WO2017130427A1

WO2017130427A1 - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing touch panel

Info

Publication number: WO2017130427A1
Application number: PCT/JP2016/059953
Authority: WO
Inventors: 尚樹平松; 春仙玉田; 伯世木村; 楓果平山
Original assignee: 日立化成株式会社
Priority date: 2016-01-28
Filing date: 2016-03-28
Publication date: 2017-08-03
Also published as: JPWO2017130427A1; TW201728999A

Abstract

A photosensitive resin composition which contains a binder polymer (component (A)), a photopolymerizable compound (component (B)) and a photopolymerization initiator (component (C)), and wherein the component (B) contains a (meth)acrylate having 6 ethylenically unsaturated bonds in each molecule and a (meth)acrylate having an isocyanuric ring skeleton.

Description

Photosensitive resin composition, photosensitive element, resist pattern forming method, and touch panel manufacturing method

The present invention relates to a photosensitive resin composition, a photosensitive element, a resist pattern forming method, and a touch panel manufacturing method.

The touch sensor unit of the touch panel includes a sensor part for detecting position information due to contact with a human finger or the like in a range (view area) for displaying visual information, and a lead wiring part for transmitting the position information to an external element. It is configured to be equipped.

The sensor part is formed with a conductive electrode pattern with little absorption and scattering of visible light. Further, a metal having a small resistance value is used for each wiring in the lead-out wiring region.

Such sensor parts and lead-out wiring parts are manufactured as shown in FIG. 2 using, for example, a negative photosensitive resin composition. FIG. 2 is a schematic cross-sectional view showing a conventional manufacturing method of the touch sensor portion of the touch panel. First, a photosensitive layer 16 is formed on a supporting substrate 12 (film substrate or glass substrate such as polyethylene terephthalate) having a transparent conductive layer 14 by applying a photosensitive resin composition (photosensitive layer forming step) (FIG. 2). (A)). Next, the exposed portion is cured by irradiating a predetermined portion of the photosensitive layer 16 with an actinic ray (exposure step). Then, a resist pattern containing a photocured product of the photosensitive resin composition is formed on the transparent conductive layer 14 by removing the uncured portion from the transparent conductive layer 14 (development process) (FIG. 2B). . Etching is performed on the resist pattern, and a part of the transparent conductive layer 14 is removed from the support base 12 to form a pattern of the transparent conductive layer at the sensor site (etching step) (FIG. 2C). ). Next, the resist pattern is peeled off from the transparent conductive layer 14 and removed (peeling step) (FIG. 2D). Subsequently, the lead wiring 18 from the pattern of the transparent conductive layer of the formed sensor part is formed by screen printing using a silver paste or the like, thereby manufacturing the touch sensor unit.

Also, due to the narrowing of the frame (bezel) of the touch panel, it is required to narrow the wiring width and pitch at the lead-out wiring site. In screen printing using silver paste, pattern formation with L / S (line width / space width) of about 50/50 (unit: μm) is the limit, but L / S is required to cope with the narrowing of the frame. Is required to form a pattern of 30/30 (unit: μm) or less.

In order to manufacture a touch sensor unit having a pattern of a lead wiring with a small L / S and a narrow pitch, a method of forming the touch sensor unit 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 using a photosensitive resin composition on a supporting substrate having a transparent conductive layer and a metal layer (first photosensitive layer forming step). ). Next, a predetermined portion of the photosensitive layer is irradiated with actinic rays to cure the exposed portion (first exposure step), and then the uncured portion is removed from the metal layer, thereby exposing the photosensitive layer to the photosensitive layer. A resist pattern containing a photocured product of the resin composition is formed (first development 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 from the metal layer and removed (first peeling step). Subsequently, 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. (Second development step). Next, only the metal layer on which the resist pattern is not formed at the sensor part is removed by etching (second etching process), and finally the resist pattern is peeled and removed to remove the touch sensor unit. Manufacturing.

In such a touch sensor manufacturing method, by using a photolithography technique, in principle, L / S can be reduced to 30/30 (unit: μm) or less, and the touch panel can be made thin and light. You can contribute a lot. On the other hand, the transparent conductive layer of the touch sensor unit is formed, for example, by forming a film of indium tin oxide (ITO) using a sputtering technique. Moreover, the metal layer formed on a transparent conductive layer is formed using the technique of sputtering similarly to a transparent conductive layer, for example. The surfaces of the transparent conductive layer and metal layer formed by using the sputtering technique have very high smoothness. Since the adhesion between the metal layer having very high smoothness and the photosensitive resin composition may be lowered, copper, an alloy of copper and nickel, an alloy of copper, nickel and titanium, and a molybdenum-aluminum-molybdenum laminate The photosensitive resin composition to be used is required to have high adhesion to a metal layer in which a body, an alloy of silver, palladium, and copper is used.

For the transparent conductive layer, for example, amorphous ITO is used from the viewpoint of easy etching. However, since amorphous ITO has a high resistance value, the resistance value is lowered by, for example, crystallization of ITO by a heating (annealing) process. However, in recent years, with the reduction in thickness and weight of touch panels, it is required to use a film base material as a support base material for the touch panel portion. When a film substrate is used as the support substrate, the dimensional stability deteriorates due to the shrinkage of the film substrate and the like when the annealing treatment is performed. Therefore, when using a film base material as a supporting base material, 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, but crystalline ITO uses a strong acid such as concentrated hydrochloric acid (> 20% by mass) and heating conditions (about 40 to 50 ° C.). ) Need to be etched. Therefore, the photosensitive resin composition to be used is required to have high acid resistance, that is, adhesion with the metal layer can be ensured even by etching using a strong acid, and corrosion of the metal layer due to the strong acid can be suppressed.

In addition, as a technique for forming a wiring pattern (also referred to as a conductor pattern) having a high resolution by reducing the L / S of the resist pattern to 30/30 (unit: μm) or less, the metal layer and the transparent conductive layer are etched together. There is a technique to do. In the conventional method of etching a transparent conductive layer after etching a metal layer, it has been difficult to obtain a wiring pattern having high resolution because in-plane variation during etching becomes large. ITO-4400Z (manufactured by ADEKA Corporation) is commercially available as a chemical solution for etching the metal layer and the transparent conductive layer at once.

Further, as a technique for improving acid resistance (adhesion after being immersed in a 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, refer to Patent Document 2).

Furthermore, various photosensitive resin compositions have been studied as photosensitive resin compositions used for forming resist patterns. For example, in a photosensitive resin composition, it has been proposed to add a specific cross-linking agent, a specific silane coupling agent, etc., and to have a binder polymer having a specific structural unit as an essential component (for example, a patent Reference 3-7).

Japanese Patent No. 4855536 Japanese Patent No. 4219641 Japanese Patent Laid-Open No. 2002-040645 JP 2002-268215 A JP 2008-112146 A JP 2009-042720 A JP 2003-107695 A

When forming a resist pattern having a high resolution with the L / S of the resist pattern being 30/30 (unit: μm) or less, defects such as chipping, cracks, meandering, and peeling of the resist pattern are likely to occur. . In particular, in this field, due to the occurrence of a defect, there is a possibility that a short circuit and a disconnection may occur in the electrode of the sensor part and the lead-out wiring. Therefore, the resist pattern is required more than before to be free from chipping, cracking, meandering, peeling and the like.

However, in the photosensitive resin composition described in Patent Document 2, it is difficult to form a resist pattern with excellent resolution, and a resist pattern may be defective. In addition, the photosensitive resin compositions described in Patent Documents 3 to 7 sometimes cause defects such as resist peeling and chipping during ITO etching. In particular, when a strong etching solution used for removing ITO is used, defects such as peeling and chipping occur in the resist pattern, and defects such as peeling and chipping do not occur in the resist pattern. However, it has been found that there is a tendency that the line shape of the wiring pattern to be formed tends to be loose. Further, it has been found that there are few defects that can occur in the resist pattern, and that the line shape of the wiring pattern is good and that it is difficult to achieve both a balanced and high level.

The present invention has been made to solve such problems, and there are few chips and cracks that can occur in a resist pattern, and the resist meanders and peels even when a strong etching solution is used. It aims at providing the photosensitive resin composition which can form the resist pattern which can suppress that generation | occurrence | production occurs. Another object of the present invention is to provide a photosensitive element, a resist pattern forming method and a touch panel manufacturing method using the photosensitive resin composition.

As a result of intensive studies to solve the above problems, the present inventors have found that a resist pattern having excellent characteristics can be formed by using a photosensitive resin composition containing a predetermined component.

That is, the first aspect of the present invention comprises (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: photopolymerization initiator. The invention relates to a photosensitive resin composition comprising (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton.

According to such a photosensitive resin composition, there are few cracks and cracks that can occur in the resist pattern, and even when a strong etching solution is used, the occurrence of resist meandering and peeling can be suppressed. . Therefore, by using such a photosensitive resin composition, a high-resolution fine circuit pattern can be formed.

The component (B) may further contain a bisphenol A type di (meth) acrylate having a (poly) oxyethylene group. According to such a photosensitive resin composition, the acid resistance of the resist pattern is further improved, and meandering and peeling due to swelling of the resist pattern during ITO etching can be more significantly suppressed.

A second aspect of the present invention includes a support and a photosensitive layer provided on one surface of the support and formed using the photosensitive resin composition according to the first aspect. Related to sex elements. According to such a photosensitive element, since it includes the photosensitive layer formed using the photosensitive resin composition according to the first aspect, even when a strong etching solution is used, the meandering and chipping of the resist are performed. It is possible to form a resist pattern that can suppress the occurrence of. Therefore, by using such a photosensitive element, a high-resolution fine circuit pattern can be efficiently formed.

According to a third aspect of the present invention, there is provided a photosensitive layer forming step of forming a photosensitive layer on a substrate using the photosensitive resin composition according to the first aspect or the photosensitive element according to the second aspect. A part of the photosensitive layer is cured by irradiation with actinic rays to form a photocured product region, and a region other than the photocured product region of the photosensitive layer is removed from the substrate. And a developing step for obtaining a resist pattern composed of the photocured product region. According to such a resist pattern forming method, the resist pattern can be prevented from causing occurrence of meandering and peeling of the resist even when a strong etching solution is used, since there are few chips and cracks that can occur in the resist pattern. Can be formed. In addition, according to such a resist pattern forming method, it is possible to form a resist pattern having excellent adhesion to a substrate having high smoothness and excellent resolution.

A fourth aspect of the present invention is a laminated base material comprising a support base material, a transparent conductive layer containing indium tin oxide provided on one surface of the support base material, and a metal layer provided on the transparent conductive layer A first step of forming a resist pattern made of a photocured product of the photosensitive resin composition according to the first aspect on the metal layer, and etching the metal layer and the transparent conductive layer, A second step of forming a laminated pattern comprising the remainder of the transparent conductive layer and the remainder of the metal layer; and a transparent electrode comprising the remainder of the transparent conductive layer by removing the metal layer from a part of the laminated pattern And a third step of forming a metal wiring composed of the remainder of the metal layer.

According to such a touch panel manufacturing method, since the resist pattern is formed from the photocured product of the photosensitive resin composition according to the first aspect, the resist pattern is sufficiently peeled off during the etching process. It is possible to manufacture a narrow-pitch touch panel (for example, a touch panel having a lead-out line with an L / S of 30/30 or less) that is suppressed and easily and efficiently.

The transparent conductive layer may contain crystalline indium tin oxide, and the etching in the second step may be etching with a strong acid. In the manufacturing method, since the resist pattern is formed from the photocured product of the photosensitive resin composition according to the first aspect, peeling of the resist pattern is sufficiently suppressed even by etching with a strong acid. . Therefore, the said manufacturing method can be applied suitably for manufacture of the touch panel using the laminated base material provided with the transparent conductive layer containing crystalline indium tin oxide.

According to the present invention, there are few chips and cracks that can occur in a resist pattern, and even when a strong etching solution is used, a resist pattern that can suppress the occurrence of resist meandering and peeling can be formed. A functional resin composition is provided. Moreover, according to this invention, the formation method of the photosensitive element using the said photosensitive resin composition, the resist pattern, and the manufacturing method of a touch panel are provided.

It is a schematic cross section which shows one Embodiment of the photosensitive element of this invention. It is a schematic cross section which shows the conventional manufacturing method of a touch panel. It is a schematic cross section which shows one aspect | mode of the manufacturing method of the touchscreen of this invention. It is a top view which shows the one aspect | mode of the touchscreen obtained using this invention.

Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present specification, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylate means acrylate or a corresponding methacrylate, and (meth) acryloxy group means acryloxy group. Or the methacryloxy group corresponding to it.

In the present specification, the (poly) oxyalkylene group means at least one polyoxyalkylene group in which an oxyalkylene group or two or more alkylene groups are linked by an ether bond. That is, (poly) oxyethylene group means at least one polyoxyethylene group in which an oxyethylene group or two or more ethylene groups are linked by an ether bond, and other similar expressions such as (poly) oxypropylene group The same applies to. The (poly) oxyethylene group may be referred to as “EO group” and the (poly) oxypropylene group may be referred to as “PO group”. Further, the term “layer” includes a structure formed in a part in addition to a structure formed over the entire surface when observed as a plan view. Further, the term “process” is included in this term as long as the intended purpose of the process is achieved, even when the process is not clearly distinguished from other processes. The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In addition, in the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.

<Photosensitive resin composition>
The photosensitive resin composition according to the present embodiment (hereinafter simply referred to as “photosensitive resin composition”) includes (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component. : A photosensitive resin containing a photopolymerization initiator, wherein the component (B) includes (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton. It is a composition.

According to such a photosensitive resin composition, it is possible to form a high-resolution resist pattern in which the occurrence of peeling and chipping is suppressed. In addition, since the resist pattern formed using the photosensitive resin composition suppresses the occurrence of meandering and peeling even when ITO is etched using a strong acid, the resulting circuit pattern has a line shape. It becomes good. Therefore, the photosensitive resin composition according to the present embodiment is suitable for etching ITO, particularly for etching a transparent conductive layer containing crystalline ITO.

Further, from the viewpoint of further suppressing chipping and cracks that may occur in the resist pattern, it may be required to improve the flexibility of the resist pattern formed from the photosensitive resin composition. According to the photosensitive resin composition concerning this embodiment, the flexibility of a resist pattern can also be improved.

(A) component: Binder polymer The photosensitive resin composition contains at least one binder polymer as the component (A). Examples of the binder polymer include a polymer obtained by radical polymerization of a polymerizable monomer (monomer).

As the polymerizable monomer (monomer), (meth) acrylic acid; (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid benzyl, (meth) acrylic acid benzyl derivative, ( (Meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid isobornyl, (meth) acrylic acid adamantyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid dimethylaminoethyl, (meta) ) Diethylaminoethyl acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, α-bromoacrylic acid, α -Chloracrylic acid, (meth) acrylic acid dicyclopente Nyloxyethyl, (meth) acrylic acid dicyclopentanyloxyethyl, (meth) acrylic acid isobornyloxyethyl, (meth) acrylic acid cyclohexyloxyethyl, (meth) acrylic acid adamantyloxyethyl, (meth) acrylic acid Dicyclopentenyloxypropyloxyethyl, dicyclopentanyloxypropyloxyethyl (meth) acrylate, dicyclopentenyloxypropyloxyethyl (meth) acrylate, adamantyloxypropyloxyethyl (meth) acrylate, β-furyl ( (Meth) acrylic acid esters such as (meth) acrylic acid and β-styryl (meth) acrylic acid; styrene; vinyl-toluene, α-methylstyrene and other polymerizable styrene derivatives substituted at the α-position or aromatic ring Diacetone Acrylamide such as chloramide; Acrylonitrile; Ether compound of vinyl alcohol such as vinyl-n-butyl ether; Maleic acid; Maleic anhydride; Maleic monoester such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate; And an unsaturated carboxylic acid derivative such as cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. These may be used alone or in any combination of two or more.

(A) The component may have a structural unit derived from (meth) acrylic acid. When the component (A) has a structural unit derived from (meth) acrylic acid, the content rate is based on the total amount of the component (A) in terms of excellent resolution and peelability (resist peelability after etching). (100 mass%, the same shall apply hereinafter) may be 10 to 60 mass%, 15 to 50 mass%, or 20 to 35 mass%. In the present specification, “total amount of component (A)” means the total amount of solid content. The same applies to “total amount of component (A) and component (B)” described later. The “solid content” refers to the non-volatile content of the photosensitive resin composition excluding volatile substances such as water and solvent. That is, it refers to components other than the solvent that remains without being volatilized in the drying step, and includes liquid, water tank-like and wax-like substances at room temperature around 25 ° C.

In addition, the component (A) may have a structural unit derived from an alkyl (meth) acrylate from the viewpoint of further improving alkali developability and peelability.

The (meth) acrylic acid alkyl ester may be an ester of (meth) acrylic acid and an alkyl alcohol having 1 to 12 carbon atoms. Examples of such (meth) acrylic acid alkyl esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, Examples thereof include hexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. These may be used alone or in any combination of two or more.

When the component (A) has a structural unit derived from a (meth) acrylic acid alkyl ester, the content is 40 to 90% by mass based on the total amount of the component (A) in terms of excellent resolution and adhesion. , 50 to 85% by mass, or 65% to 80% by mass.

The acid value of the component (A) may be 90 to 250 mgKOH / g, 100 to 240 mgKOH / g, 120 to 235 mgKOH / g, or 130 mgKOH / g to 230 mgKOH / g in terms of excellent developability and adhesion. Good.

From the viewpoint of shortening the developing time, the acid value may be 90 mgKOH / g or more, 100 mgKOH / g or more, 120 mgKOH / g or more, or 130 mgKOH / g or more.

In addition, this acid value is 250 mgKOH / g or less, 240 mgKOH / g or less, 235 mgKOH / g or less, or 230 mgKOH / g or less in that the adhesiveness of the photocured product of the photosensitive resin composition is further improved. Also good. In addition, when performing solvent image development, you may adjust the polymerizable monomer (monomer) which has carboxy groups, such as (meth) acrylic acid, to a small quantity.

The weight average molecular weight (Mw) of the component (A) is 10,000 to 200,000 in terms of excellent developability and adhesion when measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene). 20,000 to 100,000, 25,000 to 80,000, or 30,000 to 60,000. In the point which is excellent in developability, it may be 200000 or less, 100000 or less, 80000 or less, or 60000 or less. In the point which is excellent in adhesiveness, it may be 10,000 or more, 20000 or more, 25000 or more, or 30000 or more.

The dispersity (weight average molecular weight / number average molecular weight) of the component (A) may be 3.0 or less, 2.8 or less, or 2.5 or less in terms of excellent resolution and adhesion.

As the component (A), one type of binder polymer may be used alone, or two or more types of binder polymers may be used in any combination.

The content of the component (A) in the photosensitive resin composition is 30 to 70 parts by weight, 35 parts in 100 parts by weight of the total amount of the components (A) and (B) in terms of excellent film formability, sensitivity and resolution. It may be ~ 65 parts by mass or 40-60 parts by mass. In view of formability of the film (photosensitive layer), the content may be 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more. Further, from the viewpoint of improving the sensitivity and resolution in a balanced manner, the content may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less.

Component (B): Photopolymerizable compound The photosensitive resin composition contains (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton as the component (B). .

Examples of (meth) acrylate having six ethylenically unsaturated bonds in the molecule include dipentaerythritol hexa (meth) acrylate. These may have an EO group or a PO group. When the (meth) acrylate having 6 ethylenically unsaturated bonds in the molecule has an EO group, the number of EO groups in the molecule is 6 to 30, 6 to 24, or from the viewpoint of improving adhesion. It may be 6-12. When the (meth) acrylate having 6 ethylenically unsaturated bonds in the molecule has a PO group, the number of PO groups in the molecule is 6 to 30, 6 to 24, or 6 to 6 from the viewpoint of improving adhesion. 12 may be sufficient.

As those having an EO group, KAYARAD DPHA (Nippon Kayaku Co., Ltd., trade name, number of EO groups: 6), KAYARAD DPEA-12 (Nippon Kayaku Co., Ltd., trade name, number of EO groups: 12), A-DPH-6E (Shin Nakamura Chemical Co., Ltd., trade name, number of EO groups: 6) is commercially available. In addition, A-DPH-6P (Shin-Nakamura Chemical Co., Ltd., trade name, number of PO groups: 6) is commercially available as having PO groups. One (meth) acrylate having six ethylenically unsaturated bonds in the molecule may be used alone, or two or more may be used in combination.

More specifically, examples of the dipentaerythritol hexa (meth) acrylate having an EO group or a PO group include compounds represented by the following general formula (1).

In the general formula (1), each R independently represents a hydrogen atom or a methyl group. A plurality of R may be the same as or different from each other.

In general formula (1), A represents an alkylene group having 2 to 6 carbon atoms, an alkylene group having 2 to 5 carbon atoms, or an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 6 carbon atoms include ethylene group, propylene group, isopropylene group, butylene group, pentylene group and hexylene group. Among these, an ethylene group or an isopropylene group or an ethylene group may be used from the viewpoint of improving the resolution, adhesion, and resist bottom generation suppression. A plurality of A's may be the same or different.

In the general formula (1), each n is independently an integer of 0 to 20. From the viewpoint of further improving the resolution, n may be 1 to 20, 1 to 7, 1 to 5, 1 to 4, or 1 to 2. The sum of the six ns in the general formula (1) may be 6-30, 6-24, or 6-12.

In the photosensitive resin composition, the content of the (meth) acrylate having 6 ethylenically unsaturated bonds in the molecule is from the viewpoint of improving the adhesion and releasability after etching in a balanced manner. The total amount of the component (B) may be 3 to 20 parts by mass, 3 to 15 parts by mass, or 3 to 10 parts by mass.

The (meth) acrylate having an isocyanuric ring skeleton may contain a compound represented by the following general formula (2) from the viewpoint of improving the acid resistance and flexibility of the resist pattern. The (meth) acrylate having an isocyanuric ring skeleton may be used alone or in combination of two or more.

In the general formula (2), R ²¹ , R ²² and R ²³ each independently represents an alkylene group having 1 to 20 carbon atoms, and R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a methyl group. X ²¹ , X ²² and X ²³ each independently represent a (poly) oxyalkylene group (oxyalkylene group or polyoxyalkylene group) containing at least one selected from the group consisting of an EO group and a PO group. , X ²¹ , X ²² and X ²³ have a total number of EO groups and PO groups (total number in the molecule) of 0 to 120. When both the EO group and the PO group are present, the EO group and the PO group may be present at random and may form a block.

The total number of EO groups and PO groups contained in X ²¹ , X ²² and X ²³ is 3 to 60, 3 to 30, 3 to 20, or 3 to 15 from the viewpoint of flexibility and acid resistance. Also good.

Among the compounds represented by the general formula (2), commercially available compounds include UA-21 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name), UA-7100 (Shin-Nakamura Chemical Co., Ltd.). Product name).

The content of the (meth) acrylate having an isocyanuric ring skeleton is 1 to 100 parts by mass in the total amount of the component (A) and the component (B) from the viewpoint of improving the acid resistance and flexibility of the resist pattern in a balanced manner. It may be 50 parts by mass. Further, from the viewpoint of further improving acid resistance and flexibility, the lower limit may be 3 parts by mass or more, or 5 parts by mass or more. Further, from the same viewpoint, the lower limit may be 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 16 parts by mass or less.

The component (B) may further contain a photopolymerizable compound other than (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton. Other photopolymerizable compounds are not particularly limited as long as they are compounds capable of photopolymerization. The other photopolymerizable compound may be a radical polymerizable compound or a compound having an ethylenically unsaturated bond. As the compound having an ethylenically unsaturated bond, a compound having one ethylenically unsaturated bond in the molecule ((meth) acrylate), a compound having two ethylenically unsaturated bonds in the molecule ((meth) acrylate) And compounds having three or more ethylenically unsaturated bonds ((meth) acrylate) in the molecule. Another photopolymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more type.

(B) The component may further contain a compound having two ethylenically unsaturated bonds in the molecule.

Examples of the compound having two ethylenically unsaturated bonds in the molecule include bisphenol A type di (meth) acrylate, hydrogenated bisphenol A type di (meth) acrylate, and di (meth) acrylate having a urethane bond in the molecule. And polyalkylene glycol di (meth) acrylate having both (poly) oxyethylene group and (poly) oxypropylene group in the molecule, and trimethylolpropane di (meth) acrylate.

The component (B) may contain bisphenol A type di (meth) acrylate from the viewpoint of further improving acid resistance.

Examples of the bisphenol A type di (meth) acrylate include compounds represented by the following general formula (3).

In General Formula (3), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. XO and YO each independently represent an oxyethylene group or an oxypropylene group. m ₁ , m ₂ , n ₁ and n ₂ each independently represents 0 to 40. However, m ₁ + n ₁ and m ₂ + n ₂ are both 1 or more. When XO is an oxyethylene group and YO is an oxypropylene group, m ₁ + m ₂ is 1 to 40, and n ₁ + n ₂ is 0 to 20. When XO is an oxypropylene group and YO is an oxyethylene group, m ₁ + m ₂ is 0 to 20, and n ₁ + n ₂ is 1 to 40. m ₁ , m ₂ , n ₁ and n ₂ represent the number of structural units. Therefore, an integer value is shown in a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, the same applies to the number of structural units.

In terms of excellent acid resistance, in the general formula (3), when XO is an oxyethylene group and YO is an oxypropylene group, m ₁ + m ₂ is 8 to 40, 8 to 20, or 8 to 10; In addition, when XO is an oxypropylene group and YO is an oxyethylene group, n ₁ + n ₂ may be 8 to 40, 8 to 20, or 8 to 10.

When the photosensitive resin composition contains bisphenol A type di (meth) acrylate as the component (B), the content thereof is that of the components (A) and (B) from the viewpoint of improving the adhesion after etching. The total amount may be 1 to 50 parts by mass, or 5 to 50 parts by mass in 100 parts by mass.

The total content of component (B) in the photosensitive resin composition is 30 to 70 parts by weight, 35 to 65 parts by weight, 40 to 60 parts by weight with respect to 100 parts by weight as the total of component (A) and component (B). Or 35 to 55 parts by mass. When this content is 30 parts by mass or more, the sensitivity and resolution tend to be improved in a balanced manner. When the amount is 70 parts by mass or less, a film (photosensitive layer) tends to be easily formed, and a good resist pattern shape tends to be easily obtained.

Component (C): Photopolymerization initiator The photosensitive resin composition contains at least one photopolymerization initiator as the component (C). The photopolymerization initiator is not particularly limited as long as it can polymerize the component (B), and can be appropriately selected from commonly used photopolymerization initiators.

Examples of the component (C) include benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Aromatic ketones such as propanone-1; quinones such as alkyl anthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoins; benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl)- 2,4,5-triarylimidazole dimers such as 4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer; 9-phenylacridine, 1, Induction of acridine such as 7- (9,9'-acridinyl) heptane And the like. These can be used alone or in combination of two or more.

Component (C) may contain at least one 2,4,5-triarylimidazole dimer from the viewpoint of further improving sensitivity and adhesion, and 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer may be included. The 2,4,5-triarylimidazole dimer may be symmetric or asymmetric in structure.

The content of the component (C) in the photosensitive resin composition is 0.1 to 10 parts by weight, 1 to 7 parts by weight, and 2 to 6 parts by weight with respect to 100 parts by weight as the total of the components (A) and (B). Or 3 to 5 parts by mass. When this content is 0.1 parts by mass or more, good sensitivity, resolution or adhesion tends to be obtained, and when it is 10 parts by mass or less, a good resist pattern shape tends to be obtained. .

(D): Silane coupling agent The photosensitive resin composition may further contain a silane coupling agent as the component (D). As the silane coupling agent, (D1) component: a silane compound having a mercaptoalkyl group, (D2) component: a silane compound having an amino group (preferably a silane compound having a ureido group), (D3) component: (meta And silane compounds having an acryloxy group.

When the photosensitive resin composition contains the component (D1) as the component (D), the photosensitive resin composition has excellent adhesion to a substrate having high smoothness, and has excellent acid resistance that hardly peels off even by ITO etching with hydrochloric acid. The outstanding effect that the resist pattern which it has can be formed can be show | played.

Moreover, the photosensitive resin composition may contain a silane coupling agent other than the component (D1) as the component (D).

For example, in the photosensitive resin composition, the component (D1) and the component (D3) can be used in combination as the component (D). When the photosensitive resin composition contains only the component (D1) as the component (D), a resist pattern exhibiting excellent adhesion can be obtained, while development residue on a copper substrate or the like is likely to occur (that is, on the copper substrate). The formed resist pattern tends to be difficult to peel off after etching, and the etching time tends to increase. On the other hand, when the photosensitive resin composition contains the component (D1) and the component (D3) as the component (D), it suppresses the generation of development residue on the copper substrate while maintaining excellent adhesion. Thus, the etching time can be shortened.

Moreover, the photosensitive resin composition may contain all the (D1) component, (D2) component, and (D3) component as (D) component. According to such a photosensitive resin composition, higher adhesion can be realized while suppressing the occurrence of development residue on a copper substrate or the like.

The component (D1) may be a silane compound having a mercaptoalkyl group and an alkoxy group (mercaptoalkylalkoxysilane). Examples of the component (D1) include mercaptopropylmethyldimethoxysilane and mercaptopropyltrimethoxysilane. And mercaptopropyltriethoxysilane. Among these, mercaptopropyltrimethoxysilane which is easily hydrolyzed and can be crosslinked at three points is most preferable for the expression of adhesion. These can be used alone or in combination of two or more.

The component (D2) may be a silane compound having a primary amino group at the terminal. Examples of the component (D2) include 3-aminopropylmethoxysilane, aminopropylethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, Examples include 2-ureidoethyltriethoxysilane, 4-ureidobutyltrimethoxysilane, and 4-ureidobutyltriethoxysilane. Among these, considering the reactivity with the binder polymer, it may be a silane compound having a functional group having a low reactivity with a carboxylic acid group such as a ureido group, and developed when used in combination with the component (D1). Most preferred is 3-ureidopropyltriethoxysilane, in which the remaining inhibitory effect is particularly noticeable. These can be used alone or in combination of two or more.

Examples of the component (D3) include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Among these, 3-methacryloxypropyltrimethoxysilane which is easily hydrolyzed and can be crosslinked at three points is most preferable for the expression of adhesion. These can be used alone or in combination of two or more.

The content of the component (D) in the photosensitive resin composition is 0.01 to 10 parts by mass, 0. 10 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) in terms of excellent adhesion. It may be 05 to 5 parts by mass, or 0.1 to 3 parts by mass. If the content of the component (D) is more than the above range, there is a tendency that development residue on a copper substrate or the like is likely to occur, and there is insufficient curing of the resist bottom due to a decrease in resolution and a significant increase in sensitivity. May occur. On the other hand, when the content of the component (D) is within the above range, the curability at the bottom of the resist tends to be improved while sufficiently suppressing the development residue on the copper substrate or the like. By sufficiently curing to the bottom of the resist, a good resist pattern shape can be obtained and the resistance to the etching solution can be further improved.

(Other ingredients)
The photosensitive resin composition may contain components other than the components (A) to (D) as necessary. For example, the photosensitive resin composition comprises at least one selected from the group consisting of a sensitizing dye, bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leucocrystal violet. Can be contained.

(E) component: Sensitizing dye The photosensitive resin composition concerning this embodiment may further contain a sensitizing dye as (E) component. Examples of sensitizing dyes include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds. , A thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound. These can be used alone or in combination of two or more. A pyrazoline compound may be contained from the viewpoint of further improving the degree of curing of the resist bottom and excellent adhesion.

When the photosensitive resin composition contains the component (E), the content improves the degree of cure at the bottom of the resist, and further improves the adhesion, so that the total amount of the component (A) and the component (B) is 100. It may be 0.01 to 5 parts by mass, 0.01 to 1 part by mass, or 0.01 to 0.2 parts by mass with respect to parts by mass.

The photosensitive resin composition includes a polymerizable compound having at least one cationically polymerizable cyclic ether group in the molecule (such as an oxetane compound); a cationic polymerization initiator; malachite green, Victoria pure blue, brilliant green, methyl violet. Dyes such as tribromophenylsulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline, o-chloroaniline, etc .; thermochromic inhibitors; plasticizers such as p-toluenesulfonamide; pigments; fillers An antifoaming agent, a flame retardant, a stabilizer, an adhesion-imparting agent, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent, and the like. These can be used alone or in combination of two or more.

When the photosensitive resin composition contains other components (components other than the components (A) to (D)), these contents are based on 100 parts by mass of the total amount of the components (A) and (B). Each may be about 0.01 to 20 parts by mass.

[Solution of photosensitive resin composition]
The photosensitive resin composition may be a liquid composition further containing at least one organic solvent. Organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; N, N— And aprotic polar solvents such as dimethylformamide. These may be used alone or in admixture of two or more.

The content of the organic solvent contained in the photosensitive resin composition can be appropriately selected depending on the purpose and the like. For example, the photosensitive resin composition is used as a liquid composition having a solid content of about 30% by mass to 60% by mass (hereinafter, the photosensitive resin composition containing an organic solvent is also referred to as “coating liquid”). it can.

The photosensitive layer which is a coating film of the photosensitive resin composition can be formed by applying the coating liquid on the surface of a support, a metal plate, etc., which will be described later, and drying it. It does not restrict | limit especially as a metal plate, According to the objective etc., it can select suitably. As a metal plate, the metal plate which consists of metals, such as copper, copper-type alloy, iron-type alloys, such as nickel, chromium, iron, stainless steel, can be mentioned. As a preferable metal plate, a metal plate made of a metal such as copper, a copper-based alloy, or an iron-based alloy can be given.

The thickness of the photosensitive layer to be formed is not particularly limited and can be appropriately selected depending on the application. The thickness of the photosensitive layer (thickness after drying) may be about 1 to 100 μm.

When a photosensitive layer is formed on a metal plate, the surface of the photosensitive layer opposite to the metal plate may be covered with a protective layer. Examples of the protective layer include polymer films such as polyethylene and polypropylene.

<Photosensitive element>
A photosensitive element according to the present embodiment (hereinafter simply referred to as “photosensitive element”) is a photosensitive body formed using a support and the photosensitive resin composition provided on one surface of the support. A layer. According to such a photosensitive element, since it includes a photosensitive layer formed using the photosensitive resin composition, there are few chips and cracks that can occur in the resist pattern, and a strong etching solution is used. However, it is possible to suppress the occurrence of resist peeling and chipping, and to obtain a wiring pattern having a good line shape without backlash, and to form a resist pattern having a sufficiently short peeling time. In addition, it is possible to efficiently form a resist pattern having sufficient adhesion to a highly smooth substrate and having excellent acid resistance. The photosensitive element may have other layers, such as a protective layer, as needed.

FIG. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive element of the present invention. In the photosensitive element 10 shown in FIG. 1, the support 2, the photosensitive layer 4 formed using the photosensitive resin composition, and the 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. First, on the support 2, a coating solution that is a photosensitive resin composition containing an organic solvent is applied to form a coating layer, which is dried (at least a part of the organic solvent is removed from the coating layer). A photosensitive layer 4 is formed. Next, the surface of the photosensitive layer 4 opposite to the support 2 is covered with a protective layer 6, so that the support 2, the photosensitive layer 4 laminated on the support 2, and the photosensitive layer 4 are covered. The photosensitive element 10 provided with the protective layer 6 laminated | stacked is obtained. Note that the photosensitive element 10 does not necessarily include the protective layer 6.

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

The thickness of the support 2 may be 1 to 100 μm, 5 to 50 μm, or 5 to 30 μm. When the thickness of the support body 2 is 1 μm or more, the support body 2 can be prevented from being broken when the support body 2 is peeled off. Moreover, the fall of the resolution at the time of exposing through the support body 2 is suppressed because it is 100 micrometers or less.

As the protective layer 6, the adhesive force to the photosensitive layer 4 may be smaller than the adhesive force of the support 2 to the photosensitive layer 4. Specifically, as the protective layer 6, a film made of a polymer having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate; polyolefin such as polypropylene and polyethylene can be used. Commercially available products include polypropylene films such as Alfan MA-410 and E-200 manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., PS-25 such as PS-25 manufactured by Teijin Limited, and Tamapoly. An example is NF-15A manufactured by KK. The protective layer 6 may be the same as the support 2.

The thickness of the protective layer 6 may be 1 to 100 μm, 5 to 50 μm, 5 to 30 μm, or 15 to 30 μm. When the thickness of the protective layer 6 is 1 μm or more, the protective layer 6 can be prevented from being broken when the photosensitive layer 4 and the support 2 are laminated on the substrate while peeling off the protective layer 6. When it is 100 μm or less, it is excellent in handleability and inexpensiveness.

Specifically, the photosensitive element 10 can be manufactured as follows, for example. That is, the photosensitive element 10 includes a step of preparing a coating solution containing a photosensitive resin composition, a step of coating the coating solution on the support 2 to form a coating layer, and drying the coating layer. And a step of forming the photosensitive layer 4.

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

The drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, it may be performed at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive layer 4 may be 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

The thickness of the photosensitive layer 4 in the photosensitive element 10 can be appropriately selected depending on the application. The thickness after drying may be 1 to 100 μm, 1 to 50 μm, or 5 to 40 μm. Industrial coating becomes easy because the thickness of the photosensitive layer 4 is 1 μm or more. When it is 100 μm or less, adhesion and resolution tend to be sufficiently obtained.

The photosensitive element 10 can be suitably used, for example, in a resist pattern forming method described later.

<Method for forming resist pattern>
The resist pattern forming method according to the present embodiment includes (i) a photosensitive layer forming step of forming a photosensitive layer on a substrate using a photosensitive resin composition or a photosensitive element, and (ii) a part of the photosensitive layer. (Iii) removing the region other than the photocured product region of the photosensitive layer from the substrate, and curing the region of the above by irradiation with actinic rays to form a photocured product region, And a developing step of forming a resist pattern made of a photocured product (photocured product region) of the photosensitive resin composition. The method for forming a resist pattern may further include other steps as necessary. In addition, it can be said that a resist pattern is a resin pattern or a relief pattern. Hereinafter, each process is explained in full detail.

(I) Photosensitive layer forming step In the photosensitive layer forming step, a photosensitive layer is formed using a photosensitive resin composition on a substrate.

Examples of the method for forming the photosensitive layer on the substrate include a method in which a coating liquid containing a photosensitive resin composition is applied on the substrate and then dried.

Further, as a method for forming a photosensitive layer on a substrate, for example, a method of laminating the photosensitive layer of the photosensitive element on the substrate after removing the protective layer from the photosensitive element as necessary. Lamination can be performed by pressure-bonding the photosensitive layer of the photosensitive element to the substrate while heating. By this lamination, a laminate in which the substrate, the photosensitive layer, and the support are laminated in this order is obtained.

Lamination may be performed at a temperature of 70 to 130 ° C., for example, or may be performed by pressure bonding at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). These conditions can be adjusted as needed. When laminating, the substrate may be preheated, and the photosensitive layer may be heated to 70 to 130 ° C.

(Ii) Exposure Step In the exposure step, a part of the photosensitive layer is irradiated with actinic rays, whereby the exposed portion irradiated with the actinic rays is photocured to form a latent image. Here, when a photosensitive element is used in the photosensitive layer forming step, a support is present on the photosensitive layer, but when the support is transparent to actinic light, active light is transmitted through the support. Can be irradiated. On the other hand, when the support is light-shielding against actinic rays, the photosensitive layer is irradiated with actinic rays after the support is removed.

Examples of the exposure method include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork (mask exposure method). Alternatively, a method of irradiating actinic rays in an image form by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method and a DLP (Digital Light Processing) exposure method may be employed.

The wavelength of the actinic ray (exposure wavelength) may be 340 to 430 nm or 350 to 420 nm from the viewpoint of obtaining the effect of the present invention more reliably.

(Iii) Development process In the development process, a region other than the photocured product region of the photosensitive layer (that is, an uncured portion of the photosensitive layer) is removed from the substrate by a development treatment, and a resist made of the photocured product of the photosensitive layer is formed. A pattern is formed on the substrate. In addition, when the support body exists on the photosensitive layer which passed through the exposure process, a developing process is performed after removing a support body. The development processing includes wet development and dry development, and wet development is preferably used.

In wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include a method using a dipping method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like. From the viewpoint of improving resolution, the high pressure spray method is most suitable. You may develop by combining these 2 or more types of methods.

The developer can be appropriately selected according to the configuration of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution, an aqueous developer, an organic solvent developer, and the like.

Examples of the alkaline aqueous solution used for development include 0.1 to 5% by weight sodium carbonate aqueous solution, 0.1 to 5% by weight potassium carbonate aqueous solution, 0.1 to 5% by weight sodium hydroxide aqueous solution, and 0.1 to 5% by weight four. It may be a sodium borate aqueous solution or the like. The pH of the alkaline aqueous solution may be 9-11. The temperature is adjusted according to the alkali developability of the photosensitive layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.

The resist pattern is formed by removing the unexposed portion and further curing the resist pattern by heating at about 60 to 250 ° C. and / or exposing at about 0.2 to 10 J / cm ² as necessary. You may have further the process to do.

<Manufacturing method of touch panel>
The manufacturing method of the touch panel according to the present embodiment includes a step of etching the base material on which the resist pattern is formed by the resist pattern forming method. The etching process is performed on the conductor layer of the base material using the formed resist pattern as a mask (also referred to as “resist”). The touch panel is manufactured by forming the lead wiring and the pattern of the transparent electrode by the etching process.

FIG. 3 is a schematic cross-sectional view showing one embodiment of the touch panel manufacturing method of the present invention. The manufacturing method of this aspect is a laminated base material comprising 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. A first step of forming a resist pattern 29 made of a photo-cured product of the photosensitive resin composition on the metal layer 26, and etching the metal layer 26 and the transparent conductive layer 24, the remainder of the transparent conductive layer 24 and the metal A second step of forming a laminated pattern (24 + 26 in FIG. 3D) consisting of the remainder of the layer 26, a transparent electrode consisting of the remainder of the transparent conductive layer 24 by removing the metal layer from a part of the laminated pattern, and And a third step of forming a metal wiring composed of the remainder of the metal layer.

In the first step, first, as shown in FIG. 3A, the support base 22, the transparent conductive layer 24 provided on one surface of the support base 22, and the transparent conductive layer 24 were provided. A photosensitive layer 28 is formed using a photosensitive resin composition on the metal layer 26 of the laminated base material including the metal layer 26. The photosensitive layer 28 may include a support on the surface opposite to the metal layer 26.

As the metal layer 26, for example, a metal layer containing copper may be used. Examples of the metal layer containing copper include a metal layer containing copper, a copper-nickel alloy, a copper-nickel-titanium alloy, a molybdenum-aluminum-molybdenum laminate, a silver-palladium-copper alloy, and the like. Of these, a metal layer containing copper, an alloy of copper and nickel, or an alloy of copper, nickel and titanium can be suitably used from the viewpoint that the effects of the present invention can be obtained more remarkably.

The transparent conductive layer 24 contains indium tin oxide (ITO). The transparent conductive layer 24 may contain crystalline ITO from the viewpoint that the annealing process is unnecessary.

Next, a part of the photosensitive layer 28 is cured by irradiation with actinic rays to form a photocured product region, and regions other than the photocured product region of the photosensitive layer are removed from the laminated substrate. Thereby, as shown in FIG.3 (b), the resist pattern 29 is formed on a laminated base material.

In the second step, the metal layer 26 and the transparent conductive layer 24 in a region not masked by the resist pattern 29 are removed from the support substrate 22 by etching.

The etching method is appropriately selected according to the layer to be removed. For example, examples of the etching solution for removing the metal layer include a cupric chloride solution, a ferric chloride solution, and a phosphoric acid solution. Moreover, oxalic acid, hydrochloric acid, aqua regia, etc. are used as etching liquid for removing a transparent conductive layer.

When the transparent conductive layer 24 contains crystalline ITO, as an etching solution for removing the transparent conductive layer 24, a strong acid such as concentrated hydrochloric acid or aqua regia or a chemical solution for etching the metal layer and the transparent conductive layer in a lump ( For example, it is necessary to use ITO series such as ITO-4400Z). However, in the manufacturing method of this embodiment, the resist pattern is made of a photocured product of the photosensitive resin composition. However, resist pattern peeling and the like are sufficiently suppressed. The photosensitive resin composition according to the present embodiment is suitably used as an etching photosensitive resin composition using the above-described strong acid such as concentrated hydrochloric acid or aqua regia or a chemical solution that etches the metal layer and the transparent conductive layer at once. Can be used.

FIG. 3C is a diagram showing the state after the etching process. In FIG. 3C, the stack composed of the remainder of the metal layer 26, the remainder of the transparent conductive layer 24, and the remainder of the resist pattern 29 on the support substrate 22. The body is formed. In the manufacturing method of this aspect, the resist pattern 29 is removed from the laminate.

The removal of the resist pattern 29 can be performed using, for example, an aqueous solution that is more alkaline than the alkaline aqueous solution used in the development step described above. As this strongly alkaline aqueous solution, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used. Among them, a 1 to 10% by mass sodium hydroxide aqueous solution or a 1 to 10% by mass potassium hydroxide aqueous solution may be used, and a 1 to 5% by mass sodium hydroxide aqueous solution or a 1 to 5% by mass potassium hydroxide aqueous solution may be used. . Examples of the resist pattern peeling method include an immersion method and a spray method, which may be used alone or in combination.

FIG. 3D is a view showing the resist pattern after peeling. In FIG. 3D, a laminated pattern composed of the remainder of the metal layer 26 and the remainder of the transparent conductive layer 24 is formed on the support base material 22. ing.

In the third step, a part of the metal layer 26 other than a part for forming the metal wiring is removed from the laminated pattern, and the metal wiring composed of the remaining part of the metal layer 26 and the transparent electrode composed of the remaining part of the transparent conductive layer 24 are formed. Form. In this aspect, an etching method is employed as a 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 not necessarily limited to etching.

In the third step, first, the photosensitive layer 30 is formed on the laminated substrate subjected to the second step (FIG. 3E). Next, a resist 31 made of a photocured product of the photosensitive layer 30 is formed through exposure and development of the photosensitive layer 30 (FIG. 3F). The photosensitive layer may be a layer formed using the above-described photosensitive resin composition according to the present embodiment, or a layer formed using a conventionally known photosensitive resin composition for etching. May be.

Next, the metal layer 26 is removed from the portion of the laminated pattern where the resist 31 is not formed by an etching process. At this time, as the etching treatment liquid, the same one as the etching liquid for removing the metal layer can be used.

FIG. 3G is a diagram showing the state after the etching process. In FIG. 3G, a transparent electrode composed of the remaining portion of the transparent conductive layer 24 is formed on the support base material 22, and a part of the transparent electrode is formed. A laminate composed of the metal layer 26 and the resist 31 is formed on the electrode. By removing the resist 31 from the laminated body, as shown in FIG. 3 (h), the transparent electrode composed of the remaining portion of the transparent conductive layer 24 and the metal wiring composed of the remaining portion of the metal layer 26 are formed on the support substrate 22. And are formed.

FIG. 4 is a top view showing an aspect of a touch panel obtained by using the present invention. In the touch panel 100, X electrodes 52 and 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 a single lead wiring 56, The Y electrodes 54 provided in the same row in the width direction are connected to each other by one lead-out wiring 57.

The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples.

(Production Example 1: Production of binder polymer (A-1))
A polymerizable monomer (monomer) 30 g of methacrylic acid, 35 g of methyl methacrylate and 35 g of butyl methacrylate (mass ratio 30/35/35), 0.5 g of azobisisobutyronitrile, and 10 g of acetone. The solution obtained by mixing was designated as “Solution a”. A solution obtained by dissolving 0.6 g of azobisisobutyronitrile in 30 g of acetone was designated as “Solution b”.

A flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube was charged with 100 g of a mixture of 80 g of acetone and 20 g of propylene glycol monomethyl ether (mass ratio 4: 1), and nitrogen was introduced into the flask. The mixture was heated with stirring while blowing gas, and the temperature was raised to 80 ° C.

The solution a was dropped into the mixed solution in the flask at a constant dropping rate over 4 hours, and then the solution in the flask was stirred at 80 ° C. for 2 hours. Next, the solution b was dropped into the solution in the flask at a constant dropping rate over 10 minutes, and then the solution in the flask was stirred at 80 ° C. for 3 hours. Further, the temperature of the solution in the flask was raised to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a solution of binder polymer (A-1).

The nonvolatile content (solid content) of the solution of the binder polymer (A-1) was 42.8% by mass. The weight average molecular weight of the binder polymer (A-1) was 50,000, the acid value was 195 mgKOH / g, and the degree of dispersion was 2.58.

The weight average molecular weight and degree of dispersion were determined by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve. The GPC conditions are shown below.
(GPC conditions)
Pump: Hitachi / L-6000 (Hitachi, Ltd.)
Column: 3 in total, column specifications: 10.7 mmφ x 300 mm
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M (Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran (THF)
Sample concentration: 120 mg of a resin solution having a solid content of 40% by mass was sampled and dissolved in 5 mL of THF to prepare a sample.
Measurement temperature: 40 ° C
Injection volume: 200 μL
Pressure: 49Kgf / cm ² (4.8MPa)
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (Hitachi, Ltd.)

Moreover, the acid value was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile matter, thereby obtaining a solid content. And after precisely weighing 1 g of the polymer of the solid content, 30 g of acetone was added to the polymer, and this was uniformly dissolved. Next, an appropriate amount of an indicator, phenolphthalein, was added to the solution, and titration was performed using a 0.1N aqueous KOH solution. And the acid value was computed by following Formula.
Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100)
In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the mass (g) of the measured polymer solution, and I represents the ratio (mass%) of the non-volatile content in the measured polymer solution.

[Examples 1 to 7 and Comparative Examples 1 and 2]
Examples and comparative examples were performed by the following methods.

<Preparation of photosensitive resin composition (coating liquid)>
By mixing the components shown in Table 1 and Table 2 in the blending amounts (parts by mass) shown in the same table, coating solutions of the photosensitive resin compositions of Examples and Comparative Examples were obtained. The blending amount of the component (A) in the table is the mass (solid content) of the non-volatile content. “-” Means not blended. Details of each component shown in Table 1 and Table 2 are as follows.

((A) component)
A-1: Binder polymer (A-1) obtained in Production Example 1.

((B) component)
FA-321M: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (Hitachi Chemical Co., Ltd., number of EO groups: 10 (average value))
FA-3200MY: polyoxyalkylenated bisphenol A dimethacrylate (Hitachi Chemical Co., Ltd., number of EO groups: 12 (average value), number of PO groups: 4 (average value))
FA-MECH: γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate (Hitachi Chemical Co., Ltd.)
UA-13: polyoxyethylene and polyoxypropylene urethane dimethacrylate (compound having no isocyanuric ring skeleton, manufactured by Shin-Nakamura Chemical Co., Ltd., number of EO groups: 2 (average value), number of PO groups: 18 (average value))
UA-21: Tris (methacryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate (compound having isocyanuric ring skeleton, manufactured by Shin-Nakamura Chemical Co., Ltd., number of EO groups: 12 (average value))
DPEA-12: Dipentaerythritol hexaacrylate having EO group (Nippon Kayaku Co., Ltd., number of EO groups: 12 (average value))

((C) component)
B-CIM: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (Changzhou Power Electronics New Materials Co., Ltd.)

((D) component: silane coupling agent)
AY43-031: 3-Ureidopropyltriethoxysilane (Toray Dow Corning Co., Ltd.)
KBM-803: 3-Mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
SZ-6030: 3-methacryloxypropyltrimethoxysilane (Toray Dow Corning Co., Ltd.)

((E) component: sensitizing dye)
PZ-501D: 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline (Nippon Chemical Industry Co., Ltd.)

(Other components: other than (A) to (E))
LCV: Leuco Crystal Violet (Yamada Chemical Co., Ltd.)
TBC: 4-t-butylcatechol (DIC Corporation, “DIC-TBC-5P”)
SF-808H: Mixture of carboxybenzotriazole, 5-amino-1H-tetrazole and methoxypropanol (Sanwa Kasei Co., Ltd., “SF-808H”)
AZCV-PW: [4- {bis (4-dimethylaminophenyl) methylene} -2,5-cyclohexadiene-1-ylidene] (Hodogaya Chemical Co., Ltd.)

<Production of photosensitive element>
The coating solution of the photosensitive resin composition obtained above was applied on a polyethylene terephthalate film (product name “FB-40”, manufactured by Toray Industries, Inc.) having a thickness of 16 μm so as to have a uniform thickness, and 70 ° C. Then, a drying process was sequentially performed with a hot air convection dryer at 110 ° C. to form a photosensitive layer having a thickness of 15 μm after drying. A protective layer (product name “NF-15A”, manufactured by Tamapoly Co., Ltd.) is laminated on the photosensitive layer, and a photosensitive element in which a polyethylene terephthalate film (support), a photosensitive layer, and a protective layer are laminated in order. Obtained.

<Preparation of laminated substrate>
A transparent conductive layer made of crystalline ITO was formed on the upper layer of the polyethylene terephthalate material, and a metal layer made of copper was formed on the upper layer of the polyethylene terephthalate material. After heating this film base material (henceforth a "base material") and heating up at 80 degreeC, the photosensitive element produced above was laminated (laminated | stacked) on the metal layer surface of the base material. Lamination is performed under conditions of a temperature of 110 ° C. and a lamination pressure of 4 kgf / cm ² (0.4 MPa) so that the photosensitive layer of the photosensitive element is in close contact with the surface of the metal layer of the substrate while removing the protective layer. It was. In this way, a laminated substrate in which the photosensitive layer and the support were laminated on the surface of the metal layer of the substrate was obtained.

<Evaluation of sensitivity>
The obtained laminated substrate was allowed to cool to 23 ° C. Next, the laminated substrate is divided into three regions, and on one of the regions, a concentration region of 0.00 to 2.00, a concentration step of 0.05, a tablet size of 20 mm × 187 mm, each step. A phototool having a 41-step tablet having a size of 3 mm × 12 mm was adhered. For exposure, a parallel light exposure machine (product name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.) using a short arc UV lamp (product name “AHD-5000R” manufactured by Oak Manufacturing Co., Ltd.) as a light source is used. The photosensitive layer was exposed through a photo tool and a support with an energy amount (exposure amount) of 100 mJ / cm ² . At this time, other areas not used were covered with a black sheet. Moreover, it exposed with the energy amount of 200mJ / cm < ² > and 400mJ / cm < ² > separately with respect to each different area | region by the same method. The illuminance was measured using an ultraviolet illuminance meter (product name “UIT-150” manufactured by USHIO INC.) To which a 405 nm probe was applied.

After the exposure, the support was peeled off from the laminated base material, the photosensitive layer was exposed, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. was sprayed for 16 seconds to remove unexposed portions. Thus, the resist pattern which consists of a photocured material of the photosensitive resin composition was formed on the metal layer surface of a base material. A calibration curve between the exposure amount and the step step number is created from the remaining step number (step step number) of the step tablet obtained as a resist pattern (cured film) at each exposure amount, and the exposure amount at which the step step number is 17 steps is obtained. Thus, the sensitivity of the photosensitive resin composition was evaluated. The sensitivity is indicated by the exposure amount at which the number of step steps obtained from the calibration curve is 17, and the smaller the exposure amount, the better the sensitivity. The results are shown in Tables 3 and 4.

<Evaluation of adhesion>
The remaining 41 step tablet using a mask pattern having a line width (L) / space width (S) (hereinafter referred to as “L / S”) of 4/400 to 30/400 (unit: μm). The photosensitive layer of the laminated substrate was exposed with an energy amount of 17 steps. After the exposure, the same development processing as in the sensitivity evaluation was performed.

After development, the minimum value of the line width / space width values in the resist pattern in which the space portion (unexposed portion) is removed neatly and the line portion (exposed portion) is formed without causing meandering, peeling and chipping. Thus, the adhesion was evaluated. The smaller this value, the better the adhesion. The results are shown in Tables 3 and 4.

<Evaluation of resolution>
Using a mask pattern having an L / S of 1/1 to 30/30 (unit: μm), the photosensitive layer of the laminated base material is exposed with an energy amount that makes the remaining number of steps of a 41-step step tablet 17 steps. did. After the exposure, the same development processing as in the sensitivity evaluation was performed.

After development, the minimum value of the line width / space width values in the resist pattern in which the space portion (unexposed portion) is removed neatly and the line portion (exposed portion) is formed without causing meandering, peeling and chipping. The resolution was evaluated. The smaller this value, the better the resolution. The results are shown in Tables 3 and 4.

<Evaluation of adhesion after etching>
The adhesion after etching of the resist pattern was evaluated as follows. Using a mask pattern having an L / S of 4/400 to 47/400 (unit: μm), the photosensitive layer of the laminated base material is exposed with an energy amount that makes the remaining number of steps of the 41-step tablet tablet 23. did. After the exposure, the same development treatment as in the sensitivity evaluation was performed to obtain a patterned substrate.

The obtained base material was etched at 40 ° C. for 30 seconds using ITO-4400Z (trade name, manufactured by ADEKA Corporation), and then washed and dried.

The value of the line width / space width in the resist pattern in which the metal layer and the transparent conductive layer in the space portion (unexposed portion) are removed neatly and the line portion (exposed portion) is formed without causing meandering, peeling and chipping. The adhesion after etching was evaluated by the minimum value.
The smaller this value, the higher the etchant resistance and the better the adhesion. The results are shown in Tables 3 and 4.

<Evaluation of line shape after etching>
The line shape after the etching of the wiring pattern is the digital microscope for the wiring pattern formed under the resist pattern having L / S of 47/400 (unit: μm) in the evaluation of the adhesion after the etching. Observation was performed using VHX-2000 (manufactured by Keyence Corporation). Further, the side etching width was calculated from the difference between the line width of the resist pattern and the line width of the circuit pattern after etching. The line shape after etching the wiring pattern was evaluated according to the following criteria based on the value of the side etching width and the presence or absence of rattling. The results are shown in Tables 3 and 4.
A: There is no backlash in the line shape after etching the wiring pattern, and the value of the side etching width is less than 5 μm.
B: Although there is no backlash in the line shape after etching the wiring pattern, the value of the side etching width is 5 μm or more and less than 8 μm.
C: The line shape after the etching of the wiring pattern is not rattled, but the value of the side etching width is 8 μm or more.
D: Roughness is observed in the line shape after etching the wiring pattern.

<Evaluation of flexibility>
The flexibility of the resist pattern was evaluated by a mandrel test (JIS K5600-5-1). Using a polyethylene terephthalate negative (a negative that can expose the entire surface), the photosensitive layer of the laminated base material was exposed with an energy amount such that the number of remaining stages of the 41-step tablet was 17. After the exposure, the same development treatment as in the sensitivity evaluation was performed to obtain a laminated base material on which a cured film was formed. The laminated base material on which this cured film was formed was cut out to 10 mm × 100 mm to obtain a test piece for a mandrel test. The test piece was bent at 180 ° along the side of a cylindrical rod (mandrel jig) having diameters of 2, 3, 4, 5, 6, 8, 10, 12, 16, 20, 25 mm, and then tested. By pulling alternately while keeping both ends of the pieces in parallel, the two-thirds of the test piece was slid 5 times at a constant speed along the side surface of the mandrel jig. Then, the minimum diameter which does not peel and crack between a base material and a resist pattern was calculated | required. The smaller the minimum diameter, the better the flexibility. The results are shown in Tables 3 and 4.

Examples 1 to 7 in which (meth) acrylate having six ethylenically unsaturated bonds in the molecule and (meth) acrylate having an isocyanuric ring skeleton were used as the photopolymerizable compound and Comparative Examples 1 and 2 In comparison, it was found that the adhesion after etching and the line shape can be improved in a well-balanced manner and the flexibility is excellent.

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

Claims

(A) component: binder polymer,
(B) component: a photopolymerizable compound, and
(C) component: contains a photopolymerization initiator,
The photosensitive resin composition in which the said (B) component contains the (meth) acrylate which has six ethylenically unsaturated bonds in a molecule | numerator, and the (meth) acrylate which has an isocyanuric ring frame | skeleton.
The photosensitive resin composition according to claim 1, wherein the component (B) further comprises a bisphenol A type di (meth) acrylate having a (poly) oxyethylene group.
A photosensitive element comprising: a support; and a photosensitive layer formed using the photosensitive resin composition according to claim 1 or 2 provided on one surface of the support.
A photosensitive layer forming step of forming a photosensitive layer on the substrate using the photosensitive resin composition according to claim 1 or 2 or the photosensitive element according to claim 3,
An exposure step of curing a part of the photosensitive layer by irradiation with actinic rays to form a photocured product region;
A development step of removing a region other than the photocured product region of the photosensitive layer from the substrate to obtain a resist pattern composed of the photocured product region,
A method for forming a resist pattern.
On the metal layer of a laminated substrate comprising a support substrate, a transparent conductive layer containing indium tin oxide provided on one surface of the support substrate, and a metal layer provided on the transparent conductive layer, The 1st process of forming the resist pattern which consists of photocured material of the photosensitive resin composition of claim | item 1 or 2;
A second step of etching the metal layer and the transparent conductive layer to form a laminate pattern composed of the remainder of the transparent conductive layer and the remainder of the metal layer;
A third step of removing the metal layer from a part of the laminated pattern to form a transparent electrode made of the remainder of the transparent conductive layer and a metal wiring made of the remainder of the metal layer;
A method for manufacturing a touch panel.
The transparent conductive layer comprises crystalline indium tin oxide;
The touch panel manufacturing method according to claim 5, wherein the etching in the second step is etching with a strong acid.