KR20220131512A - Positive photosensitive resin composition, cured film, laminate, substrate with conductive pattern, manufacturing method of laminate, touch panel and organic EL display device - Google Patents

Abstract

It has a low reflectance and can be applied as a light-shielding layer of an opaque wiring electrode, and provides a positive photosensitive resin composition that can achieve both resolution of fine patterns, transparency of the substrate by suppressing residues on the substrate, and migration resistance. thing. A positive photosensitive resin composition comprising an alkali-soluble resin (A) having a polymerizable group in a side chain, a photosensitizer (B) and a colorant (C), wherein the polymerizable group is an acryl group and/or a methacryl group.

Description

Positive photosensitive resin composition, cured film, laminate, substrate with conductive pattern, manufacturing method of laminate, touch panel and organic EL display device

This invention relates to a positive photosensitive resin composition, a cured film, a laminated body, the board|substrate with a conductive pattern, the manufacturing method of a laminated body, a touchscreen, and an organic electroluminescent display.

In recent years, a touch panel is widely used as an input means. The touch panel includes a display unit such as a liquid crystal panel, and a touch panel sensor that detects information input at a specific position. The touch panel method is roughly classified into a resistive film method, a capacitive method, an optical method, an electromagnetic induction method, an ultrasonic method, and the like according to a method of detecting an input position. Among them, for reasons such as being optically bright, excellent in designability, simple in structure, and excellent in functionality, a capacitive touch panel is widely used.

The capacitive touch panel sensor has a first electrode and a second electrode orthogonal through an insulating layer, and is obtained by applying a voltage to an electrode on the touch panel surface, and detecting a change in capacitance when a conductor such as a finger comes into contact. The contact position is output as a signal. As a touch panel sensor used in the capacitive method, for example, a structure in which electrodes and external connection terminals are formed on a pair of opposing transparent substrates, a structure in which electrodes and external connection terminals are formed on both sides of a single transparent substrate, respectively, etc. This is known As a wiring electrode used for a touch panel sensor, it was common to use a transparent wiring electrode from a viewpoint of making a wiring electrode difficult to visually recognize, but in recent years, with high sensitivity and an enlargement of a screen, the opaque wiring electrode using a metal material is widely known.

A touch panel sensor having an opaque wiring electrode using a metal material has a problem in that the opaque wiring electrode is visually recognized by the metallic luster of the opaque wiring electrode, but a photosensitive resin composition containing a colorant is used on the opaque wiring electrode, and a light shielding layer is used. There is a method of making it difficult to be visually recognized. (For example, Patent Document 1)

International Publication No. 2018/168325

However, in the photosensitive resin composition using the colorant, residues derived from the colorant tend to occur on the substrate, particularly on the film containing the organic component, on the substrate during pattern formation, resulting in poor appearance, etc., and the transparency of the substrate may be impaired. Moreover, in order to suppress the residue, when the developing time was lengthened, it was difficult to form a fine pattern. Moreover, when a silver electrode is used as a 1st electrode and a 2nd electrode, there also existed a subject that the component in the light shielding layer formed on the electrode diffused into an insulating layer, it becomes an impurity, and silver migration is easy to generate|occur|produce.

The present invention has low reflectance and can be applied as a light-shielding layer of an opaque wiring electrode, and a positive photosensitive resin composition capable of reconciling fine pattern resolution, transparency of a substrate by suppressing residues on a substrate, and migration resistance aims to provide

The present inventors have found that the object of the present invention is achieved by combining an alkali-soluble resin having a polymerizable group in the side chain, a photosensitizer and a colorant.

That is, the positive photosensitive resin composition of the present invention contains an alkali-soluble resin (A) having a polymerizable group in a side chain, a photosensitive agent (B) and a colorant (C), wherein the polymerizable group is an acryl group and/or a methacryl group do it with

The positive photosensitive resin composition of the present invention has a low reflectance and can be applied as a light shielding layer of an opaque wiring electrode. have.

BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic which shows an example of the structure of the laminated body of this invention.
It is a schematic diagram which shows another example of the structure of the laminated body of this invention.
It is a schematic diagram which shows an example of the manufacturing method of the laminated body of this invention.
It is a schematic diagram which shows the electrode pattern for evaluation in an Example and a comparative example.
It is a top view of the laminated board for evaluation of the residue on a board|substrate in an Example and a comparative example.

The positive photosensitive resin composition of the present invention contains an alkali-soluble resin (A) having a polymerizable group in a side chain, a photosensitive agent (B) and a colorant (C), wherein the polymerizable group is an acryl group and/or a methacryl group, characterized in that do.

[Alkali-soluble resin (A) having a polymerizable group in the side chain]

The positive photosensitive resin composition of this invention contains alkali-soluble resin (A) which has a polymeric group in a side chain. By containing alkali-soluble resin (A) which has a polymeric group in a side chain, while being able to accelerate|stimulate dissolution at the time of image development, suppress a residue, and can ensure transparency of a base material, a fine pattern can be formed. Moreover, the solvent resistance of the cured film obtained by crosslinking|crosslinking a polymeric group by the heat processing after pattern formation improves. Here, "alkali solubility" refers to the property which melt|dissolves in aqueous alkali solution or organic alkali.

In order that alkali-soluble resin (A) which has a polymeric group in a side chain provides alkali solubility, it is preferable to have an acidic group in the structural unit of resin and/or its main chain terminal. As an acidic group, a carboxyl group, phenolic hydroxyl group, a sulfonic acid group, a thiol group etc. are mentioned, for example. Among these, a carboxyl group is preferable from the high solubility with respect to an alkaline developing solution.

In the present invention, the polymerizable group is an acryl group and/or a methacryl group. When the polymerizable group is an acryl group and/or a methacryl group, the crosslinking reaction by light and/or heat efficiently proceeds and the degree of curing is improved. inhibition to improve migration resistance.

Examples of the alkali-soluble resin include, but are not limited to, acrylic polymer, epoxy resin, phenol resin, caldo-based resin, polysiloxane, polyimide, polyamide, polybenzoxazole and the like. You may contain 2 or more types of these resins. Among them, acrylic polymers, caldo-based resins, and polysiloxanes are preferable from the viewpoint of ease of introduction of unsaturated double bonds, acrylic polymers and polysiloxanes are more preferable from the viewpoint of weather resistance, and acrylic polymers are more preferable from the viewpoint of easiness of synthesis.

It is preferable that alkali-soluble resin (A) which has a polymeric group in the said side chain has an organic group represented by following General formula (1). By having an organic group represented by the following general formula (1) in the alkali-soluble resin (A) having a polymerizable group in the side chain, it is possible to further suppress the residue at the time of pattern formation to secure the transparency of the substrate, and the subsequent heating step The solvent resistance of the cured film obtained by this can be improved more. An organic group can be identified by IR analysis, ¹ HNMR, GC-MS, and MALDI-MS analysis about alkali-soluble resin (A) which has a polymeric group in a side chain.

In general formula (1), X represents a C1-C4 hydrocarbon group, s represents 0 or 1, R< ¹ > represents a hydrogen atom or a methyl group.

It is more preferable that the alkali-soluble resin (A) having a polymerizable group in the side chain has a repeating unit represented by the following general formula (2).

In the general formula (2), R ² and R ³ represent a hydrogen atom or a methyl group. R ² and R ³ may be the same or different, respectively.

It is preferable that alkali-soluble resin (A) which has a polymeric group in a side chain has 5-50 mol% of repeating units represented by General formula (2) in all repeating units. When the content of the repeating unit represented by the general formula (2) is 5 mol% or more, the effect of securing transparency of the base material by suppressing residues is further improved. Also, migration resistance is further improved. As for the repeating unit represented by general formula (2), it is more preferable that it is 10 mol% or more, and it is still more preferable that it is 15 mol% or more. On the other hand, when the repeating unit represented by the general formula (2) is 50 mol% or less, a finer pattern can be formed. It is more preferable that it is 40 mol% or less, and, as for the repeating unit represented by General formula (2), it is still more preferable that it is 35 mol% or less.

The alkali-soluble resin (A) having a polymerizable group in the side chain may have a repeating unit other than the repeating unit represented by the general formula (2). As a repeating unit other than the repeating unit represented by the general formula (2), after radical copolymerization of a (meth)acrylic compound containing a carboxyl group and/or an acid anhydride group, (meth)acrylic acid ester, (meth)acrylic acid ester It is preferable that it is a repeating unit containing what is obtained by addition-reacting the epoxy compound which has a bonding group.

The acrylic polymer is obtained by radical polymerization of a monomer having an ethylenically unsaturated double bond. The repeating unit represented by the general formula (2) is obtained by adding glycidyl (meth)acrylate to an acrylic polymer containing the repeating unit represented by the general formula (3). There is no restriction|limiting in particular in the catalyst of radical copolymerization, Organic peroxides, such as an azo compound, such as azobisisobutylonitrile, and benzoyl peroxide, etc. are generally used. Moreover, there is no restriction|limiting in particular in the catalyst used for the addition reaction of (meth)acrylic-acid glycidyl, Although a well-known catalyst can be used, For example, dimethylaniline, 2,4,6- tris(dimethylaminomethyl)phenol, dimethyl Amino catalysts such as benzylamine, tin-based catalysts such as 2-ethyl tin(II) hexanoate and dibutyltin laurate, titanium-based catalysts such as 2-ethyl hexanoate titanium(IV), triphenylphosphine, etc. phosphorus-based catalysts and chromium-based catalysts such as chromium acetylacetonate and chromium chloride are used.

In the general formula (3), R ⁴ represents a hydrogen atom or a methyl group.

The same applies to the catalyst used for radical copolymerization of a repeating unit other than the repeating unit represented by the general formula (2), and a catalyst using an epoxy compound having an ethylenically unsaturated double bond group in the addition reaction.

As the (meth)acrylic compound containing a carboxyl group and/or an acid anhydride group, for example, (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, succinic acid mono(2-acryloxyethyl), phthalic acid mono(2-acryloxyethyl) , tetrahydrophthalic acid mono(2-acryloxyethyl), 2-vinylacetic acid, 2-vinylcyclohexanecarboxylic acid, 3-vinylcyclohexanecarboxylic acid, 4-vinylcyclohexanecarboxylic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, (meth)acrylic acid 4-hydroxyphenyl, (meth)acrylic acid 2-hydroxyphenyl, (meth)acrylic acid anhydride, itaconic acid, itaconic acid anhydride, succinic acid mono(2-acrylo) yloxyethyl), monophthalic acid mono(2-acryloyloxyethyl), or tetrahydrophthalic acid mono(2-acryloyloxyethyl).

As (meth)acrylic acid ester, methyl (meth)acrylate, (meth)acrylic acid tricyclodecanyl, (meth)acrylic acid benzyl, etc. are used, for example. Moreover, you may copolymerize styrene with the said (meth)acrylic acid or (meth)acrylic acid ester.

As an epoxy compound which has an ethylenically unsaturated double bond group, (meth)acrylic-acid glycidyl etc. are mentioned, for example.

As the acrylic polymer, a polymer obtained by polymerization of a polyfunctional (meth)acrylate compound and a polyvalent mercapto compound by Michael addition (beta position with respect to the carbonyl group) may be used.

It is preferable that the weight average molecular weight (Mw) of alkali-soluble resin (A) which has a polymeric group in a side chain is 1,000 or more and 15,000 or less in polystyrene conversion measured by gel permeation chromatography (GPC). When a weight average molecular weight (Mw) is 1,000 or more and the laminated body mentioned later is formed, it can suppress that a cured film melt|dissolves too much at the time of patterning and a conductive layer is exposed. A weight average molecular weight (Mw) becomes like this. More preferably, it is 5,000 or more, More preferably, it is 7,000 or more. On the other hand, when a weight average molecular weight (Mw) is 15,000 or less, a finer pattern can be formed. Moreover, dissolution at the time of image development can be accelerated|stimulated more, a residue can be suppressed more, and transparency of a base material can be ensured. The weight average molecular weight (Mw) is more preferably 12,000 or less.

In the positive photosensitive resin composition of the present invention, the content of the alkali-soluble resin (A) having a polymerizable group in the side chain is not particularly limited, and can be arbitrarily selected according to the desired film thickness and use, but the solid content is 100% by mass. In this case, it is common to set it as 10 mass % or more and 70 mass % or less.

[Photosensitizer (B)]

The positive photosensitive resin composition of the present invention contains a photosensitive agent (B).

The photosensitizer (B) generates an acid by irradiation with light, has a property of increasing alkali solubility of the light-irradiated portion of the alkali-soluble resin (A) having a polymerizable group in the side chain, and alkali-soluble contrast with the unexposed portion is obtained, While pattern formation is possible, a residue can be suppressed and transparency of a base material can be ensured. Examples of the photosensitizer include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Especially, a quinonediazide compound is preferable at the point from which a finer pattern is obtained.

The quinonediazide preferably contains a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazidesulfonyl ester compound has absorption in the i-line region of a mercury lamp, so it is suitable for i-line exposure. The 5-naphthoquinonediazidesulfonyl ester compound has absorption in the g-ray region of a mercury lamp, so it is suitable for g-ray exposure.

The positive photosensitive resin composition of this invention WHEREIN: Although there is no restriction|limiting in particular in content of the photosensitive agent (B), 0.01-50 mass % is preferable with respect to 100 mass % of solid content. When content of a photosensitive agent (B) is 0.01 mass % or more, a finer pattern can be formed. Moreover, in order to promote alkali solubility of an exposed part, a residue can be suppressed more and transparency of a base material can be ensured. Content of a photosensitive agent (B) becomes like this. More preferably, it is 10 mass % or more. Moreover, when content of the photosensitive agent (B) is 50 mass % or less, light can be transmitted to the bottom of a film|membrane, and a pattern is obtained with high exposure sensitivity. Content of a photosensitive agent (B) becomes like this. More preferably, it is 40 mass % or less.

Moreover, you may use as it is, without esterifying the said polyhydroxy compound or a polyamino compound with the sulfonic acid of a quinonediazide as needed. In this case, as an addition amount of a hydroxy compound or a polyamino compound, 1-50 mass % is preferable with respect to 100 mass % of solid content. By adding 1 mass % or more of a hydroxy compound or polyamino compound that has not been esterified, the positive resin composition obtained is hardly soluble in an alkali developer before exposure and easily dissolves in an alkali developer after exposure. There is little film loss, and development becomes easy in a short time. As for the addition amount of a hydroxy compound or a polyamino compound, 3 mass % or more is more preferable. Moreover, by making the addition amount of a hydroxy compound or a polyamino compound into 50 mass % or less, the solubility with respect to an alkali developing solution is improved more and formation of a finer pattern becomes possible. As for the addition amount of a hydroxy compound or a polyamino compound, 40 mass % or less is more preferable.

[Colorant (C)]

The positive photosensitive resin composition of this invention contains a coloring agent (C). The colorant (C) refers to a compound colored by absorbing all or part of the light of the wavelength (380 to 780 nm) of visible light.

When the positive photosensitive resin composition of this invention is formed on a conductive layer by containing a coloring agent (C), a conductive layer becomes difficult to visually recognize by light-shielding the light reflected by a conductive layer.

As a coloring agent (C), the compound which absorbs the light of the wavelength of a visible light, and colors black, red, orange, yellow, green, blue, or purple is mentioned. By combining these colorants individually or in two or more colors, the light reflected by a conductive layer can be light-shielded.

As said coloring agent (C), what has an aromatic group is preferable. By having an aromatic group, it interacts with the polymeric group of alkali-soluble resin (A) which has a polymeric group in a side chain, the solubility with respect to an alkali developing solution is increased, a residue can be suppressed more and transparency of a base material can be ensured.

As said coloring agent (C), a black agent (Ca) and/or coloring agents other than black (Cb) is mentioned. The black agent (Ca) refers to a compound colored black by absorbing light in the entire wavelength range of visible light. By containing a black agent (Ca), light-shielding property can be improved by light-shielding the light reflected by a conductive layer. In addition, the colorant (Cb) other than black refers to a compound colored in red, orange, yellow, green, blue or purple by absorbing light of a partial wavelength of visible light. By combining two or more colors of these colorants (Cb), it is possible to pseudo-black color, and light-shielding properties can be improved. Since it is excellent in hiding property from a light-shielding viewpoint, it is preferable that it is black agent (Ca).

As said coloring agent (C), it is preferable to contain 1 or more types chosen from the organic pigment (C1) mentioned later, an inorganic pigment (C2), and dye (C3). Especially, it is preferable that it is an organic pigment (C1) from a viewpoint of heat resistance and light-shielding property, and it is more preferable that it is a black organic pigment.

[Organic Pigment (C1)]

As a positive photosensitive resin composition of this invention, it is preferable that the said coloring agent (C) contains an organic pigment (C1). By containing an organic pigment (C1), while light-shielding property can be provided to the cured film of a positive photosensitive resin composition, hiding property is high and it is hard to become color fading by an ultraviolet-ray etc. As an aspect in which the said coloring agent (C) contains an organic pigment (C1), it is mentioned that the said black agent (Ca) and/or a coloring agent (Cb) other than black is an organic pigment (C1).

1-1,000 nm is preferable, as for the number average particle diameter of an organic pigment (C1), 5-500 nm is more preferable, 10-200 nm is still more preferable. The light-shielding property of the cured film of a positive photosensitive resin composition as the number average particle diameter of an organic pigment (C1) is in the said range, and dispersion stability of an organic pigment (C1) can be improved.

Here, the number average particle diameter of the organic pigment (C1) is a submicron particle size distribution analyzer (N4-PLUS; manufactured by Beckman Coulter Co., Ltd.) or a Zeta potential/particle diameter/molecular weight measuring device (Zitasizer Nano ZS). It can be calculated|required by measuring the laser scattering by Brownian motion of the organic pigment (C1) in a solution using (manufactured by Sysmex Co., Ltd.) (dynamic light scattering method). In addition, the number average particle diameter of the organic pigment (C1) in the cured film obtained from a resin composition can be calculated|required by measuring using SEM and TEM. The number average particle diameter of the organic pigment (C1) is directly measured at an magnification of 50,000 to 200,000. Here, the number average particle diameter can be calculated by the average value of the particle diameters of 100 randomly selected primary particles. When an organic pigment (C1) is a true sphere, the diameter of a true sphere is measured and let it be a number average particle diameter. When the organic pigment (C1) is not a true sphere, the longest diameter (hereinafter, "major axis diameter") and the longest diameter in the direction orthogonal to the major axis diameter (hereinafter "short axis diameter") are measured, and the major axis diameter and the minor axis diameter are measured. Let the biaxial average diameter obtained by averaging the diameters be the number average particle diameter.

Examples of the organic pigment (C1) include phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, pyranthrone pigments, dioxazine pigments, thioindigo pigments, diketopyrrolopyrrole pigments, quinophthalone pigments, Sreene pigment, indoline pigment, isoindoline pigment, isoindolinone pigment, benzofuranone pigment, perylene pigment, aniline pigment, azo pigment, azomethine pigment, condensed azo pigment, carbon black, metal complex pigments, lake pigments, toner pigments or fluorescent pigments. From the viewpoint of heat resistance, anthraquinone pigments, quinacridone pigments, pyransrone pigments, diketopyrrolopyrrole pigments, benzofuranone pigments, perylene pigments, condensed azo pigments and carbon black are preferable. Especially, it is more preferable that it is carbon black from a viewpoint of dispersion stability and transparency ensuring of the base material by residue suppression by having an aromatic group.

As a phthalocyanine type pigment, a copper phthalocyanine type compound, a halogenated copper phthalocyanine type compound, or a metal-free phthalocyanine type compound is mentioned, for example.

Examples of the anthraquinone pigment include an aminoanthraquinone compound, a diaminoanthraquinone compound, an anthrapyrimidine compound, a flavanthrone compound, an anthanthrone compound, an indanthrone compound, a pyranthrone compound, or a bi oranthrone compounds.

As an azo pigment, a disazo type compound or a polyazo type compound is mentioned, for example.

Examples of carbon black include channel black, furnace black, thermal black, acetylene black and lamp black.

The positive photosensitive resin composition of this invention WHEREIN: As for the content rate of an organic pigment (C1) with respect to 100 mass % of solid content, 5-50 mass % is preferable. Light-shielding property can be improved more as the content rate of an organic pigment (C1) is 5 mass % or more. More preferably, the content rate of an organic pigment (C1) is 10 mass % or more. On the other hand, when the content rate of an organic pigment (C1) is 50 mass % or less, image development residue can be reduced more and transparency of a base material can be ensured. More preferably, the content rate of an organic pigment (C1) is 40 mass % or less.

[Inorganic pigment (C2)]

As a positive photosensitive resin composition of this invention, it is preferable that the said coloring agent (C) contains an inorganic pigment (C2). By containing an inorganic pigment (C2), light-shielding property can be provided to the film|membrane of a positive photosensitive resin composition, and since it is an inorganic substance and it is more excellent in heat resistance and weather resistance, the heat resistance and weather resistance of the film|membrane of a resin composition can be improved. As an aspect in which the said coloring agent (C) contains an inorganic pigment (C2), it is mentioned that the said black agent (Ca) and/or a coloring agent (Cb) other than black is an inorganic pigment (C2).

Examples of the inorganic pigment (C2) include titanium, barium, zirconium, lead, silicon, aluminum, magnesium, molybdenum, cadmium, tin, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium or silver. and fine particles, oxides, complex oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides, and oxynitrides of the above metal elements. Among them, metal nitride particles are preferable from the viewpoint of further improving patternability and light-shielding properties. Further, from the viewpoint of further improving light-shielding properties, titanium, zirconium, or silver fine particles, oxides, complex oxides, sulfides, nitrides, carbides or oxynitrides are preferable, and zirconium nitride particles are particularly preferable.

The positive photosensitive resin composition of this invention WHEREIN: As for the content rate of an inorganic pigment (C2) with respect to 100 mass % of solid content, 5-50 mass % is preferable. Light-shielding property can be improved more as the content rate of an inorganic pigment (C2) is 5 mass % or more. More preferably, the content rate of an inorganic pigment (C2) is 10 mass % or more. On the other hand, when the content rate of an inorganic pigment (C2) is 50 mass % or less, image development residue can be reduced more and transparency of a base material can be ensured. More preferably, the content rate of an inorganic pigment (C2) is 40 mass % or less.

[Dye (C3)]

As a positive photosensitive resin composition of this invention, it is preferable that the said coloring agent (C) contains dye (C3). As an aspect in which the said coloring agent (C) contains the dye (C3), the thing of the said black agent (Ca) and/or a coloring agent (Cb) other than black is a dye (C3) is mentioned.

The dye (C3) refers to a compound that colors the object by chemical adsorption or strong interaction of substituents such as an ionic group or a hydroxyl group in the dye (C3) with the surface structure of the object, and is generally soluble in a solvent or the like. In addition, in the coloring by the dye (C3), since each molecule is adsorbed to the target, the coloring power is high and the coloring efficiency is high.

Examples of the dye (C3) include anthraquinone dyes, azo dyes, azine dyes, phthalocyanine dyes, methine dyes, oxazine dyes, quinoline dyes, indigo dyes, indigoid dyes, and carbonium dyes. , a srene-based dye, a perinone-based dye, a perylene-based dye, a triarylmethane-based dye, or a xanthene-based dye. From the viewpoints of solubility in solvents and heat resistance, anthraquinone dyes, azo dyes, azine dyes, methine dyes, triarylmethane dyes and xanthene dyes are preferable.

Examples of the dye for coloring black include solvent black 3, 5, 7, 22, 27, 29 or 34, mordant black 1, 11 or 17, acid black 2 or 52, or direct black 19 or 154. (All figures are C.I. numbers). In addition to the above, "NUBIAN" (registered trademark) BLACK TH-807, TH-827, TH-827K, TN-870, PC-0855, PC-5856, PC-5857, PC-5877, East PC-8550, Dong TN-873, Dong TN-877 or Dong AH-807, OIL BLACK HBB or Dong 860, "VALIFAST" (registered trademark) BLACK 1807, Dong 3904, Dong 3810, Dong 3820, Dong 3830, Dong 3840, 3866 or 3870, WATER BLACK 100-L, 191-L, 256-L, R-510, or 187-LM (all of these are made by Orient Chemical Co., Ltd.) .

Examples of the dye for coloring red include Direct Red 9, 28, 81, or 83 (all numerical values are C.I. numbers).

Examples of the dye for coloring orange include Basic Orange 21 or 23 (all numerical values are C.I. numbers).

Examples of the dye for coloring yellow include Direct Yellow 8, 9, 11, 27 or 44, or Basic Yellow 1, 28 or 40 (all numerical values are C.I. numbers).

As a dye coloring green, acid green 16 is mentioned, for example (all numerical values are C.I. number).

Examples of the dye for coloring blue include Acid Blue 9, 45, 80, 83, 90 or 185 (all numerical values are C.I. numbers).

Examples of the dye for coloring purple include Direct Violet 51, or 66, and Basic Violet 1, 2, or 3 (all numerical values are C.I. numbers).

The positive photosensitive resin composition of this invention WHEREIN: 0.01-50 mass % of content rate of dye (C3) is preferable with respect to 100 mass % of solid content. Light-shielding property can be improved more that the content rate of dye (C3) is 0.01 mass % or more. The content rate of dye (C3) becomes like this. More preferably, it is 0.05 mass % or more. On the other hand, when the content rate of dye (C3) is 50 mass % or less, image development residue can be reduced more and transparency of a base material can be ensured. The content rate of dye (C3) becomes like this. More preferably, it is 40 mass % or less.

[Dispersant]

It is preferable that the positive photosensitive resin composition of this invention contains a dispersing agent further.

The dispersing agent refers to a compound having a surface affinity group that interacts with the surface of the colorant (C) and the like and a dispersion stabilizing structure that improves the dispersion stability of the colorant (C). Examples of the dispersion stabilizing structure of the dispersant include a polymer chain and/or a substituent having an electrostatic charge. By containing a dispersing agent, the dispersion stability of a coloring agent (C) can be improved and the resolution after image development can be improved more.

Examples of the dispersing agent having a surface affinity group include a dispersing agent having an amine value and/or an acid value, and a dispersing agent having neither an amine value nor an acid value. From the viewpoint of improving the dispersion stability of the colorant (C), a dispersing agent having only an amine value and a dispersing agent having an amine value and an acid value are preferable.

The dispersing agent having a surface affinity group preferably has a structure in which an amino group and/or an acid group serving as a surface affinity group formed a salt with an acid and/or a base.

As a dispersing agent having only an amine number, for example, "DISPERBYK" (registered trademark)-161, Dong-167, Dong-2000, Dong-2008, Dong-2009, Dong-2022, Dong-2050, Dong-2055, Dong-2150 , -2155, -2163, -2164, or -2061, "BYK" (registered trademark)-9075, dong-9077, dong-LP-N6919, copper-LP-N21116 or copper-LP-N21324 ( As mentioned above, all are mentioned by Big Chemie Japan Co., Ltd. product).

As a dispersing agent having an amine value and an acid value, for example, "DISPERBYK" (registered trademark)-2001, dong-2013, dong-2020, dong-2025, dong-187 or dong-191, "BYK" (registered trademark)-9076 ( Big Chemie Japan Co., Ltd. product is mentioned.

As a dispersing agent having only an acid value, for example, "DISPERBYK" (registered trademark)-102, copper-110, copper-111, copper-118, copper-170, copper-171, copper-174, copper-2060 or copper-2096. can be heard

As a dispersing agent which does not have both an amine value and an acid value, "DISPERBYK" (trademark)-103, Dong-2152, Dong-2200, or Dong-192 (above, all are made by Big Chemie Japan Co., Ltd.) is mentioned, for example.

As an amine value of a dispersing agent, 1 mgKOH/g or more is preferable. When the amine value is within the above range, the dispersion stability of the colorant (C) can be further improved. On the other hand, as an amine value, 150 mgKOH/g or less is preferable. When the amine value is within the above range, the storage stability of the resin composition can be improved.

The amine number as used herein refers to the weight of potassium hydroxide in the amount of the acid reacting with 1 g of the dispersant and the equivalent, and the unit is mgKOH/g. After neutralizing 1 g of a dispersing agent with an acid, it can obtain|require by titrating with potassium hydroxide aqueous solution. From the value of the amine value, the amine equivalent (unit: g/mol), which is the resin weight per 1 mol of amino groups, can be calculated, and the number of amino groups in the dispersant can be calculated.

As an acid value of a dispersing agent, 1 mgKOH/g or more is preferable. The dispersion stability of a coloring agent (C) can be improved more as an acid value is in the said range. On the other hand, as an acid value, 200 mgKOH/g or less is preferable. When the acid value is within the above range, the storage stability of the resin composition can be improved.

The acid value as used herein means the weight of potassium hydroxide reacting with 1 g of the dispersant, and the unit is mgKOH/g. It can obtain|require by titrating 1 g of a dispersing agent with aqueous potassium hydroxide solution. From the value of the acid value, the acid equivalent (unit: g/mol) which is the resin weight per 1 mol of acidic groups can be computed, and the number of acidic groups in a dispersing agent can be calculated|required.

Examples of the dispersant whose dispersion stabilization structure is a substituent having a polymer chain include an acrylic resin dispersant, a polyoxyalkylene ether dispersant, a polyester dispersant, a polyurethane dispersant, a polyol dispersant, a polyethyleneimine dispersant, or a polyarylamine dispersant. have. An acrylic resin dispersing agent, a polyoxyalkylene ether type dispersing agent, a polyester type dispersing agent, a polyurethane type dispersing agent, or a polyol type dispersing agent is preferable from a viewpoint of pattern processability in an alkaline developing solution.

When the content rate of the dispersing agent to the positive photosensitive resin composition of this invention makes a coloring agent (C) 100 mass %, 1-60 mass % is preferable. When the content rate of a dispersing agent is 1 mass % or more, the dispersion stability of a coloring agent (C) can be improved more and the resolution after image development can be improved more. As for the content rate of a dispersing agent, 5 mass % or more is more preferable. On the other hand, when the content rate of a dispersing agent is 60 mass % or less, the heat resistance of a cured film can be improved. As for the content rate of a dispersing agent, 50 mass % or less is more preferable.

[thermal crosslinking agent]

The resin composition of the present invention may further contain a thermal crosslinking agent. A thermal crosslinking agent refers to the compound which has at least 2 thermally reactive functional groups, such as an alkoxymethyl group, a methylol group, an epoxy group, and an oxetanyl group, in a molecule|numerator. By containing the thermal crosslinking agent, the alkali-soluble resin (A) having a polymerizable group in the side chain or other additional components can be crosslinked to improve the heat resistance and solvent resistance of the film after thermal curing.

Preferred examples of the compound having at least two alkoxymethyl groups or methylol groups include HMON-TPPHBA, HMOMTPHAP (above, trade names, manufactured by Honshu Chemical Co., Ltd.), "NIKALAC" (registered trademark) MX-290, "NIKALAC" MX- 280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM, "NIKALAC" MX-750LM (above, trade name, manufactured by Sanwa Chemical), DCL-2001 (brand name, Daitoke) Mix Co., Ltd. product) is mentioned.

Preferred examples of the compound having at least two epoxy groups include "EPORITE" (registered trademark) 40E, "EPORITE" 100E, "EPORITE" 200E, "EPORITE" 400E, "EPORITE" 70P, "EPORITE" 200P, "Eporite" 400P, "Eporite" 1500NP, "Eporite" 80MF, "Eporite" 4000, "Eporite" 3002 (above, manufactured by Kyoeisha Chemical Co., Ltd.), VG3101 (Mitsui Chemical Co., Ltd.) )), "Tepic" (registered trademark) S, "Tepic" G, "Tepic" P, "Tepic" L, "Tepic" PAS, "Tepic" P, "Tepic" UC, "Tepic" FL (above, Nissan Chemical Industry Co., Ltd. product) etc. are mentioned.

Preferred examples of the compound having at least two oxetanyl groups include, for example, etanacol EHO, etanacol OXBP, etanacol OXTP, etanacol OXMA (above, manufactured by Ube Kyosan Co., Ltd.), oxetanated phenol novolac, and the like. have.

You may contain a thermal crosslinking agent in combination of 2 or more types.

Among these compounds, "NIKALAC" MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM from the point of heat resistance of the cured film obtained after curing by heat; It is preferable that it is a compound selected from any one of "NIKALAC" MX-750LM and DCL-2001.

As for content of a thermal crosslinking agent, 0.1-50 mass % is preferable with respect to 100 mass % of solid content. The solvent resistance of a cured film can be improved as content of a thermal crosslinking agent is 0.1 mass % or more. The content of the thermal crosslinking agent is more preferably 1% by mass or more. On the other hand, when content of a thermal crosslinking agent is 50 mass % or less, the amount of outgassing from a cured film can be reduced. As for content of a thermal crosslinking agent, 30 mass % or less is more preferable.

[Silane coupling agent]

As a positive photosensitive resin composition of this invention, it is preferable to contain a silane coupling agent further.

The silane coupling agent refers to a compound having a hydrolyzable silyl group or a silanol group. By containing a silane coupling agent, interaction in the cured film of a resin composition and the conductive layer of a foundation|substrate, or the insulating layer mentioned later increases, and the adhesiveness of the conductive layer of a foundation|substrate or an insulating layer can be improved.

As a silane coupling agent, a trifunctional organosilane or a tetrafunctional organosilane is preferable.

Examples of the trifunctional organosilane include vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-( 3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 3-trimethoxysilylpropylsuccinic anhydride, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl) -3-Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-(4- Aminophenyl) propyltrimethoxysilane, 1-[4-(3-trimethoxysilylpropyl)phenyl]urea, 1-(3-trimethoxysilylpropyl)urea, 3-triethoxysilyl-N-( 1,3-dimethylbutylidene)propylamine, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 1,3,5-tris(3-trimethoxysilylpropyl)isocyanur acid, N-t-butyl-2-(3-trimethoxysilylpropyl)succinic acid imide, or N-t-butyl-2-(3-triethoxysilylpropyl)succinic acid imide.

Examples of the tetrafunctional organosilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane or tetraacetoxysilane. .

As a silane coupling agent, vinyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-glycidoxy from a viewpoint of adhesive improvement with an underlying conductive layer or insulating layer Propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-(4- Aminophenyl) propyltrimethoxysilane, 1-[4-(3-trimethoxysilylpropyl)phenyl]urea, 1-(3-trimethoxysilylpropyl)urea, 3-triethoxysilyl-N-( 1,3-Dimethylbutylidene)propylamine, 3-isocyanatepropyltriethoxysilane, 1,3,5-tris(3-trimethoxysilylpropyl)isocyanuric acid, N-t-butyl-2-(3 -trimethoxysilylpropyl)succinimide or N-t-butyl-2-(3-triethoxysilylpropyl)succinimide, such as trifunctional organosilane, tetramethoxysilane, tetraethoxysilane, tetra-n - Preferred are tetrafunctional organosilanes such as propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane or tetraacetoxysilane.

As for content of a silane coupling agent, 0.1-15 mass % is preferable with respect to 100 mass % of solid content. When content of a silane coupling agent is 0.1 mass % or more, adhesiveness with an underlying conductive layer or an organic film can be improved more. As for content of a silane coupling agent, 0.5 mass % or more is more preferable. On the other hand, when content of a silane coupling agent is 15 mass % or less, the resolution after image development can be improved more. As for content of a silane coupling agent, 10 mass % or less is more preferable.

[Surfactants]

The positive photosensitive resin composition of the present invention may contain various surfactants such as various fluorine-based surfactants and silicone-based surfactants for improving the flowability during application. The type of surfactant is not particularly limited, for example, "Megapack" (registered trademark) "F477 (trade name)" (above, Dainippon Ink Chemicals Co., Ltd.) fluorine-based surfactants such as, "BYK- 333 (brand name)", (Bikchemi Japan Co., Ltd. product), etc. silicone type surfactant, polyalkylene oxide type surfactant, poly(meth)acrylate type surfactant, etc. can be used. You may use these 2 or more types.

[Ultraviolet absorber]

The positive photosensitive resin composition of this invention may contain a ultraviolet absorber. The light resistance of the cured film obtained by containing a ultraviolet absorber improves, and the resolution after image development improves more. There is no limitation in particular as a ultraviolet absorber, Although a well-known thing can be used, A benzotriazole type compound, a benzophenone type compound, and a triazine type compound are preferable from the point of transparency and non-coloring property.

[Polymerization inhibitor]

The photosensitive resin composition of this invention may contain a polymerization inhibitor. By containing an appropriate amount of a polymerization inhibitor, the resolution after image development improves more. There is no limitation in particular as a polymerization inhibitor, A well-known thing can be used, For example, di-t- butylhydroxytoluene, hydroquinone, p-methoxyphenol, 1, 4- benzoquinone, t-butylcatechol can be used. can be heard Moreover, "IRGANOX 1010", "IRGANOX 245", "IRGANOX 3114", "IRGANOX 565" (above, BASF make) etc. are mentioned as a commercially available polymerization inhibitor.

[solvent]

The photosensitive resin composition of this invention may contain a solvent. The solvent contained in the photosensitive resin composition of this invention becomes like this. Preferably the boiling point under atmospheric pressure is 110-250 degreeC, More preferably, it is 200 degrees C or less. Moreover, you may use two or more types of these solvents. When a boiling point is higher than 200 degreeC, the amount of residual solvent in a film|membrane increases, film shrinkage at the time of a cure becomes large, and favorable flatness is not obtained. On the other hand, when a boiling point is lower than 110 degreeC, the coating film property worsens, such as drying at the time of a coating film is too quick, and a film surface becomes rough. Therefore, it is preferable that the solvent whose boiling point under atmospheric pressure is 200 degrees C or less is 50 mass % or more of the whole solvent in the photosensitive resin composition.

Specific examples of the solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, di Propylene glycol methyl ether and diacetone alcohol are mentioned.

There is no restriction|limiting in particular in content of a solvent, Arbitrary amount can be used according to the application|coating method etc. For example, when film-forming by spin coating, it is common to set it as 50 mass % or more and 95 mass % or less of the whole photosensitive resin composition.

The positive photosensitive resin composition of this invention may contain additives, such as a dissolution inhibitor, a stabilizer, and an antifoamer, as needed.

There is no restriction|limiting in particular in the solid content concentration of the positive photosensitive resin composition of this invention, According to the application|coating method etc., arbitrary amounts of a solvent and a solute can be used. For example, when performing film formation by spin coating as mentioned later, it is common to make solid content concentration 5 mass % or more and 50 mass % or less. Here, solid content removes the solvent from the photosensitive resin composition.

The typical manufacturing method of the positive photosensitive resin composition of this invention is demonstrated. For example, after adding alkali-soluble resin (A) which has a polymeric group in a side chain, a photosensitizer (B), a coloring agent (C), and other additives to arbitrary solvents as needed, stirring and dissolving, the obtained solution is filtered Thus, a positive photosensitive resin composition is obtained. If you want to uniformly disperse the colorant (C), use a dispersion machine such as a ball mill, sand grinder, three roll mill, mild disperser, or medialess disperser, and use a dispersion in which the colorant (C) is previously dispersed in the dispersant and an organic solvent. You may prepare and manufacture.

[Cured film]

The cured film of this invention is made by hardening|curing the said positive photosensitive resin composition. The said positive photosensitive resin composition can be hardened by the method mentioned later.

Although there is no restriction|limiting in particular in the film thickness of the cured film of this invention, 0.1-10 micrometers is preferable. When the film thickness of a cured film is 0.1 micrometer or more, light-shielding property can be improved more. More preferably, the film thickness of a cured film is 0.3 micrometer or more. On the other hand, when the film thickness of a cured film is 10 micrometers or less, light can reach|attain to a deep part at the time of exposure, and a finer pattern can be formed. The film thickness of a cured film becomes like this. More preferably, it is 7 micrometers or less, More preferably, it is 5 micrometers or less.

It is preferable that the reflectance in wavelength 550nm of the cured film of this invention is 0.01 to 20 %. By making a reflectance into 0.01 % or more, it can make it difficult to visually recognize a conductive layer. On the other hand, when the reflectance is set to 20% or less, light reaches the deep part during exposure and a finer pattern can be formed. The reflectance is more preferably 15% or less, still more preferably 10% or less. In addition, reflectance points out the reflectance in 1.0 micrometer of film thickness. A reflectance can be adjusted by selection of exposure amount, developing time, and thermosetting temperature. Moreover, the reflectance of the cured film of this invention can be measured with a reflectometer with respect to the cured film of 0.1 mm x 0.1 mm or more on a transparent substrate.

The cured film of the present invention can be suitably used as a light-shielding layer of an opaque wiring electrode for a touch panel, a light-shielding film such as a black matrix of a color filter or a black column spacer of a liquid crystal display, a pixel division layer or a TFT flattening layer of an organic EL display device, etc. have. Among these, fine pattern formation is possible, and since it is low reflectance, it can use especially suitably as a light shielding layer of the opaque electrode for touch panels, a pixel division layer of an organic electroluminescent display, or a TFT planarization layer.

An example is given and demonstrated about the manufacturing method of the cured film using the positive photosensitive resin composition of this invention.

The positive photosensitive resin composition of the present invention is applied onto a base substrate by a known method such as micro gravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, or slit coating.

The coating film is prebaked in a heating device such as a hot plate or oven. It is preferable to perform a prebaking in the range of 50-150 degreeC for 30 second - 30 minutes, and to make the film thickness after a prebaking into 0.1-15 micrometers.

After prebaking, the coating film is exposed using an exposure machine such as a stepper, mirror projection mask aligner (MPA), or parallel light mask aligner (PLA). The exposure intensity is about 10-4000 J/m2 (in terms of wavelength 365 nm exposure dose), and this light is irradiated through or without a desired mask. The exposure light source is not limited, and ultraviolet rays such as g-line, h-line, and i-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, etc. can be used.

Next, by developing, the exposed portion of the coating film can be dissolved to obtain a positive pattern. As the developing method, it is preferable to immerse the coating film in the developer for 5 seconds to 10 minutes by a method such as showering, dipping, or puddle. Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), triethanolamine, diethanolamine, monoethanolamine, and dimethylaminoethanol. Or organic alkalis, such as alcoholamines, such as diethylamino ethanol, are mentioned. You may add suitably water-soluble organic solvents, such as ethanol, (gamma)-butylolactone, dimethylformamide, or N-methyl-2-pyrrolidone, to these alkaline developing solutions.

Moreover, in order to obtain a more favorable pattern, it is also preferable to add 0.01-1 mass % of surfactant, such as a nonionic surfactant, further to these alkaline developing solutions.

After development, the coating film is preferably rinsed with water, and the coating film may then be dried and baked in a range of 50 to 130°C.

After that, this coating film is heated in the range of 100-300 degreeC with heating apparatuses, such as a hotplate and oven, for about 5 minutes - 120 minutes. It is preferable that the manufacturing method of the cured film of this invention includes the process of heating a coating film at 150-250 degreeC.

[Laminate]

The laminate of this invention has a conductive layer and the cured film of this invention. As described above, the cured film of the present invention has low reflectance and can form a fine pattern while ensuring transparency of the substrate without residue, so it can be suitably used, for example, as a light shielding layer of an opaque wiring electrode, which is a conductive layer of a touch panel. .

The laminate of this invention WHEREIN: It is preferable that ratio of the film thickness of the said cured film with respect to the film thickness of a conductive layer is 1/2-5. By setting the ratio of the film thickness to 1/2 or more, the light-shielding property can be further improved, and by setting it to 5 or less, the wiring thickness can be suppressed, and the degree of freedom and flexibility of wiring design can be improved.

Moreover, it is preferable that the laminated body of this invention has an insulating layer in addition to a conductive layer and the cured film of this invention. By having an insulating layer, problems, such as short circuit which generate|occur|produce between conductive layers, can be suppressed, and a highly reliable laminated body can be formed. In addition, by protecting the light-shielding layer, it is possible to suppress a scratch or the like to prevent poor visibility and the like.

Although there is no restriction|limiting in particular in the insulating material contained in the above-mentioned insulating layer, An acrylic polymer, an epoxy resin, a phenol resin, a caldo type resin, polysiloxane, polyimide, polyamide, polybenzoxazole, etc. are mentioned. You may contain these 2 or more types.

Examples of the conductive material included in the conductive layer include copper, silver, gold, aluminum, chromium, molybdenum, titanium, and the like. In addition to the above, it may be combined with a conductive material forming the transparent electrode, for example, ITO, IZO (indium zinc oxide), AZO (aluminum-added zinc oxide), ZnO ₂ or the like. Among these, silver with the lowest specific resistance value is preferable. When a specific resistance value is low, a highly sensitive touch panel can be produced. Moreover, since a finer wiring pattern can be formed, it is preferable that the average primary particle diameter of silver is 10-200 nm. Here, the average primary particle diameter of silver can be calculated from the average value of the particle diameters of 100 randomly selected primary particles using a scanning electron microscope. The particle diameter of each primary particle can measure a major axis and a minor axis in a primary particle, and can compute it from the average value.

Moreover, it is preferable to contain 5-35 mass % of organic components which have an alkali-soluble group in a conductive layer. When the content rate of the organic component having an alkali-soluble group is 5 mass % or more, the photosensitive characteristic can be improved and a finer pattern can be formed. On the other hand, by making the content rate of the organic component which has an alkali-soluble group into 35 mass % or less, a specific resistance value can be reduced and a highly sensitive touchscreen can be formed. By containing the organic component which has an alkali-soluble group, it becomes possible to provide flexibility to a wiring pattern, and a flexible touchscreen can be produced. Although there is no restriction|limiting in particular in alkali-soluble group, For example, a carboxyl group, phenolic hydroxyl group, a sulfonic acid group, and a thiol group are mentioned. As an organic component which has an alkali-soluble group, the organic component demonstrated by the positive photosensitive resin composition can be used.

1 and FIG. 2, the schematic of an example of the structure of the laminated body of this invention is shown. 1 : is a schematic diagram of the laminated body which has the opaque wiring electrode 2 on the transparent substrate 1, and has the light-shielding layer 3 which consists of a cured film of this invention on the opaque wiring electrode 2. As shown in FIG. The laminate shown in FIG. 1 can be obtained through the process of exposing from the side opposite to the opaque wiring electrode formation surface of a transparent substrate in the manufacturing method of the laminated body mentioned later.

2 shows an opaque wiring electrode 2 (a first opaque wiring electrode) and an insulating layer 4 on a transparent substrate 1, and an opaque wiring electrode 2 (a second opaque wiring electrode) on the insulating layer 4 electrode), and is a schematic diagram of a laminate having a light-shielding layer 3 made of the cured film of the present invention at a portion corresponding to the opaque wiring electrode 2 (first opaque wiring electrode and second opaque wiring electrode) . In the laminate shown in Fig. 2, in the method for manufacturing a laminate described later, a first opaque wiring electrode, an insulating layer, and a second opaque wiring electrode are formed on one side of a transparent substrate, and the positive photosensitive resin composition of the present invention is applied. and exposing from the side opposite to the opaque wiring electrode formation surface of the transparent substrate.

Next, each process in the manufacturing method of the laminated body of this invention is demonstrated in detail. That is, the method for manufacturing a laminate of the present invention comprises a step of forming an opaque wiring electrode on one side of a transparent substrate, a step of applying the positive photosensitive resin composition of the present invention to the opaque wiring electrode formation side of the transparent substrate, It has a process of forming a light shielding layer in the site|part corresponding to an opaque wiring electrode by exposing and developing from the side opposite to the opaque wiring electrode formation surface of a transparent substrate. In FIG. 3, the schematic of an example of the manufacturing method of the laminated body of this invention is shown.

First, an opaque wiring electrode 2 is formed on one side of the transparent substrate 1 . The step of forming an opaque wiring electrode on one side of the transparent substrate includes a step of forming a first opaque wiring electrode on one side of the transparent substrate, a step of forming an insulating layer on the first opaque wiring electrode, and on the insulating layer You may have a process of forming a 2nd opaque wiring electrode in this.

As a method of forming an opaque wiring electrode, for example, a method of forming a pattern by a photolithography method using a photosensitive conductive composition, a method of forming a pattern by screen printing, gravure printing, inkjet, etc. using a conductive composition (conductive paste), metal , a method of forming a film such as a metal composite, a composite of a metal and a metal compound, or a metal alloy, and forming by a photolithography method using a resist; and the like. Among these, the method of forming by the photolithographic method using the photosensitive conductive composition from the point which can form fine wiring is preferable. Moreover, when forming two or more layers of opaque wiring electrodes through an insulating layer, each opaque wiring electrode may be formed by the same method, and you may combine different methods. You may form an insulating layer on the opaque wiring electrode of the laminated body in which the obtained opaque wiring electrode was formed.

As a method of forming the insulating layer, for example, a method of forming a pattern by photolithography using a photosensitive insulating composition, a method of applying and drying the insulating composition, or bonding a transparent substrate through an adhesive on the opaque wiring electrode forming surface side method and the like. Among these, the method of forming by the photolithographic method using the photosensitive insulating composition at the point which can form a fine pattern is preferable. As a method of bonding a transparent substrate through an adhesive, for example, the adhesive may be formed on a substrate provided with an opaque wiring electrode, and the transparent substrate may be bonded, or a transparent substrate with an adhesive formed thereon may be bonded.

Next, the positive photosensitive resin composition (5) of the present invention is applied to the opaque wiring electrode formation surface of the transparent substrate (1).

Moreover, when using the laminated body of this invention as a touch panel sensor, it is not necessary to apply|coat the positive photosensitive resin composition of this invention to the connection part with a flexo board|substrate as needed.

Next, using the opaque wiring electrode 2 as a mask, the positive photosensitive resin composition 5 of the present invention is exposed from the opposite side of the opaque wiring electrode formation surface of a transparent substrate and developed to correspond to the opaque wiring electrode. A light-shielding layer is formed on the affected area. By exposing the opaque wiring electrode as a mask, a light shielding layer corresponding to the portion corresponding to the opaque wiring electrode can be formed without requiring a separate exposure mask. The above-described step of forming an opaque wiring electrode on one side of the transparent substrate includes a step of forming a first opaque wiring electrode on one side of the transparent substrate, a step of forming an insulating layer on the first opaque wiring electrode, and the insulation In the case of having the step of forming the second opaque wiring electrode on the layer, it is preferable to form the light-shielding layer in the portions corresponding to the first opaque wiring electrode and the second opaque wiring electrode.

A step of forming an insulating layer on the light-shielding layer of the obtained laminate, a step of forming a second opaque wiring electrode on the insulating layer, a positive photosensitive composition is applied to the second opaque wiring electrode formation surface, and the second You may have a process of forming a light-shielding layer at least in the site|part corresponding to a 2nd opaque wiring electrode by exposing and developing from the side opposite to the opaque wiring electrode formation surface.

[Substrate on which conductive pattern is formed]

The substrate on which the conductive pattern of the present invention is formed is a substrate on which a conductive pattern is formed having a substrate, a conductive pattern formed on the substrate, and a cured film of the present invention, and has the cured film on at least a part of the conductive pattern formation region, and a conductive pattern non-formation region It does not have the said cured film on it. By setting it as such a structure, reflection of a conductive pattern can be suppressed, ensuring transparency of a base material.

When the board|substrate on which the conductive pattern was formed includes a connection part, it is preferable not to have the said cured film on a connection part. A stable electrical connection is attained by not having a cured film on a connection part.

Example

Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these Examples. Among the compounds used in Synthesis Examples and Examples, those using abbreviations are shown below.

AIBN: 2, 2'-azobis (isobutylonitrile)

PGMEA: Propylene glycol monomethyl ether acetate

DAA: diacetone alcohol

TMAH: tetramethylammonium hydroxide

DPHA: dipentaerythritol hexaacrylate

First, materials used in Examples and Comparative Examples will be described.

[Alkali-soluble resin (A) having a polymerizable group in the side chain]

Synthesis Example 1: Acrylic polymer (a1-1)

1g of AIBN and 50g of PGMEA were added to a 500ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Next, to the obtained solution, 7.1 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added, and the resulting acrylic polymer solution was heated and stirred at 90° C. for 4 hours. PGMEA was added so that solid content concentration might be set to 40 wt%, and the solution of the acrylic polymer (a1-1) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 11,000.

Synthesis Example 2: Acrylic polymer (a1-2)

1g of AIBN and 50g of PGMEA were added to a 500ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Next, 14.2 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours. To the obtained acrylic polymer solution PGMEA was added so that solid content concentration might be set to 40 wt%, and the solution of an acrylic polymer (a1-2) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 11,000.

Synthesis Example 3: Acrylic polymer (a1-3)

1g of AIBN and 50g of PGMEA were added to a 500ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Next, 21.3 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours. To the obtained acrylic polymer solution PGMEA was added so that solid content concentration might be set to 40 wt%, and the solution of an acrylic polymer (a1-3) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 11,000.

Synthesis Example 4: Acrylic polymer (a1-4)

1g of AIBN and 50g of PGMEA were added to a 500ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Next, 49.8 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the resulting solution was heated and stirred at 90° C. for 4 hours. PGMEA was added so that solid content concentration might be set to 40 wt%, and the solution of an acrylic polymer (a1-4) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 11,000.

Synthesis Example 5: Acrylic polymer (a1-5)

1g of AIBN and 50g of PGMEA were added to a 500ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Next, 56.9 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours. To the obtained acrylic polymer solution PGMEA was added so that solid content concentration might be set to 40 wt%, and the solution of an acrylic polymer (a1-5) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 11,000.

Synthesis Example 6: Acrylic polymer (a1-6)

1g of AIBN and 50g of PGMEA were added to a 500ml flask. After that, 51.7 g of methacrylic acid, 52.9 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Next, 71.1 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours. To the obtained acrylic polymer solution PGMEA was added so that solid content concentration might be set to 40 wt%, and the solution of an acrylic polymer (a1-6) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 11,000.

Synthesis Example 7: Acrylic polymer (a1-7)

1g of AIBN and 50g of PGMEA were added to a 500ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Then, to the obtained solution, 2.8 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added, and the resulting acrylic polymer solution was heated and stirred at 90° C. for 4 hours. PGMEA was added so that solid content concentration might be set to 40 wt%, and the solution of the acrylic polymer (a1-7) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 11,000.

Synthesis Example 8: Acrylic polymer (a1-8)

1g of AIBN and 50g of PGMEA were added to a 500ml flask. After that, 60.3 g of methacrylic acid, 35.2 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Next, 85.3 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours. To the obtained acrylic polymer solution PGMEA was added so that solid content concentration might be set to 40 wt%, and the solution of an acrylic polymer (a1-8) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 11,000.

Synthesis Example 9: Acrylic polymer (a1-9)

0.5 g of AIBN and 50 g of PGMEA were added to a 500 ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting enough inside by bubbling, it heat-stirred at 70 degreeC for 2 hours. Next, 21.3 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours. To the obtained acrylic polymer solution PGMEA was added so that solid content concentration might be set to 40 wt%, and the solution of an acrylic polymer (a1-9) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 3,000.

Synthesis Example 10: Acrylic polymer (a1-10)

0.5 g of AIBN and 50 g of PGMEA were added to a 500 ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting enough inside by bubbling, it heat-stirred at 70 degreeC for 4 hours. Next, 21.3 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours. To the obtained acrylic polymer solution PGMEA was added so that solid content concentration might be set to 40 wt%, and the solution of an acrylic polymer (a1-10) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 6,000.

Synthesis Example 11: Acrylic polymer (a1-11)

1.5 g of AIBN and 50 g of PGMEA were added to a 500 ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Next, 21.3 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours. To the obtained acrylic polymer solution PGMEA was added so that solid content concentration might be set to 40 wt%, and the solution of an acrylic polymer (a1-11) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 14,000.

Synthesis Example 12: Acrylic polymer (a1-12)

2.0 g of AIBN and 50 g of PGMEA were added to a 500 ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Next, 21.3 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours. To the obtained acrylic polymer solution PGMEA was added so that solid content concentration might be set to 40 wt%, and the solution of an acrylic polymer (a1-12) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 20,000.

Synthesis Example 13: Acrylic polymer (a1-13)

1g of AIBN and 50g of PGMEA were added to a 500ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Next, to the solution obtained, 29.4 g of [(3,4-epoxycyclohexane)-1-yl]methyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added, 90 It heat-stirred at degreeC for 4 hours, PGMEA was added to the obtained acrylic polymer solution so that solid content concentration might be set to 40 wt%, and the solution of the acrylic polymer (a1-13) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 11,500.

Synthesis Example 14: Acrylic polymer (a1-14)

1g of AIBN and 50g of PGMEA were added to a 500ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Next, 19.2 g of glycidyl acrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours, and solid content concentration in the obtained acrylic polymer solution PGMEA was added so that it became 40 wt%, and a solution of an acrylic polymer (a1-14) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 10,500.

Synthesis Example 15: Acrylic polymer (a1'-1)

1g of AIBN and 50g of PGMEA were added to a 500ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Next, 17.1 g of allyl glycidyl ether, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the resulting solution was heated and stirred at 90° C. for 4 hours. Solid content in the obtained acrylic polymer solution PGMEA was added so that the concentration became 40 wt%, and a solution of an acrylic polymer (a1'-1) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 10,000.

Synthesis Example 16: Acrylic polymer (a1'-2)

1g of AIBN and 50g of PGMEA were added to a 500ml flask. After that, 34.4 g of methacrylic acid, 61.7 g of benzyl methacrylate, 22.0 g of tricyclo[5.2.1.0(2,6)]decan-8-ylmethacrylate, and 21.3 g of glycidyl methacrylate The mixture was charged, stirred at room temperature for a while, and the inside of the flask was sufficiently purged with nitrogen by bubbling, and then heated and stirred at 70°C for 5 hours. A solution of (a1'-2) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 12,000.

Synthesis Example 17: Acrylic polymer (a1'-3)

1g of AIBN and 50g of PGMEA were added to a 500ml flask. After that, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decan-8-yl methacrylate were added, stirred at room temperature for a while, and the flask was After nitrogen-substituting the inside sufficiently by bubbling, it heat-stirred at 70 degreeC for 5 hours. Next, PGMEA was added to the obtained acrylic polymer solution so that solid content concentration might be set to 40 wt%, and the solution of the acrylic polymer (a1'-3) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 11,000.

[Photosensitizer (B)]

Synthesis Example 18: Photosensitizer (b-1)

TrisP-HAP (manufactured by Honshu Chemical Co., Ltd.), 15.3 g and 40.3 g of 5-naphthoquinonediazidesulfonyl acid chloride were dissolved in 450 g of 1,4-dioxane under a dry nitrogen stream, and the mixture was brought to room temperature. Here, 15.2 g of triethylamine mixed with 50 g of 1, 4- dioxane was dripped so that system inside might not become 35 degreeC or more. After dripping, it stirred at 30 degreeC for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Thereafter, the precipitated precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (b-1) represented by the following formula.

[Colorant (C)]

Carbon black ("MA-100 (brand name)" manufactured by Mitsubishi Chemical Co., Ltd., hereinafter referred to as "MA-100".)

Benzofuranone-based black pigment ("IRGAPHOR" (registered trademark) BLACK S0100CF manufactured by BASF (primary particle diameter of 40 to 80 nm), hereinafter referred to as "Bk-S0100CF")

Black inorganic pigment ("Titanium Nitride Particles" manufactured by Nisshin Engineering Co., Ltd.)

Black dye ("NUBIAN" (registered trademark) BLACK TN-870 manufactured by Orient Chemical Co., Ltd., hereinafter referred to as "TN-870".)

[Dispersant]

Dispersing agent having an amine value ("BYK" (registered trademark)-LP-N21116, hereinafter referred to as "BYK-21116" manufactured by Bikchemi Japan Co., Ltd.)

[crosslinking agent]

Methylol compound (referred to as ""NIKALAC" MX-270" and "MX-270" manufactured by Sanwa Chemical Co., Ltd.)

Epoxy compound ((Mitsui Chemical Co., Ltd. "VG3101")

[Silane coupling agent]

3-glycidoxypropyltrimethoxysilane ("KBM-403 (trade name)" manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as "KBM-403")

[Surfactants]

Silicone surfactant ("BYK-333 (brand name)" manufactured by Bikchemi Japan Co., Ltd., hereinafter referred to as "BYK-333".)

[solvent]

PGMEA ("PGM-AC (brand name)" manufactured by Kuraray Trading Co., Ltd.)

DAA ("DAA" manufactured by Mitsubishi Chemical Co., Ltd.).

Next, the photosensitive silver ink material and the photosensitive insulating material used in Examples and Comparative Examples will be described.

[Photosensitive silver ink material]

The method for producing the photosensitive silver ink material is shown below.

<Production of photosensitive silver ink material>

First, the conductive fine particles surface-coated with a carbon compound (manufactured by Nissin Engineering Co., Ltd.): 80.0 g, BYK-21116: 4.06 g, PGMEA: 196.14 g were mixed with a homogenizer at 1200 rpm for 30 minutes, Furthermore, the mixed liquid was disperse|distributed using the mill type disperser with which zirconia beads were filled, and the silver fine particle dispersion was obtained. With respect to 63.28 g of this silver fine particle dispersion, under a yellow light, acrylic polymer (a1-10): 4.40 g, OXE-02 (manufactured by BASF): 0.41 g, DPHA (manufactured by Nippon Kayaku Co., Ltd.): 1.30 g were mixed The photosensitive silver ink ((alpha)) was produced by adding and stirring PGMEA:7.31g and DAA:23.25g to one thing.

[Photosensitive Insulation Material]

It shows below about the manufacturing method of a photosensitive insulating material.

<Production of photosensitive insulating material>

Under a yellow light, as a photoinitiator, OXE-02 (manufactured by BASF): 0.50 g, PGMEA: 20.70 g, DAA: 37.50 g, dissolved in SIRIUS-501 (manufactured by Osaka Yuki Chemical Co., Ltd.): 1.25 g, M-315 (manufactured by Kyoesha Co., Ltd.): 2.90 g and acrylic polymer (a1-3): 28.00 g were added and stirred to prepare a photosensitive insulating material (β).

Next, preparation and each evaluation method of the cured film / laminated board which were performed by the Example and the comparative example are demonstrated.

<Pattern Production of Silver Ink Material (α)>

The silver ink material (α) was dried using a spin coater (“1H-360S (brand name)” manufactured by Mikasa Co., Ltd.) on a substrate or on a substrate on which an opaque wiring electrode having an insulating layer was formed to a film thickness of 1 μm. After spin-coating at a predetermined rotation speed as much as possible, it pre-baked at 100 degreeC for 2 minutes using the hotplate ("SCW-636 (brand name)" made by Dainippon Screen Seijo Co., Ltd.), and the pre-baked film was produced. For the prebaked film, using a parallel light mask aligner ("PLA-501F (brand name)" manufactured by Canon Corporation), an ultra-high pressure mercury lamp as a light source, and an exposure amount of 500 mJ/cm 2 (in terms of wavelength 365 nm) through a desired mask It exposed and produced the mesh-shaped pattern with a pitch of 300 micrometers shown in FIG. Thereafter, using an automatic developing device (“AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 60 seconds with a 0.07 wt% TMAH aqueous solution, followed by rinsing with water for 30 seconds to perform pattern processing.

The pattern-processed board|substrate was post-baked at 230 degreeC for 60 minutes (in air) using an oven ("IHPS-222 (brand name)" made by SPEC Co., Ltd.), and the board|substrate with opaque wiring electrodes was produced. As a result of measuring the line width of the opaque wiring electrode mesh part with an optical microscope, it was 4.0 micrometers.

<Pattern production of photosensitive insulating material (β)>

The photosensitive insulating material (β) was spin-coated on the obtained substrate on which the opaque wiring electrode was formed using a spin coater at a predetermined number of revolutions so that the film thickness after drying was 2.5 μm, and then 2 at 100°C using a hot plate. It pre-baked for minutes, and the pre-baked film|membrane was produced. With respect to the prebaked film, an ultra-high pressure mercury lamp was used as a light source using a parallel light mask aligner, and exposure was carried out at an exposure amount of 200 mJ/cm 2 (in terms of wavelength 365 nm) through an exposure mask having a desired pattern. Thereafter, shower development was performed for 60 seconds with a 0.07 wt% TMAH aqueous solution using an automatic developing device, followed by rinsing with water for 30 seconds to perform pattern processing.

The pattern-processed board|substrate was post-baked at 230 degreeC for 60 minutes (in air) using oven, and the board|substrate with the opaque wiring electrode which has an insulating layer was produced.

<Preparation of cured film of positive photosensitive resin composition>

The positive photosensitive resin composition was dried using a spin coater on the opaque wiring electrode formation surface of the obtained substrate on which the opaque wiring electrode was formed or the substrate on which the opaque wiring electrode having an insulating layer was formed, after drying at a predetermined number of revolutions so that the film thickness was 1.0 μm. After spin-coating with furnace, it pre-baked at 100 degreeC for 2 minutes using a hot plate, and produced the pre-baked film|membrane. With respect to the prebaked film, using a parallel light mask aligner, using an ultra-high pressure mercury lamp as a light source, and using an opaque wiring electrode as a mask, from the opposite side of the opaque wiring electrode formation surface, it was exposed at an exposure amount of 500 mJ/cm 2 (in terms of wavelength 365 nm). Thereafter, using an automatic developing device, shower development was performed for 60 seconds with a 0.07 wt% TMAH aqueous solution, followed by rinsing with water for 30 seconds to perform pattern processing.

The pattern-processed board|substrate was post-baked at 230 degreeC for 60 minutes (in air) using oven, and the cured film of the positive photosensitive resin composition was produced.

<Production of laminated substrate (A)>

The laminated board|substrate A shown in FIG. 1 was produced using the positive photosensitive resin composition and the silver ink material (alpha). The substrate 1 is a glass substrate sputtered with SiO ₂ on the surface, the opaque wiring electrode layer 2 is a conductive pattern layer made of a silver ink material (α), and the light shielding layer 3 is cured with a positive photosensitive resin composition. it's a curtain

(1) Pattern processability evaluation

The light-shielding layer of the mesh part of the laminated substrate A was observed with the optical microscope, the line|wire width of 10 randomly selected points|pieces was measured, and the average value was computed. The closer the value of the line width of the light-shielding layer to 4.0 µm of the line width of the opaque wiring electrode is, the better the pattern workability is.

(2) Cured film property evaluation

About the location corresponding to the pad part 6 of the laminated board A, the reflectance in wavelength 550nm was measured using the reflectometer (VSR400: Nippon Denshoku Kogyo Co., Ltd. product).

In addition, after immersing in PGMEA at 100° C. for 10 minutes for 10 minutes at a location corresponding to the pad portion 6 of the laminated substrate A, washing with water for 1 minute, and observing an image magnified by 50 times with an optical microscope, before and after immersion of the cured film appearance was observed and solvent resistance was evaluated.

2: No change in appearance.

1: A crack is generated in the light-shielding layer.

<Production of laminated substrate (B)>

Using the positive photosensitive resin composition, the silver ink material (α), and the photosensitive insulating material (β), the laminated substrate B shown in FIGS. 2 and 5 was produced. The substrate 1 is a glass substrate sputtered with SiO ₂ on the surface, the opaque wiring electrode layer 2 is a conductive pattern layer made of a silver ink material (α), and the light shielding layer 3 is cured with a positive photosensitive resin composition. The film, the insulating layer 4 is an insulating layer made of a photosensitive insulating material (β).

(3) Evaluation of residues on the substrate

In the laminated substrate B, the transmittance|permeability evaluation evaluated the residue on the board|substrate about the exposed part of the positive photosensitive resin composition on the insulating layer 4 of the laminated board shown in FIG. The transmittance|permeability in 400 nm before and behind light shielding film formation with respect to the exposed part of the positive photosensitive resin composition on the insulating layer 4 in the laminated board specifically shown in FIG. It measured using the Shoji "MultiSpec-1500 (brand name)"). And when the transmittance|permeability before light-shielding film formation was T0 and the transmittance|permeability after light-shielding film formation was made into T, the transmittance|transmittance change represented by Formula (T0-T)/T0x100 was computed.

(4) Migration resistance evaluation

The laminated board|substrate (B) WHEREIN: The migration tolerance under high temperature, high humidity was evaluated. An insulation deterioration characteristic evaluation system "ETAC SIR13" (manufactured by Kusumoto Kasei Co., Ltd.) was used for the measurement. Each electrode was attached to the connection part of the opaque wiring electrode 2, and the sample was put in the high-temperature, high-humidity tank set to 85 degreeC 85%RH conditions. After 5 minutes had elapsed after the environment in the tank was stabilized, a voltage was applied between the electrodes of the opaque wiring electrode 2, and the change with time of insulation resistance was measured. Further, a voltage of 5 V was applied to the opaque wiring electrode of the first layer as a positive electrode and the opaque wiring electrode of the second layer as a negative electrode, and the resistance value was measured at intervals of 5 minutes for 1000 hours. When the measured resistance value reached the 5th power of 10 or less, it was judged that it was a short circuit due to insulation defect, and the pressure was stopped, and the test time so far was made into the short circuit time. Migration resistance was evaluated according to the following evaluation criteria. A score of 2 or more was regarded as pass.

3: If the short-circuit time is more than 1000 hours

2: The short-circuit time is more than 280 hours and less than 1000 hours

1: Short-circuit time less than 280 hours.

(Example 1)

First, with respect to MA-100:3.00g as a colorant (C), BYK-21116:1.00g as a dispersant, PGMEA:40.00g, DPM:20.00g with a homogenizer, 1200rpm, 30 minutes mixing treatment is performed, and further , was dispersed using a high-pressure wet medialess atomization apparatus Nanomizer (Nanomizer Co., Ltd.) to obtain a dispersion. With respect to 64.00 g of this dispersion, under a yellow light, a photosensitizer (b-1): 3.00 g as a photosensitizer (B), MX-270: 0.69 g as a crosslinking agent, and PGMEA: 14.50 g as a solvent were added and dissolved, followed by dissolution with a silane coupling agent. KBM-403:0.30 g as a surfactant and BYK-333:0.01 g as a surfactant were added and stirred. As alkali-soluble resin (A) which has a polymeric group in a side chain, 40 wt% PGMEA solution (a1-1):17.50g was added to it, and it stirred. Then, it filtered with a 0.20 micrometer filter, and obtained the positive photosensitive resin composition. About the obtained positive photosensitive resin composition, (1) pattern processability, (2) hardening characteristic, (3) residue on a board|substrate, and (4) migration tolerance were evaluated. The composition and results are shown in Tables 1 and 5.

(Examples 2 to 29, Comparative Examples 1 to 5)

The positive photosensitive resin composition of the composition of Tables 1-4 was obtained by the method similar to Example 1, and evaluation similar to Example 1 was performed about each positive photosensitive resin composition. An evaluation result is shown to Tables 5-8.

Although the use of the cured film obtained by hardening|curing the photosensitive resin composition of this invention is not specifically limited, For example, Light-shielding layer of the opaque electrode for touch panels, a light-shielding film, such as a black matrix of a color filter, or a black column spacer of a liquid crystal display, organic EL It is suitably used as a pixel division layer, a TFT planarization layer, etc. of a display device.

1: Transparent substrate
2: Opaque wiring electrode
3: light-shielding layer
4: Insulation layer
5: Positive photosensitive resin composition
6: Pad part

Claims (26)

A positive photosensitive resin composition comprising an alkali-soluble resin (A) having a polymerizable group in a side chain, a photosensitizer (B) and a colorant (C), wherein the polymerizable group is an acryl group and/or a methacryl group. The method of claim 1,
The positive photosensitive resin composition whose weight average molecular weight Mw of alkali-soluble resin (A) which has a polymeric group in the said side chain is 1,000 or more and 15,000 or less. 3. The method of claim 1 or 2,
The positive photosensitive resin composition in which alkali-soluble resin (A) which has a polymeric group in the said side chain has an organic group represented by following General formula (1).

(In the general formula (1), X represents a hydrocarbon group having 1 to 4 carbon atoms, s represents 0 or 1, and R ¹ represents a hydrogen atom or a methyl group.) 4. The method according to any one of claims 1 to 3,
A positive photosensitive resin composition in which the alkali-soluble resin (A) having a polymerizable group in the side chain has a repeating unit represented by the following general formula (2).

(In general formula (2), R ² and R ³ represent a hydrogen atom or a methyl group. R ² and R ³ may be the same or different, respectively.) 5. The method of claim 4,
A positive photosensitive resin composition in which the alkali-soluble resin (A) having a polymerizable group in the side chain contains 5 to 50 mol% of the repeating unit represented by the general formula (2) among all the repeating units. 6. The method according to any one of claims 1 to 5,
The positive photosensitive resin composition in which the said photosensitive agent (B) contains a quinonediazide compound. 7. The method according to any one of claims 1 to 6,
The positive photosensitive resin composition in which the said coloring agent (C) has an aromatic group. 8. The method according to any one of claims 1 to 7,
The positive photosensitive resin composition in which the said coloring agent (C) is a black organic pigment. 9. The method of claim 8,
The positive photosensitive resin composition in which the said black organic pigment contains carbon black. 7. The method according to any one of claims 1 to 6,
The positive photosensitive resin composition in which the said coloring agent (C) contains metal nitride particle|grains. 11. The method of claim 10,
The positive photosensitive resin composition in which the said metal nitride particle contains zirconium nitride particle|grains. 12. The method according to any one of claims 1 to 11,
The positive photosensitive resin composition whose content rate of the said coloring agent (C) is 10-50 mass % in solid content. The cured film formed by hardening|curing the positive photosensitive resin composition in any one of Claims 1-12. 14. The method of claim 13,
The cured film whose reflectance in wavelength 550nm is 0.01 to 20%. 15. The method of claim 13 or 14,
The cured film whose film thickness is 0.3-7 micrometers. The laminate which has a conductive layer and the cured film in any one of Claims 13-15. 17. The method of claim 16,
The laminate whose ratio of the film thickness of the said cured film with respect to the film thickness of the said conductive layer is 1/2-5. 18. The method of claim 16 or 17,
A laminate further having an insulating layer. 19. The method according to any one of claims 16 to 18,
The laminate in which the said conductive layer contains silver. 20. The method of claim 19,
The silver has an average primary particle diameter of 10-200 nm. 21. The method according to any one of claims 16 to 20,
The laminate which contains 5-35 mass % of organic components which have an alkali-soluble group in the said conductive layer. A substrate on which a conductive pattern is formed having a substrate, a conductive pattern formed on the substrate, and a cured film according to any one of claims 13 to 15, comprising the cured film on a conductive pattern formation region and on a conductive pattern non-forming region The board|substrate with which the conductive pattern which does not have the said cured film was formed. 23. The method of claim 22,
The board|substrate in which the said conductive pattern includes a connection part, and the conductive pattern which does not have the said cured film was formed on the connection part. forming an opaque wiring electrode on one side of a transparent substrate;
The process of apply|coating the positive photosensitive resin composition in any one of Claims 1-12 to the opaque wiring electrode formation surface on the said transparent substrate;
A method for producing a laminate, comprising the steps of: forming a light-shielding layer in a portion corresponding to an opaque wiring electrode by exposing and developing from the side opposite to the opaque wiring electrode formation surface of a transparent substrate. A touch panel provided with the cured film in any one of Claims 13-15. An organic electroluminescence display provided with the cured film in any one of Claims 13-15.

Images