CN114945867B - Positive photosensitive resin composition, cured film, laminate, substrate with conductive pattern, method for producing laminate, touch panel, and organic EL display device - Google Patents

Positive photosensitive resin composition, cured film, laminate, substrate with conductive pattern, method for producing laminate, touch panel, and organic EL display device Download PDF

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CN114945867B
CN114945867B CN202080093425.5A CN202080093425A CN114945867B CN 114945867 B CN114945867 B CN 114945867B CN 202080093425 A CN202080093425 A CN 202080093425A CN 114945867 B CN114945867 B CN 114945867B
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resin composition
cured film
substrate
photosensitive resin
laminate
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CN114945867A (en
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此岛阳平
三井博子
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Toray Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
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    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
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    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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Abstract

A photosensitive resin composition is provided which has low reflectance and can be used as a light shielding layer for opaque wiring electrodes, and which can achieve both resolution of a fine pattern and ensuring transparency and migration resistance of a substrate by suppressing residues on the substrate. A positive photosensitive resin composition comprising 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.

Description

Positive photosensitive resin composition, cured film, laminate, substrate with conductive pattern, method for producing laminate, touch panel, and organic EL display device
Technical Field
The invention relates to a positive photosensitive resin composition, a cured film, a laminate, a substrate with a conductive pattern, a method for manufacturing the laminate, a touch panel, and an organic EL display device.
Background
In recent years, touch panels have been widely used as input means. The touch panel includes a display unit such as a liquid crystal panel, and a touch panel sensor for detecting information input to a specific position. Touch panels are classified into resistive film type, capacitive type, optical type, electromagnetic induction type, ultrasonic type, and the like, according to a method of detecting an input position. Among them, capacitive touch panels are widely used for reasons such as optical brightness, excellent design, simple structure, and excellent functionality.
The capacitive touch panel sensor has a second electrode orthogonal to the first electrode through an insulating layer, applies a voltage to the electrode on the touch panel surface, and outputs a contact position obtained by detecting a change in capacitance when a conductive body such as a finger is touched as a signal. As a touch panel sensor used for electrostatic capacity, 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 surfaces of one transparent substrate, and the like are known. As a wiring electrode for a touch panel sensor, a transparent wiring electrode is generally used from the viewpoint of difficulty in viewing the wiring electrode, but in recent years, an opaque wiring electrode using a metal material has been widely used due to higher sensitivity and larger screen size.
In a touch panel sensor having an opaque wiring electrode made of a metal material, there is a problem that the opaque wiring electrode is visually recognized due to the metallic luster of the opaque wiring electrode, but there is a method in which a light shielding layer is formed on the opaque wiring electrode using a photosensitive resin composition containing a colorant so as to be hardly visually recognized (for example, patent document 1).
Prior art literature
Patent literature
Patent document 1: international publication No. 2018/168325
Disclosure of Invention
Problems to be solved by the invention
However, in the photosensitive resin composition using a colorant, residues derived from the colorant are easily generated on a substrate, particularly on a film containing an organic component, at the time of pattern formation, and thus appearance defects or the like occur to deteriorate the transparency of a substrate. In addition, if the development time is prolonged to suppress residues, it is difficult to form a fine pattern. Further, in the case of using a silver electrode as the first electrode and the second electrode, a component in the light shielding layer formed on the electrode diffuses into the insulating layer to become an impurity, and there is a problem that silver migration is likely to occur.
The purpose of the present invention is to provide a positive photosensitive resin composition which has low reflectance and can be used as a light shielding layer for opaque wiring electrodes, and which has both resolution of a fine pattern and transparency and migration resistance of a substrate by suppressing residues on the substrate.
Means for solving the problems
The inventors of the present application found that the object of the present invention can be achieved by combining an alkali-soluble resin having a polymerizable group in a side chain with a sensitizer and a colorant.
Specifically, the positive photosensitive resin composition of the present invention is characterized by comprising 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.
ADVANTAGEOUS EFFECTS OF INVENTION
The positive photosensitive resin composition of the present invention has low reflectance and can be used as a light shielding layer for opaque wiring electrodes, and can achieve both resolution of a fine pattern and ensuring transparency and migration resistance of a substrate by suppressing residues on the substrate.
Drawings
Fig. 1 is a schematic diagram showing an example of the structure of the laminate of the present invention.
Fig. 2 is a schematic view showing another example of the structure of the laminate of the present invention.
Fig. 3 is a schematic diagram showing an example of a method for producing a laminate of the present invention.
Fig. 4 is a schematic diagram showing an electrode pattern for evaluation in examples and comparative examples.
FIG. 5 is a top view of a laminated substrate for evaluating residue on a substrate in examples and comparative examples.
Detailed Description
The positive photosensitive resin composition of the present invention is characterized by comprising 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.
[ alkali-soluble resin (A) having a polymerizable group in a side chain ]
The positive photosensitive resin composition of the present invention contains an alkali-soluble resin (a) having a polymerizable group in a side chain. By containing the alkali-soluble resin (a) having a polymerizable group in a side chain, dissolution at the time of development can be promoted, residues can be suppressed to ensure transparency of the base material, and a fine pattern can be formed. In addition, by heat treatment after patterning, the polymerizable groups are crosslinked, and the solvent resistance of the obtained cured film is improved. The "alkali-soluble" refers to a property of being dissolved in an aqueous alkali solution or an organic alkali.
In the alkali-soluble resin (a) having a polymerizable group in a side chain, it is preferable that the resin has an acidic group in a structural unit and/or at a terminal of a main chain thereof in order to impart alkali solubility. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Among them, carboxyl groups are preferable from the viewpoint of high solubility in an alkaline developer.
In the present invention, the polymerizable group is an acryl group and/or a methacryl group. By using an acryl group and/or methacryl group as the polymerizable group, a crosslinking reaction by light and/or heat is efficiently performed, and the curing degree is improved, and as a result, diffusion of components in the light shielding layer formed on the opaque wiring electrode into the insulating layer can be suppressed, and migration resistance can be improved.
Examples of the alkali-soluble resin include, but are not limited to, acrylic polymers, epoxy resins, phenolic resins, cardo resins, polysiloxanes, polyimides, polyamides, and polybenzoxazoles. These resins may be contained in an amount of 2 or more. Among them, acrylic polymers, cardo resins and polysiloxanes are preferable from the viewpoint of easiness of introduction of unsaturated double bonds, acrylic polymers and polysiloxanes are more preferable from the viewpoint of weather resistance, and acrylic polymers are further preferable from the viewpoint of easiness of synthesis.
The alkali-soluble resin (a) having a polymerizable group in a side chain preferably has an organic group represented by the following general formula (1). In the alkali-soluble resin (a) having a polymerizable group in a side chain, by having an organic group represented by the following general formula (1), residues can be further suppressed at the time of pattern formation to ensure transparency of a base material, and solvent resistance of a cured film obtained by a subsequent heating step can be further improved. By being on the sideIR analysis of alkali-soluble resin (A) having polymerizable group in chain, 1 HNMR, GC-MS and MALDI-MS analysis can identify organic groups.
[ chemical formula 1]
Figure BDA0003748380000000041
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.
The alkali-soluble resin (a) having a polymerizable group in a side chain more preferably has a repeating unit represented by the following general formula (2).
[ chemical formula 2]
Figure BDA0003748380000000042
In the general formula (2), R 2 R is R 3 Represents a hydrogen atom or a methyl group. R is R 2 R is R 3 The two may be the same or different.
The alkali-soluble resin (a) having a polymerizable group in a side chain preferably has 5 to 50 mol% of the repeating units represented by the general formula (2) in all the repeating units. The effect of ensuring the transparency of the substrate by suppressing the residue is further improved by having a content of the repeating unit represented by the general formula (2) of 5 mol% or more. In addition, migration resistance is further improved. The repeating unit represented by the general formula (2) is more preferably 10 mol% or more, still more preferably 15 mol% or more. On the other hand, by setting the repeating unit represented by the general formula (2) to 50 mol% or less, a finer pattern can be formed. The repeating unit represented by the general formula (2) is more preferably 40 mol% or less, still more preferably 35 mol% or less.
The alkali-soluble resin (a) having a polymerizable group in a side chain may have a repeating unit other than the repeating unit represented by the general formula (2). The repeating unit represented by the general formula (2) preferably includes repeating units having the following structure: a structure obtained by copolymerizing a (meth) acrylic compound having a carboxyl group and/or an acid anhydride group, a (meth) acrylic ester, and a (meth) acrylic ester radical, and then subjecting an epoxy compound having an ethylenically unsaturated double bond group to an addition reaction.
The acrylic polymer can be obtained by radical polymerization of a monomer having an ethylenically unsaturated double bond. The repeating unit represented by the general formula (2) can be obtained by an addition reaction of glycidyl (meth) acrylate with an acrylic polymer containing the repeating unit represented by the general formula (3). The catalyst for radical copolymerization is not particularly limited, and azo compounds such as azobisisobutyronitrile and organic peroxides such as benzoyl peroxide are generally used. The catalyst used for the addition reaction of glycidyl (meth) acrylate is not particularly limited, and known catalysts may be used, and for example, an amino catalyst such as dimethylaniline, 2,4, 6-tris (dimethylaminomethyl) phenol, dimethylbenzylamine, a tin catalyst such as tin (II) 2-ethylhexanoate, dibutyltin laurate, a titanium catalyst such as titanium (IV) 2-ethylhexanoate, a phosphorus catalyst such as triphenylphosphine, a chromium catalyst such as chromium acetylacetonate, chromium chloride, and the like may be used.
[ chemical formula 3]
Figure BDA0003748380000000061
In the general formula (3), R 4 Represents a hydrogen atom or a methyl group.
The catalyst for radical copolymerization of repeating units other than the repeating unit represented by the general formula (2) and the catalyst for addition reaction of an epoxy compound having an ethylenically unsaturated double bond group are the same as those described above.
Examples of the (meth) acrylic compound having a carboxyl group and/or an acid anhydride group include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, succinic acid mono (2-acryloyloxy) ester, phthalic acid mono (2-acryloyloxy) ester, tetrahydrophthalic acid mono (2-acryloyloxy) ester, 2-vinyl acetic acid, 2-vinyl cyclohexane carboxylic acid, 3-vinyl cyclohexane carboxylic acid, 4-vinyl cyclohexane carboxylic acid, 2-vinyl benzoic acid, 3-vinyl benzoic acid, 4-hydroxyphenyl (meth) acrylate, 2-hydroxyphenyl (meth) acrylate, methacrylic acid anhydride, itaconic acid, itaconic anhydride, succinic acid mono (2-acryloyloxyethyl) ester, phthalic acid mono (2-acryloyloxyethyl) ester, and tetrahydrophthalic acid mono (2-acryloyloxyethyl) ester.
As the (meth) acrylic acid ester, for example, methyl (meth) acrylate, tricyclodecyl (meth) acrylate, benzyl (meth) acrylate, and the like can be used. In addition, styrene may be copolymerized with the (meth) acrylic acid, (meth) acrylic acid esters described above.
Examples of the epoxy compound having an ethylenically unsaturated double bond group include glycidyl (meth) acrylate.
The acrylic polymer may be a polymer obtained by polymerizing a polyfunctional (meth) acrylate compound and a polyvalent mercapto compound by Michael addition (β -position with respect to carbonyl groups).
The weight average molecular weight (Mw) of the alkali-soluble resin (a) having a polymerizable group in a side chain is preferably 1,000 to 15,000 in terms of polystyrene measured by Gel Permeation Chromatography (GPC). When the weight average molecular weight (Mw) is 1,000 or more, the cured film can be prevented from being excessively dissolved and the conductive layer can be prevented from being exposed during patterning when a laminate to be described later is formed. The weight average molecular weight (Mw) is more preferably 5,000 or more, still more preferably 7,000 or more. On the other hand, by making the weight average molecular weight (Mw) 15,000 or less, a finer pattern can be formed. In addition, dissolution during development can be further promoted, and residues can be further suppressed, so that transparency of the 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 a side chain is not particularly limited, and may be arbitrarily selected according to the desired film thickness and use, but when the solid content is 100 mass%, it is usually 10 mass% or more and 70 mass% or less.
[ sensitizer (B) ]
The positive photosensitive resin composition of the present invention contains a sensitizer (B).
The photosensitive agent (B) generates an acid by light irradiation, has a property of increasing the alkali solubility of the light irradiation portion of the alkali-soluble resin (a) having a polymerizable group in a side chain, obtains a contrast (contrast) with the alkali solubility of the unexposed portion, can form a fine pattern, and suppresses residues to ensure the transparency of the substrate. Examples of the sensitizer include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Among them, the quinone diazide compound is preferable in that a finer pattern can be obtained.
The quinone diazide preferably contains a naphthoquinone diazide-4-sulfonyl group and a naphthoquinone diazide-5-sulfonyl group. The naphthoquinone diazide-4-sulfonyl ester compound is absorbed in the i-line region of the mercury lamp, and is suitable for i-line exposure. The naphthoquinone diazide-5-sulfonyl ester compound is absorbed in g-line region of mercury lamp, and is suitable for g-line exposure.
In the positive photosensitive resin composition of the present invention, the content of the photosensitive agent (B) is not particularly limited, but is preferably 0.01 to 50% by mass relative to 100% by mass of the solid content. By setting the content of the photosensitive agent (B) to 0.01 mass% or more, a finer pattern can be formed. In addition, since alkali solubility of the exposed portion is promoted, residues can be suppressed more to ensure transparency of the base material. The content of the sensitizer (B) is more preferably 10 mass% or more. In addition, by setting the content of the sensitizer (B) to 50 mass% or less, light can be transmitted to the bottom of the film, and a pattern can be obtained with high exposure sensitivity. The content of the sensitizer (B) is more preferably 40 mass% or less.
If necessary, the above-mentioned polyhydroxy compound and polyamino compound may be used as they are without esterifying with a sulfonic acid of quinone diazide. In this case, the amount of the hydroxyl compound or the polyamino compound added is preferably 1 to 50% by mass relative to 100% by mass of the solid content. By adding 1 mass% or more of the hydroxyl compound and the polyamino compound which are not esterified, the obtained positive resin composition is hardly dissolved in an alkaline developer before exposure, but is easily dissolved in the alkaline developer when exposure is performed, so that film loss due to development is reduced and development in a short period of time is facilitated. The amount of the hydroxyl compound or polyamino compound added is more preferably 3% by mass or more. Further, by setting the addition amount of the hydroxyl compound and the polyamino compound to 50 mass% or less, the solubility in an alkaline developer can be further improved, and a finer pattern can be formed. The amount of the hydroxyl compound or polyamino compound added is more preferably 40% by mass or less.
[ colorant (C) ]
The positive photosensitive resin composition of the present invention contains a colorant (C). The colorant (C) is a compound that absorbs all or part of the visible light having a wavelength (380 to 780 nm) to thereby cause coloring.
When the positive photosensitive resin composition of the present invention is formed on the conductive layer, the conductive layer is less likely to be visually recognized by blocking light reflected by the conductive layer.
Examples of the colorant (C) include compounds that absorb light having a wavelength of visible light and are colored black, red, orange, yellow, green, blue or purple. By combining these colorants singly or in combination of two or more colors, light reflected by the conductive layer can be blocked.
The colorant (C) preferably has an aromatic group. By having an aromatic group, the resin can interact with the polymerizable group of the alkali-soluble resin (a) having a polymerizable group in a side chain, so that the solubility of the resin in an alkali developer is increased, and residues are suppressed to ensure transparency of the substrate.
Examples of the colorant (C) include a black colorant (Ca) and/or a colorant (Cb) other than black. The black agent (Ca) is a compound that is colored black by absorbing light in the entire wavelength range of visible light. By containing the black agent (Ca), light shielding properties can be improved by shielding light reflected by the conductive layer. The coloring agent (Cb) other than black is a compound that colors 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), the colorant can be artificially colored black, and the light-shielding property can be improved. From the viewpoint of light-shielding properties, the black agent (Ca) is preferable because of excellent concealing properties.
The colorant (C) preferably contains one or more selected from the group consisting of an organic pigment (C1), an inorganic pigment (C2) and a dye (C3), which will be described later. Among them, the organic pigment (C1) is preferable, and the black organic pigment is more preferable from the viewpoints of heat resistance and light shielding property.
[ organic pigment (C1) ]
The positive photosensitive resin composition of the present invention preferably contains the organic pigment (C1) as the colorant (C). By containing the organic pigment (C1), the cured film of the positive photosensitive resin composition can be provided with light-shielding properties, and is highly concealable and less likely to be discolored by ultraviolet light or the like. Examples of the mode in which the colorant (C) contains the organic pigment (C1) include the black agent (Ca) and/or the colorant (Cb) other than black as the organic pigment (C1).
The number average particle diameter of the organic pigment (C1) is preferably 1 to 1,000nm, more preferably 5 to 500nm, still more preferably 10 to 200nm. When the number average particle diameter of the organic pigment (C1) is within the above range, the light-shielding property of the cured film of the positive photosensitive resin composition and the dispersion stability of the organic pigment (C1) can be improved.
The number average particle diameter of the organic pigment (C1) can be obtained by measuring laser light scattering (dynamic light scattering method) by Brownian motion of the organic pigment (C1) in a solution using a submicron particle size distribution measuring apparatus (N4-PLUS; manufactured by Beckmanncoulter Co., ltd.) or a Zeta potential, particle diameter and molecular weight measuring apparatus (Zetasizer Nano ZS; manufactured by Sysmex Co.). The number average particle diameter of the organic pigment (C1) in the cured film obtained from the resin composition can be determined by measurement using SEM and TEM. The number average particle diameter of the organic pigment (C1) was directly measured at a magnification of 50,000 ～ 200,000 times. The number average particle diameter can be calculated by averaging the particle diameters of 100 primary particles selected at random. When the organic pigment (C1) is a positive sphere, the diameter of the positive sphere is measured as the number average particle diameter. When the organic pigment (C1) is a non-positive sphere, the longest diameter (hereinafter referred to as "major axis diameter") and the longest diameter (hereinafter referred to as "minor axis diameter") in the direction orthogonal to the major axis diameter are measured, the major axis diameter and the minor axis diameter are averaged, and the biaxial average diameter thus obtained is used as 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, reduction (threne) pigments, indoline pigments, isoindoline pigments, isoindolinone pigments, benzofuranone pigments, perylene pigments, aniline pigments, azo pigments, azomethine pigments, condensed azo pigments, carbon black, metal complex pigments, lake pigments, toner (toner) pigments, and fluorescent pigments. From the viewpoint of heat resistance, anthraquinone pigments, quinacridone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, benzofuranone pigments, perylene pigments, condensed azo pigments, and carbon black are preferable. Among them, carbon black is more preferable from the viewpoints of dispersion stability and suppression of residues by having an aromatic group to ensure transparency of the substrate.
Examples of the phthalocyanine pigment include copper phthalocyanine compounds, halogenated copper phthalocyanine compounds, and metal-free phthalocyanine compounds.
Examples of the anthraquinone pigment include aminoanthraquinone compounds, diaminoanthraquinone compounds, anthrapyrimidine (anthrapyrimidine) compounds, flavanthrone compounds, indanthrone compounds, pyranthrone compounds, and anthrone violet compounds.
Examples of the azo pigment include a disazo compound and a polyazo compound.
Examples of the carbon black include channel black, furnace black, thermal black, acetylene black and lamp black.
In the positive photosensitive resin composition of the present invention, the content of the organic pigment (C1) is preferably 5 to 50% by mass based on 100% by mass of the solid content. When the content of the organic pigment (C1) is 5 mass% or more, the light shielding can be further improved. The content ratio of the organic pigment (C1) is more preferably 10 mass% or more. On the other hand, when the content of the organic pigment (C1) is 50 mass% or less, development residues can be further reduced to ensure transparency of the substrate. The content ratio of the organic pigment (C1) is more preferably 40 mass% or less.
[ inorganic pigment (C2) ]
The positive photosensitive resin composition of the present invention preferably contains the inorganic pigment (C2) as the colorant (C). The inclusion of the inorganic pigment (C2) can impart light-shielding properties to the film of the positive photosensitive resin composition, and since the film is an inorganic material, the heat resistance and weather resistance are more excellent, and therefore the heat resistance and weather resistance of the film of the resin composition can be improved. Examples of the form in which the colorant (C) contains the inorganic pigment (C2) include the black colorant (Ca) and/or the colorant (Cb) other than black as the inorganic pigment (C2).
Examples of the inorganic pigment (C2) include fine particles of metals such as titanium, barium, zirconium, lead, silicon, aluminum, magnesium, molybdenum, cadmium, tin, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, and oxides, composite oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides, and oxynitrides of the above-mentioned metal elements. Among them, metal nitride particles are preferable from the viewpoint of further improving the patterning property and light shielding property. In addition, from the viewpoint of further improving light-shielding properties, fine particles of titanium, zirconium or silver, oxides, composite oxides, sulfides, nitrides, carbides or oxynitrides are preferable, and zirconium nitride particles are particularly preferable.
In the positive photosensitive resin composition of the present invention, the content of the inorganic pigment (C2) is preferably 5 to 50% by mass based on 100% by mass of the solid content. When the content of the inorganic pigment (C2) is 5 mass% or more, the light-shielding property can be further improved. The content ratio of the inorganic pigment (C2) is more preferably 10 mass% or more. On the other hand, when the content of the inorganic pigment (C2) is 50 mass% or less, development residues can be further reduced to ensure transparency of the substrate. The content of the inorganic pigment (C2) is more preferably 40 mass% or less.
[ dye (C3) ]
The positive photosensitive resin composition of the present invention preferably contains the dye (C3) as the colorant (C). Examples of the mode in which the colorant (C) contains the dye (C3) include the black colorant (Ca) and/or the colorant (Cb) other than black as the dye (C3).
The dye (C3) is a compound in which a substituent such as an ionic group or a hydroxyl group in the dye (C3) is chemically adsorbed or strongly interacted with the surface structure of the object to color the object, and is usually soluble in a solvent or the like. Further, by coloring with the dye (C3), each molecule is adsorbed to the object, and therefore the coloring power is high and the color development efficiency is high.
Examples of the dye (C3) include anthraquinone dyes, azo dyes, azine dyes, phthalocyanine dyes, methine dyes, oxazine dyes, quinoline dyes, indigo (indigo) dyes, indigo (carbon) dyes, vat dyes, pyrene dyes, perylene dyes, triarylmethane dyes, and xanthene dyes. From the viewpoints of solubility in a solvent and heat resistance, anthraquinone dyes, azo dyes, azine dyes, methine dyes, triarylmethane dyes, and xanthene dyes are preferable.
Examples of the black-colored dye include solvent black 3, 5, 7, 22, 27, 29, or 34, intermediate black 1, 11, or 17, acid black 2 or 52, and direct black 19 or 154 (all values are c.i. index numbers). In addition to the above, examples are "NUBIAN" (registered trademark) BLACK TH-807, BLACK TH-827K, BLACK TN-870, BLACK PC-0855, BLACK PC-5856, BLACK PC-5857, BLACK PC-5877, BLACK PC-8550, BLACK TN-873, BLACK TN-877 or BLACK AH-807,OIL BLACK HBB or OIL BLACK 860, "VALIFAST" (registered trademark) BLACK 1807, VALIFAST BLACK 3904, VALIFAST BLACK 3810, VALIFAST BLACK 3820, VALIFAST BLACK 3830, VALIFAST BLACK 3866 or VALIFAST BLACK 3870, or WATER BLACK 100-L, WATER 191-L, WATER 256-L, WATER-510 or WATER 187-or WAR BLACK ORIENT CHEMICAL INDUSTRIES (all of which are ORIENT CHEMICAL INDUSTRIES).
Examples of the dye colored in red include direct red 9, 28, 81 or 83 (all values are c.i. index numbers).
Examples of the orange-colored dye include basic orange 21 or 23 (all the values are c.i. index numbers).
Examples of dyes that are colored yellow include direct yellow 8, 9, 11, 27, or 44, and basic yellow 1, 28, or 40 (all values are c.i. index numbers).
Examples of the dye colored green include acid green 16 (all the values are c.i. index numbers).
Examples of the dye colored in blue include acid blue 9, 45, 80, 83, 90, and 185 (all values are c.i. index numbers).
Examples of dyes that are colored violet include direct violet 51 or 66, and basic violet 1, 2, or 3 (all values are c.i. index numbers).
In the positive photosensitive resin composition of the present invention, the content of the dye (C3) is preferably 0.01 to 50% by mass based on 100% by mass of the solid content. When the content of the dye (C3) is 0.01 mass% or more, the light-shielding property can be further improved. The content ratio of the dye (C3) is more preferably 0.05 mass% or more. On the other hand, when the content of the dye (C3) is 50 mass% or less, development residues can be further reduced to ensure transparency of the substrate. The content ratio of the dye (C3) is more preferably 40 mass% or less.
[ dispersant ]
The positive photosensitive resin composition of the present invention preferably further contains a dispersant.
The dispersant is a compound having a dispersion stabilizing structure in which a surface affinity group interacts with the surface of the colorant (C) and the like to improve 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 the dispersant, the dispersion stability of the colorant (C) can be improved, and the resolution after development can be improved more.
Examples of the dispersant having a surface affinity group include a dispersant having an amine value and/or an acid value, and a dispersant having neither an amine value nor an acid value. From the viewpoint of improving the dispersion stability of the colorant (C), a dispersant having only an amine value and a dispersant having an amine value and an acid value are preferable.
The dispersant having a surface affinity group preferably has a structure in which an amino group and/or an acidic group as the surface affinity group forms a salt with an acid and/or a base.
Examples of the dispersant having only an amine value include "DISPERBYK" (registered trademark) -161, DISPERBYK-167, DISPERBYK-2000, DISPERBYK-2008, DISPERBYK-2009, DISPERBYK-2022, DISPERBYK-2050, DISPERBYK-2055, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPEYK-2164, or DISPERBYK-2061, "BYK" (registered trademark) -9075, BYK-9077, BYK-LP-N6919, BYK-LP-N21116, or BYK-LP-N21324 (all of which are manufactured by BYK Chemie Japan).
Examples of the dispersant having an amine value and an acid value include "DISPERBYK" (registered trademark) -2001, DISPERBYK-2013, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-187, and DISPERBYK-191, "BYK" (registered trademark) -9076 (BYK Chemie Japan).
Examples of the dispersant having only an acid value include "DISPERBYK" (registered trademark) -102, DISPERBYK-110, DISPERBYK-111, DISPERBYK-118, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-2060, and DISPERBYK-2096.
Examples of the dispersant having neither an amine value nor an acid value include "DISPERBYK" (registered trademark) -103, DISPERBYK-2152, DISPERBYK-2200, and DISPERBYK-192 (all of which are available from BYK Chemie Japan).
The amine value of the dispersant is preferably 1mgKOH/g or more. When the amine value is within the above range, the dispersion stability of the colorant (C) can be further improved. On the other hand, the amine value is preferably 150mgKOH/g or less. When the amine value is within the above range, the storage stability of the resin composition can be improved.
The amine number herein means the weight of potassium hydroxide equivalent to the acid reacted with 1g of dispersant, and the unit is mgKOH/g. After 1g of the dispersant was neutralized with an acid, it was obtained by titration with an aqueous potassium hydroxide solution. From the amine value, the amine equivalent (in g/mol) as the weight of the resin per 1mol of amino groups can be calculated, and the number of amino groups in the dispersant can be determined.
The acid value of the dispersant is preferably 1mgKOH/g or more. When the acid value is within the above range, the dispersion stability of the colorant (C) can be further improved. On the other hand, the acid value is preferably 200mgKOH/g or less. When the acid value is within the above range, the storage stability of the resin composition can be improved.
Here, the acid value means the weight of potassium hydroxide reacted with 1g of dispersant, and the unit is mgKOH/g. 1g of the dispersant can be titrated with an aqueous potassium hydroxide solution. The acid equivalent (in g/mol) as the weight of the resin per 1mol of the acid groups can be calculated from the value of the acid value, and the number of the acid groups in the dispersant can be determined.
Examples of the dispersing agent having a polymer chain substituent as the dispersion stabilizing structure include acrylic resin-based dispersing agents, polyoxyalkylene ether-based dispersing agents, polyester-based dispersing agents, polyurethane-based dispersing agents, polyol-based dispersing agents, polyethyleneimine-based dispersing agents, and polyacrylamide-based dispersing agents. From the viewpoint of pattern processability in an alkaline developer, an acrylic resin-based dispersant, a polyoxyalkylene ether-based dispersant, a polyester-based dispersant, a polyurethane-based dispersant, or a polyol-based dispersant is preferable.
The content ratio of the dispersant in the positive photosensitive resin composition of the present invention is preferably 1 to 60% by mass based on 100% by mass of the colorant (C). By setting the content ratio of the dispersant to 1 mass% or more, the dispersion stability of the colorant (C) can be further improved, and the resolution after development can be further improved. The content ratio of the dispersant is more preferably 5% by mass or more. On the other hand, by setting the content of the dispersant to 60 mass% or less, the heat resistance of the cured film can be improved. The content ratio of the dispersant is more preferably 50 mass% or less.
[ thermal crosslinking agent ]
The resin composition of the present invention may further contain a thermal crosslinking agent. The thermal crosslinking agent is a compound having at least 2 thermally reactive functional groups such as alkoxymethyl groups, hydroxymethyl groups, epoxy groups, oxetanyl groups, and the like in the molecule. By containing the thermal crosslinking agent, the alkali-soluble resin (a) having a polymerizable group in a side chain or other additive components can be crosslinked, and heat resistance and solvent resistance of the film after heat curing can be improved.
As preferable examples of the compound having at least 2 alkoxymethyl groups or hydroxymethyl groups, HMOM-TPPHBA, HMOMTPHAP (trade name, manufactured by Sanwa Chemical Co., ltd.), "NIKALAC" (registered trademark) MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM, "NIKALAC" MX-750LM (trade name, manufactured by Sanwa Chemical Co., ltd.), and DCL-2001 (trade name, manufactured by DAITO CHEMIX Co., ltd.) are given.
Preferable examples of the compound having at least 2 epoxy groups include "Epoligo" (registered trademark) 40E, "Epoligo" 100E, "Epoligo" 200E, "Epoligo" 400E, "Epoligo" 70P, "Epoligo" 200P, "Epoligo" 400P, "Epoligo" 1500NP, "Epoligo" 80MF, "Epoligo" 4000, "Epoligo" 3002 (manufactured by Kyowa chemical Co., ltd.), VG3101 (manufactured by Sanin chemical Co., ltd.), "TEPIC" (registered trademark) S, "TEPIC" G, "TEPIC" P, "TEPIC" L, "TEPIC" PAS, "TEPIC" VL, "TEPIC" UC "FL (manufactured by Nissan chemical industries, ltd.), and the like.
Preferable examples of the compound having at least 2 oxetanes include, for example, eternaoll EHO, eternaoll OXBP, eternaoll OXTP, eternaoll OXMA (the above is available from the company ltd.) and oxetane phenol novalac.
The thermal crosslinking agent may contain 2 or more kinds in combination.
Among these compounds, a compound selected from any one of "NIKALAC" MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM, "NIKALAC" MX-750LM, and DCL-2001 is preferable from the viewpoint of heat resistance of a cured film obtained after heat-induced curing.
The content of the thermal crosslinking agent is preferably 0.1 to 50% by mass relative to 100% by mass of the solid content. When the content of the thermal crosslinking agent is 0.1 mass% or more, the solvent resistance of the cured film can be improved. The content of the thermal crosslinking agent is more preferably 1 mass% or more. On the other hand, when the content of the thermal crosslinking agent is 50 mass% or less, the amount of outgas from the cured film can be reduced. The content of the thermal crosslinking agent is more preferably 30 mass% or less.
[ silane coupling agent ]
The positive photosensitive resin composition of the present invention preferably further contains a silane coupling agent.
The silane coupling agent is a compound having a hydrolyzable silyl group or silanol group. By containing the silane coupling agent, interaction between the cured film of the resin composition and the conductive layer or the insulating layer of the base (base) can be increased, and adhesion between the cured film and the conductive layer or the insulating layer of the base can be improved.
As the silane coupling agent, trifunctional organosilane or tetrafunctional organosilane is preferable.
Examples of the trifunctional organosilane include vinyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-epoxypropoxypropyl trimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-trimethoxysilylpropyl succinic acid, 3-trimethoxysilylpropyl succinic anhydride, 3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride, 3- (4-aminophenyl) propyltrimethoxysilane, 1- [4- (3-trimethoxysilylpropyl) phenyl ] urea, 1- (3-trimethoxysilylpropyl) urea, 3-triethoxysilyl-N- (1, 3-dimethylbutyryl) propylamine, 3-mercaptopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 1,3, 5-tris (3-trimethoxysilylpropyl) isocyanuric acid, N-tert-butyl-2- (3-trimethoxysilylpropyl) succinimide or N-tert-butyl-2- (3-triethoxysilylpropyl) succinimide.
Examples of the tetrafunctional organosilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetraacetoxysilane.
From the viewpoint of improving adhesion to a conductive layer or an insulating layer of a substrate, a trifunctional organosilane such as vinyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, 3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, 3- (4-aminophenyl) propyl trimethoxysilane, 1- [4- (3-trimethoxysilylpropyl) phenyl ] urea, 1- (3-trimethoxysilylpropyl) urea, 3-triethoxysilyl-N- (1, 3-dimethylbutenyl) propylamine, 3-isocyanatopropyl triethoxysilane, 1,3, 5-tris (3-trimethoxysilylpropyl) isocyanuric acid, N-t-butyl-2- (3-trimethoxysilylpropyl) succinimide or N-t-butyl-2- (3-triethoxysilylpropyl) succinimide is preferable, tetrafunctional organosilanes such as tetramethoxysilane, tetraethoxysilane, tetra-N-propoxysilane, tetraisopropoxysilane, tetra-N-butoxysilane or tetraacetoxysilane.
The content of the silane coupling agent is preferably 0.1 to 15% by mass relative to 100% by mass of the solid content. When the content of the silane coupling agent is 0.1 mass% or more, adhesion to the conductive layer or the organic film of the substrate can be further improved. The content of the silane coupling agent is more preferably 0.5 mass% or more. On the other hand, when the content of the silane coupling agent is 15 mass% or less, the resolution after development can be further improved. The content of the silane coupling agent is more preferably 10 mass% or less.
[ surfactant ]
In order to improve fluidity at the time of coating, the positive photosensitive resin composition of the present invention may contain various surfactants such as various fluorine-based surfactants and silicone-based surfactants. The kind of the surfactant is not particularly limited, and for example, a fluorine-based surfactant such as "MEGAFAC" (registered trademark) "F477 (trade name)" (the above is manufactured by the large Japan ink chemistry industry (ltd) "), a silicone-based surfactant such as" BYK-333 (trade name) "(manufactured by BYK Chemie Japan (ltd)"), a polyoxyalkylene-based surfactant, a poly (meth) acrylate-based surfactant, and the like can be used. More than 2 of the above compounds may also be used.
[ ultraviolet absorber ]
The positive photosensitive resin composition of the present invention may contain an ultraviolet absorber. By containing the ultraviolet absorber, the light resistance of the obtained cured film can be improved, and the resolution after development can be further improved. The ultraviolet absorber is not particularly limited, and known ultraviolet absorbers can be used, but benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds are preferable in terms of transparency and non-coloring property.
Polymerization inhibitor
The photosensitive resin composition of the present invention may contain a polymerization inhibitor. By containing a proper amount of a polymerization inhibitor, the resolution after development is further improved. The polymerization inhibitor is not particularly limited, and known polymerization inhibitors may be used, and examples thereof include di-t-butylhydroxytoluene, hydroquinone, p-methoxyphenol, 1, 4-benzoquinone, and t-butylcatechol. Examples of commercially available polymerization inhibitors include "IRGANOX 1010", "IRGANOX 245", "IRGANOX 3114", "IRGANOX 565" (manufactured by BASF as described above), and the like.
[ solvent ]
The photosensitive resin composition of the present invention may contain a solvent. The boiling point of the solvent contained in the photosensitive resin composition of the present invention is preferably 110 to 250 ℃, more preferably 200 ℃ or less at atmospheric pressure. It should be noted that a plurality of the above solvents may be used. If the boiling point is higher than 200 ℃, the amount of residual solvent in the film increases, and film shrinkage during curing increases, so that good flatness cannot be obtained. On the other hand, if the boiling point is lower than 110 ℃, the drying at the time of coating becomes too fast, the film surface becomes rough, and the like, and the coating film property becomes poor. Therefore, the solvent having a boiling point of 200 ℃ or less at atmospheric pressure is preferably 50 mass% or more of all solvents 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, dipropylene glycol methyl ether, and diacetone alcohol.
The content of the solvent is not particularly limited, and any amount may be used according to a coating method or the like. For example, when film formation is performed by spin coating, it is generally 50% by mass or more and 95% by mass or less of the entire photosensitive resin composition.
The positive photosensitive resin composition of the present invention may contain additives such as dissolution inhibitors, stabilizers, and defoaming agents, if necessary.
The concentration of the solid content of the positive photosensitive resin composition of the present invention is not particularly limited, and any amount of solvent or solute may be used depending on the coating method or the like. For example, when film formation is performed by spin coating as described later, the solid content concentration is usually set to 5 mass% or more and 50 mass% or less. Wherein the solid component is a component obtained by removing the solvent from the photosensitive resin composition.
A typical method for producing the positive photosensitive resin composition of the present invention will be described. For example, the alkali-soluble resin (a) having a polymerizable group in a side chain, the photosensitive agent (B), the colorant (C), and other additives as needed are added to an arbitrary solvent, stirred and dissolved, and then the obtained solution is filtered to obtain a positive photosensitive resin composition. When it is desired to uniformly disperse the colorant (C), a dispersion liquid obtained by dispersing the colorant (C) and the dispersant in an organic solvent in advance can be prepared by using a dispersing machine such as a ball mill, a sand mill, a three-roll mill, a mildly dispersing machine (mid-disperser), a medium-less dispersing machine (medium-less disperser), or the like.
[ cured film ]
The cured film of the present invention is obtained by curing the positive photosensitive resin composition. The positive photosensitive resin composition can be cured by a method described below.
The film thickness of the cured film of the present invention is not particularly limited, but is preferably 0.1 to 10. Mu.m. The light-shielding property can be further improved by setting the film thickness of the cured film to 0.1 μm or more. The thickness of the cured film is more preferably 0.3 μm or more. On the other hand, by setting the film thickness of the cured film to 10 μm or less, light can reach deep portions at the time of exposure, thereby forming finer patterns. The film thickness of the cured film is more preferably 7 μm or less, and still more preferably 5 μm or less.
The reflectance of the cured film of the present invention at a wavelength of 550nm is preferably 0.01 to 20%. By setting the reflectance to 0.01% or more, the conductive layer can be made invisible. On the other hand, when the reflectance is 20% or less, light can reach deep portions at the time of exposure, thereby forming finer patterns. The reflectance is more preferably 15% or less, and still more preferably 10% or less. The reflectance means a reflectance at a film thickness of 1.0 μm. The reflectance can be adjusted by selecting the exposure amount, development time, and heat curing temperature. The reflectance of the cured film of the present invention was measured by a reflectance meter for the cured film having a square or more of 0.1mm on the 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 of a black matrix of a color filter, a black column spacer (black column spacer) of a liquid crystal display, a pixel dividing layer of an organic EL display device, a TFT planarizing layer, or the like. Among them, since a fine pattern can be formed and the reflectance is low, the film can be suitably used particularly as a light shielding layer of an opaque electrode for a touch panel, a pixel dividing layer of an organic EL display device, or a TFT planarizing layer.
A method for producing a cured film using the positive photosensitive resin composition of the present invention will be described by way of example.
The positive photosensitive resin composition of the present invention is applied to a base substrate by a known method such as micro gravure coating, spin coating, dip coating, curtain coating, roll coating, spray coating, or slit coating.
The coated film is prebaked by a heating device such as a heating plate or an oven. The pre-baking is carried out at 50-150 ℃ for 30 seconds-30 minutes, and the film thickness after the pre-baking is preferably 0.1-15 mu m.
After prebaking, the coated film is exposed using an exposure machine such as a stepper, mirror projection mask aligner (MPA), parallel photomask aligner (PLA), or the like. With an exposure intensity of 10 to 4000J/m 2 The light is irradiated to the left and right (in terms of exposure amount at 365nm wavelength) with or without a desired mask. The exposure light source is not limited, and ultraviolet rays such as g-line, h-line, i-line, krF (wavelength 248 nm) laser, arF (wavelength 193 nm) laser, and the like can be used.
Then, the exposed portion of the coating film is dissolved by development, whereby a positive pattern can be obtained. As the development method, it is preferable to impregnate the coating film in the developer for 5 seconds to 10 minutes using a method such as spraying, dipping, spin-coating immersion, or the like. Examples of the developer include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), and organic bases such as alcohol amines such as triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, and diethylaminoethanol. To these alkaline developing solutions, water-soluble organic solvents such as ethanol, γ -butyrolactone, dimethylformamide and N-methyl-2-pyrrolidone may be appropriately added.
In order to obtain a more preferable pattern, a surfactant such as a nonionic surfactant is preferably further added to the alkaline developer in an amount of 0.01 to 1 mass%.
After development, the coating film is preferably rinsed with water, and then the coating film may be dried in the range of 50 to 130 ℃.
Then, the coated film is heated in a heating device such as a heating plate or an oven at a temperature ranging from 100 to 300 ℃ for about 5 to 120 minutes. The method for producing a cured film of the present invention preferably includes a step of heating the coated film at 150 to 250 ℃.
[ laminate ]
The laminate of the present invention has a conductive layer and the cured film of the present invention. As described above, the cured film of the present invention has low reflectance, can ensure transparency of a substrate without residue, and can form a fine pattern, and therefore can be suitably used as a light shielding layer of an opaque wiring electrode as a conductive layer of a touch panel, for example.
In the laminate of the present invention, the ratio of the film thickness of the cured film to the film thickness of the conductive layer is preferably 1/2 to 5. When the film thickness ratio is 1/2 or more, the light shielding property can be further improved, and when the film thickness ratio is 5 or less, the wiring thickness can be suppressed, and the degree of freedom and flexibility of wiring design can be improved.
The laminate of the present invention preferably has an insulating layer in addition to the conductive layer and the cured film of the present invention. By providing the insulating layer, a problem such as a short circuit between conductive layers can be suppressed, and a highly reliable laminate can be formed. Further, by protecting the light shielding layer, damage or the like can be suppressed, and poor visibility or the like can be prevented.
The insulating material contained in the insulating layer is not particularly limited, and examples thereof include acrylic polymers, epoxy resins, phenolic resins, cardo resins, polysiloxanes, polyimides, polyamides, polybenzoxazoles, and the like. These may be contained in an amount of 2 or more.
Examples of the conductive material contained in the conductive layer include copper, silver, gold, aluminum, chromium, molybdenum, and titanium. In addition to the above, the conductive material forming the transparent electrode may be formed with, for example, ITO, IZO (indium zinc oxide), AZO (aluminum-doped zinc oxide), znO 2 Etc. Among them, silver having the lowest resistivity is preferable. When the resistivity is low, a touch panel with high sensitivity can be manufactured. In addition, the average primary particle diameter of silver is preferably 10 to 200nm, because finer wiring patterns can be formed. The average primary particle diameter of silver can be calculated from an average value of the particle diameters of 100 primary particles randomly selected by using a scanning electron microscope. The particle diameter of each primary particle can be calculated from the average value of the long diameter and the short diameter of the primary particle.
The conductive layer preferably contains 5 to 35 mass% of an organic component having an alkali-soluble group. When the content ratio of the organic component having an alkali-soluble group is 5 mass% or more, the photosensitive characteristics can be improved, and a finer pattern can be formed. On the other hand, by setting the content ratio of the organic component having an alkali-soluble group to 35 mass% or less, the resistivity can be reduced, and a highly sensitive touch panel can be formed. By containing an organic component having an alkali-soluble group, flexibility can be imparted to the wiring pattern, and a flexible touch panel can be manufactured. The alkali-soluble group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. As the organic component having an alkali-soluble group, the organic components described in the positive photosensitive resin composition can be used.
Fig. 1 and 2 are schematic diagrams showing an example of the structure of the laminate of the present invention. Fig. 1 is a schematic view of a laminate having an opaque wiring electrode 2 on a transparent substrate 1, and a light shielding layer 3 formed of a cured film of the present invention on the opaque wiring electrode 2. The laminate shown in fig. 1 can be obtained by a step of exposing the transparent substrate from the side opposite to the opaque wiring electrode formation surface in the manufacturing method of the laminate described later.
Fig. 2 is a schematic diagram of a laminate including an opaque wiring electrode 2 (1 st opaque wiring electrode) and an insulating layer 4 on a transparent substrate 1, an opaque wiring electrode 2 (2 nd opaque wiring electrode) on the insulating layer 4, and a light shielding layer 3 formed of a cured film of the present invention in a portion corresponding to the opaque wiring electrode 2 (1 st opaque wiring electrode and 2 nd opaque wiring electrode). The laminate shown in fig. 2 can be obtained by forming the 1 st opaque wiring electrode, the insulating layer, and the 2 nd opaque wiring electrode on one surface of the transparent substrate, applying the positive photosensitive resin composition of the present invention, and exposing the transparent substrate from the side opposite to the surface on which the opaque wiring electrode is formed in the manufacturing method of the laminate described later.
Next, each step in the method for producing a laminate of the present invention will be described in detail. That is, the method for producing a laminate of the present invention comprises a step of forming an opaque wiring electrode on one surface of a transparent substrate, a step of applying the positive photosensitive resin composition of the present invention to the opaque wiring electrode-forming surface of the transparent substrate, and a step of exposing the transparent substrate from the side opposite to the opaque wiring electrode-forming surface and developing the transparent substrate to form a light shielding layer in a portion corresponding to the opaque wiring electrode. Fig. 3 is a schematic diagram showing an example of a method for producing a laminate of the present invention.
First, the opaque wiring electrode 2 is formed on one surface of the transparent substrate 1. The step of forming the opaque wiring electrode on one side of the transparent substrate may include a step of forming a 1 st opaque wiring electrode on one side of the transparent substrate, a step of forming an insulating layer on the 1 st opaque wiring electrode, and a step of forming a 2 nd opaque wiring electrode on the insulating layer.
Examples of the method for forming the opaque wiring electrode include a method for forming a pattern by photolithography using a photosensitive conductive composition, a method for forming a pattern by screen printing, gravure printing, ink jet printing, or the like using a conductive composition (conductive paste), a method for forming a film of a metal, a metal complex, a complex of a metal and a metal compound, a metal alloy, or the like, and a method for forming a film by photolithography using a resist (resistance). Among them, a method of forming by photolithography using a photosensitive conductive composition is preferable in terms of forming fine wiring. In the case where 2 or more opaque wiring electrodes are formed with an insulating layer interposed therebetween, each opaque wiring electrode may be formed by the same method, or different methods may be combined. An insulating layer may be formed on the opaque wiring electrode of the obtained laminate with an opaque wiring electrode.
Examples of the method for forming the insulating layer include a method of forming a pattern by photolithography using a photosensitive insulating composition, a method of applying an insulating composition and drying, and a method of bonding a transparent substrate to the side of the surface on which an opaque wiring electrode is formed with an adhesive interposed therebetween. Among them, a method of forming by using a photosensitive insulating composition and using photolithography is preferable in terms of forming a fine pattern. As a method of bonding the transparent substrate via the adhesive, for example, the transparent substrate may be bonded by forming the adhesive on the substrate with the opaque wiring electrode, or the transparent substrate with the adhesive 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.
When the laminate of the present invention is used as a touch panel sensor, the positive photosensitive resin composition of the present invention may not be applied to the connection portion with the flexible (flexo) substrate, if necessary.
Next, the positive photosensitive resin composition 5 of the present invention is exposed from the side opposite to the opaque wiring electrode forming surface of the transparent substrate using the opaque wiring electrode 2 as a mask, and developed, whereby a light shielding layer is formed at a portion corresponding to the opaque wiring electrode. By exposing the opaque wiring electrode as a mask, a corresponding light shielding layer can be formed at a portion corresponding to the opaque wiring electrode without requiring a separate exposure mask. In the case where the step of forming the opaque wiring electrode on one side of the transparent substrate includes the step of forming the 1 st opaque wiring electrode on one side of the transparent substrate, the step of forming the insulating layer on the 1 st opaque wiring electrode, and the step of forming the 2 nd opaque wiring electrode on the insulating layer, it is preferable that the light shielding layer be formed at a portion corresponding to the 1 st opaque wiring electrode and the 2 nd opaque wiring electrode.
The method may further comprise the steps of: and a step of forming an insulating layer on the light shielding layer of the obtained laminate, a step of forming a 2 nd opaque wiring electrode on the insulating layer, and a step of applying a positive photosensitive composition to the 2 nd opaque wiring electrode forming surface, exposing the surface of the transparent substrate opposite to the 2 nd opaque wiring electrode forming surface, and developing the exposed surface to form a light shielding layer at least in a portion corresponding to the 2 nd opaque wiring electrode.
[ substrate with conductive Pattern ]
The substrate with a conductive pattern of the present invention is a substrate with a conductive pattern comprising a substrate, a conductive pattern formed on the substrate, and a cured film of the present invention, wherein the cured film is provided on at least a part of the conductive pattern forming region, and the cured film is not provided on the conductive pattern non-forming region. With such a configuration, reflection of the conductive pattern can be suppressed while ensuring transparency of the base material.
When the substrate with a conductive pattern includes a connection portion, the connection portion preferably does not have the cured film. By not having a cured film on the connection portion, stable electrical connection can be achieved.
Examples
The present invention will be further specifically described with reference to examples, but the present invention is not limited to these examples. Abbreviations used among the compounds used in the synthesis examples and examples are as follows.
AIBN:2,2' -azobis (isobutyronitrile)
PGMEA: propylene glycol monomethyl ether acetate
DAA: diacetone alcohol
TMAH: tetramethyl ammonium hydroxide
DPHA: dipentaerythritol hexaacrylate
First, materials used in examples and comparative examples will be described.
[ alkali-soluble resin (A) having a polymerizable group in a side chain ]
Synthesis example 1: acrylic polymer (a 1-1)
AIBN 1g and PGMEA 50g were put into a 500ml flask. Then, 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were charged. After the flask was stirred at room temperature for a while and nitrogen substitution was sufficiently performed by bubbling, the flask was heated and stirred at 70℃for 5 hours. Next, 7.1g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was stirred at 90℃for 4 hours while heating, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40% by weight, thereby obtaining a solution of the acrylic polymer (a 1-1). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 11,000.
Synthesis example 2: acrylic polymer (a 1-2)
AIBN 1g and PGMEA 50g were put into a 500ml flask. 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 5 hours. Then, 14.2g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was stirred at 90℃for 4 hours while heating, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40% by weight, thereby obtaining a solution of the acrylic polymer (a 1-2). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 11,000.
Synthesis example 3: acrylic polymers (a 1-3)
AIBN 1g and PGMEA 50g were put into a 500ml flask. 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 5 hours. Then, 21.3g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was stirred at 90℃for 4 hours while heating, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40% by weight, thereby obtaining a solution of the acrylic polymer (a 1-3). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 11,000.
Synthesis example 4: acrylic polymers (a 1-4)
AIBN 1g and PGMEA 50g were put into a 500ml flask. 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 5 hours. Subsequently, 49.8g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was stirred at 90℃for 4 hours while heating, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40% by weight, thereby obtaining a solution of acrylic polymers (a 1-4). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 11,000.
Synthesis example 5: acrylic polymers (a 1-5)
AIBN 1g and PGMEA 50g were put into a 500ml flask. 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 5 hours. Subsequently, 56.9g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was stirred at 90℃for 4 hours while heating, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40% by weight, thereby obtaining a solution of acrylic polymers (a 1-5). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 11,000.
Synthesis example 6: acrylic polymers (a 1-6)
AIBN 1g and PGMEA 50g were put into a 500ml flask. 51.7g of methacrylic acid, 52.9g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 5 hours. Subsequently, 71.1g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was stirred at 90℃for 4 hours while heating, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40% by weight, thereby obtaining a solution of acrylic polymers (a 1-6). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 11,000.
Synthesis example 7: acrylic polymers (a 1-7)
AIBN 1g and PGMEA 50g were put into a 500ml flask. 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 5 hours. Then, 2.8g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was stirred at 90℃for 4 hours while heating, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40% by weight, thereby obtaining a solution of acrylic polymers (a 1-7). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 11,000.
Synthesis example 8: acrylic polymers (a 1-8)
AIBN 1g and PGMEA 50g were put into a 500ml flask. Then, 60.3g of methacrylic acid, 35.2g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were charged, and the mixture was stirred briefly at room temperature, and after the flask was sufficiently purged with nitrogen by bubbling, the flask was heated and stirred at 70℃for 5 hours. Subsequently, 85.3g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was stirred at 90℃for 4 hours while heating, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40% by weight, thereby obtaining a solution of acrylic polymers (a 1-8). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 11,000.
Synthesis example 9: acrylic polymers (a 1-9)
Into a 500ml flask, 0.5g of AIBN and 50g of PGMEA were charged. 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 2 hours. Then, 21.3g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was stirred at 90℃for 4 hours while heating, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40% by weight, thereby obtaining a solution of acrylic polymers (a 1-9). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 3,000.
Synthesis example 10: acrylic polymers (a 1-10)
Into a 500ml flask, 0.5g of AIBN and 50g of PGMEA were charged. 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 4 hours. Then, 21.3g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was stirred at 90℃for 4 hours while heating, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40% by weight, thereby obtaining a solution of acrylic polymers (a 1-10). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 6,000.
Synthesis example 11: acrylic polymers (a 1-11)
Into a 500ml flask, 1.5g of AIBN and 50g of PGMEA were charged. 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 5 hours. Then, 21.3g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was stirred at 90℃for 4 hours while heating, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40% by weight, thereby obtaining a solution of acrylic polymers (a 1-11). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 14,000.
Synthesis example 12: acrylic polymers (a 1-12)
Into a 500ml flask, 2.0g of AIBN and 50g of PGMEA were charged. 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 5 hours. Then, 21.3g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was stirred at 90℃for 4 hours while heating, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40% by weight, thereby obtaining a solution of acrylic polymers (a 1-12). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 20,000.
Synthesis example 13: acrylic polymers (a 1-13)
AIBN 1g and PGMEA 50g were put into a 500ml flask. 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 5 hours. Next, 29.4g of [ (3, 4-epoxycyclohexane) -1-ol ] methyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, 100g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90℃for 4 hours, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40% by weight, thereby obtaining a solution of acrylic polymers (a 1-13). The weight average molecular weight Mw in terms of polystyrene as measured by GPC method was 11,500.
Synthesis example 14: acrylic polymers (a 1-14)
AIBN 1g and PGMEA 50g were put into a 500ml flask. 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 5 hours. Subsequently, 19.2g of glycidyl acrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was stirred at 90 ℃ for 4 hours while heating, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40wt%, thereby obtaining a solution of acrylic polymers (a 1-14). The weight average molecular weight Mw in terms of polystyrene as measured by GPC method was 10,500.
Synthesis example 15: acrylic polymer (a 1' -1)
AIBN 1g and PGMEA 50g were put into a 500ml flask. 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 5 hours. Subsequently, 17.1g of allyl glycidyl ether, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90 ℃ for 4 hours, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40wt%, thereby obtaining a solution of acrylic polymer (a 1' -1). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 10,000.
Synthesis example 16: acrylic polymer (a 1' -2)
AIBN 1g and PGMEA 50g were put into a 500ml flask. Thereafter, 34.4g of methacrylic acid, 61.7g of benzyl methacrylate, 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate and 21.3g of glycidyl methacrylate were charged, and the mixture was stirred briefly at room temperature, and after nitrogen substitution was sufficiently performed in the flask by bubbling, the mixture was heated and stirred at 70℃for 5 hours, and PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40wt%, thereby obtaining a solution of acrylic polymer (a 1' -2). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 12,000.
Synthesis example 17: acrylic polymer (a 1' -3)
AIBN 1g and PGMEA 50g were put into a 500ml flask. 43.0g of methacrylic acid, 70.5g of benzyl methacrylate and 22.0g of tricyclo [5.2.1.0 (2, 6) ] decan-8-yl methacrylate were then introduced and stirred briefly at room temperature, and the flask was sufficiently purged with nitrogen and then heated and stirred at 70℃for 5 hours. Next, PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration became 40wt%, thereby obtaining a solution of the acrylic polymer (a 1' -3). The weight average molecular weight Mw in terms of polystyrene, as measured by GPC, was 11,000.
[ sensitizer (B) ]
Synthesis example 18: photosensitizer (b-1)
15.3g of TrisP-HAP (manufactured by Benzhou chemical industries, ltd.) and 40.3g of naphthoquinone diazide-5-sulfonyl chloride were dissolved in 450g of 1, 4-dioxane under a dry nitrogen stream, and the mixture was left at room temperature. Here, 15.2g of triethylamine mixed with 50g of 1, 4-dioxane was added dropwise so that the temperature in the system was not 35 ℃. After the dropwise addition, the mixture was stirred at 30℃for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. The precipitate which is then precipitated is dried in a vacuum dryer to obtain a quinone diazide compound (b-1) represented by the following formula.
[ chemical formula 4]
Figure BDA0003748380000000311
[ colorant (C) ]
Carbon black (trade name "MA-100", manufactured by Mitsubishi Chemical Co., ltd., hereinafter referred to as "MA-100")
Benzofuranone BLACK pigment (BASF `IRGAPHOR` (registered trademark) BLACK S0100 CF` having a primary particle diameter of 40 to 80nm, hereinafter referred to as "Bk-S0100 CF")
Black inorganic pigment (titanium nitride particle manufactured by Nisshin Engineering Co., ltd.)
Black dye (manufactured by ORIENT CHEMICAL INDUSTRIES Co., ltd. 'NUBIAN' (registered trademark) BLACK TN-870 ', hereinafter referred to as "TN-870')
[ dispersant ]
A dispersant having an amine number (BYK' (registered trademark) -LP-N21116", manufactured by BYK Chemie Japan, inc.; hereinafter referred to as" BYK-21116 ")
[ Cross-linking agent ]
Methylol compound ((Sanwa Chemical Co.) 'NIKALAC' MX-270", hereinafter referred to as" MX-270 ")
Epoxy Compound (VG 3101 manufactured by Sanjing Chemie Co., ltd.)
[ silane coupling agent ]
3-epoxypropoxypropyltrimethoxysilane (KBM-403 (trade name) manufactured by Xinyue chemical industry Co., ltd., hereinafter referred to as "KBM-403")
[ surfactant ]
An organosilicon surfactant (BYK-333 (trade name), hereinafter referred to as "BYK-333". Co., ltd.) (BYK Chemie Japan Co., ltd.)
[ solvent ]
PGMEA (product name of PGM-AC, manufactured by kuraray tracking Co., ltd.)
DAA (DAA, manufactured by Mitsubishi chemical corporation).
Next, photosensitive silver ink materials and photosensitive insulating materials used in examples and comparative examples will be described.
[ photosensitive silver ink Material ]
The following shows a method for producing a photosensitive silver ink material.
< preparation of photosensitive silver ink Material >
First, conductive fine particles (manufactured by Nisshin Engineering (ltd)) surface-coated with a carbon compound: 80.0g, BYK-21116:4.06g, PGMEA:196.14g, and a 30-minute mixing treatment was performed with a homogenizer at 1200 rpm. The mixed solution was dispersed using a mill-type dispersing machine filled with zirconia beads to obtain a silver microparticle dispersion. 63.28g of this silver microparticle dispersion was mixed with an acrylic polymer (a 1-10) under a yellow lamp: 4.40g, OXE-02 (BASF): 0.41g of DPHA (manufactured by Japanese chemical Co., ltd.): 1.30g of a mixture, to the mixture thus obtained was added PGMEA:7.31g, DAA:23.25g, and a photosensitive silver ink (. Alpha.) was prepared by stirring.
[ photosensitive insulating Material ]
The method for producing the photosensitive insulating material is described below.
< preparation of photosensitive insulating Material >
Under a yellow lamp, OXE-02 (manufactured by BASF) was used as a photopolymerization initiator: 0.50g dissolved in PGMEA:20.70g, DAA:37.50g of SIRIUS-501 (manufactured by Daiko organic chemical Co., ltd.) was added: 1.25g of M-315 (manufactured by Kyowa Co., ltd.): 2.90g of acrylic polymer (a 1-3): 28.00g of a photosensitive insulating material (. Beta.) was prepared by stirring.
Next, the production of the cured film/laminated substrate and the respective evaluation methods performed in examples and comparative examples will be described.
Patterning of silver ink Material (alpha)
The silver ink material (α) was spin-coated on a substrate or a substrate with an opaque wiring electrode having an insulating layer at a predetermined rotation speed using a spin coater (Mikasa corporation "1H-360S (trade name)") so that the film thickness after drying became 1 μm, and then prebaked for 2 minutes at 100℃using a heating plate (manufactured by Daika wire mesh corporation "SCW-636 (trade name)") to prepare a prebaked film. The pre-baked film was exposed to 500mJ/cm of light through a desired mask using an ultra-high pressure mercury lamp as a light source using a parallel photomask aligner (product name of PLA-501F, canon Co., ltd.) 2 Exposure (in terms of 365nm wavelength) was performed to produce a mesh pattern having a pitch (pitch) of 300 μm as shown in FIG. 4. Subsequently, using an automatic developing apparatus (product name "AD-2000", manufactured by the company, inc.) a pattern processing was performed by performing spray development with 0.07wt% tmah aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds.
The patterned substrate was post-baked at 230℃for 60 minutes (in air) using an oven (product name "IHPS-222" manufactured by ESPEC Co., ltd.) to prepare a substrate with an opaque wiring electrode. The line width of the net-like portion of the opaque wiring electrode was measured with an optical microscope, and found to be 4.0. Mu.m.
Patterning of photosensitive insulating Material (beta)
The photosensitive insulating material (. Beta.) was spin-coated on the substrate with opaque wiring electrode obtained at a predetermined rotation speed using a spin coater so that the film thickness became 2.5 μm after drying, and then pre-baked at 100℃for 2 minutes using a heating plate, to prepare a pre-baked film. The pre-baked film was exposed to light of 200mJ/cm using a parallel photomask aligner and an ultra-high pressure mercury lamp as a light source through an exposure mask having a desired pattern 2 Exposure was performed (in terms of 365nm wavelength). Subsequently, pattern processing was performed by using an automatic developing apparatus with a 0.07wt% tmah aqueous solution for 60 seconds of spray development followed by water for 30 seconds of rinsing.
The patterned substrate was post-baked at 230℃for 60 minutes (in air) using an oven to prepare a substrate with an opaque wiring electrode having an insulating layer.
Preparation of cured film of Positive photosensitive resin composition
The positive photosensitive resin composition was spin-coated on the surface of the substrate with an opaque wiring electrode or the substrate with an opaque wiring electrode having an insulating layer, which was obtained, using a spin coater at a predetermined rotation speed so that the film thickness became 1.0 μm after drying, and then prebaked at 100℃for 2 minutes using a heating plate, to prepare a prebaked film. For the pre-baked film, a parallel photomask aligner was used, an ultra-high pressure mercury lamp was used as a light source, an opaque wiring electrode was used as a mask, and an exposure of 500mJ/cm was performed on the side opposite to the surface on which the opaque wiring electrode was formed 2 Exposure was performed (in terms of 365nm wavelength). Subsequently, using an automatic developing apparatus, pattern processing was performed by performing spray development with 0.07wt% tmah aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds.
The patterned substrate was post-baked at 230℃for 60 minutes (in air) using an oven to prepare a cured film of the positive photosensitive resin composition.
< fabrication of laminate substrate (A) >)
The laminate substrate (a) shown in fig. 1 was produced using the positive photosensitive resin composition and the silver ink material (α). The substrate 1 is surface-sputtered with SiO 2 The opaque wiring electrode layer 2 is a conductive pattern layer formed of a silver ink material (α), and the light shielding layer 3 is a cured film formed of a positive photosensitive resin composition.
(1) Evaluation of Pattern processability
The light shielding layer of the mesh portion of the laminated substrate (a) was observed with an optical microscope, and the line width of 10 points selected at random was measured to calculate the average value. The closer the value of the line width of the light shielding layer is to the line width of the opaque wiring electrode of 4.0 μm, the better the pattern processability.
(2) Evaluation of cured film Properties
Reflectance at 550nm was measured using a reflectometer (VSR 400: manufactured by Nippon electric color industry Co., ltd.) at a position corresponding to the land portion 6 of the laminated substrate (A).
Further, the laminate substrate (a) was immersed in PGMEA at 100 ℃ for 10 minutes at a position corresponding to the land portion 6, and after washing with water for 1 minute, the image enlarged 50 times was observed under an optical microscope, and the appearance of the cured film before and after immersion was observed, to evaluate the solvent resistance.
2: no change in appearance.
1: the light-shielding layer is cracked (crack).
< fabrication of laminate substrate (B) >)
The laminated substrate (B) shown in fig. 2 and 5 was produced using the positive photosensitive resin composition, the silver ink material (α) and the photosensitive insulating material (β). The substrate 1 is a surface-sputtered SiO 2 The opaque wiring electrode layer 2 is a conductive pattern layer formed of a silver ink material (α), the light shielding layer 3 is a cured film formed of a positive photosensitive resin composition, and the insulating layer 4 is an insulating layer formed of a photosensitive insulating material (β).
(3) Evaluation of residue on substrate
In the laminated substrate (B), the residue on the substrate was evaluated by transmittance evaluation for the exposed portion of the positive photosensitive resin composition on the insulating layer 4 of the laminated substrate shown in fig. 2. Specifically, the transmittance at 400nm before and after formation of the light shielding film was measured on the exposed portion of the positive photosensitive resin composition on the insulating layer 4 of the laminated substrate shown in fig. 5 using an ultraviolet-visible spectrophotometer (manufactured by shimeji corporation, "Multispec-1500 (trade name)"). Then, when the transmittance before formation of the light shielding film is defined as T0 and the transmittance after formation of the light shielding film is defined as T, the transmittance change represented by the formula (T0-T)/t0×100 is calculated.
(4) Evaluation of migration resistance
The migration resistance of the laminated substrate (B) under high temperature and high humidity was evaluated. For the measurement, an insulation deterioration characteristic evaluation system "ETAC SIR13" (manufactured by Nanyuji chemical Co., ltd.) was used. Electrodes were mounted on the connection portions of the opaque wiring electrodes 2, respectively, and the samples were placed in a high-temperature and high-humidity tank set at 85℃and 85% RH. After 5 minutes from the time when the inside of the tank was stabilized, a voltage was applied between the electrodes of the opaque wiring electrode 2, and the change in insulation resistance with time was measured. The opaque wiring electrode of the first layer was used as a positive electrode, and the opaque wiring electrode of the second layer was used as a negative electrode, and a voltage of 5V was applied thereto, and the resistance value was measured at 5 minute intervals for 1000 hours. When the measured resistance value is equal to or less than 5. Omega. To 10, it is determined that the voltage is short-circuited due to insulation failure, and the application of the voltage is stopped, and the test time until that is taken as the short-circuit time. Migration resistance was evaluated according to the following evaluation criteria. And setting above 2 as qualified.
3: short-circuit time is more than 1000 hours
2: short-circuit time is 280 hours or more and less than 1000 hours
1: the short-circuit time is less than 280 hours.
Example 1
First, for MA-100 as colorant (C): 3.00g and BYK-21116 as dispersant: 1.00g, PGMEA:40.00g, DPM:20.00g was subjected to a mixing treatment at 1200rpm for 30 minutes with a homogenizer, and dispersed using a high-pressure wet non-medium micronizer (NanomizER Co.) to obtain a dispersion. 64.00g of a sensitizer (B-1) as sensitizer (B) was added to the dispersion under a yellow lamp: 3.00g of MX-270 as crosslinker: 0.69g of PGMEA as solvent: 14.50g and dissolved, KBM-403 was added as a silane coupling agent: 0.30g of BYK-333 as surfactant: 0.01g, and stirring. At this time, 40wt% pgmea solution (a 1-1) as alkali-soluble resin (a) having a polymerizable group in a side chain was added: 17.50g were stirred. Then, the mixture was filtered through a 0.20 μm filter to obtain a positive photosensitive resin composition. The positive photosensitive resin composition obtained was evaluated for (1) pattern processability, (2) cured film properties, (3) residue on a substrate, and (4) migration resistance. The compositions and results are shown in tables 1 and 5.
Examples 2 to 29 and comparative examples 1 to 5
Positive photosensitive resin compositions having compositions shown in tables 1 to 4 were obtained in the same manner as in example 1, and the same evaluation as in example 1 was performed for each positive photosensitive resin composition. The evaluation results are shown in tables 5 to 8.
TABLE 1
Figure BDA0003748380000000371
TABLE 2
Figure BDA0003748380000000381
TABLE 3
Figure BDA0003748380000000391
TABLE 4
Figure BDA0003748380000000401
TABLE 5
Figure BDA0003748380000000411
TABLE 6
Figure BDA0003748380000000421
TABLE 7
Figure BDA0003748380000000431
TABLE 8
Figure BDA0003748380000000441
Industrial applicability
The use of the cured film obtained by curing the photosensitive resin composition of the present invention is not particularly limited, and for example, the cured film is suitably used as a light shielding layer of an opaque electrode for a touch panel, a light shielding film of a black matrix of a color filter, a black column spacer of a liquid crystal display, a pixel dividing layer of an organic EL display device, a TFT planarizing layer, or the like.
Description of the reference numerals
1: transparent substrate
2: opaque wiring electrode
3: light shielding layer
4: insulating layer
5: positive photosensitive resin composition
6: pad part

Claims (14)

1. A positive photosensitive resin composition comprising an alkali-soluble resin (A) having a polymerizable group in a side chain, a photosensitive agent (B) and a colorant (C) having an aromatic group,
wherein the alkali-soluble resin (A) having a polymerizable group in a side chain has a repeating unit represented by the following general formula (2),
[ chemical formula 1]
Figure FDA0004103551190000011
In the general formula (2), R 2 R is R 3 Represents a hydrogen atom or a methyl group; r is R 2 R is R 3 The two may be the same or different.
2. The positive-type photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (a) having a polymerizable group in a side chain has a weight average molecular weight Mw of 1,000 to 15,000.
3. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin (a) having a polymerizable group in a side chain contains 5 to 50 mol% of the repeating unit represented by the general formula (2) in all the repeating units.
4. The positive-working photosensitive resin composition according to claim 1 or 2, wherein the content of the colorant (C) is 10 to 50% by mass in the solid content.
5. The positive-working photosensitive resin composition according to claim 1 or 2, wherein the colorant (C) is a black organic pigment containing carbon black.
6. A cured film obtained by curing the positive photosensitive resin composition according to any one of claims 1 to 5, wherein the reflectance of the cured film at a wavelength of 550nm is 0.01 to 20%.
7. A laminate comprising a conductive layer and the cured film according to claim 6.
8. The laminate according to claim 7, wherein a ratio of a film thickness of the cured film to a film thickness of the conductive layer is 1/2 to 5.
9. The laminate of claim 7 or 8, wherein the conductive layer comprises silver.
10. A substrate with a conductive pattern comprising a substrate, a conductive pattern formed on the substrate, and a cured film according to claim 6, wherein the substrate with a conductive pattern comprises the cured film on a conductive pattern forming region and does not comprise the cured film on a conductive pattern non-forming region.
11. The substrate with a conductive pattern according to claim 10, wherein the conductive pattern includes a connection portion on which the cured film is not provided.
12. A method for producing a laminate, comprising the steps of:
a step of forming an opaque wiring electrode on one surface of a transparent substrate;
a step of applying the positive photosensitive resin composition according to any one of claims 1 to 5 to an opaque wiring electrode-forming surface on the transparent substrate;
and a step of forming a light shielding layer at a portion corresponding to the opaque wiring electrode by exposing the transparent substrate from a side opposite to the opaque wiring electrode forming surface and developing the transparent substrate.
13. A touch panel comprising the cured film according to claim 6.
14. An organic EL display device comprising the cured film according to claim 6.
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Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5127245B2 (en) * 2007-01-29 2013-01-23 株式会社Ａｄｅｋａ Positive photosensitive resin composition
JP2009020246A (en) * 2007-07-11 2009-01-29 Toray Ind Inc Photosensitive resin composition, and manufacturing method for insulating resin pattern and organic electroluminescence element using it
JP5181968B2 (en) * 2007-09-28 2013-04-10 東レ株式会社 Positive photosensitive composition, method for producing cured film, cured film, and element having cured film
JP5233526B2 (en) * 2008-09-05 2013-07-10 東レ株式会社 Photosensitive composition, cured film formed therefrom, and device having cured film
JP5441542B2 (en) * 2009-07-22 2014-03-12 富士フイルム株式会社 Positive photosensitive resin composition, cured film, interlayer insulating film, organic EL display device, and liquid crystal display device
JP5821481B2 (en) * 2011-09-30 2015-11-24 東レ株式会社 Negative photosensitive resin composition and protective film and touch panel member using the same
JP2014048607A (en) * 2012-09-04 2014-03-17 Sumitomo Chemical Co Ltd Photosensitive resin composition
JP2014052401A (en) * 2012-09-05 2014-03-20 Sumitomo Chemical Co Ltd Photosensitive resin composition
JP2014091790A (en) * 2012-11-05 2014-05-19 Toyo Ink Sc Holdings Co Ltd Resin composition
JP6417669B2 (en) * 2013-03-05 2018-11-07 東レ株式会社 Photosensitive resin composition, protective film, insulating film, and method of manufacturing touch panel
JP2015193758A (en) * 2014-03-31 2015-11-05 東洋インキＳｃホールディングス株式会社 Photosensitive resin composition for overcoat and coating film using the same
WO2016047483A1 (en) * 2014-09-26 2016-03-31 東レ株式会社 Organic el display device
KR102399270B1 (en) * 2014-11-27 2022-05-19 도레이 카부시키가이샤 Resin and photosensitive resin composition
KR101609234B1 (en) * 2015-01-13 2016-04-05 동우 화인켐 주식회사 Photosensitive resin comopsition, photocurable pattern formed from the same and image display comprising the pattern
KR101611836B1 (en) * 2015-01-13 2016-04-12 동우 화인켐 주식회사 Photosensitive resin comopsition, photocurable pattern formed from the same and image display comprising the pattern
CN107407876A (en) * 2015-03-06 2017-11-28 东丽株式会社 Photosensitive polymer combination and electronic unit
KR102232969B1 (en) * 2015-04-01 2021-03-29 도레이 카부시키가이샤 Photosensitive colored resin composition
KR102540423B1 (en) * 2015-12-24 2023-06-05 미쯔비시 케미컬 주식회사 Photosensitive coloring composition, cured product, colored spacer, image display device
WO2017159543A1 (en) * 2016-03-15 2017-09-21 東レ株式会社 Photosensitive resin composition, cured film, laminate, touch panel member, and method for manufacturing cured film
KR101979980B1 (en) * 2016-03-23 2019-05-17 동우 화인켐 주식회사 Photosensitive Resin Composition
KR102367407B1 (en) * 2016-07-27 2022-02-25 도레이 카부시키가이샤 resin composition
KR102322396B1 (en) * 2016-08-25 2021-11-08 후지필름 가부시키가이샤 A curable composition and its manufacturing method, a cured film and its manufacturing method, a color filter, a solid-state image sensor, a solid-state image sensor, and an infrared sensor
WO2018066296A1 (en) * 2016-10-04 2018-04-12 富士フイルム株式会社 Dispersion composition, curable composition, cured film, color filter, solid-state imaging element, solid-state imaging device, infrared ray sensor, method for producing dispersion composition, method for producing curable composition, and method for producing cured film
CN110446974B (en) * 2017-03-29 2023-09-12 东丽株式会社 Photosensitive composition, cured film, and organic EL display device
JPWO2019059359A1 (en) 2017-09-25 2020-09-03 東レ株式会社 Colored resin composition, colored film, color filter and liquid crystal display device
CN111095103B (en) * 2017-09-28 2023-06-27 富士胶片株式会社 Photosensitive coloring composition, cured film, method for forming pattern, color filter, solid-state imaging element, and image display device
JP7012733B2 (en) * 2017-09-29 2022-01-28 富士フイルム株式会社 Photocurable compositions, laminates, and solid-state image sensors
JP6994044B2 (en) * 2017-10-06 2022-01-14 富士フイルム株式会社 Manufacturing method of cured film, manufacturing method of solid-state image sensor, manufacturing method of image display device
JP2019172975A (en) * 2018-03-26 2019-10-10 東レ株式会社 Resin composition, resin sheet and cured film
JP2019185034A (en) * 2018-03-30 2019-10-24 Jsr株式会社 Coloring composition, cured coloring film, color filter, display element, photosensitive element, and light-emitting element

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