JP6690128B2 - Photosensitive resin composition, photosensitive element, method for producing substrate with resist pattern, method for producing printed wiring board and method for producing touch panel - Google Patents

Description

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

  The touch sensor part of the touch panel has a sensor part that detects position information due to contact with a human finger, and a lead-out wiring part for transmitting the position information to an external element in a range (view area) where visual information is displayed. It is configured to be equipped.

  A pattern of an electrode having a small amount of visible light absorption and scattering and having conductivity is formed on the sensor portion. In addition, a metal having a small resistance value is used for each wiring of the lead wiring portion.

  Such a sensor part and a lead-out wiring part are manufactured as shown in FIG. 4 using, for example, a negative photosensitive resin composition. Note that FIG. 4 is a schematic cross-sectional view showing an example of a method for manufacturing the touch sensor unit of the touch panel. First, a photosensitive layer 16 is formed by coating a photosensitive resin composition on a supporting substrate 12 (film substrate such as polyethylene terephthalate or glass substrate) having a transparent conductive layer 14 (photosensitive layer forming step) (FIG. 4). (A)). Next, an actinic ray is irradiated to a predetermined portion of the photosensitive layer 16 to cure the exposed portion (exposure step). After that, the uncured portion is removed from the transparent conductive layer 14 to form a resist pattern containing a cured product of the photosensitive resin composition on the transparent conductive layer 14 (developing step) (FIG. 4B). An etching process is performed on the resist pattern to remove a part of the transparent conductive layer 14 from the support base 12 to form a pattern of the transparent conductive layer at the sensor portion (etching step) (FIG. 4C). ). Next, the resist is peeled from the transparent conductive layer 14 and removed (peeling step) (FIG. 4D). Subsequently, in order to form the lead wiring 18 from the pattern of the transparent conductive layer of the formed sensor portion, the touch sensor portion is manufactured by forming by screen printing using silver paste or the like (FIG. 4 (e)). .

  In order to manufacture a touch sensor unit having a small L / S (line width / space width) with a lead wiring pattern and a narrow lead wiring pitch, a method of forming the touch sensor portion using a photolithography technique has been proposed. (For example, see Patent Document 1). In this method for manufacturing a touch sensor unit, first, a first photosensitive layer is formed on a supporting substrate having a transparent conductive layer and a metal layer by using a photosensitive resin composition (first photosensitive layer forming step). ). Next, by irradiating a predetermined portion of the photosensitive layer with an actinic ray to cure the exposed portion (first exposure step), and then removing the uncured portion from the metal layer, the photosensitive layer is exposed to light. A resist pattern containing a cured product of the resin composition is formed (first developing step). Next, the metal layer and the transparent conductive layer are removed by an etching process (first etching step). Next, the resist pattern is peeled off and removed from the metal layer (first peeling step). Then, a second photosensitive layer is newly formed on the metal layer using the photosensitive resin composition (second photosensitive layer forming step). Next, a predetermined portion of the photosensitive layer is irradiated with actinic rays to cure the exposed portion (second exposure step), and then the uncured portion is removed from the metal layer to form a resist pattern on the metal layer. Are formed (second developing step). Next, only the metal layer where the unnecessary resist pattern is not formed in the sensor part is removed by the etching process (second etching step), and finally the resist pattern is peeled and removed to manufacture the touch sensor part. To do.

  In such a method of manufacturing a touch sensor unit, it is possible to reduce L / S to 30/30 (unit: μm) or less in principle by using a photolithography technique, and to reduce the thickness and weight of a touch panel. You can contribute greatly.

  Indium tin oxide (ITO), for example, is used for the transparent conductive layer. As the ITO, for example, amorphous ITO is used from the viewpoint of ease of etching treatment. However, since amorphous ITO has a high resistance value, the resistance value is lowered by, for example, crystallizing the ITO by heating (annealing) treatment. However, with the recent trend toward thinner and lighter touch panels, it has been required to use a film base material as a support base material for the touch panel portion. When a film base material is used as the supporting base material, annealing treatment causes shrinkage of the film base material and deteriorates dimensional stability. Therefore, it is necessary to use crystalline ITO as the transparent conductive layer before forming the pattern of the transparent conductive layer.

  Amorphous ITO can be sufficiently dissolved with a weak acid such as oxalic acid, while crystalline ITO contains a strong acid such as concentrated hydrochloric acid (> 20% by mass) or a mixed acid containing phosphoric acid, acetic acid and nitric acid. It is necessary to use and etch under heating conditions (about 40 to 50 ° C.). Therefore, it is necessary that the photosensitive resin composition used has high acid resistance, that is, the photosensitive layer does not deteriorate even by etching using a strong acid.

  As a technique for improving acid resistance (adhesion after immersion in strong acid), a photosensitive resin composition containing a specific epoxy compound, a photopolymerizable compound and a photopolymerization initiator as essential components has been proposed (for example, , Patent Document 2).

Japanese Patent No. 4855536 Japanese Patent No. 4219641

  However, conventional photosensitive resin compositions do not have sufficient resistance to an etching solution of a strong acid such as a mixed acid containing phosphoric acid, acetic acid and nitric acid, and when immersed in an etching solution, the photosensitive layer deteriorates. However, it may peel off.

  The present disclosure has been made in order to solve such a problem, and even when a coating film having a thickness of 15 μm or less is formed, it has a sufficiently high acid resistance against the above-described etching solution. And it aims at providing the photosensitive resin composition for etching masks which can form the resist pattern which has adhesiveness.

  As a result of intensive studies to solve the above problems, the present inventors have found a photosensitive resin composition having excellent properties.

  That is, the present disclosure provides (A) component: a resin having a phenolic hydroxyl group, (B) component: a compound having one or more functional groups selected from a methylol group, an alkoxyalkyl group, and a glycidyloxy group, and Provided is a photosensitive resin composition for an etching mask, which comprises (C) component: a photosensitive acid generator, and the content of a compound having an ethylenically unsaturated group is 20% by mass or less based on the total amount of the composition. To do.

  The component (B) preferably has two or more of the above functional groups.

  The present disclosure also provides a photosensitive element including a support and a photosensitive layer formed on the support, the photosensitive layer including the photosensitive resin composition according to the present disclosure described above.

  Further, the present disclosure includes a step of applying the above-described photosensitive resin composition according to the present disclosure onto a substrate, drying the photosensitive resin composition to form a photosensitive layer, and exposing the photosensitive layer to a predetermined pattern. A method for producing a substrate having a resist pattern, comprising: a step of performing a post-exposure heat treatment (hereinafter, this heat treatment is also referred to as “post-exposure bake”); The present invention also provides a method for manufacturing a printed wiring board, which includes the step of performing an etching process on a substrate with a resist pattern manufactured by the manufacturing method to form a conductor pattern.

  Further, the present disclosure provides a step of forming a photosensitive layer on a substrate by using the above-described photosensitive element according to the present disclosure, and exposing the photosensitive layer to a predetermined pattern, and performing a post-exposure heat treatment (post-exposure bake). And a step of developing the photosensitive layer after heat treatment, and a method for producing a resist pattern-provided substrate, and subjecting the resist pattern-provided substrate obtained by the production method to an etching treatment. Provided is a method for manufacturing a touch panel, including the step of forming a conductor pattern by using

  According to the present disclosure, even when a coating film having a thickness of 15 μm or less is formed, sufficiently high acid resistance and adhesion to an etching solution of a strong acid such as a mixed acid containing phosphoric acid, acetic acid and nitric acid. It is possible to provide a photosensitive resin composition for an etching mask, which can form a resist pattern having:

It is a schematic cross section which shows one Embodiment of the photosensitive element which concerns on this indication. It is a schematic cross section which shows one aspect of the manufacturing method of the touch panel which concerns on this indication. It is a top view showing one mode of a touch panel concerning this indication. It is a schematic cross section which shows an example of the manufacturing method of a touch panel.

  Hereinafter, one embodiment of the present disclosure will be specifically described, but the present disclosure is not limited thereto.

  In the present specification, the term “layer” includes not only the structure of the shape formed on the entire surface but also the structure of a part of the shape when observed as a plan view. In the present specification, the term “process” is used not only as an independent process but also in the case where the process is not clearly distinguishable from other processes, as long as the intended purpose of the process is achieved, included. In the present specification, the numerical range indicated by "to" indicates a range including the numerical values before and after "to" as the minimum value and the maximum value, respectively.

[Photosensitive resin composition for etching mask]
The photosensitive resin composition for an etching mask according to the present embodiment (hereinafter sometimes simply referred to as “photosensitive resin composition”) includes (A) component: a resin having a phenolic hydroxyl group, and (B) component: methylol. Group, an alkoxyalkyl group, and a compound having one or more functional groups selected from glycidyloxy groups, and a component (C): a photosensitive acid generator, and a compound having an ethylenically unsaturated group Is 20% by mass or less based on the total amount of the composition. The photosensitive resin composition according to the present embodiment means that it can be used for forming a mask during etching, and can be said to be a “photosensitive resin composition for etching mask formation”. In addition, in this specification, these components may only be called a (A) component, a (B) component, a (C) component, etc.

  The reason why the photosensitive resin composition according to the present embodiment is capable of forming a pattern having a sufficiently high acid resistance with respect to an etching solution of a strong acid such as a mixed acid containing phosphoric acid, acetic acid, and nitric acid, and the like. Infer as follows. First, most conventional etching mask resists employ a system for curing an acrylic resin and a photopolymerizable (meth) acrylic monomer. On the other hand, the present disclosure adopts a system for curing a resin having a phenolic hydroxyl group and a cationically polymerizable monomer. The resist pattern obtained from the latter system has significantly improved hydrophobicity compared to the resist pattern obtained from the former system, so that the intrusion of the etching solution into the film is suppressed, and the resist pattern formed by the etching solution is suppressed. It is thought that the deterioration of can be suppressed.

  Further, the photosensitive resin composition according to the present embodiment, if necessary, contains (D) component: solvent, (E) component: silane coupling agent, (F) component: sensitizer, and the like. You can also

<(A) component>
The photosensitive resin composition according to this embodiment contains a resin having a phenolic hydroxyl group. The resin having a phenolic hydroxyl group is not particularly limited, but a resin soluble in an alkaline aqueous solution is preferable, and a novolac resin is particularly preferable. Such a novolac resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst.

  Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3. -Xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol , Catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like.

  Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

  Specific examples of the novolac resin include phenol / formaldehyde condensed novolac resin, cresol / formaldehyde condensed novolac resin, and phenol-naphthol / formaldehyde condensed novolac resin.

  Examples of the component (A) other than the novolac resin include polyhydroxystyrene and its copolymer, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, and phenol-dicyclopentadiene condensation resin. To be The component (A) may be used alone or in combination of two or more.

  The weight average molecular weight of the component (A) is preferably 100,000 or less, and more preferably 1,000 to 80,000, from the viewpoint of further excellent resolution, developability, thermal shock resistance, heat resistance and the like of the obtained cured film. It is more preferably 2000 to 50000, further preferably 2000 to 20000, particularly preferably 5000 to 15000.

In the present embodiment, the weight average molecular weight of each component can be measured, for example, by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene under the following conditions.
Equipment used: Hitachi L-6000 (Hitachi, Ltd.)
Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (Hitachi Chemical Co., Ltd., trade name, 3 in total)
Column specifications: 10.7mmφ x 300mm
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 1.75 mL / min Detector: L-3300RI (manufactured by Hitachi, Ltd.)

  The content of the component (A) is 30 to 90 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition (however, the component (D) is excluded when the component (D) is used). It is preferably 40 to 80 parts by mass. When the content of the component (A) is within this range, the film formed using the obtained photosensitive resin composition tends to have further excellent developability with an alkaline aqueous solution.

<(B) component>
The photosensitive resin composition according to this embodiment contains a compound having one or more functional groups selected from a methylol group, an alkoxyalkyl group, and a glycidyloxy group. The alkoxyalkyl group means a group in which an alkyl group is bonded to an alkyl group via an oxygen atom. The two alkyl groups may be different from each other, and are, for example, alkyl groups having 1 to 10 carbon atoms. Further, the compound having a methylol group or the compound having an alkoxyalkyl group as the component (B) may further have at least one selected from the group consisting of an aromatic ring, a heterocycle and an alicycle. Here, the aromatic ring means a hydrocarbon group having aromaticity (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring. The heterocycle means a cyclic group having at least one nitrogen atom, oxygen atom, sulfur atom or the like (for example, a cyclic group having 3 to 10 carbon atoms), and examples thereof include a pyridine ring and an imidazole ring. . Further, the alicycle means a cyclic hydrocarbon group having no aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), and examples thereof include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring and A cyclohexane ring is mentioned.
As the compound having a methylol group or the compound having an alkoxyalkyl group, a compound having a hydroxymethylamino group or an alkoxymethylamino group is preferable. Further, the compound having a methylol group or the compound having an alkoxyalkyl group may further have a phenolic hydroxyl group (however, the component (A) is not included).

  By containing the component (B), it is possible to react the component (B) with the component (A) to form a bridged structure when the photosensitive layer after exposure is heated, and / or (B). The components) can be homopolymerized with each other, and the photosensitive layer can be insolubilized. The component (B) can be used alone or in combination of two or more.

  As will be described later, by containing the component (C) in the photosensitive resin composition, an acid is generated by irradiation with actinic rays or the like. By employing a catalyst of the generated acid, a negative pattern is formed by the reaction between the alkoxyalkyl groups in the component (B) or between the alkoxyalkyl groups in the component (B) and the component (A) with dealcoholization. can do. Further, by the catalytic action of the generated acid, the methylol groups in the component (B) or the methylol groups in the component (B) react with the component (A) with dealcoholization to form a negative pattern. Can be formed. Further, a negative pattern can be formed by the addition reaction between the glycidyloxy groups in the component (B) or between the glycidyloxy groups in the component (B) and the component (A).

  Examples of the compound having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, and (poly) (N -Hydroxymethyl) urea and the like. Further, nitrogen-containing compounds obtained by alkyl etherifying a part or all of hydroxymethylamino groups of these compounds may be used. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, or a mixture thereof, which may contain an oligomer component partially self-condensed. Specific examples thereof include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl) urea, and the like.

Specifically, the compound having an alkoxymethylamino group is preferably a compound represented by the general formula (1) or a compound represented by the general formula (2).

In general formula (1), a plurality of R's each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

  In general formula (2), a plurality of R's each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

  Among the compounds having a methylol group or the compounds having an alkoxyalkyl group, the compounds further having a phenolic hydroxyl group are not exposed to the reaction with the component (C) or the component (A), and are unexposed during development with an alkaline aqueous solution. The dissolution rate of the part can be increased, and the sensitivity can be improved. The molecular weight of the compound further having a phenolic hydroxyl group is preferably 94 to 2000 in terms of weight average molecular weight in consideration of improving the solubility in alkaline aqueous solution, photosensitivity, mechanical properties and the like in a balanced manner, and 108 to It is more preferably 2000 and even more preferably 108 to 1500. When it is difficult to measure a compound having a low molecular weight by the above-mentioned weight average molecular weight measuring method, the molecular weight can be measured by another method and the average thereof can be calculated.

一般式（３）中、Ｚは単結合又は２価の有機基を示し、Ｒ^２４及びＲ^２５はそれぞれ独立に水素原子又は１価の有機基を示し、Ｒ^２６及びＲ^２７はそれぞれ独立に１価の有機基を示し、ａ及びｂはそれぞれ独立に１〜３の整数を示し、ｃ及びｄはそれぞれ独立に０〜３の整数を示す。ここで、１価の有機基としては、例えば、メチル基、エチル基、プロピル基等の炭素原子数が１〜１０であるアルキル基；ビニル基等の炭素原子数が２〜１０であるアルケニル基；フェニル基等の炭素原子数が６〜３０であるアリール基；これらの炭化水素基の水素原子の一部又は全部をフッ素原子等のハロゲン原子で置換した基が挙げられる。Ｒ^２４〜Ｒ^２７が複数ある場合には、互いに同一でも異なっていてもよい。 As the compound further having the phenolic hydroxyl group, a conventionally known compound can be used. However, the compound represented by the following general formula (3) has the effect of promoting the dissolution of the unexposed area and the curing of the photosensitive resin film. It is preferable because it has an excellent balance of the effect of preventing the melting of

In formula (3), Z represents a single bond or a divalent organic group, R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent organic group, and R ²⁶ and R ²⁷ each independently represent 1 Represents a valent organic group, a and b each independently represent an integer of 1 to 3, and c and d each independently represent an integer of 0 to 3. Here, examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, and a propyl group; an alkenyl group having 2 to 10 carbon atoms such as a vinyl group. An aryl group having 6 to 30 carbon atoms such as a phenyl group; a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom. When there are a plurality of R ^{24 to} R ²⁷ , they may be the same or different.

The compound represented by the general formula (3) is preferably the compound represented by the general formula (4).

In formula (4), X ¹ represents a single bond or a divalent organic group, and a plurality of R's each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

Moreover, you may use the compound represented by General formula (5) as a compound which further has the said phenolic hydroxyl group.

  In general formula (5), a plurality of R's each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

Further, in the general formula (3), the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. The divalent organic group represented by Z includes an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group; an alkylidene having 2 to 10 carbon atoms such as an ethylidene group. Group; arylene group having 6 to 30 carbon atoms such as phenylene group; group obtained by substituting a part or all of hydrogen atoms of these hydrocarbon groups with halogen atoms such as fluorine atom; sulfonyl group; carbonyl group; ether bond Sulfide bond; amide bond and the like. Among these, Z is preferably a divalent organic group represented by the following general formula (6).

In formula (6), X ² represents a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), A group in which a part or all of hydrogen atoms are replaced with a halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond or an amide bond is shown. R ²⁸ represents a hydrogen atom, a hydroxyl group (hydroxy group), an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms) or a haloalkyl group, and e represents an integer of 1 to 10. A plurality of R ²⁸ and X ² may be the same or different from each other. Here, the haloalkyl group means an alkyl group substituted with a halogen atom.

The compound having a glycidyloxy group preferably has three or more glycidyloxy groups in the molecule. The upper limit of the number of functional groups is not particularly limited, but is 12 for example. Specific examples of the compound having a glycidyloxy group as the component (B) include compounds represented by the general formulas (7) to (10).

In formulas (7) to (10), R ¹ , R ⁵ , R ¹⁶ and R ¹⁹ each independently represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group or a group represented by the following formula (11). ^{shown, R 2, R 3, R} 4, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 17, R 18, and ^{R 20} Each independently represents a hydroxyl group, a glycidyloxy group, a group represented by the following general formula (12) or a group represented by the following general formula (13).

In the general formula (11), R ²¹ represents a hydroxyl group or a glycidyloxy group.

In General Formula (12), R ²² represents a hydroxyl group or a glycidyloxy group, and n represents an integer of 1 to 10.

In formula (13), R ²³ represents a hydroxyl group or a glycidyloxy group, and m represents an integer of 1 to 10.

  Examples of the compound having a glycidyloxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl. Ether, glycerin diglycidyl ether, dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerin triglycidyl ether, Glycerol propoxyle Triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, diglycidyl 1,2-cyclohexane dicarboxylate, and the like. These compounds having a glycidyloxy group can be used alone or in combination of two or more.

  Among the compounds having a glycidyloxy group, trimethylolethane triglycidyl ether or trimethylolpropane triglycidyl ether is preferable in terms of excellent sensitivity and resolution.

  The compound having a glycidyloxy group is, for example, Epolite 40E, Epolite 100E, Epolite 70P, Epolite 200P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (above, Kyoeisha Chemical Co., Ltd., trade name), alkyl type epoxy. Resin ZX-1542 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L and Denacol EX-850L (above, Nagase Chemtec Co., Ltd.) Manufactured, trade name).

  The content of the component (B) is preferably 5 to 60 parts by mass, more preferably 10 to 45 parts by mass, and 10 to 35 parts by mass with respect to 100 parts by mass of the component (A). Is particularly preferred. When the content of the component (B) is 5 parts by mass or more, the reaction in the exposed area is sufficient, so that the resolution is unlikely to decrease and the chemical resistance tends to be good. If so, the photosensitive resin composition tends to be formed into a film on a desired support, and the resolution tends to be improved. In this specification, 100 parts by mass of the component (A) means 100 parts by mass of the solid content of the component (A).

<(C) component>
The photosensitive resin composition according to this embodiment contains a photosensitive acid generator. The photosensitive acid generator is a compound that generates an acid by irradiation with actinic rays or the like. Due to the catalytic effect of the acid generated from the light-sensitive acid generator, not only the components (B) react with each other, but the component (B) also reacts with the component (A), and thus the photosensitive resin composition of the developer is prepared. By reducing the solubility, a negative pattern can be formed.

  The component (C) is not particularly limited as long as it is a compound capable of generating an acid upon irradiation with actinic rays and the like. For example, onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds Etc. Above all, it is preferable to use an onium salt compound or a sulfonimide compound from the viewpoint of easy availability. In particular, when a solvent is used as the component (D), it is preferable to use an onium salt compound from the viewpoint of solubility in the solvent. The specific examples are shown below.

  Examples of onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts and pyridinium salts. Specific preferred examples of the onium salt compound include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate and the like diaryliodonium salts; triphenylsulfonium Triarylsulfonium salts such as trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate; 4-t-butylphenyl-diphenylsulfonium trifluoromethanesulfonate; 4-t-butylphenyl-diphenylsulfonium p- Toluene sulfonate; 4,7 And di -n- butoxy naphthyl tetrahydrothiophenium trifluoromethanesulfonate, and the like.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). (Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (p-toluenesulfonyloxy) -1,8- Examples include naphthalimide and N- (10-camphorsulfonyloxy) -1,8-naphthalimide.

  As the component (C), a compound having trifluoromethanesulfonate, hexafluoroantimonate, hexafluorophosphate or tetrafluoroborate as an anion is preferable in terms of further excellent sensitivity and resolution. The component (C) can be used alone or in combination of two or more.

  The content of the component (C) is, with respect to 100 parts by mass of the component (A), from the viewpoint of improving the sensitivity, resolution, pattern shape and the like of the photosensitive resin composition according to the present embodiment. The amount is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass.

<(D) component>
The photosensitive resin composition according to the present embodiment may further contain a solvent as the component (D) in order to improve the handleability of the photosensitive resin composition and adjust the viscosity and storage stability. You can The component (D) is preferably an organic solvent. The type of such an organic solvent is not particularly limited as long as it can exhibit the above performance, but for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoalkyl ether acetates such as ethylene glycol monoethyl ether acetate, etc. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc. propylene glycol monoalkyl ethers; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether Propylene glycol dialkyl ethers such as; Propylene glycol Propylene glycol monoalkyl ether acetates such as Cole monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, propione Acid carboxylic acid esters such as n-butyl acid and isobutyl propionate; methyl 3-methoxypropionate, 3-methoxy Other esters such as ethyl ropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; 2-butanone, 2-heptanone, 3 Ketones such as heptanone, 4-heptanone and cyclohexanone; amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; and lactones such as γ-butyrolactone. These organic solvents may be used alone or in combination of two or more.

  The content of the component (D) is preferably 30 to 200 parts by mass, more preferably 60 to 120 parts by mass, based on 100 parts by mass of the total amount of the photosensitive resin composition excluding the component (D). preferable.

<(E) component>
The photosensitive resin composition according to this embodiment may contain a silane coupling agent as the component (E). By including the component (E), it is possible to further improve the adhesion strength between the photosensitive layer and the base material after the resin pattern is formed.

  As the component (E), those which are generally available can be used, and examples thereof include alkylsilane, alkoxysilane, vinylsilane, epoxysilane, aminosilane, acryloylsilane, methacryloylsilane, mercaptosilane, sulfidesilane, isocyanatesilane and sulfa. Silane, styrylsilane and alkylchlorosilane can be used.

  Specific examples of the component (E) include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyl. Trimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, Diphenyldimethoxysilane, triphenylsilanol, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, n-octyl Methylchlorosilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane , 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , Bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Nyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples thereof include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane and aminosilane.

  As the component (E), an epoxysilane having one or more glycidyloxy groups is preferable, and an epoxysilane having a trimethoxysilyl group or a triethoxysilyl group is more preferable. Alternatively, acryloylsilane or methacryloylsilane may be used.

  The content of the component (E) is preferably 1 to 20 parts by mass, and more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the component (A).

<(F) component>
The photosensitive resin composition according to this embodiment may contain a sensitizer as the component (F). Examples of the sensitizer include 9,10-dibutoxyanthracene. The component (F) may be used alone or in combination of two or more. By containing the component (F), the photosensitivity of the photosensitive resin composition can be improved.

  The content of the component (F) is preferably 0.01 to 1.5 parts by mass, more preferably 0.05 to 0.5 part by mass, relative to 100 parts by mass of the component (A). .

  Further, the photosensitive resin composition according to the present embodiment contains a low molecular weight phenolic compound having a molecular weight of less than 1000 (hereinafter referred to as “phenolic compound (a)”) in addition to the component (A). Good. For example, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, tris (4-hydroxyphenyl) ) Ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6 -Bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) ) -1-Methylethyl} phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane and the like. These phenol compounds (a) may be in the range of 0 to 40 parts by mass, particularly 0 to 30 parts by mass, relative to 100 parts by mass of the component (A).

  In addition, the photosensitive resin composition according to the present embodiment may contain other components than the above components. Examples of other components include a suppressor of a reaction associated with irradiation with actinic rays, an adhesion aid, and the like.

  In the photosensitive resin composition according to the present embodiment, the content of the compound having an ethylenically unsaturated group needs to be 20% by mass or less based on the total amount of the composition. If the content of the compound having an ethylenically unsaturated group is 20% by mass or less based on the total amount of the composition, phosphoric acid, acetic acid, and nitric acid can be generated even if a coating film having a thickness of 15 μm or less is formed. It is possible to provide a photosensitive resin composition for an etching mask, which can form a resist pattern having sufficiently high acid resistance and adhesion to an etching solution of a strong acid such as a mixed acid containing.

  Examples of the compound having an ethylenically unsaturated group include a (meth) acrylate compound, a polymer having a (meth) acryloyl group, a compound having a vinyl group and a compound having an allyl group. It should be noted that any compound having an ethylenically unsaturated group, even if it corresponds to the above-mentioned component (A), component (B) and component (C), is considered to correspond to the compound. For example, pentaerythritol tri (meth) acrylate corresponds to the compound having the ethylenically unsaturated group.

[Photosensitive element]
Next, the photosensitive element according to this embodiment will be described.
The photosensitive element according to the exemplary embodiment includes a support and a photosensitive layer formed on the support, and the photosensitive layer includes the above-described photosensitive resin composition. The photosensitive element according to this exemplary embodiment may further include a protective layer on the photosensitive layer, the protective layer covering the photosensitive layer.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive element of the present disclosure. In the photosensitive element 10 shown in FIG. 1, a support 2, a photosensitive layer 4 formed using a photosensitive resin composition, and a protective layer 6 are laminated in this order. The photosensitive layer 4 can also be referred to as a coating film of a photosensitive resin composition. The coating film is one in which the photosensitive resin composition is in an uncured state.

  The photosensitive element 10 can be obtained as follows, for example. A photosensitive layer is formed by applying a coating liquid, which is a photosensitive resin composition containing an organic solvent, onto a support 2 to form a coating layer, and drying the coating layer (at least a part of the organic solvent is removed from the coating layer). 4 is formed. Then, by covering the surface of the photosensitive layer 4 opposite to the support 2 with the protective layer 6, the support 2, the photosensitive layer 4 laminated on the support 2, and the photosensitive layer 4 are formed. A photosensitive element 10 is obtained, which comprises a protective layer 6 laminated. The photosensitive element 10 does not necessarily have to include the protective layer 6.

  As the above-mentioned support, for example, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, or polyethylene can be used. The thickness of the support (polymer film) is preferably 5 to 25 μm. In addition, one of the above-mentioned polymer films may be used as a support and the other as a protective film, which is laminated on both surfaces of the photosensitive layer so as to sandwich the photosensitive layer.

  As the protective layer, for example, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, or polyethylene can be used.

  The photosensitive layer can be formed by applying the photosensitive resin composition onto a support or a protective layer. Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method and a spin coating method. Although the thickness of the photosensitive layer varies depending on the use, it is preferably 1 to 100 μm, more preferably 1 to 50 μm, and particularly preferably 1 to 30 μm after drying the photosensitive layer.

[Method for producing base material with resist pattern]
Next, a method for manufacturing the substrate with a resist pattern according to this embodiment will be described.
The method for producing a substrate with a resist pattern according to the present embodiment includes a step of forming a photosensitive layer, a step of exposing the photosensitive layer to a predetermined pattern and performing a post-exposure heat treatment (post-exposure bake), and a post-heat treatment. And developing the photosensitive layer. As the step of forming the photosensitive layer, the step of applying the above-mentioned photosensitive resin composition onto a substrate and drying the photosensitive resin composition to form a photosensitive layer, and the above-described step on the substrate. The process of forming a photosensitive layer using a photosensitive element is mentioned.

  In the method of manufacturing a substrate with a resist pattern according to this embodiment, first, on a substrate (resin-coated copper foil, copper clad laminate, silicon wafer with a metal sputtered film, alumina substrate, etc.) on which a resist pattern is to be formed. Then, a photosensitive layer containing the above-mentioned photosensitive resin composition is formed. Examples of the method for forming the photosensitive layer include a method in which a photosensitive resin composition is applied (for example, applied) to a substrate, dried, and a solvent or the like is volatilized to form a coating film (photosensitive layer). Examples include a method of transferring the photosensitive layer in the sexual element onto a substrate.

  As a method for applying the above-mentioned photosensitive resin composition to a substrate, for example, a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method or the like can be used. Further, the thickness of the coating film can be appropriately controlled by adjusting the coating means and the solid content concentration and viscosity of the photosensitive resin composition.

Next, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. Examples of the actinic ray used for the exposure include a ray of a g-line stepper; an ultraviolet ray of a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an i-ray stepper, etc .; an electron beam; a laser beam and the like. The thickness is appropriately selected depending on the thickness of the photosensitive layer. For example, in the case of ultraviolet irradiation from a high pressure mercury lamp, the thickness of the photosensitive layer is about 100 to 5000 mJ / cm ² at a thickness of 10 to 50 μm.

  Further, a heat treatment (post-exposure bake) is performed after the exposure. By baking after exposure, the curing reaction of the components (A) and (B) by the acid generated from the photosensitive acid generator can be promoted. The conditions of the post-exposure bake differ depending on the composition of the photosensitive resin composition, the content of each component, the thickness of the photosensitive layer, etc., but it is usually preferable to heat at 70 to 150 ° C. for 1 to 60 minutes, and 80 to 120. It is more preferable to heat at 1 ° C for 1 to 60 minutes.

  Next, the exposed and / or post-exposure baked coating film is developed with an alkaline developer to dissolve and remove regions other than the cured part (unexposed part) to obtain a desired resist pattern. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The developing conditions are usually 20 to 40 ° C. and 1 to 10 minutes.

  Examples of the alkaline developer include alkaline aqueous solutions obtained by dissolving alkaline compounds such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and choline in water to a concentration of about 1 to 10% by mass, aqueous ammonia. And the like, such as an alkaline aqueous solution. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline aqueous solution. After developing with the alkaline developing solution, it is washed with water and dried. The alkaline developer is preferably an aqueous solution of potassium hydroxide or tetramethylammonium hydroxide in terms of excellent resolution.

[Method for manufacturing printed wiring board]
The photosensitive resin composition according to this embodiment can be suitably used, for example, for manufacturing a printed wiring board.

  The method for manufacturing a printed wiring board according to the present embodiment includes a step of forming a conductor pattern by performing an etching process on the resist-patterned base material manufactured by the above-described resist-patterned base material manufacturing method. In addition, you may provide the process of performing a plating process.

[Method of manufacturing touch panel]
The photosensitive resin composition according to this embodiment can be suitably used for manufacturing a touch panel.

  The touch panel manufacturing method according to the present embodiment includes a step of forming a conductor pattern by performing an etching process on the resist-patterned substrate manufactured by the above-described resist-patterned substrate manufacturing method. In addition, you may provide the process of performing a plating process.

  The etching process is performed on the transparent conductive layer, the metal layer and the like of the circuit forming substrate using the formed resist pattern as a mask. The touch panel is manufactured by forming a pattern of the lead-out wiring portion and the sensor portion by the etching process.

  FIG. 2 is a schematic cross-sectional view showing one aspect of the method for manufacturing the touch sensor unit of the touch panel of the present disclosure. The manufacturing method of the present embodiment is a laminated base material including a support base material 22, a transparent conductive layer 24 provided on one surface of the support base material 22, and a metal layer 26 provided on the transparent conductive layer 24, The first step of forming a resist pattern 29 containing a cured product of the photosensitive resin composition according to the present embodiment on the metal layer 26, and the metal layer 26 and the transparent conductive layer 24 are etched to form the transparent conductive layer 24. 2) and a second step of forming a laminated pattern (24 + 26 in FIG. 2D) composed of the remaining portion of the metal layer 26 and the remaining portion of the transparent conductive layer 24 by removing the metal layer from a part of the laminated pattern. And a third step of forming a transparent electrode layer and a metal wiring made of the remainder of the metal layer.

  In the first step, first, as shown in FIG. 2A, the support base material 22, the transparent conductive layer 24 provided on one surface of the support base material 22, and the transparent conductive layer 24 were provided. A photosensitive layer 28 containing a photosensitive resin composition is formed on the metal layer 26 of the laminated base material including the metal layer 26. The photosensitive layer 28 may include the above support on the surface opposite to the metal layer 26.

  Examples of the metal layer 26 include copper, an alloy of copper and nickel, a molybdenum-aluminum-molybdenum laminate, an alloy of silver, palladium, and copper. Among these, the metal layer 26 preferably contains copper or an alloy of copper and nickel from the viewpoint that the effect of the present disclosure can be more remarkably obtained.

  Examples of the transparent conductive layer 24 include amorphous ITO and crystalline ITO. The transparent conductive layer 24 preferably contains crystalline ITO from the viewpoint of eliminating the need for annealing.

  Then, a part of the photosensitive layer 28 is cured by irradiation with actinic rays and heating to form a cured product region of the photosensitive layer, and a region (uncured portion) other than the cured product region of the photosensitive layer is laminated substrate. Remove from above. As a result, as shown in FIG. 2B, the resist pattern 29 is formed on the laminated base material.

  In the second step, the metal layer 26 and the transparent conductive layer 24 in the area not masked by the resist pattern 29 are removed from the support base material 22 by the etching process.

  The method of etching treatment is appropriately selected depending on the layer to be removed. Examples of the etching solution for removing the metal layer include an aqueous solution of cupric chloride, an aqueous solution of ferric chloride, an aqueous solution of phosphoric acid, acetic acid, and nitric acid. Examples of the etching solution for removing the transparent conductive layer include oxalic acid aqueous solution, hydrochloric acid, aqua regia, and the like.

  When the transparent conductive layer 24 contains crystalline ITO, it is necessary to use a strong acid such as concentrated hydrochloric acid as an etching solution for removing the transparent conductive layer 24. However, in the manufacturing method of this embodiment, the resist pattern is Since the cured product of the photosensitive resin composition according to the present embodiment is included, the adhesiveness between the metal layer 26 and the resist pattern is secured even under the etching treatment with a strong acid, and peeling of the resist pattern is sufficiently suppressed.

  FIG. 2C is a diagram showing the state after the etching treatment. In FIG. 2C, a laminated body including the remaining portion of the metal layer 26, the remaining portion of the transparent conductive layer 24, and the resist pattern 29 is formed on the supporting base material 22. Has been formed. In the manufacturing method of the present aspect, the resist pattern 29 is removed from this laminated body.

  For removing (peeling) the resist pattern 29, for example, an aqueous solution having a stronger alkalinity than the alkaline developer described above can be used. Especially, it is preferable to use 1-20 mass% sodium hydroxide aqueous solution or 1-20 mass% potassium hydroxide aqueous solution, and to use 1-10 mass% sodium hydroxide aqueous solution or 1-10 mass% potassium hydroxide aqueous solution. More preferable. Examples of the method for removing the resist pattern include a dipping method and a spray method. These methods may be used alone or in combination.

  FIG. 2D is a diagram showing the state after the resist pattern 29 is peeled off. In FIG. 2D, a laminated pattern made up of the remaining portion of the metal layer 26 and the remaining portion of the transparent conductive layer 24 is formed on the supporting base material 22. Has been formed.

  In the third step, except for a part of the metal layer 26 for forming the metal wiring, the metal wiring made of the remaining portion of the metal layer 26 and the transparent electrode made of the remaining portion of the transparent conductive layer 24 are removed from the laminated pattern. To form. In this embodiment, the method of etching is adopted as the method of removing the metal layer 26 in the third step, but the method of removing the metal layer 26 in the third step is the method of removing the metal layer 26. Of these, any material can be used as long as it can remove a portion other than the portion for forming the metal wiring, and is not necessarily limited to etching.

  In the third step, first, the photosensitive layer 30 is formed on the laminated base material that has undergone the second step (FIG. 2E). Then, the photosensitive layer 30 is exposed and developed to form a resist pattern 31 containing a cured product of the photosensitive layer 30 (FIG. 2F). The photosensitive layer may be a layer made of the photosensitive resin composition according to this embodiment, or may be a layer containing a conventionally known photosensitive resin composition for an etching mask.

  Next, by etching, the metal layer 26 in a portion of the laminated pattern where the resist pattern 31 is not formed (a region not masked by the resist pattern 31) is removed. At this time, as the etching liquid, the same etching liquid as that for removing the metal layer described above can be used.

  2 (g) is a diagram showing the state after the etching treatment. In FIG. 2 (g), a transparent electrode made up of the remaining transparent conductive layer 24 is formed on the supporting base material 22, and a part of the transparent electrode is transparent. A laminated body including the metal layer 26 and the resist pattern 31 is formed on the electrode. By removing the resist pattern 31 from the laminated body, as shown in FIG. 2H, the transparent wiring made of the remaining portion of the transparent conductive layer 24 and the metal wiring made of the remaining portion of the metal layer 26 are formed on the supporting base material 22. And are formed.

[Touch panel]
FIG. 3 is a top view showing one aspect of a touch panel obtained by utilizing the present disclosure. In the touch panel 100, the X electrodes 52 and the Y electrodes 54, which are transparent electrodes, are alternately arranged in parallel, and the X electrodes 52 provided in the same row in the longitudinal direction are connected to each other by one lead wire 56, and The Y electrodes 54 provided in the same row in the width direction are connected to each other by one lead wiring 57.

  Although the preferred embodiment of the present disclosure has been described above, the present disclosure is not limited to the above embodiment.

  Hereinafter, the present disclosure will be described in detail with reference to Examples, but the present disclosure is not limited to these Examples. In the following examples and comparative examples, parts are used in the meaning of parts by mass unless otherwise specified.

[Examples 1 to 3 and Comparative Example 1]
<Preparation of photosensitive resin composition>
Compounds (B-1 to B-3) having two or more methylol groups, alkoxyalkyl groups or glycidyloxy groups per 100 parts by mass of the novolac resin (A-1), a photosensitive acid generator (C-1). , And the solvent (D-1) were blended in the amounts (unit: parts by mass) shown in Table 1 below to obtain a photosensitive resin composition.

<Preparation of photosensitive element>
The above-mentioned photosensitive resin composition was applied onto a polyethylene terephthalate film (manufactured by Teijin DuPont Films Ltd., product name: Purex A53, "Purex" is a registered trademark) (support) and the thickness of the photosensitive resin composition was The solution was applied so as to be uniform and dried for 10 minutes by a hot air convection dryer at 90 ° C. to form a photosensitive layer having a thickness of 15 μm after drying. A polyethylene film (manufactured by TamaPoly Co., Ltd., product name: NF-15) was attached to the photosensitive layer as a protective layer to obtain a photosensitive element in which the support and the photosensitive layer and the protective layer were sequentially laminated. It was

<Production of laminated base material>
As a film substrate (hereinafter, simply referred to as "substrate"), a transparent conductive layer made of crystalline ITO and a metal layer made of copper are formed on a polyethylene terephthalate film, and a metal layer is further formed on the transparent conductive layer. A metal layer made of an alloy of copper and nickel having an average thickness of 20 nm was formed on the surface of the above by a vacuum deposition method. After heating the film substrate to 80 ° C., the photosensitive element prepared above was laminated on the surface of the metal layer of the substrate to form a photosensitive layer on the substrate. Lamination was performed under conditions of a temperature of 110 ° C. and a laminating pressure of 0.4 MPa, with the photosensitive layer of the photosensitive element being in close contact with the surface of the metal layer of the substrate while removing the protective layer. Thus, a laminated base material was obtained in which the photosensitive layer and the support were laminated on the metal layer of the base material.

<Evaluation of etching liquid resistance>
The support of the laminated base material having a thickness of the photosensitive layer of 15 μm was peeled off, and then a glass mask having a square mask pattern of 5 cm in length and width was adhered to the short arc UV lamp (Oak Manufacturing Co., Ltd., product A parallel light exposure machine (trade name "EXM-1201" manufactured by Oak Manufacturing Co., Ltd.) using a name "AHD-5000R") as a light source is used to form a photosensitive layer so that the irradiation energy amount is 1000 mJ / cm ^2. Exposed. Subsequently, the exposed sample was heated on a hot plate at 100 ° C. for 5 minutes. Then, it was immersed in a 3 mass% potassium hydroxide aqueous solution for 1 minute to remove the unexposed portion. A sample having a square pattern of 5 cm in length and width obtained in the above step was heated to 25 ° C. or 50 ° C., a 25 mass% hydrochloric acid aqueous solution or phosphoric acid (50 mass%), acetic acid (25%), nitric acid (5%). It was immersed in the mixed aqueous solution for 10 minutes, and the presence or absence of peeling of the resist film and the extent to which the etching solution penetrated from the end of the resist pattern and the metal layer existing under the resist pattern was etched were evaluated as the side etching amount. . At this time, the smaller the side etching amount, the better. The evaluation results are shown in Table 1 below.

Ｂ−３：ペンタエリスリトールトリアクリレート（日本化薬（株）製、商品名：ＰＥＴ−３０）
Ｃ−１：トリアリールスルホニウム塩（サンアプロ（株）製、商品名：ＣＰＩ−３１０Ｂ）
Ｄ−１：メチルエチルケトン（和光純薬工業（株）製） The abbreviations in Table 1 are as follows.
A-1: Cresol novolac resin (manufactured by Asahi Organic Materials Co., Ltd., trade name: TR4020G)
B-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: MX-270)
B-2: Trimethylolpropane triglycidyl ether (manufactured by Nippon Steel & Sumitomo Metal Corporation, trade name: ZX-1542, see the following formula (14))

B-3: Pentaerythritol triacrylate (Nippon Kayaku Co., Ltd., trade name: PET-30)
C-1: Triarylsulfonium salt (manufactured by San-Apro Ltd., trade name: CPI-310B)
D-1: Methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.)

  As is clear from Table 1, Comparative Example 1 cannot withstand etching using a mixed aqueous solution of phosphoric acid, acetic acid, and nitric acid, and results in peeling. On the other hand, in Examples 1 to 3, peeling was not observed even in etching using a mixed aqueous solution of phosphoric acid, acetic acid, and nitric acid, and the side etching amount was sufficiently small, and it was found that excellent results were obtained. .

  2 ... Support, 4 ... Photosensitive layer, 6 ... Protective layer, 10 ... Photosensitive element, 12 ... Support base material, 14 ... Transparent conductive layer, 16 ... Photosensitive layer, 18 ... Lead wiring, 22 ... Support base material, 24 ... Transparent conductive layer, 26 ... Metal layer, 28 ... Photosensitive layer, 29 ... Resist pattern, 30 ... Photosensitive layer, 31 ... Resist pattern, 52 ... Transparent electrode (X electrode), 54 ... Transparent electrode (Y electrode), 56, 57 ... Lead wiring, 100 ... Touch panel.

Claims (6)

(A) component: a resin having a phenolic hydroxyl group,
Component (B): a compound represented by the following general formula (1) and a compound having a glycidyloxy group, and
Component (C): Photosensitive acid generator,
Contains
The compound having a glycidyloxy group contains trimethylolpropane triglycidyl ether,
The photosensitive acid generator comprises a triarylsulfonium salt,
A negative photosensitive resin composition for an etching mask, wherein the content of the compound having an ethylenically unsaturated group is 20% by mass or less based on the total amount of the composition.

[In the following general formula (1), plural R's each independently represent an alkyl group. ] A support and a photosensitive layer formed on the support,
The said photosensitive layer is a photosensitive element containing the photosensitive resin composition of Claim 1 . A step of applying the photosensitive resin composition according to claim 1 on a substrate and drying the photosensitive resin composition to form a photosensitive layer;
Exposing the photosensitive layer to a predetermined pattern, and performing a heat treatment after exposure,
A step of developing the photosensitive layer after the heat treatment,
A method for producing a substrate with a resist pattern, comprising: Forming a photosensitive layer on the substrate using the photosensitive element according to claim 2 ;
Exposing the photosensitive layer to a predetermined pattern, and performing a heat treatment after exposure,
A step of developing the photosensitive layer after the heat treatment,
A method for producing a substrate with a resist pattern, comprising: A method for manufacturing a printed wiring board, which comprises a step of forming a conductor pattern by subjecting a substrate with a resist pattern manufactured by the manufacturing method according to claim 3 to an etching treatment. A method of manufacturing a touch panel, comprising a step of forming a conductor pattern by subjecting a substrate with a resist pattern manufactured by the method of claim 4 to an etching treatment.

Images