TW201728998A - Photosensitive resin composition, photosensitive element, method for forming resist pattern and method for manufacturing touch panel - Google Patents

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 six ethylenically unsaturated bonds in each molecule and a (meth)acrylate having one ethylenically unsaturated bond in each molecule; and the content of the (meth)acrylate having one ethylenically unsaturated bond in each molecule is 10 parts by mass or less per 100 parts by mass of the total of the component (A) and the component (B).

Description

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

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

The touch sensor portion of the touch panel is configured to include a sensor portion and a lead wiring portion, and the sensor portion is located in a range (view area) for displaying visual information, and is detected by a human finger. The position information generated by the contact of the etc., the lead wiring portion is used to transmit the position information to the external component.

A pattern of an electrode having less absorption and scattering of visible light and having conductivity is formed in the sensor portion. Further, a metal having a small resistance value is used for each wiring of the lead-out wiring portion.

Such a sensor portion and a lead-out wiring portion are produced by, for example, a negative-type photosensitive resin composition as shown in FIGS. 2(a) to 2(e). 2(a) to 2(e) are schematic cross-sectional views showing a prior art manufacturing method of the touch sensor portion of the touch panel. First, a photosensitive layer 16 (photosensitive layer) is formed on a support substrate 12 (a film substrate or a glass substrate of polyethylene terephthalate or the like) having a transparent conductive layer 14 by application of a photosensitive resin composition or the like. Forming step) (Fig. 2(a)). Next, a predetermined portion of the photosensitive layer 16 is irradiated with actinic rays to harden the exposed portion (exposure step). Thereafter, the uncured portion is removed from the transparent conductive layer 14, whereby a resist pattern of the photocured material containing the photosensitive resin composition is formed on the transparent conductive layer 14 (developing step) (Fig. 2(b)) . The resist pattern is etched to remove a portion of the transparent conductive layer 14 from the support substrate 12 to form a pattern of the transparent conductive layer of the sensor portion (etching step) (Fig. 2(c)). Then, the resist pattern is peeled off from the transparent conductive layer 14 and removed (peeling step) (Fig. 2(d)). Then, the lead wiring 18 from the pattern of the transparent conductive layer of the formed sensor portion is formed by screen printing using silver paste or the like, thereby manufacturing the touch sensor portion.

In addition, the narrowness of the frame (bezel) of the touch panel requires narrowing of the wiring width and pitch in the lead wiring portion. In screen printing using silver paste, the pattern formation of L/S (line width/space width) of about 50/50 (unit: μm) is set as a limit, but in order to cope with the narrowing of the frame, L/S is required. It is formed in a pattern of 30/30 (unit: μm) or less.

In order to manufacture a touch sensor portion having a pattern of lead wires having a small L/S and a small pitch, a method of forming a touch sensor portion using a technique of photolithography has been proposed (for example, see Patent Document 1). In the method of manufacturing the touch sensor unit, first, a first photosensitive layer is formed on a support substrate having a transparent conductive layer and a metal layer using a photosensitive resin composition (first photosensitive layer forming step). Next, a predetermined portion of the photosensitive layer is irradiated with actinic rays to harden the exposed portion (first exposure step), and thereafter, the unhardened portion is removed from the metal layer, thereby forming a photosensitive resin composition on the metal layer. A resist pattern of the photocured material (first development step). Then, the metal layer and the transparent conductive layer are removed by an etching process (first etching step). Then, the resist pattern is peeled off and removed from the metal layer (first peeling step). Then, the photosensitive resin composition is reused to form a second photosensitive layer on the metal layer (second photosensitive layer forming step). Then, a predetermined portion of the photosensitive layer is irradiated with actinic rays to harden the exposed portion (second exposure step), and thereafter, the unhardened portion is removed from the metal layer, thereby forming a resist pattern on the metal layer (p. 2 development step). Then, only the metal layer in which the resist pattern is not formed, which is unnecessary in the sensor portion, is removed by the etching process (second etching step), and finally, the resist pattern is peeled off and removed, thereby manufacturing the touch. Sensor section.

In the manufacturing method of the touch sensor portion, by using the technique of photolithography, the L/S can be changed to 30/30 (unit: μm) or less, and the touch panel can be thin and light. Quantification makes a big contribution. On the other hand, the transparent conductive layer of the touch sensor portion is formed, for example, by forming a film of Indium Tin Oxide (ITO) by using a sputtering technique. Further, similarly to the transparent conductive layer, the metal layer formed on the transparent conductive layer is formed by, for example, a sputtering technique. The surface of the transparent conductive layer and the metal layer formed by the sputtering technique has a very high smoothness. Since the adhesion between the metal layer having a very high smoothness and the photosensitive resin composition is lowered, the alloy of copper, copper and nickel, the alloy of copper and nickel and titanium, molybdenum-aluminum-molybdenum is used. A metal layer such as a laminate or a mixture of silver, palladium, and copper requires high adhesion to the photosensitive resin composition to be used.

Further, from the viewpoint of easiness of the etching treatment, for example, amorphous ITO is used for the transparent conductive layer. However, since the amorphous ITO has a high electric resistance value, for example, crystallization of ITO is performed by a heating (annealing) treatment, thereby lowering the electric resistance value. However, in recent years, with the thin and light weight of the touch panel, it is required to use a film substrate as a supporting substrate of the touch panel portion. When a film substrate is used as the support substrate, if the annealing treatment is performed, shrinkage of the film substrate or the like is caused, and dimensional stability is deteriorated. Therefore, when a film substrate is used as the support substrate, crystalline ITO must be used as the transparent conductive layer before the pattern of the transparent conductive layer is formed.

The amorphous ITO can be sufficiently dissolved by a weak acid such as oxalic acid. However, the crystalline ITO must be etched under a heating condition (about 40 to 50 ° C) using a strong acid such as concentrated hydrochloric acid (>20% by mass). Therefore, the photosensitive resin composition to be used is required to have high acid resistance, that is, it is required to ensure adhesion to the metal layer even by etching using a strong acid, and to suppress corrosion of the metal layer caused by strong acid. .

In addition, as a method of forming a wiring pattern (also referred to as a conductor pattern) having high resolution by setting L/S of the resist pattern to 30/30 (unit: μm) or less, there are a pair of metal layers and a transparent conductive layer. A method of etching at the same time. In the method of etching the transparent conductive layer after etching the metal layer, the in-plane unevenness at the time of etching becomes large, and thus it is difficult to obtain a wiring pattern having high resolution. As a chemical liquid for simultaneously etching the metal layer and the transparent conductive layer, ITO-4400Z (manufactured by ADEKA Co., Ltd.) can be obtained commercially.

In addition, as a technique for improving the acid resistance (adhesion after immersion 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).

Further, as a photosensitive resin composition for forming a resist pattern, various photosensitive resin compositions have been studied. For example, it is proposed to add a specific crosslinking agent, a specific decane coupling agent, or the like to the photosensitive resin composition, and to use a binder polymer having a specific structural unit as an essential component (for example, refer to Patent Document 3 to Patent). Document 7). Prior art literature

Patent Document 1: Japanese Patent No. 4855536 Patent Document 2: Japanese Patent No. 4219641 Patent Document 3: Japanese Patent Laid-Open Publication No. JP-A No. 2002-040645A Patent Publication No. JP-A-2002-268215 Patent Document 5: Japanese Patent Laid-Open Publication No. 2008-112146, Japanese Patent Laid-Open Publication No. Hei. No. Hei.

[Problems to be Solved by the Invention] When a resist pattern having a high resolution is formed by setting the L/S of the resist pattern to 30/30 (unit: μm) or less, undulation of the resist pattern is likely to occur ( It can also be called 蜿蜒), missing, flaking and so on. In particular, in this field, there is a possibility that a short circuit or a disconnection occurs in the electrode and the lead wiring of the sensor portion due to the occurrence of defects. Therefore, undulations, deletions, flaking, and the like are not required to be generated in the resist pattern more than before.

However, in the photosensitive resin composition described in Patent Document 2, it is difficult to form a resist pattern having excellent resolution, and there is a case where a resist pattern is defective. In addition, the photosensitive resin composition described in Patent Document 3 to Patent Document 7 may cause defects such as peeling or missing of the resist during ITO etching. In particular, it is known that when a strong etching liquid for removing ITO is used, there is a tendency that defects such as peeling and missing occur in the resist pattern, and there is no problem such as peeling and missing in the resist pattern. It is also easy to cause looseness in the line shape of the formed wiring pattern. Further, it is known that it is difficult to achieve good balance and high level of defects which can be generated in the resist pattern, and the wire shape of the wiring pattern is good and the peeling property of the resist pattern is good, and the peeling time is short.

The present invention has been made to solve such a problem, and an object of the invention is to provide a photosensitive resin composition capable of suppressing peeling and loss of a resist even when a strong etching liquid is used. It is produced, and a wiring pattern having a good line shape without looseness can be obtained, and a resist pattern having a peeling time sufficiently short can be formed. Further, an object of the present invention is to provide a photosensitive element using the photosensitive resin composition, a method of forming a resist pattern, and a method of manufacturing a touch panel.

[Means for Solving the Problem] As a result of repeated efforts by the inventors of the present invention to solve the above problems, it has been 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 relates to a photosensitive resin composition comprising (A) component: a binder polymer, (B) component: a photopolymerizable compound, and (C) component: photopolymerization initiation The component (B) contains a (meth) acrylate having six ethylenically unsaturated bonds in the molecule, and a (meth) acrylate having one ethylenically unsaturated bond in the molecule, and In 100 parts by mass of the total amount of the component (A) and the component (B), the content of the (meth) acrylate having one ethylenically unsaturated bond in the molecule is 10 parts by mass or less.

According to such a photosensitive resin composition, since the crosslinking density can be easily controlled in the photocured material of the photosensitive resin composition, even when a strong etching liquid is used, peeling and occurrence of the resist can be suppressed. Also, a wiring pattern having a good line shape without looseness can be obtained, and a resist pattern having a peeling time sufficiently short can be formed. Therefore, by using such a photosensitive resin composition, a highly-analyzed fine circuit pattern can be formed.

The component (B) may further contain a bisphenol A type di(meth)acrylate having a (poly)oxyethyl 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 can be more remarkably suppressed during ITO etching.

A second aspect of the present invention relates to a photosensitive element comprising: a support; and a photosensitive layer formed on the one surface of the support using the photosensitive resin composition of the first aspect. According to the photosensitive element, since the photosensitive layer formed using the photosensitive resin composition of the first aspect is provided, even when a strong etching liquid is used, peeling and occurrence of the resist can be suppressed, and A wiring pattern having a good line shape without looseness can be obtained, and a resist pattern having a peeling time sufficiently short can be formed. Therefore, by using such a photosensitive element, a high-resolution fine circuit pattern can be formed.

A third aspect of the present invention relates to a method of forming a resist pattern, comprising: a photosensitive layer forming step of using the photosensitive resin composition of the first form or the photosensitive element of the second form at a base a photosensitive layer formed on the material; an exposure step of hardening a portion of the photosensitive layer by irradiation of actinic rays to form a photohardenable region; and a developing step of the photocured material of the photosensitive layer A region other than the region is removed from the substrate to obtain a resist pattern including the photohardenable region. According to the method for forming a resist pattern, even when a strong etching liquid is used, peeling and occurrence of a resist can be suppressed, and a wiring pattern having a good line shape without looseness can be obtained, and A resist pattern having a sufficiently short peeling time can be formed. In addition, according to the method for forming a resist pattern, 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 relates to a method of manufacturing a touch panel, comprising: a first step of providing a transparent conductive layer containing indium tin oxide on a surface of a support substrate and a surface of the support substrate; a resist pattern of the photocured material containing the photosensitive resin composition of the first aspect is formed on the metal layer of the laminated base material of the metal layer provided on the transparent conductive layer; Etching the metal layer and the transparent conductive layer to form a buildup pattern including a residual portion of the transparent conductive layer and a residual portion of the metal layer; and a third step of removing the metal layer from a portion of the build-up pattern And forming a transparent electrode including a residual portion of the transparent conductive layer and a metal wiring including a residue of the metal layer.

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

The transparent conductive layer may include crystalline indium tin oxide, and the etching in the second step may be etching using a strong acid. In the above-described manufacturing method, since the resist pattern is formed of the photocured material of the photosensitive resin composition of the first aspect, the resist pattern is sufficiently suppressed even by etching with a strong acid. Stripping and so on. Therefore, the manufacturing method can be suitably applied to the manufacture of a touch panel using a laminated substrate including a transparent conductive layer containing crystalline indium tin oxide.

Advantageous Effects of Invention According to the present invention, there is provided a photosensitive resin composition capable of suppressing occurrence of peeling and loss of a resist even when a strong etching liquid is used, and is obtainable A wiring pattern having a good line shape without looseness, and a resist pattern having a sufficiently short peeling time can be formed. Moreover, according to the present invention, a photosensitive element using the photosensitive resin composition, a method of forming a resist pattern, and a method of manufacturing a touch panel are provided.

Hereinafter, embodiments for carrying out the invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present specification, the term "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the term "(meth)acrylate" means an acrylate or a methacrylate corresponding thereto, so-called (meth) The acryloxy group means an acryloxy group or a methacryloxy group corresponding to the propylene group.

In the present specification, the (poly)oxyalkylene group means at least one of a polyoxyalkylene group in which an alkyloxy group or two or more alkylene groups are bonded by an ether bond. In other words, the (poly)oxyl extended ethyl group means at least one of a polyoxyalkylene group in which an oxy-ethyl group or two or more exoethyl groups are bonded by an ether bond, (poly)oxypropanyl group, and the like. The same is true for other similar expressions. Further, the (poly)oxyl extended ethyl group may be referred to as "EO group", and the (poly)oxyl extended propyl group may be referred to as "PO group". In addition, the term "layer" also includes a partially formed shape in addition to the structure of the shape formed in a comprehensive manner when viewed as a plan view. In addition, the term "step" is not only an independent step, but even if it cannot be clearly distinguished from other steps, it is included in the term as long as the intended purpose of the step is achieved. In addition, the numerical range represented by "~" indicates the range in which the numerical values described before and after "~" are respectively included as the minimum value and the maximum value. Further, in the numerical range recited in the specification, the upper limit or the lower limit of the numerical range of one stage may be replaced with the upper limit or the lower limit of the numerical range of the other stage. In addition, within the numerical ranges described in the specification, the upper or lower limit of the numerical range may be replaced with the value shown in the embodiment.

<Photosensitive Resin Composition> The photosensitive resin composition of the present embodiment (hereinafter, simply referred to as "photosensitive resin composition") is a photosensitive resin composition including (A) component: a binder polymer, (B) component: a photopolymerizable compound, and (C) component: a photopolymerization initiator, and the (B) component contains (meth)acrylate which has six ethylenic unsaturated bonds in a molecule, and intramolecular a (meth) acrylate having one ethylenically unsaturated bond, and having 100 ethylenic unsaturation in the molecule in 100 parts by mass of the total of the component (A) and the component (B) The content of the (meth) acrylate of the bond is 10 parts by mass or less (but more than 0 parts by mass).

According to such a photosensitive resin composition, a high-resolution resist pattern in which generation of peeling and missing is suppressed can be formed. Further, in the resist pattern formed using the photosensitive resin composition, even when ITO is etched using a strong acid, peeling and missing tend to occur, so that the line shape of the obtained circuit pattern becomes good. Therefore, the photosensitive resin composition of the present embodiment is suitable as a photosensitive resin composition for ITO etching, and is particularly suitable as a photosensitive resin composition for etching which is a transparent conductive layer containing crystalline ITO.

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

Examples of the polymerizable monomer (monomer) include (meth)acrylic acid; alkyl (meth)acrylate; cycloalkyl (meth)acrylate; benzyl (meth)acrylate; Benzyl acrylate derivative, decyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, bicyclo (meth) acrylate Amyl ester, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-tri(meth)acrylate Fluoroethyl ester, 2,2,3,3-tetrafluoropropyl (meth)acrylate, α-bromoacrylic acid, α-chloroacrylic acid, dicyclopentenyloxyethyl (meth)acrylate, (methyl) Dicyclopentyloxyethyl acrylate, isobornyloxyethyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, adamantylethyl (meth)acrylate, (meth)acrylic acid Dicyclopentenyloxypropoxyethyl ester, dicyclopentyloxypropoxyethyl (meth)acrylate, dicyclopentenyloxypropoxyethyl (meth)acrylate, (meth)acrylic acid Adamantyloxypropoxyethyl ester, (methyl) propyl (meth) acrylate such as β-furanyl olefin, β-styrene (meth) acrylate; styrene; vinyl toluene, α-methyl styrene, etc. substituted at the α-position or aromatic ring a styrene derivative which can be polymerized; an acrylamide such as diacetone acrylamide; an ether compound of a vinyl alcohol such as acrylonitrile or vinyl-n-butyl ether; maleic acid; maleic anhydride; Maleic acid monoester of maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monoisopropyl ester; fumaric acid, cinnamic acid, α-cyano cinnabar An unsaturated carboxylic acid derivative such as acid, itaconic acid, crotonic acid or propiolic acid. These may be used singly or in combination of two or more kinds arbitrarily.

The component (A) may have a structural unit derived from (meth)acrylic acid. When the component (A) has a structural unit derived from (meth)acrylic acid, the resolution and the releasability (resistance of the resist after etching) are excellent, and the total amount of the component (A) is used as a reference. (100% by mass, the same applies hereinafter), and the content thereof may be 10% by mass to 60% by mass, 15% by mass to 50% by mass, or 20% by mass to 35% by mass. In the present specification, the "total amount of the component (A)" means the total amount of the solid components therein. The same applies to the "total amount of (A) component and (B) component" which will be described later. In addition, the "solid content" means a non-volatile component other than a substance which volatilizes water, a solvent, etc. of a photosensitive resin composition. That is, it means a component other than the solvent which does not volatilize in the drying step, and also includes a component which is liquid, saccharide or waxy 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 methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Ethyl pentyl acrylate, hexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. These may be used singly or in combination of two or more kinds arbitrarily.

When the component (A) has a structural unit derived from an alkyl (meth)acrylate, the content of the component (A) can be adjusted based on the total amount of the component (A). 40% by mass to 90% by mass, 50% by mass to 85% by mass, or 65% by mass to 80% by mass.

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

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 from the viewpoint of shortening the development time.

In addition, from the viewpoint of further improving the adhesion of the photocured material of the photosensitive resin composition, the acid value may be 250 mgKOH/g or less, 240 mgKOH/g or less, 235 mgKOH/g or less, or 230 mgKOH/ g below. In addition, when solvent development is performed, a polymerizable monomer (monomer) having a carboxyl group such as (meth)acrylic acid can be adjusted to a small amount.

The weight average molecular weight (Mw) of the component (A) is measured by gel permeation chromatography (GPC) (by conversion using a calibration curve of standard polystyrene), and developability The viewpoint of excellent adhesion is 10,000 to 200,000 to 20,000 to 100,000, 25,000 to 80,000, or 30,000 to 60,000. From the viewpoint of excellent developability, it may be 200,000 or less, 100,000 or less, 80,000 or less, or 60,000 or less. From the viewpoint of excellent adhesion, it may be 10,000 or more, 20,000 or more, 25,000 or more, or 30,000 or more.

The degree of dispersion (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 from the viewpoint 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 arbitrarily in combination.

In the total amount of the component (A) and the component (B), the content of the component (A) in the photosensitive resin composition may be 30 mass, from the viewpoint of the film forming property, the sensitivity, and the resolution. The amount is from 70 parts by mass, from 35 parts by mass to 65 parts by mass, or from 40 parts by mass to 60 parts by mass. The content of the film (photosensitive layer) may be 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more from the viewpoint of the formability of the film (photosensitive layer). In addition, the content may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less from the viewpoint of improving the sensitivity and the resolution in a well-balanced manner.

(B) Component: Photopolymerizable compound The photosensitive resin composition contains (meth) acrylate having six ethylenically unsaturated bonds in the molecule, and (meth)acrylic acid having one ethylenically unsaturated bond in the molecule. The ester is used as the component (B).

Examples of the (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. Further, when the (meth) acrylate having 6 ethylenically unsaturated bonds in the molecule has an EO group, the number of EO groups in the molecule may be 6 to 30, 6 from the viewpoint of improving adhesion. ~24 or 6~12.

The dipentaerythritol hexa(meth) acrylate having an EO group or a PO group is more specifically, for example, a compound represented by the following formula (1). [Chemical 1]

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

In the 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 an ethyl group, a propyl group, an extended isopropyl group, a butyl group, a pentyl group and a hexyl group. Among these, in view of improving the resolution, the adhesion, and the inhibition of the lower end of the resist, it may be an ethyl group or an isopropyl group, or an ethyl group. Furthermore, a plurality of A's may be the same or different from each other.

In the formula (1), n is independently an integer of 0 to 20, respectively. For the purpose 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 the six n in the formula (1) may be 6 to 30, 6 to 24 or 6 to 12.

In the total amount of the component (A) and the component (B), 100 parts by mass of the photosensitive resin composition has 6 molecules in the molecule, in order to improve the adhesion and the releasability after the etching. The content of the (meth) acrylate having an ethylenically unsaturated bond may be from 3 parts by mass to 20 parts by mass, from 3 parts by mass to 15 parts by mass, or from 3 parts by mass to 10 parts by mass. The (meth) acrylate having six ethylenically unsaturated bonds in the molecule may be used alone or in combination of two or more.

Examples of the (meth) acrylate having one ethylenically unsaturated bond in the molecule include a mercaptophenoxy poly(ethoxy acrylate) (also referred to as "nonylphenoxy polyethylene glycol acrylate". Ester"), 2-hydroxy-3-phenoxypropyl (meth)acrylate, phthalic acid-based compound and alkyl (meth)acrylate. Among these, 2-hydroxy-3-phenoxypropyl (meth)acrylate or phthalic acid may be contained from the viewpoint of improving the resolution, the adhesion, and the peeling property after curing in a well-balanced manner. At least one of the formic acid compounds.

Examples of the phthalic acid-based compound having one ethylenically unsaturated bond in the molecule include γ-chloro-β-hydroxypropyl-β'-methacryloxyethyl-phthalic acid. Ester, 2-propenyloxyethyl-2-hydroxyethyl-phthalic acid and 2-propenyloxyethyl-phthalic acid.

In the total amount of the component (A) and the component (B), 100 parts by mass of the photosensitive resin composition has one ethylenicity in the molecule. The content of the (meth) acrylate of the saturated bond is 10 parts by mass or less, and may be 8 parts by mass or less or 5 parts by mass or less. In addition, the lower limit is more than 0 parts by mass, and from the viewpoint of improving the peeling property, it may be 0.1 part by mass or more. The (meth) acrylate having one ethylenically unsaturated bond in the molecule may be used alone or in combination of two or more.

The component (B) may further contain a (meth) acrylate having six ethylenically unsaturated bonds in the molecule and a photopolymerizable compound other than the (meth) acrylate having one ethylenically unsaturated bond in the molecule. . The other photopolymerizable compound is not particularly limited as long as it is a photopolymerizable compound. The other photopolymerizable compound may be a radically polymerizable compound or a compound having an ethylenically unsaturated bond. Examples of the compound having an ethylenically unsaturated bond include a compound having two ethylenically unsaturated bonds in the molecule ((meth)acrylate) and a compound having three or more ethylenically unsaturated bonds in the molecule (( Methyl) acrylate). Other photopolymerizable compounds may be used alone or in combination of two or more.

The component (B) 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 intramolecular urethane. An ester-bonded di(meth)acrylate, a polyalkylene glycol di(meth)acrylate having both (poly)oxyethyl and (poly)oxypropyl groups in the molecule, and trimethylolpropane Di(meth)acrylate.

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

The bisphenol A type di(meth) acrylate is a compound represented by the following general formula (2).

[Chemical 2]

In the formula (2), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. XO and YO each independently represent an oxy-ethyl or oxy-propyl 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 each 1 or more. When XO is an oxyethyl group and YO is an oxypropyl group, m ₁ + m ₂ is from 1 to 40, and n ₁ + n ₂ is from 0 to 20. When XO is an oxypropyl group and YO is an oxyethyl 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 constituent units constituting the unit. Therefore, an integer value is represented in a single molecule, and as a collection of a plurality of molecules, a rational number as an average value is represented. Hereinafter, the same is true for the number of constituent units constituting the unit.

From the viewpoint of excellent acid resistance, in the general formula (2), when XO is an oxyethyl group and YO is an oxypropyl group, m ₁ + m ₂ may be 8 to 40, 8 to 20, or 8 to 10 When XO is an oxypropyl group and YO is an oxyethyl group, n ₁ + n ₂ may be 8 to 40, 8 to 20, or 8 to 10.

The component (B) is contained in the formula (2) from the viewpoint that the line shape of the obtained wiring pattern is more excellent, and m ₁ + m ₂ when the XO is an oxy-ethyl group is 1 to 30, or YO is oxygen. The compound having n ₁ + n _{2 in the case} of ethyl group is 1 to 30, and the content thereof may be 30 parts by mass to 50 parts by mass, 30 parts by mass to 45 parts by mass or 30% by mass based on 100 parts by mass of the total amount of the component (B). Parts - 40 parts by mass.

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

The content of the entire component (B) in the photosensitive resin composition may be 30 parts by mass to 70 parts by mass, and 35 parts by mass to 65 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). 40 parts by mass to 60 parts by mass, or 35 parts by mass to 55 parts by mass. When the content is 30 parts by mass or more, the sensitivity and the resolution tend to be improved in a good balance. When it is 70 parts by mass or less, the film (photosensitive layer) tends to be easily formed, and there is a tendency that a favorable resist pattern shape is easily obtained.

(C) component: 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 suitably selected from photopolymerization initiators which are usually used.

As the component (C), benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1 can be mentioned. An aromatic ketone such as [4-(methylthio)phenyl]-2-morpholinyl-acetone-1; an anthracene such as an alkyl group; a benzoin ether compound such as a benzoin alkyl ether; a benzoin, an alkyl benzoin, etc. Benzoin compound; benzyl derivative such as benzyl dimethyl ketal; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5- 2,4,5-triarylimidazole dimer such as diphenylimidazole dimer; acridine derivative such as 9-phenyl acridine or 1,7-(9,9'-acridinyl)heptane . These may be used alone or in combination of two or more.

The (C) component may contain at least one of 2,4,5-triarylimidazole dimers and may also contain 2-(o-chlorophenyl)-4,5- from the viewpoint of further sensitivity and adhesion. Diphenylimidazole dimer. The structure of the 2,4,5-triarylimidazole dimer may be symmetrical or asymmetric.

The content of the component (C) in the photosensitive resin composition may be 0.1 parts by mass to 10 parts by mass, and 1 part by mass to 7 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). Parts by mass to 6 parts by mass, or 3 parts by mass to 5 parts by mass. When the content is 0.1 part by mass or more, good sensitivity, resolution, or adhesion tend to be obtained, and when it is 10 parts by mass or less, a favorable resist pattern shape tends to be easily obtained.

(D): decane coupling agent The photosensitive resin composition may further contain a decane coupling agent as the component (D). Examples of the decane coupling agent include a component (D1): a decane compound having a mercaptoalkyl group, and a component (D2): a decane compound having an amine group (preferably a decane compound having a ureido group), and a component (D3) having ( Methyl) decyloxy decane compound.

When the photosensitive resin composition contains the component (D1) as the component (D), the following effects can be obtained: excellent adhesion to a substrate having high smoothness and ITO by using hydrochloric acid can be obtained. In the etching, it is also difficult to produce an excellent acid-resistant resist pattern such as peeling.

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

For example, as the photosensitive resin composition, the component (D1) and the component (D3) may 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, and on the other hand, development residue on the copper substrate or the like is likely to occur (ie, The resist pattern formed on the copper substrate tends to be peeled 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), excellent adhesion can be maintained, and development of a copper substrate or the like can be suppressed, and etching can be performed. The time is shortened.

Further, the photosensitive resin composition may contain both the (D1) component, the (D2) component, and the (D3) component as the component (D). According to such a photosensitive resin composition, generation of development residue on a copper substrate or the like can be suppressed, and higher adhesion can be achieved.

The (D1) component may be a decane compound (mercaptoalkyl alkoxy decane) having a mercaptoalkyl group and an alkoxy group. As such a component (D1), mercaptopropylmethyldimethoxydecane may be mentioned. , mercaptopropyltrimethoxydecane, mercaptopropyltriethoxydecane, and the like. Among these, in view of the appearance of adhesion, it is preferably a mercaptopropyltrimethoxydecane which is easily hydrolyzed and can be crosslinked at three points. These may be used alone or in combination of two or more.

The component (D2) may be a decane compound having a primary amino group at the terminal, and examples of such a component (D2) include 3-aminopropylmethoxydecane, aminopropyl ethoxy decane, and N. -2-(Aminoethyl)-3-aminopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, 3-ureidopropyltrimethoxydecane,ureidomethyltrimethoxy Baseline, ureidomethyltriethoxydecane, 2-ureidoethyltrimethoxydecane, 2-ureidoethyltriethoxydecane, 4-ureidobutyltrimethoxydecane, 4-urea Butyl triethoxy decane and the like. Among these, a decane compound having a functional group having a low reactivity with a carboxylic acid group such as a ureido group, in consideration of reactivity with a binder polymer, may preferably be used in combination with the component (D1). 3-ureidopropyltriethoxydecane having a suppressing effect of development residue was particularly noticeably observed. These may be used alone or in combination of two or more.

Examples of the component (D3) include 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, and 3-methylpropeneoxime. Propylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane. Among these, in view of the appearance of adhesion, 3-methylpropenyloxypropyltrimethoxydecane which is easily hydrolyzed and can be crosslinked at three points is preferable. These may be used alone or in combination of two or more.

The content of the component (D) in the photosensitive resin composition may be 0.01 parts by mass to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B). 0.05 parts by mass to 5 parts by mass, or 0.1 parts by mass to 3 parts by mass. When the content of the component (D) is more than the above range, the development of the copper substrate or the like tends to be likely to occur, and the bottom of the resist may be caused by a sharp rise in the resolution and sensitivity. The hardening of the hardening is equal. On the other hand, when the content of the component (D) is within the above range, the development residue on the copper substrate or the like is sufficiently suppressed, and the hardenability of the bottom of the resist tends to be improved. By sufficiently hardening to the bottom of the resist, a good resist pattern shape can be obtained, and the resistance to the etching liquid becomes better.

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

(E) component: sensitizing dye The photosensitive resin composition of this embodiment can further contain a sensitizing dye as (E) component. Examples of the sensitizing dye include a dialkylaminobenzophenone compound, a pyrazoline compound, an anthraquinone compound, a coumarin compound, a xanthone compound, a thioxanthone compound, an oxazole compound, and benzene. And an oxazole compound, a thiazole compound, a benzothiazole compound, a triazole compound, a stilbene compound, a triazine compound, a thiophene compound, a naphthyl imine compound, a triarylamine compound, and an amino acridine compound. These may 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 hardening of the bottom of the resist and excellent adhesion.

When the photosensitive resin composition contains the component (E), the amount of hardening of the bottom of the resist is increased, and the adhesion is improved, and the total amount of the components (A) and (B) is 100 parts by mass. The content may be from 0.01 part by mass to 5 parts by mass, from 0.01 part by mass to 1 part by mass, or from 0.01 part by mass to 0.2 part by mass.

Further, the photosensitive resin composition may contain a polymerizable compound (oxetane compound or the like) having at least one cyclic ether group capable of cationic polymerization in the molecule; a cationic polymerization initiator; malachite green (malachite green) ), Victoria pure blue, brilliant green, methyl violet, etc.; tribromophenyl hydrazine, diphenylamine, benzylamine, triphenylamine, diethyl Light chromogenic reagent such as aniline, o-chloroaniline; thermal color development inhibitor; plasticizer such as p-toluenesulfonamide; pigment; filler; antifoaming agent; flame retardant; stabilizer; adhesion imparting agent; Leveling agent; stripping accelerator; antioxidant; perfume; imaging agent; These may 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)), the content of the components may be 100 parts by mass based on the total amount of the components (A) and (B). It is about 0.01 part by mass to 20 parts by mass.

[Solution of Photosensitive Resin Composition] The photosensitive resin composition may be a liquid composition containing at least one of an 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; toluene, and the like. An aromatic hydrocarbon solvent; an aprotic polar solvent such as N,N-dimethylformamide or the like. 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 in accordance with the purpose and the like. For example, the photosensitive resin composition can be used as a liquid composition in which the solid content is about 30% by mass to 60% by mass (hereinafter, a photosensitive resin composition containing an organic solvent is also referred to as a "coating liquid").

The coating liquid is applied onto the surface of a support, a metal plate or the like to be described later, and dried to form a photosensitive layer as a coating film of the photosensitive resin composition. The metal plate is not particularly limited and may be appropriately selected depending on the purpose and the like. Examples of the metal plate include metal plates containing metals such as copper, copper alloys, iron-based alloys such as nickel, chromium, iron, and stainless steel. As a preferable metal plate, a metal plate containing a metal such as copper, a copper-based alloy, or an iron-based alloy can be mentioned.

The thickness of the photosensitive layer to be formed is not particularly limited and may be appropriately selected in accordance with the use thereof. The thickness of the photosensitive layer (thickness after drying) may be about 1 μm to 100 μm.

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

<Photosensitive element> The photosensitive element (hereinafter, simply referred to as "photosensitive element") of the present embodiment includes a support and a photosensitive layer formed using the photosensitive resin composition provided on one surface of the support. . According to such a photosensitive element, since the photosensitive layer formed using the photosensitive resin composition is provided, even when a strong etching liquid is used, peeling and occurrence of the resist can be suppressed and obtained. A wiring pattern having a good line shape without looseness, and a resist pattern having a sufficiently short peeling time can be formed. Further, it is possible to efficiently form a resist pattern having excellent adhesion 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.

Fig. 1 is a schematic cross-sectional view showing an 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 may also be referred to as a coating film of a photosensitive resin composition. Further, the coating film is one in which the photosensitive resin composition is in an unhardened state.

The photosensitive element 10 can be obtained, for example, in the following manner. First, a coating liquid as a photosensitive resin composition containing an organic solvent is applied onto the support 2 to form a coating layer, which is dried (at least a part of the organic solvent is removed from the coating layer). The photosensitive layer 4 is formed. Then, the surface of the photosensitive layer 4 opposite to the support 2 is coated with the protective layer 6, whereby the photosensitive layer 4 having the support 2, laminated on the support 2, and laminated on the photosensitive layer 4 can be obtained. The photosensitive element 10 of the upper protective layer 6. Further, the photosensitive element 10 does not have to have the protective layer 6.

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

The thickness of the support 2 may be 1 μm to 100 μm, 5 μm to 50 μm, or 5 μm to 30 μm. When the thickness of the support 2 is 1 μm or more, the support 2 can be prevented from being damaged when the support 2 is peeled off. In addition, when the thickness of the support 2 is 100 μm or less, the decrease in the resolution at the time of exposure through the support 2 is suppressed.

As the protective layer 6, the adhesion to the photosensitive layer 4 may be smaller than the adhesion of the support 2 to the photosensitive layer 4. Specifically, as the protective layer 6, a film containing a polyester such as polyethylene terephthalate or a polymer having heat resistance and solvent resistance such as a polyolefin such as polypropylene or polyethylene can be used. As a commercially available product, Alpha (ALPHAN) MA-410, E-200, and a polypropylene film manufactured by Shin-Etsu Film Co., Ltd., manufactured by Oji Paper Co., Ltd., Teijin Co., Ltd. A PS series polyethylene terephthalate film such as PS-25 was produced, and NF-15A manufactured by Tamapoly Co., Ltd. Further, the protective layer 6 may be the same as the support 2 .

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

Specifically, the photosensitive element 10 can be manufactured, for example, in the following manner. In other words, the photosensitive element 10 can be produced by a production method including a step of preparing a coating liquid containing a photosensitive resin composition, and applying the coating liquid onto the support 2 to form The step of coating the layer and the step of drying the coating layer to form the photosensitive layer 4.

The application of the coating liquid onto the support 2 can be carried out by a known method such as roll coating, notched wheel 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 can be carried out at 70 ° C to 150 ° C for about 5 minutes to 30 minutes. After drying, the amount of the residual organic solvent in the photosensitive layer 4 can be 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step.

The thickness of the photosensitive layer 4 in the photosensitive element 10 can be suitably selected according to the use. It may be 1 μm to 100 μm, 1 μm to 50 μm, or 5 μm to 40 μm in terms of the thickness after drying. By the thickness of the photosensitive layer 4 being 1 μm or more, industrial coating is easy. When it is 100 μm or less, the adhesion and the resolution tend to be sufficiently obtained.

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

<Method for Forming Resist Pattern> The method for forming a resist pattern 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 member; (ii) An exposure step of hardening a portion of the photosensitive layer by irradiation of actinic rays to form a photohardenable region; and (iii) developing step of applying a region other than the photohardenable region of the photosensitive layer from the substrate The resist pattern of the photocured material (photohardenable region) containing the photosensitive resin composition is formed on the substrate. The method of forming the resist pattern may further have other steps as needed. Further, the resist pattern may also be referred to as a resin pattern or a relief pattern. Hereinafter, each step will be described in detail.

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

The method of forming the photosensitive layer on the substrate is, for example, a method in which a coating liquid containing a photosensitive resin composition is applied onto a substrate and then dried.

Further, as a method of forming the photosensitive layer on the substrate, for example, a method of laminating the photosensitive layer of the photosensitive element on the substrate after removing the protective film from the photosensitive element is exemplified. Lamination can be carried out by pressing a photosensitive layer facing the photosensitive element while pressing onto the substrate. By this lamination, a laminate in which a substrate, a photosensitive layer, and a support film are laminated in this order can be obtained.

The lamination can be carried out, for example, at a temperature of from 70 ° C to 130 ° C, and can be carried out by pressure bonding at a pressure of about 0.1 MPa to 1.0 MPa (about 1 kgf / cm ² to 10 kgf / cm ² ). These conditions can be adjusted as needed. When laminating, the substrate may be pre-heat treated, or the photosensitive layer may be heated to 70 ° C to 130 ° C.

(ii) Exposure step In the exposure step, a portion 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 rays, the actinic radiation can be transmitted through the support. On the other hand, when the support exhibits light-shielding properties to actinic rays, the photosensitive layer is irradiated with actinic rays after the support is removed.

As an exposure method, a method of irradiating an actinic ray in an image shape (mask exposure method) by a negative mask pattern or a positive mask pattern called an artwork is mentioned. In addition, direct exposure of the exposure method by laser direct imaging (LDI) exposure method or digital light processing (DLP) exposure method may be employed to irradiate the actinic ray in an image form. Methods.

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

(iii) Developing step In the developing step, a region other than the photohardenable region of the photosensitive layer (i.e., an uncured portion of the photosensitive layer) is removed from the substrate by a developing treatment, and a photosensitive film is formed on the substrate. A resist pattern of the layer of photohardened material. Further, when the support is present on the photosensitive layer subjected to the exposure step, the support is removed and the development step is performed. In the development treatment, there are wet development and dry development, and wet development can be suitably used.

In the wet development, a developing solution corresponding to the photosensitive resin composition is used, and development is carried out by a known developing method. Examples of the development method include a immersion method, a liquid coating method, a spray method, and a method such as brushing, slap, scraping, and shaking immersion. From the viewpoint of improving the resolution, a high pressure spray method is most suitable. It is also possible to combine two or more of the above methods for development.

The developer can be appropriately selected in accordance with the configuration of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution, an aqueous developing solution, and an organic solvent-based developing solution.

The alkaline aqueous solution for development may be 0.1% by mass to 5% by mass of sodium carbonate solution, 0.1% by mass to 5% by mass of potassium carbonate solution, 0.1% by mass to 5% by mass of sodium hydroxide solution, or 0.1% by mass to 55%. Mass% sodium tetraborate solution, etc. The pH of the alkaline aqueous solution may be from 9 to 11. Further, the temperature is adjusted in accordance with the alkali developability of the photosensitive layer. A surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.

The method of forming the resist pattern may further include the step of, after removing the unexposed portion, heating at about 60 ° C to 250 ° C and/or exposure of about 0.2 J/cm ² to 10 J/cm ^{2 as necessary} . Thereby, the resist pattern is further hardened.

<Manufacturing Method of Touch Panel> The method of manufacturing the touch panel of the present embodiment includes a step of performing etching treatment on a substrate on which a resist pattern is formed by the method of forming the resist pattern. The formed resist pattern is used as a mask (also referred to as a "resist"), and the conductor layer of the substrate or the like is etched. A pattern of the lead wiring and the transparent electrode is formed by an etching process, thereby manufacturing a touch panel.

3(a) to 3(h) are schematic cross-sectional views showing an embodiment of a method of manufacturing a touch panel of the present invention. The manufacturing method of the present aspect includes the first step of providing a laminated base material including the support base material 22, the transparent conductive layer 24 provided on one surface of the support base material 22, and the metal layer 26 provided on the transparent conductive layer 24. A resist pattern 29 containing a photocured material of a photosensitive resin composition is formed on the metal layer 26; and in a second step, the metal layer 26 and the transparent conductive layer 24 are etched to form a residue and a metal including the transparent conductive layer 24. a layered pattern of the remaining portion of the layer 26 (24+26 in FIG. 3(d)); and a third step of removing the metal layer from a portion of the build-up pattern to form a transparent electrode including the residue of the transparent conductive layer 24 and a metal containing layer Metal wiring of the residual part.

In the first step, first, as shown in FIG. 3(a), the support substrate 22, the transparent conductive layer 24 provided on one side of the support substrate 22, and the metal layer provided on the transparent conductive layer 24 are provided. On the metal layer 26 of the laminated substrate of 26, the photosensitive layer 28 is formed using a photosensitive resin composition. The photosensitive layer 28 may have a support on a surface opposite to the metal layer 26.

The metal layer 26 may be, for example, a metal layer containing copper. Further, examples of the metal layer containing copper include a metal layer containing copper, an alloy of copper and nickel, an alloy of copper with nickel and titanium, a molybdenum-aluminum-molybdenum laminate, and an alloy of silver and palladium and copper. Among these, a metal layer containing an alloy of copper, copper and nickel or an alloy of copper and nickel and titanium can be suitably 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 be a crystalline ITO, from the viewpoint of not requiring annealing treatment.

Then, a portion of the photosensitive layer 28 is hardened by irradiation of actinic rays to form a photohardenable region, and then a region other than the photocured region of the photosensitive layer is removed from the laminated substrate. Thereby, as shown in FIG. 3(b), a 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 covered by the resist pattern 29 are removed from the support substrate 22 by etching.

The etching treatment method is appropriately selected corresponding to the layer to be removed. For example, examples of the etching liquid for removing the metal layer include a copper chloride solution, a ferric chloride solution, a phosphoric acid solution, and the like. Further, as the etching liquid for removing the transparent conductive layer, oxalic acid, hydrochloric acid, aqua regia or the like can be used.

When the transparent conductive layer 24 is a crystalline ITO, as the etching liquid for removing the transparent conductive layer 24, it is necessary to use a strong acid such as concentrated hydrochloric acid or aqua regia or a chemical solution which simultaneously etches the metal layer and the transparent conductive layer ( For example, in the ITO series of ITO-4400Z, the resist pattern is a photocured material containing the photosensitive resin composition, and therefore, even under etching treatment using a strong acid, Peeling or the like of the resist pattern is sufficiently suppressed. The photosensitive resin composition of the present embodiment can be suitably used as a photosensitive resin composition for etching using a strong acid such as concentrated hydrochloric acid or aqua regia or a chemical liquid which simultaneously etches a metal layer and a transparent conductive layer as an etching liquid.

3(c) is a view showing an etching process, and in FIG. 3(c), a residual portion including the metal layer 26, a residual portion of the transparent conductive layer 24, and a residue of the resist pattern 29 are formed on the support substrate 22. Laminated body. In the manufacturing method of the present embodiment, the resist pattern 29 is removed from the laminate.

The removal of the resist pattern 29 can be performed, for example, using an aqueous solution which is more alkaline than the alkaline aqueous solution used in the development step. As the strongly alkaline aqueous solution, a 1% by mass to 10% by mass aqueous sodium hydroxide solution, a 1% by mass to 10% by mass aqueous potassium hydroxide solution, or the like can be used. In particular, a 1% by mass to 10% by mass aqueous sodium hydroxide solution or a 1% by mass to 10% by mass aqueous potassium hydroxide solution may be used, and a 1% by mass to 5% by mass aqueous sodium hydroxide solution or 1% by mass to 5% by mass may be used. An aqueous solution of potassium hydroxide. Examples of the release method of the resist pattern include a immersion method, a spray method, and the like, and these may be used singly or in combination.

3(d) is a view showing a state in which the resist pattern is peeled off, and in FIG. 3(d), a build-up pattern including a residual portion of the metal layer 26 and a residual portion of the transparent conductive layer 24 is formed on the support substrate 22.

In the third step, a portion other than a portion of the metal layer 26 for forming a metal wiring is removed from the build-up pattern to form a metal wiring including a residue of the metal layer 26 and a transparent electrode including a residue of the transparent conductive layer 24. . Further, in the present embodiment, as a method of removing the metal layer 26 in the third step, a method of etching is employed. However, 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 which has passed through the second step (Fig. 3(e)). Next, the resist 31 containing the photocured material of the photosensitive layer 30 is formed by exposure and development of the photosensitive layer 30 (Fig. 3(f)). In addition, the photosensitive layer may be a layer formed using the photosensitive resin composition of the present embodiment, or may be a layer formed using a conventionally known photosensitive resin composition for etching.

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

3(g) is a view showing an etching process, and in FIG. 3(g), a transparent electrode including a residual portion of the transparent conductive layer 24 is formed on the support substrate 22, and is formed on a part of the transparent electrodes. A laminate of the metal layer 26 and the resist 31. The resist 31 is removed from the laminate, and as shown in FIG. 3(h), a transparent electrode including a residual portion of the transparent conductive layer 24 and a metal wiring including a residue of the metal layer 26 are formed on the support substrate 22.

4 is a plan view showing an aspect of a touch panel obtained by the present invention. In the touch panel 100, the X electrode 52 and the Y electrode 54 which are transparent electrodes are alternately arranged in parallel, and the X electrodes 52 provided in the same row in the longitudinal direction are connected to each other by one lead wiring 56, and are provided separately. The Y electrodes 54 on the same column in the width direction are connected to each other by one lead wiring 57.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the embodiments. Example

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

(Production Example 1: Production of Binder Polymer (A-1)) 30 g of methacrylic acid, 35 g of methyl methacrylate, and butyl methacrylate as a polymerizable monomer (monomer) (mass ratio: 30/35/35) was mixed with 0.5 g of azobisisobutyronitrile and 10 g of acetone, and the obtained solution was referred to as "solution a". A solution obtained by dissolving 0.6 g of azobisisobutyronitrile in 30 g of acetone was designated as "solution b".

Into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube, a mixture of 80 g of acetone and 20 g of propylene glycol monomethyl ether (mass ratio of 4:1) was placed in a flask, and then placed in a flask. Nitrogen gas was blown and heated while stirring, and the temperature was raised to 80 °C.

The dropping rate was fixed, and the solution a was added dropwise to the mixed solution in the flask over 4 hours, and then the solution in the flask was stirred at 80 ° C for 2 hours. Then, the dropping rate was fixed, and the solution b was added dropwise to the solution in the flask over 10 minutes, and then the solution in the flask was stirred at 80 ° C for 3 hours. Further, the solution in the flask was heated to 90 ° C for 30 minutes, and the mixture was kept at 90 ° C for 2 hours, and then cooled to obtain a solution of the binder polymer (A-1).

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

Further, the weight average molecular weight and the degree of dispersion were measured by gel permeation chromatography (GPC) and converted using a calibration curve of standard polystyrene. The conditions for GPC are shown below. (GPC condition) Pump: Hitachi/L-6000 (Hitachi Manufacturing Co., Ltd.) Pipe column: The following three total, pipe size: 10.7 mmf × 300 mm Gelpack GL-R440 Gelpack GL-R450 Gelpack GL-R400M ( Above, Hitachi Chemical Co., Ltd.) Solvent: Tetrahydrofuran (THF) Sample concentration: 120 mg of a resin solution having a solid content of 40% by mass was extracted and dissolved in 5 mL of THF to prepare a sample. Measurement temperature: 40 ° C Injection amount: 200 μL Pressure: 49 Kgf/cm ² (4.8 MPa) Flow rate: 2.05 mL/min Detector: Hitachi L-3300 type RI (Hitachi Manufacturing Co., Ltd.)

Further, the acid value was measured in the following manner. First, a solution of the binder polymer was heated at 130 ° C for 1 hour to remove volatile components, thereby obtaining a solid component. Further, after accurately weighing 1 g of the polymer of the solid component, 30 g of acetone was added to the polymer and uniformly dissolved. Then, an appropriate amount of phenolphthalein as an indicator was added to the solution, and titration was carried out using a 0.1 N aqueous KOH solution. Further, the acid value was calculated by the following formula. Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100) wherein Vf represents the titer (mL) of the aqueous KOH solution, Wp represents the mass (g) of the measured polymer solution, and I represents the measured polymerization. The proportion (% by mass) of non-volatile components in the solution.

[Examples 1 to 8 and Comparative Examples 1 to 3] The examples and comparative examples were carried out by the following methods.

<Preparation of Photosensitive Resin Composition (Coating Liquid)> The components shown in Tables 1 and 2 were mixed in the amounts (parts by mass) shown in the table, whereby Examples and Comparative Examples were obtained. A coating liquid of a photosensitive resin composition. The amount of the component (A) in the table is the mass of the solid component. Furthermore, "-" means not deployed. The details of each component shown in Table 1 and Table 2 are as follows.

(Component (A)) A-1: The binder polymer (A-1) obtained in Production Example 1.

((B) component) FA-321M: 2,2-bis(4-(methacryloxypentapentaethoxy)phenyl)propane (Hitachi Chemical Co., Ltd., number of EO groups: 10 (average )) BPE-900: 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (Xinzhongcun Chemical Industry Co., Ltd., number of EO groups: 17 (average)) BPE-1300H: 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (Xinzhongcun Chemical Industry Co., Ltd., number of EO groups: 30 (average value)) FA- 3200MY: Polyoxyalkylene bisphenol A dimethacrylate (Hitachi Chemical Co., Ltd., number of EO groups: 12 (average value), number of PO groups: 4 (average value)) R-128H: Acrylic acid 2-hydroxy-3-phenoxypropyl ester (Nippon Chemical Co., Ltd.) FA-MECH: γ-chloro-β-hydroxypropyl-β'-methacryloxyethyl-phthalic acid Ester (Hitachi Chemical Co., Ltd.) FA-318A: Nonylphenoxy Polyethylene Glycol Acrylate (Hitachi Chemical Co., Ltd.) DPEA-12: Dipentaerythritol hexaacrylate with EO group (Nippon Chemical Co., Ltd.) Limited number, EO groups: 12 (average value))

((C) component) B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (Changzhou Power Electronic New Material Co., Ltd.)

((D) component: decane coupling agent) AY43-031: 3-ureidopropyl triethoxy decane (Dongli Dow Corning Co., Ltd.) KBM-803: 3-mercaptopropyltrimethoxydecane (Shin-Etsu Chemical) Industrial Co., Ltd.) SZ-6030: 3-Methylacryloxypropyltrimethoxydecane (Dongli 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: (A) component to (E) component) LCV: colorless crystal violet (Yamada Chemical Industry Co., Ltd.) TBC: 4-tert-butyl catechol (Di Ai Sheng (DIC) Co., Ltd.," DIC-TBC-5P") SF-808H: a mixture of carboxybenzotriazole, 5-amino-1H-tetrazole, methoxypropanol (Sanhe Chemical Co., Ltd., "SF-808H") AZCV- PW: [4-{bis(4-dimethylaminophenyl)methylene}-2,5-cyclohexadiene-1-ylidene] (Baotu Valley Chemical Industry Co., Ltd.)

[Table 1]

[Table 2]

<Production of Photosensitive Element> The coating liquid of the photosensitive resin composition obtained above was applied to a polyethylene terephthalate film having a thickness of 16 μm so that the thickness became uniform (Toray) The hot air convection dryer of 70 ° C and 110 ° C was sequentially dried by a Co., Ltd. product name "FB-40" to form a photosensitive layer having a film thickness of 15 μm after drying. A protective layer (manufactured by Jade Polymer Co., Ltd., product name "NF-15A") is attached to the photosensitive layer, and a polyethylene terephthalate film (support), a photosensitive layer, and a protective layer are sequentially laminated. The photosensitive element of the layer.

<Preparation of laminated substrate> A film substrate is prepared in which a transparent conductive layer containing crystalline ITO is formed on the upper layer of the polyethylene terephthalate material, and copper is further formed on the upper layer of the transparent conductive layer. A metal substrate and a film substrate on which the outermost surface of the metal layer is subjected to rustproof treatment. After heating the film substrate (hereinafter referred to as "substrate") to 80 ° C, the photosensitive element produced above was laminated (laminated) on the surface of the metal layer of the substrate. The lamination is carried out under the conditions of a temperature of 110 ° C and a lamination pressure of 4 kgf/cm ² (0.4 MPa) by removing the protective film on one side and adhering the photosensitive layer of the photosensitive element to the surface of the metal layer of the substrate. . In this manner, a laminated substrate in which a photosensitive layer and a support are laminated on the surface of the metal layer of the substrate is obtained.

<Evaluation of Sensitivity> The obtained laminated substrate was left to cool until it became 23 °C. Then, the laminated substrate is divided into three regions so that the concentration region is 0.00 to 2.00, the concentration phase is 0.05, the size of the exposure table is 20 mm × 187 mm, and the size of each stage is 3 mm × 12 mm. The 41-step stage tablet has a phototool attached to the support of one of the areas. The exposure is a parallel light exposure machine (Aoke Manufacturing Co., Ltd.) which uses a short-ultraviolet (UV) lamp (Orc Manufacturing Co., Ltd., product name "AHD-5000R") as a light source. The product name "EXM-1201") exposed the photosensitive layer via the optical device and the support at an energy (exposure amount) of 100 mJ/cm ² . At this time, other areas not used are covered by a black sheet. Further, the other regions were exposed to light at an energy of 200 mJ/cm ² and 400 mJ/cm ² by the same method. In addition, the illuminance was measured using an ultraviolet illuminometer (manufactured by Ushio Electric Co., Ltd., product name "UIT-150") using a 405 nm corresponding probe.

After the exposure, the support was peeled off from the laminated substrate, the photosensitive layer was exposed, and a 1% by mass aqueous sodium carbonate solution at 30 ° C was sprayed for 16 seconds, thereby removing the unexposed portion. Thus, a resist pattern containing a photocured material of the photosensitive resin composition is formed on the surface of the metal layer of the substrate. According to the number of remaining stages (the number of stages) of the stage exposure meter obtained as the resist pattern (cured film) at each exposure amount, a calibration curve of the exposure amount and the number of stages is prepared, and the number of stages is determined. The exposure amount of the 17-stage was used to evaluate the sensitivity of the photosensitive resin composition. The sensitivity is represented by the number of stages obtained from the self-calibration curve being changed to the exposure amount of 17 stages, and the smaller the amount of exposure, the better the sensitivity. The results are shown in Tables 3 and 4.

<Evaluation of Adhesiveness> 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) is used. The number of remaining segments of the staged exposure meter becomes 17 segments of energy to expose the photosensitive layer of the laminated substrate. After the exposure, the same development processing as the evaluation of the sensitivity was performed.

After development, in the value of the line width/space width in the resist pattern formed by the space portion (unexposed portion) being cleanly removed and the line portion (exposed portion) not being flawed, peeled off, and missing The minimum value is used to evaluate the adhesion. The smaller the value, the better the adhesion. The results are shown in Tables 3 and 4.

<Evaluation of Analyticity> Using a mask pattern of L/S of 1/1 to 30/30 (unit: μm), the number of remaining segments of the 41-stage staged exposure meter is changed to 17-stage energy to the laminated substrate. The photosensitive layer is exposed. After the exposure, the same development processing as the evaluation of the sensitivity was performed.

After development, in the value of the line width/space width in the resist pattern formed by the space portion (unexposed portion) being cleanly removed and the line portion (exposed portion) not being flawed, peeled off, and missing The minimum value is used to evaluate the resolution. The smaller the value, the better the resolution. The results are shown in Tables 3 and 4.

<Evaluation of Adhesiveness After Etching> The adhesion after etching of the resist pattern was evaluated as follows. Using a mask pattern of L/S of 4/400 to 47/400 (unit: μm), the photosensitive layer of the laminated substrate was exposed by an energy of 23 stages in the number of remaining segments of the 41-stage staged exposure meter. After the exposure, the same development treatment as the evaluation of the sensitivity was performed to obtain a substrate on which a pattern was formed.

The obtained substrate was etched at 40 ° C for 30 seconds using ITO-4400Z (manufactured by Adico Co., Ltd., trade name), and then washed with water and dried.

The line width/space width in the resist pattern formed by the metal layer and the transparent conductive layer of the space portion (unexposed portion) being cleanly removed and the line portion (exposed portion) not being flawed, peeled off, and missing The minimum value of the values is used to evaluate the adhesion after etching. The smaller the value, the higher the etching resistance and the better the adhesion. The results are shown in Tables 3 and 4.

<Evaluation of the shape of the line after the etching> The line shape after the etching of the wiring pattern was formed by using a digital microscope VHX-2000 (manufactured by Keyence Co., Ltd.) in the evaluation of the adhesion after the etching. The wiring pattern under the resist pattern of L/S of 47/400 (unit: μm) was observed. Further, the undercut width is 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 of the wiring pattern was evaluated based on the following values based on the value of the side etching width and the presence or absence of looseness. The results are shown in Tables 3 and 4. A: No looseness was observed in the line shape after etching of the wiring pattern, and the value of the side etching width was less than 5 μm. B: No looseness was observed in the line shape after etching of the wiring pattern, but the value of the side etching width was 5 μm or more. C: Looseness was observed in the line shape after etching of the wiring pattern.

<Evaluation of peelability> Using PET negative type: 60 mm × 45 mm square (solid: no pattern), the photosensitive layer of the laminated substrate was subjected to energy of 17 stages by the number of remaining stages of the 41-stage staged exposure meter. exposure. After the exposure, the same development treatment as the evaluation of the sensitivity was performed, and a laminated substrate having a cured film of 60 mm × 45 mm square formed on the substrate was obtained. The laminated substrate was immersed in a 2.5 mass% sodium hydroxide aqueous solution at 50 ° C to carry out peeling evaluation. The time until the cured film was completely peeled off from the substrate after the laminated substrate was immersed was defined as the peeling time (second). Moreover, the size of the peeling sheet after peeling was visually observed, and it evaluated by the following reference. The shorter the peeling time and the smaller the peeling sheet size, the better the peeling property. The results are shown in Tables 3 and 4. S: less than 40 mm square. M: 40 mm to 50 mm square. L: flake (greater than 50 mm square).

[table 3]

[Table 4]

It is understood that (meth)acrylate having six ethylenically unsaturated bonds in the molecule and 10 parts by mass or less (the total amount of the components (A) and (B) are 100 as compared with the comparative examples 1 to 3. In Examples 1 to 8 in which a (meth) acrylate having one ethylenically unsaturated bond in the molecule is used as a photopolymerizable compound, the etched density of the resist pattern can be improved in a well-balanced manner. The shape of the wire after etching and the peeling property of the resist pattern.

2‧‧‧Support
4‧‧‧Photosensitive layer
6‧‧‧Protective layer
10‧‧‧Photosensitive components
12‧‧‧Support substrate
14‧‧‧Transparent conductive layer
16‧‧‧Photosensitive layer
18‧‧‧Leading wiring
22‧‧‧Support substrate
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‧‧‧ lead wiring
100‧‧‧ touch panel

Fig. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive element of the present invention. 2(a) to 2(e) are schematic cross-sectional views showing a prior art manufacturing method of the touch panel. 3(a) to 3(h) are schematic cross-sectional views showing an embodiment of a method of manufacturing a touch panel of the present invention. 4 is a plan view showing an aspect of a touch panel obtained by the present invention.

2‧‧‧Support

4‧‧‧Photosensitive layer

6‧‧‧Protective layer

10‧‧‧Photosensitive components

Claims (6)

A photosensitive resin composition comprising (A) component: a binder polymer, (B) component: a photopolymerizable compound, and (C) component: a photopolymerization initiator, wherein the component (B) contains an intramolecular component a (meth) acrylate having six ethylenically unsaturated bonds, and a (meth) acrylate having one ethylenically unsaturated bond in the molecule, and the component (A) and the component (B) In the total amount of 100 parts by mass, the content of the (meth) acrylate having one ethylenically unsaturated bond in the molecule is 10 parts by mass or less. The photosensitive resin composition according to claim 1, wherein the component (B) further contains a bisphenol A type di(meth)acrylate having a (poly)oxyethyl group. A photosensitive element comprising: a support; and a photosensitive layer formed on one surface of the support using the photosensitive resin composition according to claim 1 or 2. A method of forming a resist pattern, comprising: a photosensitive layer forming step of using the photosensitive resin composition according to claim 1 or 2, or the photosensitive material according to claim 3 Forming a photosensitive layer on the substrate; exposing step of hardening a portion of the photosensitive layer by irradiation of actinic rays to form a photohardenable region; and developing step of depositing the photosensitive layer A region other than the photohardenable region is removed from the substrate to obtain a resist pattern including the photohardenable region. A method for manufacturing a touch panel, comprising: a first step, comprising: a support substrate; a transparent conductive layer containing indium tin oxide provided on one side of the support substrate; and a transparent conductive layer disposed on the transparent conductive layer a resist pattern containing the photocured material of the photosensitive resin composition according to the first or second aspect of the invention of the patent application is formed on the metal layer of the laminated substrate of the metal layer; The metal layer and the transparent conductive layer are etched to form a buildup pattern including a residual portion of the transparent conductive layer and a residual portion of the metal layer; and a third step of removing the metal from a portion of the build-up pattern The layer forms a transparent electrode including a residue of the transparent conductive layer and a metal wiring including a residue of the metal layer. The method of manufacturing a touch panel according to claim 5, wherein the transparent conductive layer contains crystalline indium tin oxide, and the etching in the second step is etching using a strong acid.