WO2017033868A1 - Photosensitive resin composition - Google Patents

Abstract

This photosensitive resin composition contains an alkali-soluble polymer (A), a compound (B) having an ethylenic double bond, and a photopolymerization initiator (C), wherein the alkali-soluble polymer (A) has a glass transition temperature (Tg_total) determined by mathematical formula (I) (in mathematical formula (I), W_i represents the mass of each comonomer forming the alkali-soluble polymer, Tg_i represents the glass transition temperature when each of the comonomers of the alkali-soluble polymer is a homopolymer, W_total represents the total mass of the alkali-soluble polymer, and n represents the total number of types of the comonomers forming the alkali-soluble polymer) not higher than 100°C, and the compound (B) having an ethylenic double bond contains a compound that has an ethylenic double bond and a triazine-trione structure.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition.

A printed wiring board is generally manufactured by photolithography. With photolithography, a layer made of a photosensitive resin composition is formed on a substrate, a resist pattern is formed by pattern exposure and development on the coating film, and then a conductor pattern is formed by etching or plating, In this method, a desired wiring pattern is formed on the substrate by removing the resist pattern on the substrate.

In the production of printed wiring boards, photosensitive elements are often used. There are many known examples of a method for forming a wiring pattern using this photosensitive element and a photosensitive resin composition suitable for this method (Patent Documents 1 to 4).

JP 2011-233769 A International Publication No. 2009/022724 JP 2004-101617 A JP 2013-109323 A

In forming a wiring pattern by photolithography, it is required that the obtained pattern is free from defects such as chipping and disconnection. In particular, in pattern formation by etching, the conductor material that should be etched only in the vertical direction by the etchant is also etched in the horizontal direction, and the top width of the resulting wiring pattern is smaller than the base width of the resist film. ”May occur, and suppression of the side etch is demanded.
By the way, in recent years, with the spread of smartphones (registered trademark) and the like, the demand for touch panel displays is increasing. In many cases, the photosensitive element is also used for manufacturing a wiring portion in the sensor of the touch panel. In the case of a touch panel sensor, high definition and high density are required for wiring manufactured through an etching process. In other words, when the line / space size of a normal printed wiring board in an etching method is up to about 40 μm / 40 μm, the touch panel sensor requires high definition of about 25 μm / 25 μm or more. There is. In order to realize such a high-definition wiring, in the conductor pattern formed through the etching process, in addition to the small amount of side etching, the straightness of the line pattern (uniformity of the line width) High is desirable.
On the other hand, all of the materials described in Patent Documents 1 to 4 have room for further improvement from the viewpoint of suppressing the side etch amount.
The present invention has been made in view of the above situation. That is, the objective of this invention is providing the photosensitive resin composition which can form the resist pattern in which the amount of side etching at the time of an etching process was suppressed.

The present inventors have found that the above object can be achieved by the following technical means, and have reached the present invention. The present invention is as follows.

｛数式（Ｉ）中、Ｗ_ｉは、アルカリ可溶性高分子を構成するコモノマーそれぞれの質量であり、
Ｔｇ_ｉは、アルカリ可溶性高分子を構成するコモノマーのそれぞれがホモポリマーであった場合のガラス転移温度であり、
Ｗ_{ｔｏｔａｌ}は、アルカリ可溶性高分子の合計質量であり、そして
ｎは、該アルカリ可溶性高分子を構成するコモノマーの種類の数である。｝によって求めたガラス転移温度が１００℃以下であり、
前記（Ｂ）エチレン性二重結合を有する化合物は、エチレン性二重結合とトリアジン－トリオン構造とを有する化合物を含有する、
ことを特徴とする感光性樹脂組成物。 [1] containing (A) an alkali-soluble polymer, (B) a compound having an ethylenic double bond, and (C) a photopolymerization initiator,
The (A) alkali-soluble polymer is represented by the following formula (I):

{In Formula (I), _Wi is the mass of each comonomer constituting the alkali-soluble polymer,
Tg _i is the glass transition temperature when the respective comonomers constituting the alkali-soluble polymer is a homopolymer,
W _total is the total mass of the alkali-soluble polymer, and n is the number of comonomer types constituting the alkali-soluble polymer. }, The glass transition temperature determined by
The compound (B) having an ethylenic double bond contains a compound having an ethylenic double bond and a triazine-trione structure.
The photosensitive resin composition characterized by the above-mentioned.

[2] The compound (B) having an ethylenic double bond and a triazine-trione structure in the compound having an ethylenic double bond is an isocyanurate compound having an ethylenic double bond. The photosensitive resin composition as described.
[3] The photosensitive resin composition according to [1] or [2], wherein the compound (B) having an ethylenic double bond further includes a compound obtained by modifying bisphenol A.
[4] The compound obtained by modifying bisphenol A in the compound (B) having an ethylenic double bond is an ethylenic double bond at both ends of polyethylene glycol in which 10 to 30 mol of ethylene oxide is added to bisphenol A. The photosensitive resin composition according to [3], which is a compound having a bond.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the (C) photopolymerization initiator includes a hexaarylbiimidazole compound.
[6] The photosensitive resin composition according to any one of [1] to [5], further containing a leuco dye.
[7] The (A) alkali-soluble polymer is
[1] to [6] including (A-1) an alkali-soluble polymer having a weight average molecular weight of 50,000 or more and (A-2) an alkali-soluble polymer having a weight average molecular weight of less than 50,000. The photosensitive resin composition as described in any one of these.
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the ethylenic double bond concentration is 1.1 mmol / g or more based on the solid content of the photosensitive resin composition. object.

[9] A photosensitive element comprising a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of [1] to [8] on a support.
[10] A laminating step of forming a photosensitive resin composition layer on a substrate using the photosensitive element according to [9], an exposure step of exposing the photosensitive resin composition layer, and the photosensitive resin composition A resist pattern forming method comprising: a developing step of forming a resist pattern by removing an unexposed portion of a physical layer with a developer.

[11] A laminating process for forming a photosensitive resin composition layer on a substrate using the photosensitive element according to [9], an exposure process for exposing the photosensitive resin composition layer, and the photosensitive resin composition A development process for forming a resist pattern by removing an unexposed portion of the layer with a developer, a conductor pattern formation process for etching or plating a substrate on which the resist pattern is formed, and a peeling process for peeling the resist pattern. A method for manufacturing a wiring board, comprising:

According to the present invention, there is provided a photosensitive resin composition capable of forming a resist pattern in which the amount of side etching during the etching process is suppressed.

Hereinafter, a mode for carrying out the present invention (hereinafter abbreviated as “the present embodiment”) will be specifically described. The photosensitive resin composition of the present embodiment contains (A) an alkali-soluble polymer, (B) a compound having an ethylenic double bond, and (C) a photopolymerization initiator.

｛数式（Ｉ）中、Ｗ_ｉは、アルカリ可溶性高分子を構成するコモノマーそれぞれの質量であり、
Ｔｇ_ｉは、アルカリ可溶性高分子を構成するコモノマーのそれぞれがホモポリマーであった場合のガラス転移温度であり、
Ｗ_{ｔｏｔａｌ}は、アルカリ可溶性高分子の合計質量であり、そして
ｎは、該アルカリ可溶性高分子を構成するコモノマーの種類の数である。｝
　（Ａ）アルカリ可溶性高分子として複数種の高分子の混合物を用いる場合、本実施形態におけるガラス転移温度は、高分子全部の平均値として定まる値である。 <(A) Alkali-soluble polymer>
The (A) alkali-soluble polymer in the present embodiment has a glass transition temperature (Tg _total ) determined by the following formula (I) of 100 ° C. or lower.

{In Formula (I), _Wi is the mass of each comonomer constituting the alkali-soluble polymer,
Tg _i is the glass transition temperature when the respective comonomers constituting the alkali-soluble polymer is a homopolymer,
W _total is the total mass of the alkali-soluble polymer, and n is the number of comonomer types constituting the alkali-soluble polymer. }
(A) When a mixture of a plurality of types of polymers is used as the alkali-soluble polymer, the glass transition temperature in the present embodiment is a value determined as an average value of all the polymers.

When determining the glass transition temperature Tgi, as the glass transition temperature of a homopolymer composed of a comonomer that forms the corresponding alkali-soluble polymer, Brandrup, J. et al. Immergut, E .; H. Edit “Polymer handbook, Third edition, John willy & sons, 1989, p.209 Chapter VI“ Glass transition temperatures of polymers ”is used.

The Tgi of each comonomer used in the examples described later is as follows (all are literature values).
Methacrylic acid: Tg = 501K
Benzyl methacrylate: Tg = 327K
Methyl methacrylate: Tg = 378K
Styrene: Tg = 373K
2-ethylhexyl acrylate: Tg = 223K
The alkali-soluble polymer exhibiting the glass transition temperature (Tg _total ) as described above is preferably a copolymer of an acid monomer and another monomer.

There is no particular limitation on the lower limit of the glass transition temperature (Tg _total ) of the (A) alkali-soluble polymer obtained by the above formula (I). The glass transition temperature (Tg _total ) may be 10 ° C. or higher, 30 ° C. or higher, 50 ° C. or higher, or 70 ° C. or higher.

(A) The alkali-soluble polymer is preferably obtained by polymerizing at least one of the first monomers described below. The (A) alkali-soluble polymer is more preferably obtained by copolymerizing at least one of the first monomers and at least one of the second monomers described later. .

The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like. Among these, (meth) acrylic acid is particularly preferable. In this specification, “(meth) acryl” means acryl or methacryl, and “(meth) acrylate” means “acrylate” and “methacrylate”.

(A) The copolymerization ratio of the first monomer in the alkali-soluble polymer is preferably 10% by mass to 30% by mass, and preferably 15% by mass to 25% by mass with respect to the total mass of all monomers. More preferably.

The second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, etc. ) Acrylic acid esters; esters of vinyl alcohol such as vinyl acetate; and (meth) acrylonitrile, styrene, and polymerizable styrene derivatives (eg, methylstyrene, vinyltoluene, tert-butoxystyrene, Tokishisuchiren, 4-vinylbenzoic acid, styrene dimer, styrene trimer), and the like. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferable.

(A) The copolymerization ratio of the second monomer in the alkali-soluble polymer is preferably 70% by mass to 90% by mass, and 75% by mass to 85% by mass with respect to the total mass of all monomers. More preferably.

In this embodiment, from the viewpoint of improving the resolution of the resist pattern, the (A) alkali-soluble polymer preferably has an aromatic group in the side chain of the structure.

(A) Alkali-soluble polymer having an aromatic group in the side chain is a compound having an aromatic group as at least one of the first monomer and the second monomer. Can be used. Examples of the monomer having an aromatic group include (meth) acrylic acid aralkyl esters such as benzyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, styrene, cinnamic acid, polymerizable styrene derivatives ( Examples thereof include methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, and the like. From the viewpoint of suppressing side etching, (meth) acrylic acid aralkyl ester is preferable, and benzyl (meth) acrylate is particularly preferable.

The copolymerization ratio of the compound having an aromatic group is 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, and 70% by mass with respect to the total mass of all monomers. % Or more, or 80% by mass or more is preferable. There is no restriction | limiting in particular as an upper limit of the copolymerization ratio of the compound which has an aromatic group. From the viewpoint of maintaining alkali solubility, the copolymerization ratio of the compound having an aromatic group is preferably 95% by mass or less, more preferably 90% by mass or less.

In this embodiment, (A) the alkali-soluble polymer is a known polymerization method, preferably an addition of one or more monomers selected from the first monomer and the second monomer. It can be prepared by polymerization, more preferably by radical polymerization.

(A) The acid equivalent of the alkali-soluble polymer (the acid equivalent of the entire mixture when a plurality of types of copolymers are included) is the development resistance of the photosensitive resin layer, and the resolution and adhesion of the resist pattern. From the viewpoint of the above, it is preferably 100 or more, and from the viewpoint of developability and peelability of the photosensitive resin layer, it is preferably 600 or less. (A) The acid equivalent of the alkali-soluble polymer is more preferably from 200 to 500, and even more preferably from 250 to 450.

(A) The weight average molecular weight of the alkali-soluble polymer (hereinafter sometimes abbreviated as “Mw”) (in the case where a plurality of types of alkali-soluble polymers are used in combination) means the total Mw) It is preferably 5,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 65,000. Dispersity (Mw / Mn), which is the ratio of the weight average molecular weight to the number average molecular weight (hereinafter sometimes abbreviated as “Mn”) (when a plurality of types of alkali-soluble polymers are used in combination, the total dispersion Degree) is preferably 1.0 to 6.0.
(A) It is preferable that the weight average molecular weight and dispersity of the alkali-soluble polymer are in the above ranges from the viewpoint of obtaining appropriate developability, high coating strength, and resist thickness uniformity.

(A) When using a plurality of alkali-soluble polymers in combination as alkali-soluble polymers,
(A-1) an alkali-soluble polymer having Mw of 50,000 or more, and (A-2) an alkali-soluble polymer having Mw of less than 50,000,
It is particularly preferable that

The Mw of the alkali-soluble polymer (A-1) is more preferably 50,000 to 100,000, still more preferably 50,000 to 75,000, and 50,000 to 65,000. It is particularly preferred. The Mw of the alkali-soluble polymer (A-1) being in this range makes the product life longer when the photosensitive resin composition of the present embodiment is applied to a photosensitive element (dry film resist). It is preferable from the viewpoint.
On the other hand, the Mw of the alkali-soluble polymer (A-2) is preferably 5,000 or more and less than 50,000, more preferably 10,000 to 45,000, and 10,000 to 35. Is particularly preferred. The Mw of the alkali-soluble polymer (A-2) is preferably in this range from the viewpoint of achieving both developability and a small side etch amount.

The content ratio of the alkali-soluble polymer (A-1) component in the whole of the (A) alkali-soluble polymer is preferably 3% by mass to 30% by mass, more preferably 5% by mass to 25% by mass. More preferably, it is 10 mass% or more and 20 mass% or less. Setting the ratio of component (A-1) to be used in the above range is preferable from the viewpoint of resolution.
The content of the alkali-soluble polymer (A-2) component in the whole of the (A) alkali-soluble polymer is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less. More preferably, it is 10 mass% or more and 35 mass% or less. Setting the use ratio of the component (A-2) in the above range results in a long product life when the photosensitive resin composition of the present embodiment is applied to a photosensitive element (dry film resist). This is preferable from the viewpoint of simultaneously realizing a small side etch amount of the conductor pattern.

The proportion of the (A) alkali-soluble polymer used in the photosensitive resin composition of the present embodiment is preferably from 25% by mass to 85% by mass, preferably from 35% by mass to the total amount of the solid content of the photosensitive resin composition. 75 mass% is more preferable. (A) Setting the use ratio of the alkali-soluble polymer within the above range is preferable from the viewpoints of resolution, developability, developer swellability of exposed portions, resist pattern peelability, and product life of the photosensitive element. Furthermore, in consideration of the uniformity of the line width in the conductor pattern to be formed, it is particularly preferable that the use ratio of (A) the alkali-soluble polymer is 50 mass% to 70 mass%.

<(B) Compound having ethylenic double bond>
The compound (B) having an ethylenic double bond in the photosensitive resin composition of the present embodiment is a compound having polymerizability by having an ethylenically unsaturated group in its structure. The compound (B) having an ethylenic double bond in this embodiment contains a compound having an ethylenic double bond and a triazine-trione structure.

で表される構造をいう。上記式において、窒素原子から出ている線は結合手を示す。 (B) The triazine-trione structure possessed by the compound having an ethylenic double bond is represented by the following formula:

The structure represented by. In the above formula, the line coming out from the nitrogen atom represents a bond.

で表される化合物、（ＥＯ）変性イソシアヌレート誘導トリ（メタ）アクリレート（エチレンオキサイド平均２７ｍｏｌ付加物）等を挙げることができる。
　このような化合物としては市販品を用いることができ、例えば、ＵＡ－７１００、Ａ－９３００－１ＣＬ（以上、新中村化学工業社製）；アロニックスＭ－３２７（東亞合成社製）等を挙げることができる。 Examples of the compound having an ethylenic double bond and a triazine-trione structure include an isocyanurate compound having an ethylenic double bond, and among them, two or more ethylenic double bonds and one or more A compound having a triazine-trione structure is preferred.
Specific examples of such compounds include, for example, ethoxylated isocyanuric acid tri (meth) acrylate, ε-caprolactone-modified tris (2- (meth) acryloxyethyl) isocyanurate, triallyl isocyanurate,

And (EO) -modified isocyanurate-derived tri (meth) acrylate (ethylene oxide average 27 mol adduct).
Commercially available products can be used as such compounds, and examples include UA-7100, A-9300-1CL (above, Shin-Nakamura Chemical Co., Ltd.); Aronix M-327 (Toagosei Co., Ltd.), and the like. Can do.

In this embodiment, as the compound (B) having an ethylenic double bond, the above-described compound having an ethylenic double bond and a triazine-trione structure can be used in combination with another compound. .
Examples of such other compounds include:
A compound obtained by adding (meth) acrylic acid to one end of polyalkylene oxide,
A compound in which (meth) acrylic acid is added to one end of polyalkylene oxide and the other end is converted to an alkyl ether or allyl ether, etc. (other compounds of the first group);
A compound having a (meth) acryloyl group at both ends of the alkylene oxide chain,
A compound having a (meth) acryloyl group at both ends of an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are bonded together randomly or in a block;
Compounds modified with bisphenol A, etc. (other compounds of the second group);
Compounds having three or more (meth) acryloyl groups in one molecule, etc. (other compounds in Group 3);
Etc.

As other compounds of the first group, specifically, for example,
Phenoxyhexaethylene glycol mono (meth) acrylate, which is a (meth) acrylate of a compound in which polyethylene glycol is added to a phenyl group,
4-Normal nonylphenoxyheptaethylene glycol dipropylene glycol (meth) which is a (meth) acrylate of a compound in which polypropylene glycol with an average of 2 mol of propylene oxide added and polyethylene glycol with an average of 7 mol of ethylene oxide added to nonylphenol Acrylate,
4-Normal nonylphenoxypentaethylene glycol monopropylene glycol (meth) which is a (meth) acrylate of a compound in which polypropylene glycol with an average of 1 mol of propylene oxide added and polyethylene glycol with an average of 5 mol of ethylene oxide added to nonylphenol 4-Normal nonylphenoxyoctaethylene glycol (meth) acrylate (M-114, manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding polyethylene glycol added with ethylene oxide with an average of 8 moles of acrylate to nonylphenol.
Etc.

Specifically, as other compounds of the second group, for example, tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) Polyethylene glycos such as acrylate, octaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and compounds having (meth) acryloyl groups at both ends of 12 mol ethylene oxide chain -Poly (meth) acrylate; polypropylene glycol di (meth) acrylate; polybutylene glycol di (meth) acrylate. Examples of the polyalkylene oxide di (meth) acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound include, for example, a glycol obtained by adding an average of 3 moles of ethylene oxide to both ends of polypropylene glycol added with an average of 12 moles of propylene oxide. In addition to polypropylene glycol added with an average of 18 moles of propylene oxide, glycol dimethacrylate added with an average of 15 moles of ethylene oxide at both ends, respectively.
Examples thereof include compounds having an ethylenic double bond at both ends of polyalkylene glycol obtained by adding alkylene oxide to bisphenol A.

It is possible to use a compound having an ethylenic double bond at both ends of a polyalkylene glycol obtained by adding alkylene oxide to bisphenol A as a compound obtained by modifying bisphenol A among the other compounds of the second group. And from the viewpoint of adhesion. The ethylenic double bond in this compound is preferably contained in the compound in a form contained in a (meth) acryloyl group.
For modification by adding alkylene oxide to bisphenol A, for example, ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, hexylene oxide modification and the like are known. A compound having a (meth) acryloyl group at both ends of a polyalkylene glycol obtained by adding ethylene oxide to bisphenol A is preferred.

Examples of such compounds include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane (for example, NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaethoxy) phenyl) propane (for example, NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.). Furthermore, di (meth) acrylate of polyalkylene glycol obtained by adding an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide to both ends of bisphenol A, or an average of 2 moles of propylene oxide and an average of 15 respectively to both ends of bisphenol A. Also preferred are compounds modified with ethylene oxide and propylene oxide, such as di (meth) acrylate of polyalkylene glycol to which a molar amount of ethylene oxide is added. The number of moles of ethylene oxide in the compound having (meth) acryloyl groups at both ends by modifying bisphenol A with alkylene oxide is 10 moles or more from the viewpoint of improving resolution, adhesion, and flexibility. 30 mol or less is preferable.

Other compounds in the third group add an alkyleneoxy group such as an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group to a central skeleton having a group capable of adding an alkylene oxide group in the molecule of 3 moles or more. It is obtained by (meth) acrylate conversion of the alcohol obtained. Examples of the compound that can be a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings.
More specifically, for example, trimethylolpropane ethylene oxide (EO) 3 mole modified triacrylate, trimethylolpropane EO6 mole modified triacrylate, trimethylolpropane EO9 mole modified triacrylate, trimethylolpropane EO12 mole modified triacrylate. An acrylate etc. can be mentioned. Examples of such compounds include glycerol EO 3 mol-modified triacrylate (for example, A-GLY-3E manufactured by Shin-Nakamura Chemical Co., Ltd.) and glycerol EO 9 mol-modified triacrylate (for example, manufactured by Shin-Nakamura Chemical Co., Ltd.). A-GLY-9E), glycerin EO 6 mol and propylene oxide (PO) 6 mol modified triacrylate (A-GLY-0606PE), glycerol EO 9 mol PO9 mol modified triacrylate (A-GLY-0909PE), etc. Can do. Furthermore, pentaerythritol 4EO-modified tetraacrylate (for example, SR-494 manufactured by Sartomer Japan Co., Ltd.), pentaerythritol 35EO-modified tetraacrylate (for example, NK ester ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. be able to.

In the photosensitive resin composition of the present embodiment, the proportion of the compound having an ethylenic double bond and a triazine-trione structure is 5% by mass to 30% with respect to the total mass of the solid content of the photosensitive resin composition. % By mass is preferable, 7% by mass to 25% by mass is more preferable, and 7% by mass to 20% by mass is still more preferable. Setting the use ratio within this range is preferable from the viewpoint of obtaining a photosensitive resin composition having an excellent balance of side etch amount, resolution, and developability.
In the photosensitive resin composition of the present embodiment, the proportion of the compound modified with bisphenol A is preferably 12% by mass to 45% by mass, and 17% by mass with respect to the total mass of the solid content of the photosensitive resin composition. More preferably, it is preferably ˜40% by mass, more preferably 22% by mass to 40% by mass. The use ratio of the compound in this range is suitable from the viewpoint of obtaining a photosensitive resin composition having an excellent balance between resolution and developability.

(B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid mass of the photosensitive resin composition is preferably 5% by mass to 70% by mass. Setting this ratio to 5% by mass or more is preferable from the viewpoint of sensitivity, resolution, and adhesion, more preferably 20% by mass or more, and further preferably 30% by mass or more. On the other hand, setting this ratio to 70% by mass or less is preferable from the viewpoint of suppressing the delay of peeling of the edge fuse and the cured resist, and it is more preferable to set this ratio to 50% by mass or less.

The ethylenic double bond concentration of the photosensitive resin composition of the present embodiment is preferably 1.1 mmol / g or more based on the solid content of the photosensitive resin composition. More preferably, it is 1.2 mmol / g or more. Setting the ethylenic double bond concentration in such a range is preferable from the viewpoint of forming a resist pattern having excellent etching solution resistance and suppressing the side etch amount in the conductor pattern.
On the other hand, if the ethylenic double bond concentration in the photosensitive resin composition is excessively high, the storage stability of the composition may be impaired. From the viewpoint of avoiding this, the ethylenic double bond concentration is preferably 4.0 mmol / g or less, more preferably 3.5 mmol / g or less, based on the solid content of the photosensitive resin composition. More preferably, it is 3.2 mmol / g or less.

<(C) Photopolymerization initiator>
(C) Examples of the photopolymerization initiator include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, and benzoin ether compounds. , Dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-aryl amino acid ester compounds, halogen compounds, and the like.

Examples of hexaarylbiimidazole compounds include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl). ) -4 ′, 5′-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-) Chlorophenyl) -diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2′-bis- (2-fluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3-difluoromethylphenyl)- , 4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,4-difluorophenyl) -4,4 ′, 5,5′-tetrakis- ( 3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2 '-Bis- (2,6-difluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4-tri Fluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,5-trifluorophenyl) -4,4 ′, 5,5'-tetrakis- (3-methoxy Phenyl) -biimidazole, 2,2′-bis- (2,3,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2 '-Bis- (2,4,5-trifluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4, 6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4,5-tetrafluorophenyl)- 4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ′, 5 5'-tetrakis- (3-methoxyphenyl) -bi Examples include imidazole and 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole. It is done. Among these, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable from the viewpoint of high sensitivity, resolution, and adhesion.

Examples of the N-aryl-α-amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. In particular, N-phenylglycine is preferable because of its high sensitizing effect.

Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloro. Anthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone and the like.

Examples of aromatic ketone compounds include benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, and the like. be able to.
Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4 -Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl- Examples thereof include 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1. Examples of commercially available acetophenone compounds include Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals. From the viewpoint of adhesion, 4,4′-bis (diethylamino) benzophenone is preferable.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phosphine oxide, and bis (2,6-dimethoxybenzoyl) -2. 4,4-trimethyl-pentyl phosphine oxide and the like. Examples of commercially available acylphosphine oxide compounds include Lucilin TPO manufactured by BASF and Irgacure-819 manufactured by Ciba Specialty Chemicals.

Examples of the benzoin compound and benzoin ether compound include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.
Examples of the dialkyl ketal compound include benzyl dimethyl ketal and benzyl diethyl ketal.
Examples of the thioxanthone compound include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.
Examples of dialkylaminobenzoic acid ester compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, 2-ethylhexyl-4- (dimethylamino) benzoate, and the like.

Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, and the like. . Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 manufactured by Ciba Specialty Chemicals.

As the acridine compound, 1,7-bis (9,9'-acridinyl) heptane or 9-phenylacridine is preferable in terms of sensitivity, resolution, availability, and the like.

Examples of the pyrazoline derivative include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline and 1-phenyl from the viewpoint of adhesion and rectangularity of the resist pattern. -3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline are preferred .

Examples of ester compounds of N-aryl amino acids include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, N-phenylglycine 1-butyl ester, N-phenylglycine 2-butyl ester, N-phenylglycine tert-butyl ester, N-phenylglycine pentyl ester, N-phenylglycine hexyl ester, N-phenylglycine pentyl ester, N -Octyl ester of phenylglycine and the like.

Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds, diallyl iodonium compounds, etc. In particular, tribromomethylphenylsulfone is preferred.

The proportion of the photopolymerization initiator (C) used in the photosensitive resin composition of the present embodiment is preferably 0.01% by mass to 20% by mass with respect to the total mass of the solid content of the photosensitive resin composition. 0.5% by mass to 10% by mass is more preferable. (C) By setting the use ratio of the photopolymerization initiator within this range, sufficient sensitivity can be obtained, light can be sufficiently transmitted to the bottom of the resist, high resolution can be obtained, and the conductor pattern can be obtained. The photosensitive resin composition which is excellent in balance with the amount of side etch in can be obtained.

(C) It is preferable to use a hexaarylbisimidazole compound as a photopolymerization initiator. In this case, the use ratio of the hexaarylbisimidazole compound is preferably 0.1% by mass to 10% by mass, and preferably 0.5% by mass to 5% by mass with respect to the total mass of the solid content of the photosensitive resin composition. Is more preferable.

(C) As the photopolymerization initiator, it is particularly preferable to use an aromatic ketone compound and a hexaarylbisimidazole compound in combination. In this case, the proportion of the aromatic ketone compound used is preferably 0.5% by mass or less, more preferably 0.01% by mass to 0.4% by mass with respect to the total mass of the solid content of the photosensitive resin composition. preferable. The use ratio of the hexaarylbisimidazole compound is preferably 0.1% by mass to 10% by mass and more preferably 0.5% by mass to 5% by mass with respect to the total mass of the solid content of the photosensitive resin composition. .

<Other ingredients>
The photosensitive resin composition of the present embodiment may contain only the components (A) to (C) described above, or may contain other components together with them. Examples of other components that can be used here include leuco dyes, base dyes, antioxidants, and stabilizers.

<Leuco dye>
The leuco dye can be blended in the photosensitive resin composition of the present embodiment in order to impart suitable color developability and excellent peeling characteristics to the resist cured film.
Specific examples of the leuco dye include leuco crystal violet (tris [4- (dimethylamino) phenyl] methane), 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, and the like. be able to. Of these, leuco crystal violet is preferred.

The proportion of the leuco dye used in the photosensitive resin composition of the present embodiment is preferably 0.01% by mass to 2% by mass with respect to the total mass of the solid content of the photosensitive resin composition. It is more preferably 1% by mass to 1.5% by mass. By setting the use ratio of the leuco dye within this range, it is possible to realize good color developability and sensitivity.
In the photosensitive resin composition of the present embodiment, it is preferable to increase the usage ratio of the leuco dye from the viewpoint of reducing the side etch amount of the formed conductor pattern. However, if the content of the leuco dye is excessively large, the resolution may be adversely affected. Photosensitivity that is particularly excellent in the balance between the amount of side etch and the resolution when the ratio of the leuco dye used is 0.2% by mass to 1.2% by mass with respect to the total mass of the solid content of the photosensitive resin composition. In particular, a functional resin composition can be obtained.

<Base dye>
Examples of the base dye include basic green 1 [CAS number (hereinafter the same): 633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), malachite green oxalate [ 2437-29-8] (for example, Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Co., Ltd.), brilliant green [633-03-4], fuchsin [632-99-5], methyl violet [603-47-4] , Methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl green [82-94-0], Victoria Blue B [2580-56-5], basic blue 7 [2390-60 -5] (for example, Aizen Victoria Pur e Blue BOH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), rhodamine B [81-88-9], rhodamine 6G [989-38-8], basic yellow 2 [2465-27-2] and the like. Among these, one or more selected from Basic Green 1, Malachite Green Oxalate, and Basic Blue 7 are preferable, and Basic Green 1 is particularly preferable from the viewpoint of hue stability and exposure contrast.

The use ratio of the base dye in the photosensitive resin composition of the present embodiment is preferably 0.001% by mass to 3% by mass, more preferably 0.001% by mass with respect to the total mass of the solid content of the photosensitive resin composition. The range is from 01% by mass to 2% by mass, and more preferably from 0.01% by mass to 1.2% by mass. By setting the use ratio within this range, good colorability can be obtained.

<Stabilizer>
From the viewpoint of improving the thermal stability or storage stability of the photosensitive resin composition, or both, it is preferable to use a stabilizer. Examples of the stabilizer include at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazole compounds, carboxybenzotriazole compounds, and alkylene oxide compounds having a glycidyl group. These can be used alone or in combination of two or more.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4) -Hydroxyphenyl) propionate], nitrosophenylhydroxyamine aluminum salt (for example, aluminum salt added with 3 mol of nitrosophenylhydroxylamine), diphenylnitrosamine and the like. Among these, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] or an aluminum salt added with 3 mol of nitrosophenylhydroxylamine is preferable. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole, 1- (2-di-n- And a 1: 1 mixture of (butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazole. Among these, a 1: 1 mixture of 1- (2-di-n-butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazole is preferable. . Moreover, these can be used individually by 1 type or in combination of 2 or more types.

Examples of the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole. These can be used alone or in combination of two or more.

Examples of the alkylene oxide compound having a glycidyl group include neopentyl glycol diglycidyl ether (for example, Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), Bisphenol A-propylene oxide 2 mol adduct diglycidyl ether (for example, Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (for example, Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.) . These can be used alone or in combination of two or more.

In the present embodiment, the total content of the radical polymerization inhibitor, the benzotriazole compound, the carboxybenzotriazole compound, and the alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably 0.001% by mass to 3%. The range is by mass, more preferably from 0.05 to 1% by mass. This total content is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, while, on the other hand, from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. It is preferable that it is 3 mass% or less. *

<Photosensitive resin composition preparation solution>
In this embodiment, the photosensitive resin composition preparation liquid can be prepared by adding a solvent to the above photosensitive resin composition. Suitable solvents used here include ketones such as methyl ethyl ketone (MEK); alcohols such as methanol, ethanol and isopropyl alcohol. It is preferable to prepare the preparation liquid by adding a solvent to the photosensitive resin composition so that the viscosity of the preparation liquid of the photosensitive resin composition is 500 mPa · sec to 4,000 mPa · sec at 25 ° C.

<Photosensitive element>
Another aspect of the present invention is a photosensitive element (photosensitive laminate) having a support and a photosensitive resin composition layer formed on the support from the above-described photosensitive resin composition of the present embodiment. I will provide a. The photosensitive element of this embodiment may have a protective layer on the surface of the photosensitive resin composition layer opposite to the support, if necessary.

<Support>
As the support, a transparent substrate that transmits light emitted from the exposure light source is preferable. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, Examples thereof include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, those stretched as necessary can be used.
The haze of the support is preferably from 0.01% to 5.0%, more preferably from 0.01% to 2.5%, still more preferably from 0.01% to 1.0%.
A thinner support is advantageous in terms of image formation and economy, but it is necessary to maintain strength. Considering both of these, a support of 10 to 30 μm can be preferably used.

<Photosensitive resin composition layer>
The photosensitive resin composition layer in the photosensitive element of the present embodiment is a layer made of the photosensitive resin composition of the present embodiment described above. When the photosensitive resin composition used for forming the photosensitive resin composition layer contains a solvent, the solvent is preferably removed in the photosensitive resin composition layer, but the solvent remains. It doesn't matter.
The thickness of the photosensitive resin composition layer in the photosensitive element of the present embodiment is preferably 5 to 100 μm, more preferably 5 to 50 μm. The thinner the thickness, the higher the resolution, and the thicker the film strength. Therefore, the thickness of the composition layer can be appropriately selected within the above range depending on the application.

<Protective film>
An important characteristic of the protective layer in the photosensitive element of the present embodiment is that the adhesive strength between the photosensitive resin composition layer is sufficiently smaller than the adhesive strength between the support and the photosensitive resin composition layer, and it is easily peeled off. It can be done. As the protective layer, for example, a polyethylene film, a polypropylene film and the like can be preferably used, and for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used.
The thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm.

<Method for producing photosensitive element>
The photosensitive element of this embodiment can be produced by sequentially laminating a support, a photosensitive resin composition layer, and, if necessary, a protective layer. As a method for laminating the support, the photosensitive resin composition layer, and the protective layer, a known method can be employed.
For example, the photosensitive resin composition of the present embodiment is prepared as the above-described photosensitive resin composition preparation solution, and first coated on a support using a bar coater or a roll coater and dried, and then on the support. A photosensitive resin composition layer made of the photosensitive resin composition is formed. Next, if necessary, a photosensitive element can be produced by laminating a protective layer on the formed photosensitive resin composition layer.

<Method for forming resist pattern>
A resist pattern can be formed on a substrate using the photosensitive element as described above. The resist pattern forming method includes a lamination step of forming a photosensitive resin composition layer on a substrate using the photosensitive element of the present embodiment, an exposure step of exposing the photosensitive resin composition layer, and the photosensitive property. A developing step of forming a resist pattern by removing an unexposed portion of the resin composition layer with a developing solution is included in the order described above.

In the method for forming a resist pattern of the present embodiment, first, in a laminating step, a photosensitive resin composition layer is formed on a substrate using a laminator. Specifically, when the photosensitive element has a protective layer, after the protective layer is peeled off, the photosensitive resin composition layer is heat-pressed and laminated on the substrate surface using a laminator. Examples of the material of the substrate used include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and a flexible base material on which a conductive thin film is laminated. Examples of the conductive thin film include ITO, copper, copper-nickel alloy, and silver; examples of the material constituting the flexible base include polyethylene terephthalate (PET);
Each can be mentioned. Said board | substrate may have a through hole for respond | corresponding to a multilayer board | substrate.

The photosensitive element of this embodiment can be suitably applied to the production of a touch panel sensor by an etching method. An etching method is generally used to form the wiring (conductor pattern) in the touch panel sensor. As described above, the touch panel sensor is required to form a wiring with a much finer size as compared with a normal printed wiring board. Here, when the etching method using the photosensitive element in the prior art is employed, the amount of side etching of the formed conductor pattern is large, so that there is a limit to the product yield of the touch panel sensor manufacturing. However, since the photosensitive element of this embodiment is excellent in reducing the amount of side etching, the touch panel sensor can be manufactured with a high yield.

Here, the photosensitive resin composition layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces of the substrate as necessary. The heating temperature at this time is preferably 40 ° C. to 160 ° C. By performing thermocompression bonding twice or more, the adhesion of the resulting resist pattern to the substrate is further improved. When two or more press bondings are performed, a two-stage laminator equipped with two rolls may be used, or a laminate of the substrate and the photosensitive resin composition layer is repeated several times to form a roll. It may be crimped through.

Next, in the exposure step, the photosensitive resin composition layer is exposed using an exposure machine. This exposure may be performed through the support without peeling off the support, or may be performed after peeling off the support, if necessary.
By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after a development process described later. The pattern exposure may be performed by either a method of exposing through a photomask or a maskless exposure method. In the case of exposure through a photomask, the exposure amount is determined by the light source illuminance and the exposure time. The exposure amount may be measured using a light meter.
In maskless exposure, a photomask is not used and exposure is performed directly on the substrate by a drawing apparatus. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. In maskless exposure, the drawing pattern is controlled by a computer, and the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.
The photosensitive element of this embodiment is preferably applied to a method of exposing through a photomask in that the effect of improving the resolution and reducing the amount of side etching is maximized.

Next, in the development step, the unexposed part of the photosensitive resin composition layer is removed with a developer. After exposure, when there is a support on the photosensitive resin composition layer, it is preferably subjected to a development step after removing the support.
In the development step, the unexposed area is developed and removed using a developer comprising an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, for example, an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is preferably used. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin composition layer, but an aqueous Na ₂ CO ₃ solution having a concentration of 0.2% by mass to 2% by mass is preferably used. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.
The temperature of the developer in the development step is preferably maintained at a constant temperature in the range of 18 ° C to 40 ° C.

A resist pattern is obtained by the above-described process. In some cases, a heating step of 100 ° C. to 300 ° C. may be further performed. By carrying out this heating step, chemical resistance can be further improved. For heating, a heating furnace of an appropriate system such as hot air, infrared rays, far infrared rays or the like can be used.

<Method for forming wiring board>
The present invention further discloses a method for forming a wiring board. The method for forming the wiring board includes a laminating step of forming a photosensitive resin composition layer on a substrate using the photosensitive element of the present embodiment,
An exposure process for exposing the photosensitive resin composition layer, a development process for forming a resist pattern by removing unexposed portions of the photosensitive resin composition layer with a developer, and etching the substrate on which the resist pattern is formed Alternatively, a conductor pattern forming step for plating and a peeling step for peeling the resist pattern are included in the order described above. By the above method, a wiring board having a desired conductor pattern formed on the substrate can be obtained.

The laminating step, the exposing step, and the developing step are the same as in the above <resist pattern forming method>. After the resist pattern is formed by the above-described resist pattern forming method, the wiring board having the conductor pattern formed on the substrate can be obtained through the following conductor pattern forming step and peeling step.
In the conductor pattern forming step, a conductor pattern can be formed on the substrate surface (for example, a copper surface) exposed by the developing step on the substrate on which the resist pattern is formed, using a known etching method or plating method.

The conductor pattern (wiring) formed by the method for forming a conductor pattern of the present embodiment as described above has a very small side etch amount. That is, in the formation of the conductive pattern by etching, the conductive material that should be etched only in the vertical direction by the etching solution is also etched in the horizontal direction, and the top width of the obtained conductive pattern is smaller than the base width of the resist film. Side etch "may occur. However, according to the method using the photosensitive element of this embodiment, it is possible to obtain a conductor pattern in which the amount of side etching is extremely reduced.

Specifically, the side etch amount of the resist pattern obtained using the photosensitive resin composition of the present embodiment is preferably 8 μm or less. More preferably, it is 7 μm or less. This provides an advantage that fine wiring can be formed, which is preferable.

The photosensitive resin composition, photosensitive element, and conductor pattern forming method in the present embodiment are extremely suitable for the production of, for example, a printed wiring board, a lead frame, a substrate having an uneven pattern, a semiconductor package, a touch panel sensor, and the like. Can be applied to.

<Touch panel sensor>
The method for forming the photosensitive resin composition, the photosensitive element, and the conductor pattern in the present embodiment is particularly suitable for manufacturing a touch panel sensor. The touch panel sensor is manufactured by forming a lead-out wiring composed of a conductor pattern formed by the above method on a flexible base material having a sputtered copper layer. And a touch panel can be obtained by laminating | stacking a liquid crystal display element, said touch-panel sensor, and glass in this order.

The evaluation values of the various parameters described above are measurement values measured according to the measurement methods in the examples described later unless otherwise specified.

Hereinafter, the photosensitive resin composition of the present embodiment will be specifically described by way of examples.
The sample preparation methods and the sample evaluation methods in Examples and Comparative Examples are as follows.

<Weight average molecular weight and degree of dispersion>
The sample was measured by gel permeation chromatography (GPC), and using a calibration curve of polystyrene (Shodex STANDARD SM-105 manufactured by Showa Denko KK), the weight average molecular weight (Mw), number average molecular weight (Mn), and The degree of dispersion (Mw / Mn) was calculated.
Specifically, the measurement was performed under the following conditions using gel permeation chromatography manufactured by JASCO Corporation.
Differential refractometer: RI-1530
Pump: PU-1580
Degasser: DG-980-50
Column oven: CO-1560
Column: KF-8025, KF-806M × 2, and KF-807 connected in series in this order Eluent: THF

<Acid equivalent>
The acid equivalent means the mass (gram) of a polymer having 1 equivalent of a carboxyl group in the molecule. Hiranuma Sangyo Co., Ltd. Hiranuma automatic titrator (COM-555) was used, and the acid equivalent was measured by potentiometric titration using a 0.1 mol / L aqueous sodium hydroxide solution.

<Glass transition temperature (Tg _total )>
(A) a glass transition temperature _{(Tg total)} of the alkali-soluble polymer, using literature values described above as Tg _i for each comonomer, was calculated by the equation (I).

<Production of photosensitive element>
Each component shown in Table 1 was mixed, and methyl ethyl ketone (MEK) was further added to prepare a photosensitive resin composition having a solid content concentration of 61% by mass.
The obtained photosensitive resin composition was uniformly coated on a polyethylene terephthalate film (product name “FB40”, manufactured by Toray Industries, Inc.) having a thickness of 16 μm as a support, and then adjusted to 95 ° C. The photosensitive resin composition layer having a thickness of 10 μm was formed on the support by heating and drying in a warm drier for 2 minutes.
Next, a 33 μm-thick polyethylene film (product name “GF-858”, manufactured by Tamapoly Co., Ltd.), which is a protective layer, is attached to the surface of the photosensitive resin composition layer opposite to the support, thereby providing a photosensitive layer. A sex element was obtained.

<Substrate used for evaluation>
As a substrate for evaluation, a flexible base material in which ITO and thin film copper of 5 μm or less were deposited in this order on PET was used.

<Laminate>
While peeling the polyethylene film of the photosensitive element obtained in each example or comparative example on the substrate, a hot roll laminator (Asahi Kasei Co., Ltd., AL-70) was used to roll temperature 105 ° C., air pressure 0.35 MPa. And laminating at a laminating speed of 1.5 m / min.

<Exposure>
Using a chrome glass mask, exposure was carried out with a parallel light exposure machine (Oak Co., Ltd., HMW-801) using a Stuffer 21-step tablet with an exposure amount of 4 steps.

<Development>
After peeling off the support from the photosensitive resin composition layer after exposure, a minimum development time of a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. using an alkali developer (produced by Fuji Kiko Co., Ltd., dry film developer). The unexposed portion of the photosensitive resin composition layer was dissolved and removed by spraying twice as long as. After the development, a substrate having an evaluation cured film was obtained by performing a water washing treatment.
The minimum development time refers to the minimum time required until the unexposed portion of the photosensitive resin composition layer is completely dissolved and removed.

<Side etch amount>
For the evaluation of the side etch amount, a laminate substrate after 15 minutes had elapsed after the <Lamination> was used.
The laminate substrate was exposed to a pattern of line / space = 30 μm / 30 μm and then developed by the method described in <Development> above.
First, the resist bottom width Wb of the pattern was measured with an optical microscope.
Next, for the substrate having this line / space pattern, 1.5 times the minimum etching time under the conditions of hydrochloric acid concentration 2 mass%, ferric chloride 2 mass%, and temperature 30 ° C. using the dipping method. Etched. Here, the minimum etching time refers to the minimum time required for the copper foil on the substrate to be completely dissolved and removed under the above conditions.
After the etching, an NaOH aqueous solution having a concentration of 3% by mass was used as a peeling station, and the top width Wt of the copper line pattern obtained by peeling off the cured film on the substrate at a temperature of 50 ° C. was measured with an optical microscope.
And the following formula:
Side etch (μm) = (Wb-Wt) / 2
Was used to calculate the amount of side etch.

<Examples 1 to 13 and Comparative Examples 1 to 3>
The composition of the photosensitive resin composition used in Examples and Comparative Examples is shown in Table 1.
Details of each component name described in Table 1 are shown in Table 2, respectively. The amount of each component in Table 1 is in mass parts in terms of solid content.
The evaluation results of the amount of side etching performed using each composition are shown in Table 1.

<Evaluation example of line width uniformity>
The compositions prepared in Examples 2 and 9 and Comparative Examples 1 and 2 were evaluated for line width uniformity.
For the evaluation of the line width uniformity, the line / space formed in the evaluation of <side etching amount> = 30 μm / 30 μm copper line pattern was observed with an optical microscope over a range of 6 mm in length, and the thickest line width Wmax And the narrowest line width Wmin, and the difference Wmax−Wmin was evaluated. The evaluation results are shown in Table 3.

<Evaluation example of resolution and adhesion>
The compositions prepared in Examples 2 and 10 to 13 were evaluated for resolution and adhesion by the following methods.
[Resolution]
An evaluation substrate 15 minutes after lamination is exposed through a chromium glass mask having a number of line patterns with a ratio of 1: 1 between the exposed area and the unexposed area at different mask widths, and then a minimum development time of 2 Development was performed twice as long to obtain a cured resist line. At this time, the minimum mask width in which the obtained cured resist line was normally formed was evaluated as a resolution value.
The term “cured resist line is normally formed” means that both the fall of the line pattern and the close contact between adjacent line patterns are not observed.

[Adhesion]
An evaluation substrate 15 minutes after laminating is exposed through a chromium glass mask having a number of line patterns with a ratio of 1: 100 between the exposed area and the unexposed area at different mask widths, and then the minimum development time of 2 Development was performed twice as long to obtain a cured resist line. At this time, the minimum mask width in which the obtained cured resist line was normally formed was evaluated as an adhesion value.

Claims (11)

(A) an alkali-soluble polymer, (B) a compound having an ethylenic double bond, and (C) a photopolymerization initiator,
The (A) alkali-soluble polymer is represented by the following formula (I):

{In Formula (I), _Wi is the mass of each comonomer constituting the alkali-soluble polymer,
Tg _i is the glass transition temperature when the respective comonomers constituting the alkali-soluble polymer is a homopolymer,
W _total is the total mass of the alkali-soluble polymer, and n is the number of comonomer types constituting the alkali-soluble polymer. }, The glass transition temperature determined by
The compound (B) having an ethylenic double bond contains a compound having an ethylenic double bond and a triazine-trione structure.
The photosensitive resin composition characterized by the above-mentioned. The photosensitive compound according to claim 1, wherein the compound (B) having an ethylenic double bond and a triazine-trione structure in the compound having an ethylenic double bond is an isocyanurate compound having an ethylenic double bond. Resin composition. The photosensitive resin composition according to claim 1 or 2, wherein the compound (B) having an ethylenic double bond further comprises a compound obtained by modifying bisphenol A. The compound obtained by modifying bisphenol A in the compound (B) having an ethylenic double bond has an ethylenic double bond at both ends of polyethylene glycol obtained by adding 10 mol or more and 30 mol or less of ethylene oxide to bisphenol A. The photosensitive resin composition of Claim 3 which is a compound. The photosensitive resin composition according to any one of claims 1 to 4, wherein the (C) photopolymerization initiator contains a hexaarylbiimidazole compound. 6. The photosensitive resin composition according to claim 1, further comprising a leuco dye. The (A) alkali-soluble polymer is
7. The method according to claim 1, comprising (A-1) an alkali-soluble polymer having a weight average molecular weight of 50,000 or more, and (A-2) an alkali-soluble polymer having a weight average molecular weight of less than 50,000. A photosensitive resin composition according to claim 1. The photosensitive resin composition according to any one of claims 1 to 7, wherein the ethylenic double bond concentration is 1.1 mmol / g or more based on the solid content of the photosensitive resin composition. 9. A photosensitive element comprising a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 8 on a support. A lamination step of forming a photosensitive resin composition layer on a substrate using the photosensitive element according to claim 9, an exposure step of exposing the photosensitive resin composition layer, and the photosensitive resin composition layer A resist pattern forming method comprising: a developing step of forming a resist pattern by removing an unexposed portion with a developer. A laminating step of forming a photosensitive resin composition layer on a substrate using the photosensitive element according to claim 9, an exposure step of exposing the photosensitive resin composition layer, an unexposed portion of the photosensitive resin composition layer. A developing step of forming a resist pattern by removing the exposed portion with a developer, a conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed, and a peeling step of peeling off the resist pattern. A method for manufacturing a wiring board.