KR102522237B1 - Photosensitive resin composition, photosensitive element, method for forming resist pattern and method for manufacturing touch panel - Google Patents

Abstract

(A) component: a binder polymer, (B) component: a photopolymerizable compound, and (C) component: a photopolymerization initiator, wherein the (B) component has six ethylenically unsaturated bonds in a molecule (meta) It contains an acrylate and (meth)acrylate having one ethylenically unsaturated bond in the molecule, and the content of the (meth)acrylate having one ethylenically unsaturated bond in the molecule is (B) The photosensitive resin composition which is 10 mass parts or less in 100 mass parts of total amounts of a component.

Description

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

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

The touch sensor part of the touch panel includes a sensor part for detecting positional information due to a contact of a human finger or the like in a range (view area) displaying visual information, and for transmitting positional information to an external element. It consists of a configuration having a lead-out wiring portion.

At the sensor portion, a pattern of electrodes having little absorption and scattering of visible light and having conductivity is formed. In addition, a metal having a low resistance value is used for each wiring in the lead-out wiring portion.

Such a sensor site and outgoing wiring site are manufactured as shown in FIG. 2 using, for example, a negative photosensitive resin composition. 2 is a schematic cross-sectional view showing a conventional manufacturing method for a touch sensor part of a touch panel. First, the photosensitive layer 16 is formed on a support substrate 12 (a film substrate such as polyethylene terephthalate or a glass substrate) having a transparent conductive layer 14 by application of a photosensitive resin composition or the like ( photosensitive layer forming process) (FIG. 2(a)). Next, actinic light is irradiated to a predetermined portion of the photosensitive layer 16 to cure the exposed portion (exposure process). After that, by removing the uncured portion from the top of the transparent conductive layer 14, a resist pattern containing a photocured product of the photosensitive resin composition is formed on the transparent conductive layer 14 (development step) (FIG. 2 (b)). An etching process is performed on the resist pattern, and a part of the transparent conductive layer 14 is removed from the support substrate 12 to form a pattern of the transparent conductive layer at the sensor site (etching process) (FIG. 2(c) ). Next, the resist pattern is peeled off and removed from the transparent conductive layer 14 (peeling process) (FIG. 2(d)). Subsequently, the touch sensor unit is manufactured by forming lead wires 18 from the pattern of the transparent conductive layer of the formed sensor portion by screen printing using silver paste or the like.

In addition, with the narrowing of the frame (bezel) of the touch panel, narrowing of the wiring width and pitch in the outgoing wiring portion is required. In screen printing using silver paste, pattern formation with an L/S (line width/space width) of about 50/50 (unit: μm) is considered to be the limit, but L/S is 30/30 to cope with the narrowing of the picture frame. (Unit: μm) or less pattern formation is required.

In order to manufacture a touch sensor unit having a pattern of outgoing wires having a small L/S and a narrow pitch, a method of forming a touch sensor unit using a photolithography technique has been proposed (see Patent Document 1, for example). In this touch sensor part manufacturing method, first, a 1st photosensitive layer is formed on the support base material which has a transparent conductive layer and a metal layer using a photosensitive resin composition (1st photosensitive layer forming process). Next, a predetermined portion of the photosensitive layer is irradiated with actinic light to cure the exposed portion (first exposure step), and thereafter, the uncured portion is removed from the metal layer to form a photocured product of the photosensitive resin composition on the metal layer. A resist pattern including is formed (first developing process). Next, the metal layer and the transparent conductive layer are removed by etching treatment (first etching step). Next, the resist pattern is peeled off and removed from the metal layer (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 light to cure the exposed portion (second exposure step), and then, by removing the uncured portion from the metal layer, a resist pattern is formed on the metal layer ( 2nd developing process). Next, only the unnecessary metal layer on which the resist pattern is not formed is removed from the sensor portion by an etching process (second etching process), and finally, the resist pattern is peeled off and removed to manufacture the touch sensor unit.

In such a method of manufacturing a touch sensor unit, by using a photolithography technique, it is possible to make L/S 30/30 (unit: μm) or less in principle, greatly contributing to thinning and lightening of touch panels. can do. On the other hand, the transparent conductive layer of the touch sensor part is formed by, for example, forming a film of indium tin oxide (ITO) using a sputtering technique. In addition, the metal layer formed on the transparent conductive layer is formed using the technique of sputtering similarly to the transparent conductive layer, for example. The surfaces of the transparent conductive layer and the metal layer formed 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 decrease, copper, an alloy of copper and nickel, an alloy of copper, nickel and titanium, a molybdenum-aluminum-molybdenum laminate, a silver-palladium and High adhesiveness is requested|required of the photosensitive resin composition used with respect to the metal layer in which an alloy with copper etc. are used.

Moreover, from a viewpoint of the ease of an etching process, amorphous ITO is used for a transparent conductive layer, for example. However, since amorphous ITO has a high resistance value, the resistance value is lowered by, for example, crystallizing ITO by heating (annealing) treatment. However, in recent years, along with thinness and weight reduction of touch panels, it is required to use a film substrate as a support substrate for a touch panel portion. In the case of using a film substrate as the supporting substrate, dimensional stability deteriorates, such as shrinkage of the film substrate when subjected to annealing treatment. Therefore, when using a film base material as a support base material, it becomes necessary to use crystalline ITO as a transparent conductive layer before forming the pattern of a transparent conductive layer.

Amorphous ITO can be sufficiently dissolved with a weak acid such as oxalic acid, but crystalline ITO requires the use of a strong acid such as concentrated hydrochloric acid (>20% by mass) and further etching under heating conditions (about 40 to 50°C). there is Therefore, the photosensitive resin composition used is required to have high acid resistance, that is, to be able to secure adhesion to the metal layer by etching using strong acid, and to be able to suppress corrosion of the metal layer by strong acid.

In addition, as a method of forming a wiring pattern (which can also be referred to as a conductor pattern) having high resolution by making the L/S of the resistor pattern 30/30 (unit: μm) or less, etching the metal layer and the transparent conductive layer at once There is a way. In conventional methods of etching the metal layer and then etching the transparent conductive layer, it is difficult to obtain a wiring pattern having high resolution because the in-plane variation at the time of etching becomes large. As a chemical solution for etching the metal layer and the transparent conductive layer at once, ITO-4400Z (manufactured by ADEKA Corporation) is commercially available.

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

In addition, as a photosensitive resin composition used for formation of a resist pattern, various photosensitive resin compositions are examined. For example, in the photosensitive resin composition, adding a specific crosslinking agent, a specific silane coupling agent, etc., using a binder polymer having a specific structural unit as an essential component, etc. have been proposed (eg, patent See Documents 3-7).

Patent Document 1: Japanese Patent No. 4855536 Patent Document 2: Japanese Patent No. 4219641 Patent Document 3: Japanese Unexamined Patent Publication No. 2002-040645 Patent Document 4: Japanese Unexamined Patent Publication No. 2002-268215 Patent Document 5: Japanese Unexamined Patent Publication No. 2008-112146 Patent Document 6: Japanese Unexamined Patent Publication No. 2009-042720 Patent Document 7: Japanese Unexamined Patent Publication No. 2003-107695

In the case of forming a resist pattern with high resolution by setting L/S of the resist pattern to 30/30 (unit: μm) or less, defects such as bending (also called meandering), chipping, peeling, etc. of the resist pattern It is easier for this to happen. In particular, in this field, there is a possibility that a short circuit or disconnection may occur in the electrode and lead wiring at the sensor site due to the occurrence of a defect. Therefore, it is required more than before that resist patterns do not have bends, chips, peeling, or the like.

However, in the photosensitive resin composition described in Patent Literature 2, it is difficult to form a resist pattern having excellent resolution, and the resist pattern may be defective. In addition, in the photosensitive resin compositions described in Patent Documents 3 to 7, defects such as peeling and chipping of the resist may occur during ITO etching. In particular, when a strong etchant used to remove ITO is used, defects such as peeling and chipping occur in the resist pattern, or wiring formed even if defects such as peeling and chipping do not occur in the resist pattern. It has been found that there is a tendency for wobble to occur or to easily occur in the line shape of the pattern. In addition, it has been found that it is difficult to achieve both a good line shape of the wiring pattern with few defects that may occur in the resist pattern and a good peelability and short peeling time of the resist pattern at a high level in a well-balanced manner.

The present invention has been made in order to solve such problems, and even when a strong etchant is used, peeling and chipping of the resist can be suppressed, and a wiring pattern having a good line shape without wobble can be obtained. It is an object of the present invention to provide a photosensitive resin composition capable of forming a resistor pattern having a sufficiently short peeling time while being able to be formed. Another object of the present invention is to provide a method of forming a photosensitive element, a resist pattern, and a method of manufacturing a touch panel using the photosensitive resin composition.

The inventors of the present invention, as a result of repeated studies in order to solve the above problems, found that a resist pattern having excellent characteristics can be formed by using a photosensitive resin composition containing predetermined components.

That is, the 1st aspect of this invention contains (A) component: a binder polymer, (B) component: a photopolymerizable compound, and (C) component: a photoinitiator, and said (B) component This includes (meth)acrylate having 6 ethylenically unsaturated bonds in the molecule and (meth)acrylate having 1 ethylenically unsaturated bond in the molecule, and having 1 ethylenically unsaturated bond in the molecule ( It is related with the photosensitive resin composition whose content of meth)acrylate is 10 mass parts or less in 100 mass parts of total amounts of the said (A) component and the said (B) component.

According to such a photosensitive resin composition, since it is easy to control the crosslinking density in the photocured product of the photosensitive resin composition, peeling and chipping of the resist can be suppressed even when a strong etchant is used, and shaking is prevented. It is possible to obtain a wiring pattern having a good line shape without any problems and to form a resistor pattern with a sufficiently short peeling time. Therefore, a high-resolution fine circuit pattern can be formed by using such a photosensitive resin composition.

The said (B) component may further contain the bisphenol-A di(meth)acrylate which has a (poly)oxyethylene group. According to such a photosensitive resin composition, the acid resistance of the resist pattern is further improved, and peeling due to swelling of the resist pattern at the time of ITO etching can be further remarkably suppressed.

A second aspect of the present invention relates to a photosensitive element comprising 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. Since such a photosensitive element includes a photosensitive layer formed using the photosensitive resin composition according to the first aspect, peeling and chipping of the resist can be suppressed even when a strong etchant is used, and , it is possible to obtain a wiring pattern having a good line shape without wobbling and at the same time to form a resistor pattern with a sufficiently short peeling time. Therefore, by using such a photosensitive element, a high-resolution fine circuit pattern can be formed.

A third aspect of the present invention is 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; An exposure step of curing a part of the photosensitive layer by irradiation with actinic light to form a photocured region; and removing an area of the photosensitive layer other than the photocured region from the base material to form the photocured region. It is related with the formation method of the resist pattern which has a developing process which obtains the formed resist pattern. According to such a resist pattern formation method, even when a strong etchant is used, peeling and chipping of the resist can be suppressed, and a wiring pattern having a good line shape without wobble can be obtained. , a resist pattern with a sufficiently short peeling time can be formed. In addition, according to such a method for forming a resist pattern, it is possible to form a resist pattern having excellent adhesion even to a substrate having high smoothness and excellent resolution.

The fourth aspect of the present invention is a laminated substrate having 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. On the metal layer, A first step of forming a resist pattern made of a photocured product of the photosensitive resin composition according to the first aspect, etching the metal layer and the transparent conductive layer, and removing the remainder of the transparent conductive layer and the metal layer. a second step of forming a laminated pattern composed of the remainder of the laminated pattern; and a step of removing the metal layer from a part of the laminated pattern to form a transparent electrode composed of the remainder of the transparent conductive layer and a metal wiring composed of the remainder of the metal layer. It relates to a manufacturing method of a touch panel having three steps.

According to the manufacturing method of such a touch panel, since the resist pattern is formed from the photocured material of the photosensitive resin composition according to the first aspect, peeling of the resist pattern in the etching process is sufficiently suppressed and easily It is possible to efficiently manufacture a narrow pitch touch panel (for example, a touch panel having an L/S of 30/30 or less outgoing wiring).

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 above manufacturing method, since the resist pattern is formed from a photocured material of the photosensitive resin composition according to the first aspect, peeling or the like of the resist pattern is sufficiently suppressed even by etching with a strong acid. Therefore, the above manufacturing method can be suitably applied to the manufacture of a touch panel using a laminated substrate provided with a transparent conductive layer containing crystalline indium tin oxide.

According to the present invention, even when a strong etchant is used, peeling and chipping of the resist can be suppressed, and a wiring pattern having a good line shape without wobble can be obtained, and the peeling time can be sufficiently reduced. A photosensitive resin composition capable of forming a short resist pattern 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.

Fig. 1 is a schematic cross-sectional view showing one embodiment of a photosensitive element of the present invention.
Fig. 2 is a schematic cross-sectional view showing a conventional manufacturing method for a touch panel.
[Fig. 3] A schematic cross-sectional view showing one aspect of a method for manufacturing a touch panel according to the present invention.
[Fig. 4] It is a top view showing one aspect of a touch panel obtained by using the present invention.

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

In addition, in this specification, a (poly)oxyalkylene group means at least 1 sort(s) of the oxyalkylene group or the polyoxyalkylene group in which two or more alkylene groups were connected by the ether bond. That is, the (poly)oxyethylene group means at least one of an oxyethylene group or a polyoxyethylene group in which two or more ethylene groups are connected by an ether bond, and the same applies to other similar expressions such as a (poly)oxypropylene group. In addition, a (poly)oxyethylene group is sometimes referred to as an "EO group" and a (poly)oxypropylene group is referred to as a "PO group". In addition, the term "layer" includes a structure formed on a part of the structure in addition to a structure formed on the entire surface when observed in a plan view. In addition, the term "process" is included in this term, not only in an independent process, but also in a case where it cannot be clearly distinguished from other processes, provided that the intended purpose of the process is achieved. In addition, the numerical range expressed using "-" shows the range which includes the numerical value described before and after "-" as a minimum value and a maximum value, respectively. In addition, in the numerical range described step by step in this specification, you may replace the upper limit or lower limit of the numerical range of a certain stage with the upper limit or lower limit of the numerical range of another stage. In addition, in the numerical range described in this specification, you may replace the upper limit value or the lower limit value of the numerical range with the value shown in the Example.

<Photosensitive resin composition>

The photosensitive resin composition (hereinafter, simply referred to as "photosensitive resin composition") according to the present embodiment includes (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: photopolymerization initiator. , wherein the component (B) contains (meth)acrylate having 6 ethylenically unsaturated bonds in the molecule and (meth)acrylate having 1 ethylenically unsaturated bond in the molecule, and in the molecule A photosensitive resin in which the content of (meth)acrylate having one ethylenically unsaturated bond is 10 parts by mass or less (however, more than 0 parts by mass) in 100 parts by mass of the total amount of the component (A) and the component (B) is a composition

According to such a photosensitive resin composition, it is possible to form a high-resolution resist pattern in which peeling and generation of chips are suppressed. In addition, since the resist pattern formed using the photosensitive resin composition tends to be less prone to peeling and chipping even when ITO is etched using a strong acid, the obtained circuit pattern has a good line shape. Therefore, the photosensitive resin composition according to this embodiment is suitable for ITO etching, particularly for etching a transparent conductive layer containing crystalline ITO.

(A) Component: Binder polymer

The photosensitive resin composition contains at least 1 sort(s) of binder polymer as (A) component. As a binder polymer, the polymer obtained by radically polymerizing a polymerizable monomer (monomer) is mentioned, for example.

As the polymerizable monomer (monomer), (meth)acrylic acid; (meth)acrylic acid alkyl esters, (meth)acrylic acid cycloalkyl esters, (meth)acrylic acid benzyl, (meth)acrylic acid benzyl derivatives, (meth)acrylic acid furfuryl, (meth)acrylic acid ) tetrahydrofurfuryl acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, (meth)acrylate Glycidyl acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, α-bromoacrylic acid, α-chloroacrylic acid, Dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, isobornyloxyethyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, adamantyloxyethyl (meth)acrylate, ( meth)acrylate dicyclopentenyloxypropyloxyethyl, (meth)acrylate dicyclopentanyloxypropyloxyethyl, (meth)acrylate dicyclopentenyloxypropyloxyethyl, (meth)acrylate adamantyloxypropyloxyethyl, β -(meth)acrylic acid esters such as furyl(meth)acrylic acid and β-styryl(meth)acrylic acid; styrene; polymerizable styrene derivatives substituted at the α-position or aromatic ring such as vinyltoluene and α-methylstyrene; Acrylamides such as acetone acrylamide; Acrylonitrile; Ether compounds of vinyl alcohol such as vinyl-n-butyl ether; Maleic acid; Maleic anhydride; Monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc. maleic acid monoesters; unsaturated carboxylic acid derivatives such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid and propiolic acid; and the like. These can be used individually or in combination of 2 or more types arbitrarily.

(A) 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 is based on the total amount of the component (A) (100 mass) in terms of resolution and peelability (resist peelability after etching). 10 to 60% by mass, 15 to 50% by mass, or 20 to 35% by mass may be used as %, the same below). In addition, in this specification, "the whole amount of (A) component" means the whole amount of solid content in it. In addition, the "total amount of (A) component and (B) component" mentioned later is also the same. In addition, "solid content" refers to the non-volatile matter except for volatilizing substances, such as water and a solvent, of the photosensitive resin composition. That is, it refers to components other than the solvent that remains without volatilization in the drying step, and includes liquid, starch syrup, and waxy components at room temperature around 25°C.

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

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 alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate and and 2-ethylhexyl (meth)acrylate. These can be used individually or in combination of 2 or more types arbitrarily.

When the component (A) has a structural unit derived from an alkyl (meth)acrylate, the content is 40 to 90% by mass based on the total amount of the component (A), in terms of resolution and adhesion. It may be 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 view of excellent developability and adhesiveness.

From the point of shortening development time, this 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.

Moreover, 250 mgKOH/g or less, 240 mgKOH/g or less, 235 mgKOH/g or less, or 230 mgKOH/g or less may be sufficient as this acid value from the point which further improves the adhesiveness of the photocured material of the photosensitive resin composition. In addition, when performing solvent development, you may adjust a small amount of polymerizable monomers (monomers) which have a carboxyl group, such as (meth)acrylic acid.

(A) The weight average molecular weight (Mw) of component is 10000 to 200000, 20000 in terms of excellent developability and adhesion when measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene) It may be -100000, 25000-80000, or 30000-60000. In terms of excellent developability, it may be 200000 or less, 100000 or less, 80000 or less, or 60000 or less. In terms of excellent adhesion, it may be 10000 or more, 20000 or more, 25000 or more, or 30000 or more.

(A) The degree of dispersion (weight average molecular weight/number average molecular weight) of the component may be 3.0 or less, 2.8 or less, or 2.5 or less in terms of 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 combination arbitrarily.

The content of the component (A) in the photosensitive resin composition is 30 to 70 parts by mass and 35 to 65 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B) in terms of film formability, sensitivity, and resolution. Part by mass or 40 to 60 parts by mass may be sufficient. From the point of formation of a film (photosensitive layer), this content may be 30 mass parts or more, 35 mass parts or more, or 40 mass parts or more. In addition, in terms of well-balanced improvement in sensitivity and resolution, this content may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less.

(B) component: photopolymerizable compound

The photosensitive resin composition contains, as component (B), (meth)acrylate having six ethylenically unsaturated bonds in the molecule and (meth)acrylate having one ethylenically unsaturated bond in the molecule.

As (meth)acrylate which has 6 ethylenically unsaturated bonds in a molecule|numerator, dipentaerythritol hexa(meth)acrylate is mentioned, for example. These may have EO group or PO group. Further, when (meth)acrylate having six ethylenically unsaturated bonds in the molecule has an EO group, the number of EO groups in the molecule may be 6 to 30, 6 to 24, or 6 to 12 from the viewpoint of improving adhesion. do.

As dipentaerythritol hexa(meth)acrylate which has EO group or PO group, more specifically, the compound represented by the following general formula (1) is mentioned, for example.

In general formula (1), R represents a hydrogen atom or a methyl group each independently.

In general formula (1), A represents a C2-C6 alkylene group, a C2-C5 alkylene group, or a C2-C4 alkylene group. As a C2-C6 alkylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, and a hexylene group etc. are mentioned, for example. Among these, from the standpoint of improving resolution, adhesion, and suppression of register hemming, an ethylene group or an isopropylene group may be used, or an ethylene group may be used. In addition, a plurality of A's may be the same as or different from each other.

In general formula (1), n is an integer of 0-20 each independently. From the standpoint 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 total of six n in Formula (1) may be 6 to 30, 6 to 24, or 6 to 12.

In the photosensitive resin composition, the content of (meth)acrylate having six ethylenically unsaturated bonds in the molecule is, from the viewpoint of improving the adhesiveness and peelability after etching in a well-balanced manner, (A) component and (B) component It may be 3 to 20 parts by mass, 3 to 15 parts by mass, or 3 to 10 parts by mass in 100 parts by mass of the total amount. The (meth)acrylates having six ethylenically unsaturated bonds in the molecule may be used alone or in combination of two or more.

Examples of (meth)acrylates having one ethylenically unsaturated bond in the molecule include nonylphenoxypolyethyleneoxyacrylate (also referred to as “nonylphenoxypolyethylene glycol acrylate”), 2-hydroxy-3- and phenoxypropyl (meth)acrylate, phthalic acid-based compounds, and (meth)acrylic acid alkyl esters. Among these, at least any one of 2-hydroxy-3-phenoxypropyl (meth)acrylate or a phthalic acid-based compound may be included from the viewpoint of improving resolution, adhesiveness, and release characteristics after curing in a well-balanced manner.

Examples of the phthalic acid compound having one ethylenically unsaturated bond in the molecule include γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate, 2-acryloyloxyethyl -2-hydroxyethyl-phthalic acid and 2-acryloyloxyethyl-phthalic acid.

In the photosensitive resin composition, the content of (meth)acrylate having one ethylenically unsaturated bond in the molecule is, from the viewpoint of reducing peeling and chipping of the resist after etching, (A) component and (B) component In 100 parts by mass of the total amount, it may be 10 parts by mass or less, 8 parts by mass or less, or 5 parts by mass or less. Moreover, the lower limit is more than 0 parts by mass and may be 0.1 parts by mass or more from the viewpoint of improving the peelability. The (meth)acrylates having one ethylenically unsaturated bond in the molecule may be used alone or in combination of two or more.

Component (B) may further contain other photopolymerizable compounds other than (meth)acrylate having six ethylenically unsaturated bonds in the molecule and (meth)acrylate having one ethylenically unsaturated bond in the molecule. Other photopolymerizable compounds are not particularly limited as long as they are capable of photopolymerization. The other photopolymerizable compound may be a radically polymerizable compound or a compound having an ethylenically unsaturated bond. Examples of compounds having ethylenically unsaturated bonds include compounds having two ethylenically unsaturated bonds in a molecule ((meth)acrylate), compounds having three or more ethylenically unsaturated bonds in a molecule ((meth)acrylate), and the like. can Other photopolymerizable compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

(B) component may further contain the compound which has two ethylenically unsaturated bonds in a molecule|numerator.

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

(B) component may also contain bisphenol-A di(meth)acrylate from a viewpoint of further improving acid resistance.

Examples of the bisphenol A di(meth)acrylate include compounds represented by the following general formula (2).

In General Formula (2), 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 represent 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 of the structural unit. Therefore, it represents an integer value for a single molecule, and represents a rational number, which is an average value, for an aggregate of plural types of molecules. Hereinafter, the number of structural units of the structural unit is the same.

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

From the standpoint of excellent line shape of the wiring pattern to be obtained, component (B) is, in General Formula (2), when XO is an oxyethylene group, m ₁ + m ₂ is 1 to 30, or when YO is an oxyethylene group contains a compound in which n ₁ + n ₂ of is 1 to 30, and the content may be 30 to 50 parts by mass, 30 to 45 parts by mass, or 30 to 40 parts by mass in 100 parts by mass of the total amount of the component (B).

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

Content of the whole (B) component in the photosensitive resin composition is 30-70 mass parts, 35-65 mass parts, 40-60 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, or , 35 to 55 parts by mass may be sufficient. When this content is 30 parts by mass or more, sensitivity and resolution tend to improve in a well-balanced manner. When it is 70 parts by mass or less, it tends to make it easier to form a film (photosensitive layer), and it tends to make it easier to obtain a good resist pattern shape.

(C) component: photopolymerization initiator

The photosensitive resin composition contains at least 1 sort(s) of photoinitiator as (C)component. 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.

As component (C), benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]- Aromatic ketones such as 2-morpholino-propanone-1; Quinones such as alkylanthraquinone; Benzoin ether compounds such as benzoin alkyl ether; Benzoin compounds such as benzoin and alkylbenzoin; Benzyldimethylketal, etc. Benzyl derivatives; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, etc.; 4,5-triarylimidazole dimer; Acridine derivatives, such as 9-phenylacridine and 1,7-(9,9'-acridinyl) heptane, etc. are mentioned. These can be used individually or in combination of 2 or more types.

(C) component may contain at least 1 sort(s) of 2,4,5-triaryl imidazole dimer from a viewpoint of further improving sensitivity and adhesiveness, 2-(o-chlorophenyl) -4, A 5-diphenylimidazole dimer may also be included. The 2,4,5-triarylimidazole dimer may have a symmetrical or asymmetrical structure.

Content of (C)component in the photosensitive resin composition is 0.1-10 mass parts, 1-7 mass parts, 2-6 mass parts, or, with respect to 100 mass parts of total amounts of (A) component and (B) component, It may be 3 to 5 parts by mass. When this content is 0.1 parts by mass or more, it tends to be easy to obtain good sensitivity, resolution or adhesion, and when it is 10 parts by mass or less, it tends to be easy to obtain a good resist pattern shape.

(D): Silane coupling agent

The photosensitive resin composition may further contain a silane coupling agent as (D)component. As a silane coupling agent, component (D1): a silane compound having a mercaptoalkyl group, component (D2): a silane compound having an amino group (preferably a silane compound having a ureid group), component (D3): (meth)acrylic The silane compound which has an oxy group is mentioned.

When the photosensitive resin composition contains the component (D1) as the component (D), it is excellent in adhesion to a substrate having high smoothness, and also has excellent acid resistance that is resistant to peeling or the like even by ITO etching with hydrochloric acid. It can form, can show an outstanding effect.

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

For example, the photosensitive resin composition can use a component (D1) and a component (D3) together as (D) component. When the photosensitive resin composition contains only the component (D1) as the component (D), a resist pattern exhibiting excellent adhesion is obtained, while development residues on a copper substrate or the like are easily generated (ie, a resist pattern formed on a copper substrate, It tends to be difficult to peel 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), while maintaining excellent adhesion, generation of development residues to copper substrates and the like is suppressed, and the etching time is shortened. can do.

In addition, the photosensitive resin composition may contain all of the (D1) component, (D2) component, and (D3) component as (D)component. According to such a photosensitive resin composition, higher adhesiveness is realizable, suppressing generation|occurrence|production of the development residue with respect to a copper substrate etc.

As the component (D1), a silane compound (mercaptoalkylalkoxysilane) having a mercaptoalkyl group and an alkoxy group may be used, and as such component (D1), mercaptopropylmethyldimethoxysilane, mercaptopropyltrimethoxysilane, Captopropyltriethoxysilane etc. are mentioned. Among these, mercaptopropyltrimethoxysilane, which easily undergoes hydrolysis and is capable of crosslinking at three points, is most preferred for expression of adhesiveness. These can be used individually or in combination of 2 or more types.

(D2) As a component, the silane compound which has a primary amino group at the terminal may be sufficient, As such a (D2) component, 3-aminopropyl methoxysilane, aminopropyl ethoxysilane, N-2- (amino Ethyl)-3-aminopropyltrimethoxysilane, 3-ureidpropyltriethoxysilane, 3-ureidpropyltrimethoxysilane, ureaidmethyltrimethoxysilane, ureaidmethyltriethoxysilane, 2- Urade ethyl trimethoxysilane, 2-ureid ethyl triethoxysilane, 4-ureid butyl trimethoxysilane, 4-ureid butyl triethoxysilane, etc. are mentioned. Among these, in consideration of 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 ureide group, and when used in combination with the component (D1), the effect of suppressing development residue is particularly remarkable. 3 -Ureidpropyltriethoxysilane is most preferred. These can be used individually or in combination of 2 or more types.

(D3) As a component, for example, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Ethoxysilane is mentioned. Among these, 3-methacryloxypropyltrimethoxysilane, which easily undergoes hydrolysis and is capable of crosslinking at three points, is most preferable for expression of adhesiveness. These can be used individually or in combination of 2 or more types.

The content of the component (D) in the photosensitive resin composition is 0.01 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.05 to 5 parts by mass, with respect to 100 parts by mass of the total amount of the component (A) and the component (B), in view of excellent adhesion. , 0.1 to 3 parts by mass may be sufficient. If the content of component (D) is greater than the above range, there is a tendency for development residue to be easily generated on copper substrates and the like, and also, insufficient curing of the bottom of the resist due to a decrease in resolution and a significant increase in sensitivity may occur. may occur. On the other hand, when the content of 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 is obtained, and the resistance to the etchant is further improved.

(other ingredients)

The photosensitive resin composition may contain components other than the said (A) - (D) component as needed. For example, the photosensitive resin composition contains at least one selected from the group consisting of a sensitizing dye, bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, and leuco crystal violet. may contain

(E) An ingredient: Sensitizing dye

The photosensitive resin composition according to this embodiment may further contain a sensitizing dye as (E) component. Examples of the sensitizing dye include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, and benzothiazole. compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. These can be used individually or in combination of 2 or more types. A pyrazoline compound may be contained from the viewpoint of further improving the degree of curing at the bottom of the resistor and providing excellent adhesion.

When the photosensitive resin composition contains component (E), its content improves the curing degree of the bottom of the resist and further improves adhesion, with respect to 100 parts by mass of the total amount of component (A) and component (B), 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.

Further, the photosensitive resin composition is a polymerizable compound having at least one cationically polymerizable cyclic ether group in a molecule (such as an oxetane compound); a cationic polymerization initiator; dyes such as malachite green, Victoria pure blue, brilliant green, and methyl violet; Photochromic agents such as ribomophenylsulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline, and o-chloroaniline; anti-coloring agents; plasticizers such as p-toluenesulfonamide; pigments; fillers; antifoaming agents; flame retardants; Stabilizer; Adhesion imparting agent; Leveling agent; Peeling accelerator; Antioxidant; Flavoring agent; Imaging agent; Thermal crosslinking agent; etc. may be contained. These can be used individually or in combination of 2 or more types.

When the photosensitive resin composition contains other components (components other than components (A) to (D)), these contents are each 0.01 part by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). It may be about 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. Examples of the organic solvent 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; and aprotic polar solvents such as N,N-dimethylformamide. These may be used alone or in combination 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 can be used as a liquid composition having a solid content of about 30% to 60% by mass (hereinafter, a photosensitive resin composition containing an organic solvent is also referred to as “coating liquid”).

The photosensitive layer which is a coating film of the photosensitive resin composition can be formed by apply|coating a coating liquid on the surface of the support body mentioned later, a metal plate, etc., and drying it. The metal plate is not particularly limited and may be appropriately selected depending on the purpose or the like. As a metal plate, the metal plate which consists of metals, such as iron type alloys, such as copper, a copper type alloy, nickel, chromium, iron, and stainless steel, is mentioned. As a preferable metal plate, the metal plate which consists of metals, such as copper, a copper type alloy, and an iron type alloy, is mentioned.

The thickness of the photosensitive layer to be formed is not particularly limited and may be appropriately selected according to its use. 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. As a protective layer, polymer films, such as polyethylene and a polypropylene, etc. are mentioned.

<Photosensitive element>

A photosensitive element (hereinafter simply referred to as "photosensitive element") according to this embodiment includes a support and a photosensitive layer provided on one surface of the support and formed using the photosensitive resin composition. According to such a photosensitive element, since it has a photosensitive layer formed using the photosensitive resin composition, peeling and chipping of the resist can be suppressed even when a strong etching solution is used, and in addition, it has good quality without shaking. A wiring pattern having a line shape can be obtained, and a resistor pattern with a sufficiently short peeling time can be formed. In addition, it is possible to efficiently form a resist pattern having sufficient adhesion even to a substrate having high smoothness and having excellent acid resistance. The photosensitive element may have other layers, such as a protective layer, as needed.

1 is a schematic cross-sectional view showing one embodiment of a photosensitive element of the present invention. 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. In addition, as for the coating film, the photosensitive resin composition is in an uncured state.

The photosensitive element 10 can be obtained, for example, as follows. First, the photosensitive layer 4 is formed by applying a coating liquid, which is a photosensitive resin composition containing an organic solvent, onto the support 2 to form a coating layer, and drying this (removing at least a part of the organic solvent from the coating layer). form Next, the surface of the photosensitive layer 4 on the opposite side to the support 2 is covered with the protective layer 6, thereby providing the support 2, the photosensitive layer 4 laminated on the support 2, and the photosensitive layer. A photosensitive element 10 having a protective layer 6 laminated on the layer 4 can be obtained. In addition, the photosensitive element 10 does not necessarily need to 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 micrometer or more, when peeling the support body 2, it can suppress that the support body 2 is torn. Moreover, by being 100 micrometers or less, the fall of the resolution at the time of exposure through the support body 2 is suppressed.

As the protective layer 6, the adhesive force to the photosensitive layer 4 may be smaller than the adhesive force of the support body 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. As commercially available products, polypropylene films such as Alpine MA-410 and E-200 manufactured by Ojise City Co., Ltd. and manufactured by Shin-Etsu Film Co., Ltd., polyethylene terephthalate films of PS series such as PS-25 manufactured by Teijin Co., Ltd., and Tamapoly Co., Ltd. The first NF-15A can be mentioned. In addition, the protective layer 6 may be the same as that of the support body 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. If the thickness of the protective layer 6 is 1 μm or more, tearing of the protective layer 6 is suppressed when the photosensitive layer 4 and the support 2 are laminated on a substrate while the protective layer 6 is peeled off. can do. If it is 100 micrometers or less, it is excellent in handling property and cheapness.

The photosensitive element 10 can be specifically manufactured, for example, as follows. That is, the photosensitive element 10 includes a step of preparing a coating solution containing a photosensitive resin composition, a step of applying the coating solution on the support 2 to form a coating layer, and drying the coating layer to be photosensitive. It can manufacture with the manufacturing method including the process of forming the layer 4.

The application of the coating solution 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.

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, you may carry out about 5 to 30 minutes at 70-150 degreeC. After drying, the amount of the organic solvent remaining in the photosensitive layer 4 may be 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in a later step.

The thickness of the photosensitive layer 4 in the photosensitive element 10 can be appropriately selected according to the intended use. The thickness after drying may be 1 to 100 μm, 1 to 50 μm, or 5 to 40 μm. When the thickness of the photosensitive layer 4 is 1 μm or more, industrial coating becomes easy. If it is 100 micrometers or less, there exists a tendency for sufficient adhesiveness and resolution to be obtained.

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

<Formation method of register pattern>

The resist pattern formation method according to the present embodiment includes (i) a photosensitive layer forming step of forming a photosensitive layer on a base material using a photosensitive resin composition or a photosensitive element; (ii) activating a part of the photosensitive layer region; An exposure step of curing by irradiation with light to form a photocured region, and (iii) removing a region other than the photocured region of the photosensitive layer from the substrate to form a photocured region of the photosensitive resin composition (photocured product) on the substrate. region) and a developing step of forming a resist pattern. The formation method of a resist pattern may further have other steps as needed. In addition, a resist pattern can also be called a resin pattern or a relief pattern. Hereinafter, each process is explained in detail.

(i) photosensitive layer formation process

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

As a method of forming a photosensitive layer on a substrate, for example, a method of applying a coating liquid containing a photosensitive resin composition onto a substrate and then drying it is exemplified.

Moreover, as a method of forming a photosensitive layer on a base material, after removing a protective layer from a photosensitive element as needed, for example, a method of laminating the photosensitive layer of a photosensitive element on a base material is mentioned. The lamination can be performed by pressing the photosensitive layer of the photosensitive element to the substrate while heating. With this lamination, a laminate can be obtained in which the substrate, the photosensitive layer, and the support are laminated in this order.

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

(ii) exposure process

In the exposure process, by irradiating actinic light to a part of the photosensitive layer, the exposed portion irradiated with actinic light is photocured and a latent image is formed. Here, when a photosensitive element is used in the photosensitive layer forming step, a support exists on the photosensitive layer, but when the support has transparency to actinic light, actinic light can be irradiated through the support. On the other hand, when the support exhibits light blocking properties with respect to actinic light, the photosensitive layer is irradiated with actinic light after removing the support.

As an exposure method, a method (mask exposure method) in which actinic light is irradiated onto an image through a negative or positive mask pattern called artwork is exemplified. Alternatively, a method of irradiating actinic light onto an image by a direct drawing exposure method such as a laser direct imaging (LDI) exposure method and a digital light processing (DLP) exposure method may be employed.

The wavelength (exposure wavelength) of actinic light 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) developing process

In the developing step, regions other than the photocured region of the photosensitive layer (i.e., the uncured portion of the photosensitive layer) are removed from the substrate by developing treatment to form a resist pattern made of the photocured photocured photosensitive layer on the substrate. In the case where a support exists on the photosensitive layer that has undergone the exposure process, the development process is performed after the support is removed. [0032] In the development treatment, there are wet development and dry development, but wet development is suitably used.

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

A developing solution can be suitably selected according to the structure of the photosensitive resin composition. As a developing solution, an alkaline aqueous solution, aqueous developing solution, organic solvent developing solution, etc. are mentioned.

As the alkaline aqueous solution used for development, a 0.1 to 5 mass% sodium carbonate aqueous solution, a 0.1 to 5 mass% potassium carbonate aqueous solution, a 0.1 to 5 mass% sodium hydroxide aqueous solution, a 0.1 to 5 mass% sodium tetraborate aqueous solution, or the like may be used. The pH of the alkaline aqueous solution may be 9 to 11. In addition, the temperature is adjusted according to the alkali developability of the photosensitive layer. In the alkaline aqueous solution, a surface active agent, an antifoaming agent, and a small amount of an organic solvent for accelerating development may be incorporated.

The method for forming the resist pattern further includes a step of 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 after removing the unexposed portion. may be

<Manufacturing method of touch panel>

The method for manufacturing a touch panel according to the present embodiment includes a step of etching a base material on which a resist pattern is formed by the resist pattern formation method described above. The etching process is performed on the conductor layer or the like of the base material using the formed resist pattern as a mask (which can also be referred to as "resistor"). A touch panel is manufactured by forming a pattern of outgoing wirings and transparent electrodes by an etching process.

3 is a schematic cross-sectional view showing one aspect of the method for manufacturing a touch panel of the present invention. The manufacturing method of this aspect is a laminated substrate provided with a support substrate 22, a transparent conductive layer 24 provided on one surface of the support substrate 22, and a metal layer 26 provided on the transparent conductive layer 24. , the first step of forming a resist pattern 29 made of a photocured photosensitive resin composition on the metal layer 26, and etching the metal layer 26 and the transparent conductive layer 24 to form a transparent conductive layer ( 24) and the metal layer 26 are formed in the second step of forming a laminated pattern (24+26 in Fig. 3(d)), and the metal layer is removed from a part of the laminated pattern, and the transparent conductive layer 24 ) and a third step of forming a transparent electrode composed of the remainder of the metal layer and a metal wiring composed of the remainder of the metal layer.

In the first step, first, as shown in Fig. 3(a), 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 top The photosensitive layer 28 is formed using the photosensitive resin composition on the metal layer 26 of the laminated substrate provided with the metal layer 26 provided thereon. The photosensitive layer 28 may have a support on the surface opposite to the metal layer 26 .

As the metal layer 26, a metal layer containing copper may be used, for example. Examples of the metal layer containing copper include metal layers containing copper, alloys of copper and nickel, alloys of copper, nickel and titanium, molybdenum-aluminum-molybdenum laminates, alloys of silver, palladium and copper, and the like. Among these, a metal layer containing copper, an alloy of copper and nickel, or an alloy of copper, nickel and titanium can be preferably used from the viewpoint of obtaining the effect of the present invention more remarkably.

The transparent conductive layer 24 contains indium tin oxide (ITO). The transparent conductive layer 24 may contain crystalline ITO from the viewpoint of making an annealing treatment unnecessary.

Subsequently, a part of the region of the photosensitive layer 28 is cured by irradiation with actinic light to form a photocured region, and regions other than the photocured 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 the laminated substrate.

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

A method of etching treatment is appropriately selected depending on the layer to be removed. For example, as an etchant for removing a metal layer, a cupric chloride solution, a ferric chloride solution, a phosphoric acid solution, etc. are mentioned. In addition, as an etchant for removing the transparent conductive layer, oxalic acid, hydrochloric acid, aqua regia, or the like is used.

When the transparent conductive layer 24 is made of crystalline ITO, as an etchant 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 together ( For example, it is necessary to use ITO series such as ITO-4400Z), but in the production method of this embodiment, since the resist pattern is made of a photocured product of the photosensitive resin composition, the resist pattern remains intact even under etching treatment with strong acid or the like. Peeling and the like are sufficiently suppressed. The photosensitive resin composition according to the present embodiment can be suitably used as a photosensitive resin composition for etching using a strong acid such as the above-mentioned concentrated hydrochloric acid or aqua regia or a chemical solution for etching a metal layer and a transparent conductive layer collectively as an etchant.

FIG. 3(c) is a view showing after etching treatment, and in FIG. 3(c), the remainder of the metal layer 26, the remainder of the transparent conductive layer 24, and the resist pattern 29 are formed on the supporting substrate 22. A laminated body consisting of the remainder of is formed. In the manufacturing method of this aspect, the resist pattern 29 is removed from this laminated body.

Removal of the resist pattern 29 can be performed using, for example, an aqueous solution having a stronger alkalinity than the alkaline aqueous solution used in the above-described development step. As this strongly alkaline aqueous solution, 1-10 mass % sodium hydroxide aqueous solution, 1-10 mass % potassium hydroxide aqueous solution, etc. are used. Among them, a 1 to 10 mass% aqueous sodium hydroxide solution or a 1 to 10 mass% aqueous potassium hydroxide solution may be used, or a 1 to 5 mass% aqueous sodium hydroxide solution or a 1 to 5 mass% aqueous potassium hydroxide solution may be used. As a peeling method of a resist pattern, an immersion method, a spray method, etc. are mentioned, These may be used independently or may be used together.

Fig. 3(d) is a diagram showing the resist pattern after peeling, and in Fig. 3(d), the laminated pattern composed of the remainder of the metal layer 26 and the remainder of the transparent conductive layer 24 on the supporting substrate 22. this is formed

In the third step, the metal layer 26 is removed from the laminated pattern except for a part for forming the metal wiring, and the metal wiring composed of the remainder of the metal layer 26 and the transparent electrode composed of the remainder of the transparent conductive layer 24 are removed. form In addition, in this aspect, as a method of removing the metal layer 26 in the third step, a method of etching is employed, 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 that has passed through the second step (FIG. 3(e)). Subsequently, the photosensitive layer 30 is exposed and developed to form a resist 31 made of a photocured material of the photosensitive layer 30 (FIG. 3(f)). In addition, the photosensitive layer may be a layer formed using the photosensitive resin composition according to the present embodiment described above, or may be a layer formed using a conventionally known photosensitive resin composition for etching.

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

Fig. 3(g) is a diagram showing the etching treatment, and in Fig. 3(g), a transparent electrode made of the rest of the transparent conductive layer 24 is formed on the support substrate 22, and a part of A laminated body composed of a metal layer 26 and a resistor 31 is formed on the transparent electrode. By removing the resistor 31 from this laminated body, as shown in FIG. 3(h), the transparent electrode consisting of the remainder of the transparent conductive layer 24 and the remainder of the metal layer 26 are formed on the support substrate 22. A metal wiring made of parts is formed.

Fig. 4 is a top view showing one aspect of a touch panel obtained using the present invention. In the touch panel 100, X electrodes 52 and Y electrodes 54, which are transparent electrodes, are alternately placed side by side, and the X electrodes 52 provided in the same row in the longitudinal direction form one lead wire ( 56), and Y electrodes 54 provided in the same column in the width direction are connected to each other by one lead wire 57.

As mentioned above, although the preferable embodiment of this invention was described, this invention is not limited to the said embodiment.

Example

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

(Production Example 1: Production of binder polymer (A-1))

A solution obtained by mixing 30 g of polymerizable monomers (monomers) 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 was called "solution a". A solution obtained by dissolving 0.6 g of azobisisobutyronitrile in 30 g of acetone was referred to as "solution b".

100 g of a mixture of 80 g of acetone and 20 g of propylene glycol monomethyl ether (mass ratio 4:1) was put into a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet pipe, and nitrogen gas was blown into the flask and stirred. While heating, the temperature was raised to 80°C.

After the said solution a was dripped at the said liquid mixture in a flask with the dripping rate constant over 4 hours, the solution in a flask was stirred at 80 degreeC for 2 hours. Subsequently, the solution b was added dropwise to the solution in the flask over 10 minutes at a constant dropping rate, and then the solution in the flask was stirred at 80°C for 3 hours. Further, the solution in the flask was heated up to 90°C over 30 minutes, kept warm at 90°C for 2 hours, and then cooled to obtain a solution of binder polymer (A-1).

The non-volatile content (solid content) of the solution of the binder polymer (A-1) was 42.8% by mass. In addition, the weight average molecular weight of the binder polymer (A-1) was 50000, the acid value was 195 mgKOH/g, and the degree of dispersion was 2.58.

In addition, the weight average molecular weight and degree of dispersion were measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The conditions of GPC are shown below.

(GPC conditions)

Pump: Hitachi/　L-6000 type (Hitachi Seisakusho Co., Ltd.)

Column: 3 columns in total as below, Column specification: 10.7mmφ×300mm

Gelpack　GL-R440

Gelpack　GL-R450

Gelpack　GL-R400M (above, Hitachigasei 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 degrees Celsius

Injection amount: 200 μL

Pressure: 49Kgf/cm ² (4.8MPa)

Flow rate: 2.05mL/min

Detector: Hitachi L-3300 RI (Hitachi Seisakusho Co., Ltd.)

In addition, the acid value was measured as follows. First, a solution of a binder polymer was heated at 130°C for 1 hour to remove a volatile component to obtain a solid content. Then, after accurately weighing 1 g of the solid polymer, 30 g of acetone was added to the polymer, and this was dissolved uniformly. Next, an appropriate amount of phenolphthalein as an indicator was added to the solution, and titration was performed using a 0.1 N KOH aqueous solution. And the acid value was computed by the following Formula.

Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100)

In the formula, Vf represents the titrated amount (mL) of the KOH aqueous solution, Wp represents the mass (g) of the measured polymer solution, and I represents the ratio (% by mass) of the non-volatile matter in the measured polymer solution.

[Examples 1 to 8 and Comparative Examples 1 to 3]

Examples and comparative examples were carried out in the following manner.

<Preparation of photosensitive resin composition (coating liquid)>

The coating liquid of the photosensitive resin composition of the Example and the comparative example was obtained by mixing each component shown in Table 1 and Table 2 by the compounding quantity (mass part) shown in the same table|surface. The compounding quantity of (A) component in a table|surface is the mass of solid content. In addition, "-" means unmixed. Details of each component shown in Table 1 and Table 2 are as follows.

(Component (A))

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))

BPE-900: 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (Shin Nakamura Chemical Industry Co., Ltd., number of EO groups: 17 (average value))

BPE-1300H: 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (Shin Nakamura Chemical Industry Co., Ltd., number of EO groups: 30 (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))

R-128H: 2-hydroxy-3-phenoxypropyl acrylate (Nippon Kayaku Co., Ltd.)

FA-MECH: γ-chloro-β-hydroxypropyl-β'-methacryloxyethyl-o-phthalate (Hitachi Chemical Co., Ltd.)

FA-318A: Nonylphenoxypolyethylene glycol acrylate (Hitachi Chemical Co., Ltd.)

DPEA-12: dipentaerythritol hexaacrylate having an 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 (Sangju Strong Electronic New Materials Co., Ltd.)

(Component (D): silane coupling agent)

AY43-031: 3-ureidpropyltriethoxysilane (Torre Dow Corning Co., Ltd.)

KBM-803: 3-Mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)

SZ-6030: 3-methacryloxypropyltrimethoxysilane (Torre Dow Corning Co., Ltd.)

((E) component: sensitizing dye)

PZ-501D: 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline (Japan Chemical Industry Co., Ltd.)

(Other components: (A) to (E) other than components)

LCV: Leuko Crystal Violet (Yamada Gakuko Kogyo Co., Ltd.)

TBC: 4-t-butylcatechol (DIC Corporation, "DIC-TBC-5P")

SF-808H: A 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 Industry Co., Ltd.)

<Production of photosensitive element>

The coating liquid of the photosensitive resin composition obtained above was applied to a uniform thickness on a polyethylene terephthalate film (manufactured by Toray Corporation, product name "FB-40") having a thickness of 16 μm, respectively, and hot air convection at 70 ° C. and 110 ° C. The drying treatment was carried out sequentially with a drying machine to form a photosensitive layer having a film thickness of 15 µm after drying. A photosensitive element in which a protective layer (manufactured by Tamapoly Co., Ltd., product name "NF-15A") is bonded on the photosensitive layer, and a polyethylene terephthalate film (support), a photosensitive layer, and a protective layer are laminated in this order. got

<Manufacture of laminated substrate>

A transparent conductive layer made of crystalline ITO was formed on a polyethylene terephthalate material, and a metal layer made of copper was formed on the upper layer, and a film substrate was prepared on which an anti-rust treatment was applied to the outermost surface of the metal layer. After heating this film substrate (hereinafter referred to as “substrate”) and raising the temperature to 80° C., the photosensitive element produced above was laminated (laminated) on the surface of the metal layer of the substrate. The lamination was carried out under conditions of a temperature of 110° C. and a lamination pressure of 4 kgf/cm ² (0.4 MPa) while removing the protective layer so that the photosensitive layer of the photosensitive element adhered to the surface of the metal layer of the substrate. 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 until it reached 23°C. Next, the laminated substrate is divided into three areas, and on the support in one of the areas, 41 layers with a concentration area of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm × 187 mm, and each step size of 3 mm × 12 mm. A photo tool with a single step tablet was brought into close contact. Exposure was carried out using a parallel light exposure machine (manufactured by Oak Seisakusho Co., Ltd., product name "EXM-1201") using a short arc UV lamp (product name "AHD-5000R" made by Oak Seisakusho Co., Ltd.) as a light source, 100 mJ/cm ² The photosensitive layer was exposed to light through the photo tool and the support at an energy amount (exposure amount) of . At this time, other unused areas were covered with a black sheet. In addition, the different regions were exposed to energy amounts of 200 mJ/cm ² and 400 mJ/cm ² respectively in the same manner. In addition, for the measurement of illuminance, an ultraviolet illuminance meter (manufactured by Ushio Denki Co., Ltd., product name "UIT-150") to which a 405 nm compatible probe was applied was used.

After exposure, the support was peeled off from the laminated base material, the photosensitive layer was exposed, and an unexposed portion was removed by spraying a 1% by mass aqueous solution of sodium carbonate at 30°C for 16 seconds. In this way, a resist pattern made of a photocured material of the photosensitive resin composition was formed on the surface of the metal layer of the base material. The photosensitive resin composition is obtained by creating a calibration curve between the exposure amount and the step number from the remaining number of steps (step number) of the step tablet obtained as a register pattern (cured film) at each exposure amount, and obtaining the exposure amount at which the number of step steps becomes 17 steps. of the sensitivity was evaluated. Sensitivity is expressed by the exposure amount at which the number of steps obtained from the calibration curve becomes 17, and the smaller the exposure amount, the better the sensitivity. The results are shown in Table 3 and Table 4.

<Evaluation of adhesion>

Using a mask pattern with a line width (L) / space width (S) (hereinafter referred to as "L/S") of 4/400 to 30/400 (unit: µm), a 41-step step tablet remains. The photosensitive layer of the laminated base material was exposed to light with an amount of energy at which the number of stages was 17. After exposure, development processing similar to the evaluation of the above sensitivity was performed.

After development, the space portion (unexposed portion) is clearly removed, and the line portion (exposed portion) is formed by the minimum value of the line width / space width values in the resist pattern formed without meandering, peeling, or chipping. , the adhesion was evaluated. It means that adhesiveness is so good that this numerical value is small. The results are shown in Table 3 and Table 4.

<Evaluation of resolution>

A mask pattern having an L/S of 1/1 to 30/30 (unit: µm) was used, and the photosensitive layer of the laminated base material was exposed with an energy amount such that the number of remaining steps of the 41-step tablet was 17 steps. After exposure, development processing similar to the evaluation of the above sensitivity was performed.

After development, the space portion (unexposed portion) is clearly removed, and the line portion (exposed portion) is formed by the minimum value of the line width / space width values in the resist pattern formed without meandering, peeling, or chipping. , evaluated the resolution. The smaller this number means the better the resolution. The results are shown in Table 3 and Table 4.

<Evaluation of adhesion after etching>

The adhesiveness of the resist pattern after etching was evaluated as follows. Using a mask pattern with an L/S of 4/400 to 47/400 (unit: μm), the photosensitive layer of the laminated base material was exposed with an energy amount such that the number of remaining steps of the 41-step tablet was 23 steps. 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 with water and dried.

Among the values of the line width/space width in the resist pattern formed without the metal layer and the transparent conductive layer of the space portion (unexposed portion) being clearly removed and the line portion (exposed portion) meandering, peeling, or chipping. Adhesion after etching was evaluated by the minimum value. This means that the smaller the numerical value, the higher the liquid resistance and the better the adhesion. The results are shown in Table 3 and Table 4.

<Evaluation of line shape after etching>

The line shape after etching of the wiring pattern was determined by using a digital microscope VHX-2000 (manufactured by Keyence Corporation) for the wiring pattern formed under the resist pattern with an L/S of 47/400 (unit: µm) in evaluating the adhesion after etching. ) was used to observe. 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. Based on the value of the side etching width and the presence or absence of wobble, the line shape after etching of the wiring pattern was evaluated based on the following criteria. The results are shown in Table 3 and Table 4.

A: Unevenness is not observed in the line shape after etching of the wiring pattern, and the value of the side etching width is less than 5 µm.

B: The line shape after etching of the wiring pattern does not fluctuate, but the value of the side etching width is 5 μm or more.

C: Unevenness is seen in the line shape after the etching of the wiring pattern.

<Evaluation of peelability>

Using a PET negative: 60 mm x 45 mm square (solid: no pattern), the photosensitive layer of the laminated base material was exposed with an energy amount such that the remaining number of steps of the 41-step tablet was 17 steps. After the exposure, the same development treatment as in the evaluation of the above sensitivity was performed to obtain a laminated substrate having a 60 mm x 45 mm square cured film formed on the substrate. Peeling evaluation was performed by immersing this laminated substrate in a 2.5% by mass aqueous solution of sodium hydroxide at 50°C. The time from when the laminated substrate was immersed until the cured film was completely peeled off from the substrate was taken as the peeling time (seconds). In addition, the size of the peeling piece after peeling was visually observed and evaluated according to the following criteria. The shorter the peeling time and the smaller the peeled piece size, the better the peeling property. The results are shown in Table 3 and Table 4.

S: Smaller than 40mm angle.

M: 40mm to 50mm each.

L: Sheet-like (larger than 50 mm square).

As a photopolymerizable compound, (meth)acrylate having 6 ethylenically unsaturated bonds in a molecule, and 10 parts by mass or less (out of 100 parts by mass of the total amount of component (A) and component (B)) of one ethylene in the molecule In Examples 1 to 8 using (meth)acrylate having a sexually unsaturated bond, compared with Comparative Examples 1 to 3, the adhesiveness after etching the resist pattern, the line shape after etching the wiring pattern, and the peelability of the resist pattern were balanced. I knew that it was possible to improve.

2… support, 4 . . . photosensitive layer, 6 . . . protective layer, 10 . . . photosensitive element, 12 . . . supporting substrate, 14 . . . transparent conductive layer, 16 . . . photosensitive layer, 18 . . . outgoing wiring, 22 . . . supporting substrate, 24 . . . transparent conductive layer, 26 . . . metal layer, 28 . . . photosensitive layer, 29 . . . register pattern, 30... photosensitive layer, 31 . . . register, 52... transparent electrode (X electrode), 54 . . . transparent electrode (Y electrode), 56, 57... Outgoing wiring, 100... touch panel.

Claims (7)

(A) component: binder polymer,
(B) component: a photopolymerizable compound, and
(C) Component: Contains a photopolymerization initiator,
The component (B) contains (meth)acrylate having 6 ethylenically unsaturated bonds in the molecule and (meth)acrylate having 1 ethylenically unsaturated bond in the molecule,
The (meth)acrylate having one ethylenically unsaturated bond in the molecule includes a phthalic acid-based compound,
The phthalic acid compound is γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, or 2- Acryloyloxyethyl-phthalic acid,
The photosensitive resin composition in which the content of (meth)acrylate having one ethylenically unsaturated bond in the molecule is 10 parts by mass or less in 100 parts by mass of the total amount of the component (A) and the component (B). The method of claim 1,
The photosensitive resin composition in which the said (B) component further contains the bisphenol-A di(meth)acrylate which has a (poly)oxyethylene group. A photosensitive element comprising a support and a photosensitive layer provided on one surface of the support and formed using the photosensitive resin composition according to claim 1 or 2. A photosensitive layer forming step of forming a photosensitive layer on a substrate using the photosensitive resin composition according to claim 1 or 2;
an exposure step of curing a part of the photosensitive layer by irradiation with actinic light to form a photocured region;
A developing step of obtaining a resist pattern composed of the photocured region by removing an area of the photosensitive layer other than the photocured region from the base material.
A method of forming a resist pattern having a. The photosensitive resin composition according to claim 1 or 2 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. A first step of forming a resist pattern made of a photocured material of
a second step of etching the metal layer and the transparent conductive layer to form a lamination pattern comprising a remainder of the transparent conductive layer and a 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 manufacturing method of a touch panel having a. The method of claim 5,
The transparent conductive layer contains crystalline indium tin oxide,
The method of manufacturing a touch panel wherein the etching in the second step is etching with a strong acid. A photosensitive layer forming step of forming a photosensitive layer on a substrate using the photosensitive element according to claim 3;
an exposure step of curing a part of the photosensitive layer by irradiation with actinic light to form a photocured region;
A developing step of obtaining a resist pattern composed of the photocured region by removing an area of the photosensitive layer other than the photocured region from the base material.
A method of forming a resist pattern having a.

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