposure was performed at an exposure amount of 20 mJ / cm ² using an exposure machine (trade name “Paragon-9000 m” manufactured by Nippon Orbotech Co., Ltd.) using a semiconductor-excited solid laser as a light source.

  After the exposure, the polyethylene terephthalate film was peeled off from the evaluation laminated substrate to expose the photosensitive resin layer. The exposed photosensitive resin layer was sprayed (development treatment) with a 1.0% by mass aqueous sodium carbonate solution at 30 ° C. for 50 seconds to remove unexposed portions. Thus, the cured film which consists of a hardened | cured material of the photosensitive resin composition was formed in the copper surface of the laminated substrate for evaluation. By measuring the number of steps of the step tablet of the obtained cured film, the sensitivity (photosensitivity) of the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 14 and the photosensitive elements obtained therefrom was evaluated. did. The higher the number of steps of the step tablet, the higher the sensitivity. The results are shown in Table 4.

[Evaluation of adhesion and resolution]
An evaluation pattern having a line width / space width of n / 3n (unit: μm, n = 5 μm to 30 μm at 5 μm intervals) for evaluation of adhesion on the evaluation multilayer substrate, and line width / Photo tool data having an evaluation pattern having a space width of 3 n / n (unit: μm, n = 5 μm to 30 μm and 5 μm interval) was used. The exposure was performed at an exposure amount of 20 mJ / cm ² using an exposure machine (trade name “Paragon-9000 m” manufactured by Nippon Orbotech Co., Ltd.) using a semiconductor-excited solid laser as a light source. Subsequently, development processing was performed under the same conditions as in the evaluation of the photosensitivity to remove unexposed portions. The adhesion was evaluated by the smallest value (unit: μm) of the line width in which the cured film remained by the development process. Further, the resolution was evaluated by the smallest value (unit: μm) of the space width between the line widths where the portion not photocured by the development treatment could be removed cleanly. The evaluation of adhesion and resolution is better as the numerical value is smaller. The results are shown in Table 4.

[Tent reliability]
The tent reliability was evaluated using a hole breakage number measuring substrate 40 as shown in FIG. 3 manufactured as follows. A copper-clad laminate (trade name MCL-E-67 manufactured by Hitachi Chemical Co., Ltd.) has a diameter of 4 mm to 6 mm, and three independent round holes 41 and three round holes are connected to each other. The three continuous holes 42 whose intervals were gradually shortened were each produced by a die cutting machine. The burr produced when the round hole 41 and the triple hole 42 were produced was removed using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, and this was removed from the hole tearing number measuring substrate 40. did.

  The obtained substrate for hole breakage number measurement was heated to 80 ° C., and the protective film was peeled off from the photosensitive element obtained above, so that the photosensitive resin layer faced the copper surface. 6 and Comparative Examples 1 to 14 were laminated under the conditions of 120 ° C. and 0.4 MPa to prepare laminated substrates for tent reliability evaluation.

After lamination, the laminated substrate for tent reliability evaluation is cooled, and when the temperature of the laminated substrate for tent reliability evaluation reaches 23 ° C., a semiconductor-excited solid laser is used as the light source for the polyethylene terephthalate film (support film) surface. The exposure was performed at an exposure amount of 20 mJ / cm ² using an exposure machine (manufactured by Nippon Orbotech Co., Ltd., trade name “Paragon-9000 m”).

  After exposure, the film was allowed to stand at room temperature (25 ° C.) for 15 minutes, and then the polyethylene terephthalate film was peeled off from the laminated substrate for tent reliability evaluation and developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 50 seconds. After development, the number of hole breaks of the three consecutive holes was measured, the deformed tent tear rate was calculated as the number of hole breaks with respect to the total number of three consecutive holes, and the tent reliability (%) was evaluated. The higher this number, the higher the tent reliability. The results are shown in Table 4.

  From Table 4, when using the photosensitive element concerning Examples 1-6 using the photosensitive resin composition of this invention, in any case, it compares with the case where the photosensitive element concerning Comparative Examples 1-14 is used. And showed good adhesion, resolution and excellent tent reliability. Regarding the photosensitive element according to the comparative example, the photosensitivity was the same as that of the photosensitive element according to the example, but the adhesion, resolution, or tent reliability was inferior.

2 Support Film 4 Photosensitive Resin Layer 6 Protective Film 10 Photosensitive Element 40 Hole Breaking Number Measurement Board 41 Round Hole 42 Triple Hole 100A Multilayer Printed Wiring Board 101 Copper-Clad Laminate 102 Wiring Pattern 103 Interlayer Insulating Layer 104 Opening 105 Seed Layer 106 Resist pattern 107 Wiring pattern 108 Solder resist

Claims (5)

(A) component: binder polymer,
(B) component: a photopolymerizable compound;
(C) component: a photopolymerization initiator,
(D) component: (poly) ethylene oxide [-(C ₂ H ₄ O) _n- : n is 1 or more] as a structural unit,
Component (A): The binder polymer has a structural unit derived from at least one selected from the group consisting of (A1) styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative, and a binder The content of the structural unit in the total solid content of the polymer is 10% by mass to 60% by mass,
The content of the structural unit of the (poly) ethylene oxide [— (C ₂ H ₄ O) _n —] relative to the total solid content of the component (A) and the component (B) is 25% by mass or more. Photosensitive resin composition.   The photosensitive resin composition according to claim 1, wherein the (A) binder polymer contains a structural unit derived from (A2) alkyl (meth) acrylate (the alkyl group has 1 to 20 carbon atoms). A support film;
A photosensitive resin layer that is a coating film of the photosensitive resin composition according to claim 1 or 2 provided on the support film;
A photosensitive element. A laminating step of laminating a photosensitive resin layer formed using the photosensitive resin composition according to claim 1 or 2 on a substrate;
An exposure step of irradiating at least a part of the photosensitive resin layer with actinic rays to cure the region;
A developing step of forming a resist pattern composed of a cured product of the photosensitive resin composition on the substrate by removing an unexposed portion other than the region of the photosensitive resin layer from the substrate,
The manufacturing method of the board | substrate with a resist pattern which has this.   The manufacturing method of a printed wiring board including the process of etching or plating the board | substrate with which the resist pattern was formed by the method of Claim 4.