KR20220158678A - Manufacturing method of resin composition, wiring board and conductive pattern - Google Patents

Abstract

(일반식(1) 중, X는 Si, Ti 또는 Zr 원자를 나타낸다. R¹∼R³은 각각 독립적으로 히드록시기, 메톡시기, 에톡시기, 프로폭시기, 이소프로폭시기, 부톡시기, 이소부톡시기 또는 탄소수 1∼6개의 탄화수소기를 나타낸다. R¹∼R³은 각각 동일해도 상이해도 좋지만, 적어도 하나는 히드록시기, 메톡시기, 에톡시기, 프로폭시기, 이소프로폭시기, 부톡시기 또는 이소부톡시기이다.)A resin composition capable of obtaining a pattern having both good dispersibility (that is, good conductivity in the case of a resin composition containing conductive particles) and adhesiveness even in a fine pattern is provided. Contains fine particles, a compound (B) having a structure represented by Formula (1) and a functional group that generates an amino group by heat, and a binder resin (C), wherein the fine particles contain an organic pigment (F) or carbon The resin composition which is an inorganic particle (G) which has a coating layer which says.

(In general formula (1), X represents Si, Ti or Zr atom. R ¹ to R ³ are each independently a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group. represents a group or a hydrocarbon group having 1 to 6 carbon atoms R ¹ to ^{R 3} may be the same or different, but at least one is a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group to be.)

Description

Manufacturing method of resin composition, wiring board and conductive pattern

The present invention relates to a method for manufacturing a resin composition, a wiring board, and a conductive pattern.

In recent years, various displays such as televisions, mobile devices, car navigation systems, and digital signage are becoming larger and higher in definition. Since the wiring length of electronic wiring becomes longer with an increase in size, there is a growing demand for improved wiring conductivity, that is, lower resistance, from the viewpoint of maintaining power consumption. Even for high-definition, if the electronic wiring is miniaturized, the cross-sectional area of the wiring is reduced, so it is necessary to increase the conductivity in order to equalize the wiring resistance.

As a method of forming a conductive pattern used for electronic wiring, a method in which a pattern is formed on a substrate using a resin composition containing conductive particles and a binder resin, and then heated to bring the conductive particles into contact with each other to obtain a conductive pattern is common. (Patent Document 1). As a method of forming a pattern on a board|substrate, a screen printing method, an inkjet method, or a photolithography method is mentioned, for example. Among them, it is said that the screen printing method and the inkjet method are not suitable for forming fine patterns, and the photolithography method is suitable for forming fine patterns.

Here, a technique is known in which the surface energy of the particles is reduced by using conductive fine particles having a sufficiently small particle diameter, and the fusion between the conductive particles is promoted to increase the conductivity of the electronic wiring. As a resin composition using conductive fine particles having a sufficiently small particle diameter, a resin composition using surface-coated silver fine particles (Patent Document 2) is exemplified. By using the surface-coated silver fine particles, the surface energy of the silver fine particles can be appropriately controlled.

On the other hand, high definition is similarly required for color patterns used for color filters and the like. The colored pattern is formed by the same method as the conductive pattern using a colored pigment-containing resin composition containing a pigment and a binder resin.

Japanese Unexamined Patent Publication No. 2000-199954 Japanese Unexamined Patent Publication No. 2013-196997

However, in a resin composition using surface-coated silver fine particles, when fusion on the surface of the silver fine particles is promoted by high-temperature heating or the like in order to increase conductivity, there is a problem that adhesion to the base material is reduced. On the other hand, although there is a method of adding an adhesion improving agent having an amino group in order to impart adhesion, there is a problem of deteriorating the dispersibility of fine silver particles in the resin composition and reducing conductivity. Therefore, coexistence of adhesiveness and an electrical conductivity improvement was difficult.

Moreover, also in the color pigment containing resin composition, when the adhesion improving agent which has an amino group is added, the dispersibility of a pigment deteriorates and the subject that storage stability is reduced occurred.

The present invention has been devised in view of such drawbacks of the prior art, and its object is to obtain a pattern excellent in dispersibility and adhesiveness, particularly in a resin composition containing conductive particles, in order to increase conductivity, fusion of the surface of fine silver particles It is an object of the present invention to provide a resin composition capable of maintaining adhesion to a substrate even when the By using such a resin composition, a pattern in which good dispersibility (that is, good conductivity in the case of a resin composition containing conductive particles) and adhesiveness are compatible can be obtained.

As a result of intensive studies, the inventors of the present invention have found that incorporating a compound (B) having a structure that enhances adhesion to a substrate and a functional group that generates an amino group by heat in the resin composition is very effective in solving the above problems.

That is, the present invention contains fine particles, a compound (B) having a structure represented by Formula (1) and a functional group that generates an amino group by heat, and a binder resin (C), wherein the fine particles contain an organic pigment (F) , or a resin composition that is an inorganic particle (G) having a coating layer containing carbon.

(In general formula (1), X represents Si, Ti or Zr atom. R ¹ to R ³ are each independently a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group. represents a group or a hydrocarbon group having 1 to 6 carbon atoms R ¹ to ^{R 3} may be the same or different, but at least one is a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group to be.)

According to the resin composition of the present invention, even in a fine pattern, it becomes possible to obtain a pattern in which good dispersibility (that is, good conductivity in a resin composition containing conductive particles) and adhesiveness are compatible.

The resin composition of the present invention contains microparticles, a compound (B) having a structure represented by Formula (1) and a functional group generating an amino group by heat, and a binder resin (C), wherein the microparticles contain an organic pigment (F ), or an inorganic particle (G) having a coating layer containing carbon.

[Organic pigment (F)]

The resin composition of the present invention preferably contains the organic pigment (F) as fine particles.

Examples of organic pigments include colored organic pigments, such as diketopyrrolopyrrole pigments; azo pigments such as azo, disazo, and polyazo; phthalocyanine-based pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine; anthraquinone-based pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, and violanthrone; quinacridone-based pigments; dioxazine-based pigments; perinone pigments; perylene-based pigments; thioindigo-based pigments; isoindoline-based pigments; isoindolinone-based pigments; quinophthalone pigments; Trene-based pigments; metal complex pigments; and the like.

As an organic pigment, a black organic pigment, a mixed color organic pigment, etc. are mentioned, for example. As a black organic pigment, carbon black, perylene black, aniline black, a benzofuranone pigment etc. are mentioned, for example. Examples of mixed color organic pigments include those obtained by mixing two or more kinds of pigments having colors such as red, blue, green, purple, yellow, magenta, and cyan to pseudo-black. You may contain 2 or more types of these organic pigments. Among these, carbon black is preferable from the viewpoint of further improving the light-shielding properties of the colored film and adjusting the conductivity of the colored film.

Moreover, in this invention, in order to make the effect more remarkable, it is preferable that the surface of the organic pigment (F) is acidified. While the dispersion stability is improved by acidifying the surface, it becomes possible to improve the substrate adhesion through interaction with the compound (B). Methods for acidifying the surface of carbon black include oxidizing the surface with O ₃ (Japanese Patent Laid-Open No. 11-181326), wet oxidation treatment of the surface (Japanese Patent No. 4464081), and sulfonic acid groups. A method of surface modification with an organic group composed of non-polymeric groups such as (International Publication No. 2006/044676) and the like are known.

In the resin composition of the present invention, the content of the organic pigment (F) is preferably 10 to 70% by mass relative to 100% by mass of the solid content. When the content ratio is 10% by mass or more, a film having coloring power can be formed as a thin film. The content ratio is preferably 20% by mass or more. On the other hand, when the content ratio is 70% by mass or less, while being able to improve the dispersion stability of the organic pigment (F), adhesion to the substrate can also be ensured. The content ratio is preferably 60% by mass or less. Here, the total solid content refers to all components except the solvent among the components contained in the resin composition.

[Inorganic Particles (G) Having a Coating Layer Containing Carbon]

The resin composition of the present invention preferably contains inorganic particles (G) having a coating layer containing carbon (hereinafter sometimes simply referred to as "inorganic particles (G)"). The inorganic particles (G) are, for example, particles surface-coated with a carbon compound or the like. Examples of the carbon compound include aromatic hydrocarbons and aliphatic hydrocarbons, or oxides, nitrides, sulfides, and phosphides thereof. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, or oxides thereof are preferable from the viewpoint of being able to suppress fusion between the inorganic particles (G) at low temperatures. By containing the inorganic particles (G), various functions such as conductivity and light-shielding properties can be imparted to the cured product of the resin composition of the present invention. In addition, since the surface of the inorganic particles (G) is covered with a coating layer containing carbon, fusion between the inorganic particles (G) at low temperatures is suppressed, and resolution reduction due to particle coarsening and generation of residues are prevented. can be suppressed In addition, adhesion can be improved by reacting with a functional group that generates an amino group by heat described later.

As inorganic particle (G), electroconductive particle (A) is mentioned. Examples of the conductive particles include gold (Au), silver (Ag), copper (Cu), nickel (Ni), tin (Sn), bismuth (Bi), lead (Pb), zinc (Zn), and palladium (Pd). ), platinum (Pt), aluminum (Al), tungsten (W) or molybdenum (Mo) and the like. Among them, metal fine particles containing at least one element selected from the group consisting of gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum and aluminum are preferable. From the viewpoint of improving conductivity, silver fine particles is more preferable.

As a method of coating the surface of the inorganic particles with a coating layer containing carbon, a method of bringing a reactive gas and inorganic particles into contact with, for example, a thermal plasma method (Japanese Patent Laid-Open No. 2007-138287) is exemplified. It is preferable that the surfaces of the inorganic particles (G) are completely covered, but as long as the present object is achieved, the presence of partially covered particles is acceptable.

The average thickness of the coating layer is preferably 0.1 to 10 nm. Within this range, fine pattern workability is improved by suppressing fusion between inorganic fine particles, and desired functions can be further improved by heat treatment at a temperature of 300°C or lower.

The average thickness of the coating layer is calculated by measuring the mass reduction of the inorganic particles (G) by thermobalance, assuming that the value is all due to carbon combustion, and calculating the average thickness of the coating layer from the particle diameter with the carbon density set to 2.0. can do. Conductive particles having a known particle diameter (Dp) are coated with carbon to an average thickness A (μm), and the number of carbon-coated conductive particles is set to n. If W ₁ (g) is the mass initially weighed in the thermobalance measurement, the mass after carbon is completely burned is W ₂ (g), and the density of the inorganic particles is ρ, if Dp and W ₂ are known from the following equation, n can be calculated.

W ₂ =π/6×Dp ₃ ρ×n

And the average thickness A of a coating layer is computable from the following formula.

W ₁ -W ₂ = {4/3×π(Dp/2+A) ³ -π/6×Dp ³ }×2.0×n

The conductive particles (A) that are the inorganic particles (G) may have an acidic or basic surface depending on the type of material for forming the coating layer containing carbon. The pH of a suspension obtained by suspending the conductive particles (A) in water at a concentration of 1% by mass is preferably 4.0 to 10.0. This pH is measured as follows. In 2.7 g of pure water, 0.3 g of conductive particles (A) is added, a suspension having a concentration of 1% by mass is prepared, stirred for 5 minutes after that, and left still for 15 minutes. The supernatant of the obtained suspension is collected and measured using a pH meter. When the pH is 4.0 or more, the carbon coating layer strongly interacts with the dispersant described later, so that even a small dispersant content can be stably dispersed. While suppressing reaction of electroconductive particle (A) and binder resin (C) because pH is 10.0 or less, the pH of a resin composition can be maintained in an appropriate range, and storage stability can be made favorable. In order to control the pH of the suspension of electroconductive particle (A), for example, when producing electroconductive particle (A) by a thermal plasma method, it can achieve by changing the kind of reactive gas or introduction ratio.

It is preferable that the average primary particle diameter of the microparticles is 1 to 700 nm. In particular, it is preferable that the average primary particle diameter of electroconductive particle (A) is 1-700 nm. When the average primary particle diameter is 1 nm or more, the specific surface area of the particles can be reduced, and even a small amount of the dispersant can be stably dispersed. In addition, a fine pattern can be formed when the average primary particle diameter is 700 nm or less. Here, the average primary particle diameter of fine particles is calculated from the average value of particle diameters of 100 primary particles randomly selected using a scanning electron microscope. The particle diameter of each primary particle is calculated from the average value obtained by measuring the major axis and minor axis of the primary particle.

In the resin composition of the present invention, it is preferable that the content ratio of the inorganic particles (G) is 65 to 95% by mass with respect to 100% by mass of the solid content. When the content ratio is 65% by mass or more, the residual organic component does not disturb the contact between the inorganic particles (G), and when the inorganic particles (G) are the conductive particles (A), the conductivity is further improved. The content ratio is preferably 75% by mass or more. On the other hand, when the content is 95% by mass or less, the residual organic component stabilizes the dispersibility of the inorganic particles (G) in the resin composition, a fine pattern can be formed, and residue on the substrate can be reduced. The content ratio is preferably 85% by mass or less. Here, the total solid content refers to all components except the solvent among the components contained in the resin composition.

The ratio of the inorganic particles (G) to the total solid content can be calculated by quantitatively analyzing all components of the resin composition. In addition, the ratio of each component mentioned later is also computable by the same method.

The analysis method of all the components of the resin composition is as follows.

(i) The resin composition is diluted with an organic solvent, ¹ H-NMR measurement, GC measurement and GC/MS measurement are conducted to examine the outline.

(ii) After extracting the resin composition with an organic solvent, centrifugation is performed to separate soluble components and insoluble components.

(iii) The insoluble component is extracted with a highly polar organic solvent and then centrifuged to further separate the soluble component and the insoluble component.

(iv) IR measurement, ¹ H-NMR measurement, and GC/MS measurement are performed on the liquid mixture of the soluble components obtained in (ii) and (iii) above. In addition, the mixed liquid is fractionated by GPC. IR measurement and ¹ H-NMR measurement are performed on the obtained aliquot. In addition, GC measurement, GC/MS measurement, pyrolysis GC/MS measurement, and MALDI/MS measurement are performed on the fractionated product as necessary.

(v) Conduct IR measurement or TOF-SIMS measurement on the insoluble component obtained in (iii) above. When the presence of organic matter is confirmed, pyrolysis GC/MS or TPD/MS measurement is performed.

(vi) By comprehensively judging the measurement results of (i), (iv) and (v), the content of each component contained in the resin composition can be obtained. In addition, as the highly polar organic solvent used in the above (iii), chloroform or methanol is preferable.

[Compound (B) having a structure represented by formula (1) and a functional group generating an amino group by heat]

The resin composition of the present invention contains a compound (B) having a structure represented by the following general formula (1) and a functional group generating an amino group by heat (hereinafter sometimes simply referred to as “compound (B)”).

In general formula (1), X represents a Si, Ti or Zr atom. R ¹ to ^{R 3} each independently represent a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, or a hydrocarbon group having 1 to 6 carbon atoms. R ¹ to ^{R 3} may be the same or different, but at least one is a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group.

Examples of the hydrocarbon group having 1 to 6 carbon atoms include aliphatic hydrocarbon groups. The aliphatic hydrocarbon group may be straight-chain or branched, and may be partially or wholly cyclic. Examples of the hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, or a cyclohexyl group. Among these, a methyl group, an ethyl group, or a propyl group is preferable from the viewpoint of having little steric hindrance and preventing adhesion to the substrate.

After forming a pattern, the compound (B) generates an amino group by, for example, heating in a temperature range of 100 to 300°C for 5 to 120 minutes. The formed amino group interacts with the surface of the organic pigment (F) or the inorganic particle (G), and the structure represented by the general formula (1) interacts with the substrate, thereby improving the adhesion between the pattern and the substrate. Adhesion can be evaluated by a cross-cut test based on JIS K5600-5-6 (1999). In addition, among R ¹ to ^{R 3} , a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group are desorbed by heating to form a silanol group, and the silanol groups undergo condensation polymerization with each other. A compound (E) having a structure represented by general formula (2) and an amino group is produced.

(In formula (2), Y represents a Si, Ti or Zr atom. R ⁴ to R ⁶ are each independently a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group. Represents a group, a hydrocarbon group having 1 to 6 carbon atoms, or a bridging oxygen. R ⁴ to R ⁶ may be the same or different, but at least one is a bridging oxygen.)

On the other hand, since there is no amino group in the compound (B) in the resin composition before heating, the compound (B) does not react with the surface of the organic pigment (F) or the inorganic particles (G) and can exist stably. Therefore, during storage of the resin composition, function inhibition due to change in viscosity or deterioration in the dispersibility of the organic pigment (F) or inorganic particles (G) is prevented, and in the coating film of the resin composition, the transmittance of the substrate due to the development residue is reduced. there is nothing that causes In addition, pattern workability can be improved. Here, heating for the purpose of generating an amino group and heating for the purpose of imparting a function to the resin composition pattern may be performed simultaneously.

As the central element X of General formula (1), it is preferable that it is Si from a reactive viewpoint. Moreover, as ^R1 - ^R3 of General formula (1), it is preferable that it is a methoxy group or an ethoxy group, and it is more preferable that it is a methoxy group from an adhesive viewpoint with a base material.

Examples of the functional group that generates an amino group by heat include an amide group, an imine group, a ureido group, and an isocyanate group. By using at least 1 sort(s) of these functional groups, stability of a resin composition and a coating film can be improved, and adhesiveness with the base material after heating can be further improved. Particularly preferred is a ureido group from the viewpoint of enhancing the dispersion stability of the organic pigment (F) or the inorganic particles (G) of the resin composition, further improving conductivity, and suppressing residues.

Compound (B) is specifically 3-trimethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) )Propylamine, 3-tripropoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3-trimethoxysilyl-N-(phenylmethylene)propylamine, 3-triethoxysilyl- N-(phenylmethylene)propylamine, 3-tripropoxysilyl-N-(phenylmethylene)propylamine, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-isocyanatepropyltri ethoxysilane and 3-isocyanatepropyltrimethoxysilane. Especially, as a compound which has a ureido group, 3-ureidopropyl triethoxysilane and 3-ureidopropyl trimethoxysilane are more preferable. Especially preferably, 3-ureidopropyltrimethoxysilane is mentioned.

In the resin composition of the present invention, the content of compound (B) is preferably 0.1 to 10 parts by mass per 100 parts by mass of the fine particles. In particular, it is preferable that it is 0.1-2.5 mass parts with respect to 100 mass parts of electroconductive particles (A). Adhesiveness can be improved more because content is 0.1 mass part or more. The content of compound (B) is more preferably 0.5 parts by mass or more. On the other hand, when the content is 2.5 parts by mass or less, conductivity can be further improved. The content of compound (B) is more preferably 1.0 parts by mass or less.

In the resin composition of the present invention, the content of the compound (B) is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the organic pigment (F). Adhesiveness can be improved more because content is 0.5 mass part or more. The content of compound (B) is more preferably 1.0 parts by mass or more. On the other hand, storage stability can be improved more because content is 10 mass parts or less. The content of compound (B) is more preferably 7.0 parts by mass or less.

[Binder Resin (C)]

The resin composition of the present invention contains a binder resin (C). The binder resin (C) is appropriately selected according to the viscosity of the resin composition and is not particularly limited. Examples of the binder resin (C) include cellulose resins such as ethyl cellulose and nitrocellulose, acetal resins such as polyvinyl butyral, and acrylic resins obtained by polymerizing butyl methacrylate and methyl methacrylate. Although preferably used, acrylic resins are particularly preferred from the viewpoint of ease of composition design. Here, the acrylic resin refers to a resin obtained by copolymerizing at least a (meth)acrylic monomer with a resin component. Here, examples of the (meth)acrylic monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and tert-butyl (meth)acrylate. rate, tert-butoxycarbonyl (meth)acrylate, benzyl (meth)acrylate, methyladamantyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, dicy Clopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, isobornyl (meth)acrylate or phenyl (meth)acrylate Acrylates are mentioned.

As the copolymerization component other than the (meth)acrylic monomer, a compound having a carbon-carbon double bond can be used. Examples of such compounds include aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, or p-hydroxylstyrene, (meth)acrylamide, and N-methylol. Amide type unsaturated compounds such as (meth)acrylamide or N-vinylpyrrolidone, (meth)acrylonitrile, allyl alcohol, vinyl acetate, cyclohexyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n -Butyl vinyl ether, i-butyl vinyl ether, 2-hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether.

The binder resin (C) preferably has an acid dissociable group. An acid dissociable group is an organic group that undergoes thermal oxidative decomposition and decomposition by the action of an acid under heating. By having such an acid dissociable group, for example, by heating at 100 to 300 ° C. in an acidic atmosphere, the acid dissociable group is easily thermally oxidatively decomposed and decomposed, the cured product of the resin composition of the present invention shrinks, and the fine particles in the cured product Ratio can be raised and function can be further improved. As a result, for example, when the fine particles are inorganic particles (G), it becomes easy to obtain desired conductivity with a specific resistance of 10 to 1,000 μΩ·cm. In this case, when a photoacid generator and/or a thermal acid generator described later are used in combination, the effect becomes more remarkable.

The acid dissociable group is preferably an organic group having 4 to 15 carbon atoms. When the number of carbon atoms of the acid dissociable group is 4 or more, the function is further improved without causing large bubbles to be generated in the cured product to prevent contact between fine particles due to vaporization at low temperature after desorption. The number of carbon atoms in the acid dissociable group is preferably 6 or more. On the other hand, when the number of carbon atoms of the acid dissociable group is 15 or less, the dissociable group does not remain in the cured product to prevent contact between fine particles after desorption, and the function is further improved. In addition, even if bubbles are generated in the cured product, it is easy to make them disappear by heating.

Examples of the acid dissociable group include a tert-butyl group, a tert-butoxycarbonyl group, a benzyl group, a methyladamantyl group, or a tetrahydropyranyl group.

The binder resin (C) is preferably a resin copolymerized with 20 to 80 mol% of a compound having an acid dissociable group. In particular, when the binder resin (C) is an acrylic resin, it is preferable to contain 20 to 80 mol% of (meth)acrylic acid ester having an acid dissociable group as a monomer component in the acrylic resin.

It is preferable to use the resin composition of the present invention as a photosensitive resin composition because fine wiring patterns can be formed. In order to set it as a photosensitive resin composition, it is preferable that it further has the photosensitive agent (D) mentioned later, and that binder resin (C) has an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, and an acid anhydride group, but a carboxyl group is particularly preferable from the viewpoints of reactivity and versatility.

It is preferable from the ease of composition design that the binder resin (C) is an acrylic resin having an alkali-soluble group. When the binder resin (C) is an acrylic resin having an alkali-soluble group, as a compound containing a carboxyl group which is a copolymerization component imparting alkali solubility, for example, (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid or fumaric acid or these acid anhydrides of

The carboxylic acid equivalent of the binder resin (C) is preferably 50 to 1,000 g/mol. The carboxylic acid equivalent of binder resin (C) is computable by measuring an acid value. In addition, the double bond equivalent of the binder resin (C) is preferably 150 to 10,000 g/mol because both the hardness and the crack resistance are compatible at a high level. The double bond equivalent of the binder resin (C) can be calculated by measuring the iodine value.

The weight average molecular weight (Mw) of the binder resin (C) is preferably 1,000 to 100,000 in terms of polystyrene measured by gel permeation chromatography (GPC). By setting the weight average molecular weight (Mw) within the above range, good coating properties are obtained, and the solubility to the developing solution at the time of pattern formation also becomes good.

When the resin composition of the present invention is used as a photosensitive resin composition, in order to increase the speed of the curing reaction by exposure of the photosensitive resin composition, the binder resin (C) has a (meta) carbon-carbon double bond at the side chain or molecular terminal. It is preferable to use an acrylic copolymer. As a functional group which has a carbon-carbon double bond, a vinyl group, an allyl group, or a (meth)acryl group is mentioned, for example. In order to add such a functional group to the (meth)acrylic copolymer, a compound or (meth)acrylic copolymer having a glycidyl group or isocyanate group and a carbon-carbon double bond for the mercapto group, amino group, hydroxyl group or carboxyl group in the (meth)acrylic copolymer There is a method of adding acrylic acid chloride or allyl chloride.

Examples of the compound having a glycidyl group and a carbon-carbon double bond include glycidyl (meth)acrylate, allyl glycidyl ether or glycidyl ethyl acrylate, crotyl glycidyl ether, and glycidyl chlorine. tonate or glycidyl isocrotonate. As a compound which has an isocyanate group and a carbon-carbon double bond, (meth)acryloyl isocyanate or (meth)acryloyloxyethyl isocyanate is mentioned, for example.

In the resin composition of the present invention, the content of the binder resin (C) is preferably in the range of 1 to 30% by mass based on 100% by mass of the solid content. By setting it as 1 mass % or more, it can adjust to the viscosity of the resin composition suitable for application|coating, and can further improve a function by setting it as 30 mass % or less.

[Photosensitizer (D)]

When using the resin composition of this invention as a photosensitive resin composition, it is preferable to contain a photosensitizer (D) from a viewpoint of forming a fine pattern. By containing the photosensitizer (D), positive or negative photosensitivity can be imparted to the resin composition.

As the photosensitizer (D), a photopolymerization initiator, a photoacid generator, and a photobase generator are preferably used. Examples of the photopolymerization initiator include acetophenone-based compounds, benzophenone-based compounds, benzoin ether-based compounds, α-aminoalkylphenone-based compounds, thioxanthone-based compounds, organic peroxides, imidazole-based compounds, titanocene-based compounds, and tria. A gin-based compound, an acylphosphine oxide compound, a quinone compound, or an oxime ester-based compound is exemplified, but an oxime ester-based compound having a high sensitivity even when added in a small amount is preferred, and an oxime ester-based compound having a carbazole skeleton is more preferred. .

Specific examples of the oxime ester compound having no carbazole skeleton include 1,2-propanedione-3-cyclopentane, 1-[4-(phenylthio)-2-(O-benzoyloxime)], and 1,2-octane. dione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], etc., and specific examples of the oxime ester-based compound having a carbazole skeleton include 3-cyclopentylethane, 1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazol-3-yl], 1-(0-acetyloxime), and the like.

In the resin composition of the present invention, the content of the photopolymerization initiator (D) is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the binder resin (C).

Although a quinonediazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, an iodonium salt etc. are mentioned as a photo-acid generator, A quinonediazide compound is more preferable. The quinonediazide compound includes those having a 5-naphthoquinonediazidesulfonyl group and those having a 4-naphthoquinonediazidesulfonyl group, both of which are preferably used. The quinonediazide sulfonic acid ester is obtained by combining sulfonic acid of quinonediazide with a polyhydroxy compound through an ester, sulfonic acid of quinonediazide with a sulfonamide bond to a polyamino compound, and quinonediazide with a polyhydroxypolyamino compound. Examples include those in which sulfonic acid is bonded to an ester bond and/or a sulfonamide bond. In the resin composition of the present invention, the content of the photoacid generator is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the binder resin (C).

Examples of photobase generators include amide compounds and ammonium salts.

As an amide compound, for example, 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate, 9-antrylmethyl-N,N-dimethylcarbamate, 1-(anthraquinone- 2nd) Ethylimidazole carboxylate, (E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine, etc. are mentioned.

Examples of the ammonium salt include 1,2-diisopropyl-3-(bisdimethylamino)methylene)guanidium 2-(3-benzoylphenyl)propionate, (Z)-{[bis(dimethylamino)methyl Leaden]amino}-N-cyclohexylamino)methanimininiumtetrakis(3-fluorophenyl)borate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltri A phenyl borate etc. are mentioned.

In the resin composition of the present invention, the content of the photobase generator is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the binder resin (C).

[Dispersant]

The resin composition of the present invention may contain a dispersant. By containing a dispersing agent, microparticles|fine-particles can exist stably in a resin composition.

As a dispersing agent, an amine type thing is preferable. Examples of commercially available amine-based dispersants include DISPERBYK (registered trademark) 142, 145, 161, 167, 180, 2001, 2008, 2022, 2150, 6919 or 21116 (all of which are manufactured by Big Chemie Japan). have.

Further, in order to improve dispersibility, the dispersant preferably has an acrylic block copolymer structure. Examples of commercially available amine-based dispersants having an acrylic block copolymer structure include DISPERBYK (registered trademark) 2001, 2008, 2022, 2150, 6919 or 21116.

In the resin composition of the present invention, the content of the dispersant is preferably 1 to 10 parts by mass relative to 100 parts by mass in total of the fine particles and other particles described later in the resin composition. By setting the content of the dispersant within this range, fine particles are well dispersed in the resin composition, and fine pattern processing is possible, and when the fine particles are conductive particles (A), contact and fusion of the conductive particles (A) proceed in the resin composition. and higher functions can be obtained.

[Acrylic monomer]

From the viewpoint of adjusting photosensitivity and improving pattern processability, the resin composition of the present invention may contain an acrylic monomer within a range that does not impede contact and fusion between conductive particles when the fine particles are conductive particles (A). none.

As an acrylic monomer, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ) acrylate or dipentaerythritol penta(meth)acrylate or alkyl modified products, alkyl ether modified products or alkyl ester modified products thereof.

The content of the acrylic monomer in the resin composition is preferably in the range of 10 to 200 parts by mass with respect to 100 parts by mass of the binder resin (C).

[solvent]

The resin composition of the present invention may contain a solvent. Examples of the solvent include propylene glycol monomethyl ether, propylene glycol monobutyl ether, diacetone alcohol, propylene glycol monoethyl ether acetate, ethyl acetoacetate, cyclopentanone, cyclohexanone, γ-butyrolactone, and ethylene glycol mono. Butyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol dimethyl ether, propylene glycol diacetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, dimethyl sulfoxide, methyl ethyl ketone, isobutyl acetate, butyl acetate, propyl acetate, isopropyl acetate or acetylacetone. have.

[Polymerization inhibitor]

The resin composition of the present invention may contain a polymerization inhibitor. The resolution after development improves by containing an appropriate amount of polymerization inhibitors. The polymerization inhibitor is not particularly limited, and known ones can be used. For example, di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, t -Butyl catechol can be mentioned. Moreover, "IRGANOX 1010" and "IRGANOX 245" (above, BASF make) etc. are mentioned as a commercially available polymerization inhibitor.

[UV absorbent]

The resin composition of the present invention may contain a UV absorber. By containing an ultraviolet absorber, the light resistance of the obtained cured product is improved, and the resolution after development is improved in applications requiring pattern processing. The ultraviolet absorber is not particularly limited and known ones can be used, but benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds are preferably used from the viewpoint of transparency and non-coloring properties.

[other particles]

The resin composition of the present invention may contain particles other than the organic pigment (F) and inorganic particles (G) in order to improve dispersibility or control conductivity. Examples of other particles include conductive particles not coated on the surface, metal oxide fine particles, and inorganic pigments.

As for the particle diameter of these other particle|grains, 1-100 nm is preferable. When the particle diameter is 1 nm or more, the use of a dispersant for dispersion stabilization can be reduced, and when the fine particles are conductive particles (A), the conductivity can be further improved. On the other hand, when the particle diameter is 100 nm or less, the resolution of the pattern is improved, and fine pattern formation can be performed.

[Thermal acid generator and photoacid generator]

The resin composition of the present invention may contain a thermal acid generator. When the binder resin (C) is a binder resin having an acid dissociable group, decomposition of the acid dissociable group is promoted by the generated acid, and the heat treatment temperature in air can be lowered. Moreover, you may contain a photo-acid generator. The photoacid generator is as described above.

As the thermal acid generator, which is a compound that generates an acid by heat, for example, SI-150L, SI-160L, SI-180L or SI-200 (above, all are manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyl Dimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium or 2-methylbenzyl-4-benzoyl and oxyphenylmethylsulfonium or methanesulfonic acid salts, trifluoromethanesulfonic acid salts, camphorsulfonic acid salts or p-toluenesulfonic acid salts thereof. Among them, 4-hydroxyphenyldimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium or 2 -Methylbenzyl-4-benzoyloxyphenylmethylsulfonium or methanesulfonic acid salts, trifluoromethanesulfonic acid salts, camphorsulfonic acid salts or p-toluenesulfonic acid salts thereof can be preferably used.

In the resin composition of the present invention, the content of the thermal acid generator promotes the decomposition of the acid dissociable group in the binder resin (C) containing the acid dissociable group, does not interfere with the contact between the inorganic particles (G), and achieves a higher function. For obtaining, it is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the binder resin (C).

[sensitizer]

When the resin composition of the present invention contains a photoacid generator, the resin composition may further contain a sensitizer. The sensitizer is preferably vaporized by heat treatment or faded by light irradiation even when remaining in the cured product of the resin composition of the present invention. it is more preferable

Examples of the sensitizer vaporized by heat treatment or discolored by light irradiation include coumarins such as 3,3'-carbonylbis(diethylaminocoumarin), anthraquinones such as 9,10-anthraquinone, and benzos. Aromatic ketones such as phenone, 4,4'-dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone or benzaldehyde, or biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene, Triphenylene, pyrene, anthracene, 9-phenylanthracene, 9-methoxyanthracene, 9,10-diphenylanthracene, 9,10-bis(4-methoxyphenyl)anthracene, 9,10-bis(triphenylsilyl) ) Anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene (DPA; manufactured by Kawasaki Chemical Co., Ltd.), 9,10-dibutoxyanthracene (DBA; Kawasaki Chemical Co., Ltd.), 9,10-dipentaoxy anthracene, 2-t-butyl-9,10-dibutoxy anthracene, or condensed aromatics such as 9,10-bis(trimethylsilylethynyl)anthracene.

As the sensitizer vaporized by heat treatment, those in which sublimation, evaporation, or thermal decomposition products due to thermal decomposition are sublimated or evaporated by heat treatment are preferable. The vaporization temperature of the sensitizer is preferably 150 to 300° C. because it does not vaporize at the drying temperature, but decomposes and vaporizes during thermal curing, and when the fine particles are conductive particles (A), the conductive particles contact and fuse.

In the resin composition of the present invention, the content of the sensitizer is 100 parts by mass of the binder resin (C) so that the sensitizing effect for photosensitizing the photoacid generator is sufficient and the contact between the fine particles is not disturbed and a higher function is obtained. 0.001 to 20 parts by mass is preferable, and 0.005 to 15 parts by mass is more preferable.

[Pigments and/or dyes having absorption in visible light]

The resin composition of the present invention may contain pigments and/or dyes capable of absorbing visible light, in the case where the fine particles are conductive particles (A), within a range that does not impede contact and fusion between the conductive particles. Reflection of visible light of the pattern after heating can be suppressed when the resin composition contains an inorganic pigment and/or dye having visible light absorption. It is also preferable that the said inorganic particle (G) is an inorganic pigment.

Examples of pigments that absorb visible light include lactam pigments, perylene pigments, phthalocyanine pigments, isoindoline pigments, diaminoanthraquinone pigments, dioxazine pigments, indanthrone pigments, carbon black, or inorganic pigments. can be heard

As a blue pigment, C.I. Pigment Blue (hereinafter referred to as "PB") 15, PB15:1, PB15:2, PB15:3, PB15:4, PB15:5, PB15:6, PB16 or PB60. As a purple pigment, C.I. Pigment violet (following, "PV") 19, PV23, or PV37 is mentioned. As a red pigment, C.I. Pigment Red (hereinafter referred to as "PR") 149, PR166, PR177, PR179, PR209 or PR254. As a green pigment, C.I. Pigment Green (hereinafter referred to as “PG”) 7, PG36 or PG58. As a yellow pigment, C.I. Pigment Yellow (henceforth "PY") 150, PY138, PY139 or PY185 is mentioned. As the black pigment, for example, furnace black such as HCF, MCF, LFF, RCF, SAF, ISAF, HAF, XCF, FEF, GPF or SRF, thermal black such as FT or MT, carbon such as channel black or acetylene black Black or lactam-based pigments (for example, "Irgaphor" (registered trademark) BLACK S0100CF; manufactured by BASF). Among them, carbon black excellent in heat resistance, light resistance and visible light absorption is preferred, and furnace black or lactam-based pigments are more preferred from the viewpoint of dispersibility.

In the resin composition of the present invention, the content of the pigment capable of absorbing visible light is preferably 0.1 to 10% by mass with respect to the total solid content in the composition.

Examples of dyes that absorb visible light include ferrocene-based dyes, fluorenone-based dyes, perylene-based dyes, triphenylmethane-based dyes, coumarin-based dyes, diphenylamine-based dyes, quinacridone-based dyes, and quinophthalone-based dyes. , phthalocyanine-based dyes or xanthene-based dyes, but black dyes with excellent heat resistance, light resistance and visible light absorption are preferred, VALIFAST (registered trademark) Black 1888, VALIFAST (registered trademark) Black 3830, NUBIAN (registered trademark) Black PA-2802 or OIL Black 860 are preferred.

In the resin composition of the present invention, the content of the dye capable of absorbing visible light is preferably 0.1 to 10% by mass with respect to the total solid content in the composition.

[adhesion improver]

The resin composition of the present invention may further contain an adhesion improving agent in addition to the compound (B). As an adhesion improving agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryl Silane coupling agents, such as oxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, or 3-acryloxypropyl triethoxysilane, are mentioned.

[Surfactants]

The resin composition of the present invention may further contain a surfactant as needed.

As the surfactant, for example, an anionic surfactant such as ammonium lauryl sulfate or polyoxyethylene alkyl ether sulfate triethanolamine, a cationic surfactant such as stearylamine acetate or lauryltrimethylammonium chloride, lauryldimethylamine oxide or lauryl Amphoteric surfactants such as carboxymethylhydroxyethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or sorbitan monostearate, fluorine-based surfactants or silicone-based surfactants can be heard

In the resin composition of the present invention, the content of the surfactant is preferably 0.001 to 10% by mass with respect to the entire composition in order to improve the coating property and the uniformity of the surface of the coating film. When the content of the surfactant is 0.001% by mass or more, applicability and the uniformity of the coating film surface are improved. As for content of surfactant, 0.01 mass % or more is more preferable. On the other hand, when the content of the surfactant is 10% by mass or less, coating film defects such as cissing and sinking and aggregation of particles can be suppressed.

The wiring board of the present invention preferably has a conductive pattern made of a cured product of the resin composition of the present invention containing conductive particles (A). The substrate of the wiring board of the present invention is preferably a transparent substrate. A glass substrate and a resin film are mentioned as a transparent substrate. It is preferable that the transparent substrate is a glass substrate from the viewpoint of easy permeation of the developing solution during pattern formation and suppression of residues. Examples of the glass substrate include a glass substrate having a SiO ₂ layer or a SiO ₂ layer on the surface, an alkali-free glass substrate, and the like. As a resin film, the film etc. which consist of at least 1 sort(s) selected from the group which consists of polyimide, polyimide siloxane, polyether sulfone, polybenzoxazole, aramid, polysulfone, and an epoxy resin are mentioned. A SiO ₂ layer may be included on the surface of the resin film. By using these as a substrate, a wiring board having high adhesion to a conductive pattern made of a cured product of the resin composition of the present invention can be obtained.

Further, the wiring board of the present invention may have a film containing an organic component in addition to the conductive pattern made of a cured product of the resin composition of the present invention. From the viewpoint of protecting the conductive pattern, it is preferable to form a film containing an organic component on top of the conductive pattern. By having a film containing an organic component, damage caused by an external force or the like can be prevented, and a highly reliable wiring board can be obtained.

Moreover, the wiring board of this invention can be used suitably as a member for touch panels. When using as a member for touch panels, it can use for the routing wiring which connects the touch sensor wiring and touch sensor wiring arrange|positioned in mesh shape. It is also preferable to simultaneously form the touch sensor wiring and the routing wiring. The substrate of the wiring board of the present invention may be used as a cover glass, or a cover material may be bonded onto the wiring board of the present invention through OCA.

In the wiring board of the present invention, it is preferable that the conductive pattern has a width of 1 to 6 μm. When the width of the conductive pattern is 1 μm or more, it is difficult to be affected by defects caused by foreign matter or the like, and a conductive pattern having a desired shape can be formed. On the other hand, when the width of the conductive pattern is 6 μm or less, the wiring becomes difficult to be visually recognized. As for the width|variety of a conductive pattern, 4 micrometers or less are more preferable.

It is preferable that the wiring board of this invention further has a black layer. By having a black layer, while being able to reduce the reflectance of a wiring pattern and being able to suppress reflection of external light, visibility of wiring can be suppressed and visibility can be improved significantly. As a method of forming the black layer, after forming the wiring pattern, a black positive photosensitive composition is applied to the entire surface, and exposed from the surface of the substrate through the wiring pattern, leaving the upper part of the wiring pattern to be soluble in the developing solution and removing it by development. can be heard

[Method for producing resin composition]

The resin composition of the present invention is prepared by mixing fine particles, compound (B), and binder resin (C), and then using a ball mill, sand grinder, three roll mill, mild disperser, medialess disperser, or other disperser. When it is desired to uniformly disperse the fine particles, prepare a dispersion in which the fine particles are dispersed in an organic solvent in advance using a dispersant, and mix this dispersion with a solution containing a monomer, polymer, adhesion improver, surfactant, polymerization inhibitor, etc. You may manufacture by the method of doing. In particular, the dispersion of inorganic particles (G) having a coating layer containing carbon is preferably dispersed using a mild disperser or a medialess disperser in order to prevent damage to the surface coating layer. it is more preferable The dispersion of inorganic particles (G) having a coating layer containing carbon is, for example, a mild disperser NANO GETTER (registered trademark) (Ashizawa Finetech Co., Ltd.) or a high-pressure wet medialess atomization device NANOMIZER (Nanomizer Co., Ltd.) )), etc., to disperse the inorganic particles (G) having a coating layer containing carbon in an organic solvent.

[Method of producing conductive and colored patterns]

The method for producing a conductive pattern of the present invention includes a coating step of applying the resin composition of the present invention to a desired pattern shape on a substrate to obtain a coated film, a drying step of drying the coated film to obtain a dried film, and heating the dried film. A heating process for obtaining a conductive film is provided.

The method for producing a conductive pattern of the present invention includes a coating step of obtaining a coated film by applying the resin composition of the present invention onto a substrate in a desired pattern shape.

As a base material used in the application step, a silicon wafer, a ceramic substrate, or an organic substrate is exemplified. Examples of ceramic substrates include soda glass, soda glass obtained by sputtering SiO ₂ on the surface, alkali-free glass, glass substrates such as borosilicate glass or quartz glass, alumina substrates, aluminum nitride substrates, or silicon carbide substrates. Examples of the organic substrate include an epoxy substrate, a polyetherimide resin substrate, a polyether ketone resin substrate, a polysulfone resin substrate, a polyimide film, and a polyester film.

As a method of applying the resin composition of the present invention onto a substrate surface, for example, application using a spin coater, bar coater, blade coater, roll coater, die coater, calender coater or meniscus coater, screen printing, spray application, or A deep coat may be used.

The manufacturing method of the conductive pattern of the present invention includes a drying step of obtaining a dried film by drying the coated film.

As a drying method in a drying process, drying by a hot plate, a hot air dryer (oven), reduced-pressure drying, vacuum drying, or infrared irradiation is mentioned, for example.

The temperature and time of drying may be appropriately determined depending on the composition of the resin composition and the film thickness of the coated film to be dried, but it is preferable to heat in a temperature range of 50 to 150°C for 10 seconds to 30 minutes.

Among them, it is preferable to use a combination of heating on a hot plate or a hot air dryer (oven) and drying under reduced pressure because the solvent can be dried and removed while suppressing thermal curing of the resin contained in the coating film. The ultimate pressure for drying under reduced pressure is preferably 5 to 200 Pa, and more preferably 10 to 100 Pa.

The method for producing a conductive pattern of the present invention includes a heating step of obtaining a conductive film by heating a dried film.

By heating the dry film of the resin composition, conductivity is obtained, and compound (B) has an amino group and interacts with the coating layer of the inorganic particles (G) having a coating layer containing carbon, so that adhesion to the substrate is improved.

As a heating method in a heating process, the thing similar to a drying process is mentioned. The atmosphere, temperature and time of heating may be appropriately determined depending on the composition of the resin composition and the film thickness of the coating film to be heated, but it is preferable to heat in the air at a temperature in the range of 100 to 300 ° C. for 5 to 120 minutes. 150-270 degreeC is more preferable, It is heating for 30-120 minutes in the temperature range of 160-260 degreeC more preferably.

Further, between the drying step and the heating step described above, an exposure step of exposing the dried film to obtain an exposed film and a developing process of developing the exposed film to form a pattern, and forming a conductive pattern by a photolithography method is also provided. desirable. In this case, since the compound (B) does not have an amino group and does not react with the inorganic particles (G) in the exposure step, it is possible to form a good pattern with good developer solubility and no development residue in the subsequent development step. After forming the pattern, amino groups are expressed in the heating step to improve adhesion to the substrate.

As a light source used in the exposure process, for example, j-line, i-line, h-line, or g-line of a mercury lamp is preferable.

Examples of the alkaline substance used for the alkaline developer in the development step include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, or ammonia water; 1 such as ethylamine or n-propylamine; Primary amines, secondary amines such as diethylamine or di-n-propylamine, tertiary amines such as triethylamine or methyldiethylamine, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH) , quaternary ammonium salts such as choline, triethanolamine, diethanolamine, monoethanolamine, alcohol amines such as dimethylaminoethanol or diethylaminoethanol, or pyrrole, piperidine, 1,8-diazabicyclo [5,4, organic alkalis such as cyclic amines such as 0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane or morpholine; A water-soluble organic solvent such as rolactone, dimethylformamide or N-methyl-2-pyrrolidone may be appropriately added.

Further, in order to obtain a better conductive pattern, it is also preferable to further add 0.01 to 1% by mass of a surfactant such as a nonionic surfactant to these alkaline developing solutions.

When the conductive pattern is formed in a mesh shape on the substrate, it can be used as a transparent conductive wire included in a touch panel, a display panel such as liquid crystal or organic EL, or a wearable terminal.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Among the compounds used in the Synthesis Examples and Examples, those using abbreviations are shown below.

AIBN: 2,2'-azobis (isobutyronitrile)

TMAH: tetramethylammonium hydroxide.

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

[Organic pigment (F)]

(F-1) Carbon black whose surface was modified with a sulfonic acid group (TPK1227 manufactured by Cabot).

(F-2) Carbon black not subjected to special surface treatment (MA-100 manufactured by Mitsubishi Chemical)

[Inorganic Particles (G) Having a Coating Layer Containing Carbon]

(A-1) The average thickness of the said coating layer is 3 nm, and the silver particle whose primary particle diameter is 50 nm (made by Nisshin Engineering Co., Ltd.). The pH of the water suspension at a concentration of 1% by mass is 8.0.

(A-2) The average thickness of the said coating layer is 3 nm, and the silver particle whose primary particle diameter is 40 nm (made by Nisshin Engineering Co., Ltd.). The pH of the water suspension at a concentration of 1% by mass is 4.5.

(A-3) Silver particles having a primary particle diameter of 200 nm (product name: DJA03N; manufactured by Toyoko Chemical Industry Co., Ltd.). The pH of the water suspension at a concentration of 1% by mass is 5.0. No coating layer containing carbon.

[Compound (B) having a structure represented by formula (1) and a functional group generating an amino group by heat]

(B-1) KBM-585: 3-ureidopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

(B-2) KBE-585: 3-ureidopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

(B-3) KBE-9007: 3-isocyanate propyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

(B'-4) KBE-903: 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.).

[Binder Resin (C)]

(C-1)

2.0 g of AIBN and 50 g of PGMEA were added to a 500 ml flask. Thereafter, 38.7 g of methacrylic acid, 79.3 g of benzyl methacrylate, and 22.0 g of tricyclo[5.2.1.0(2,6)]decan-8-ylmethacrylate were added, stirred at room temperature for a while, and the flask After sufficiently nitrogen-substituting the inside by bubbling, it heat-stirred at 70 degreeC for 5 hours. Subsequently, 21.3 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90°C for 4 hours, and solid content in the obtained acrylic polymer solution. A solution of binder resin (C-1) was obtained by adding PGMEA to a concentration of 40 wt%. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 18,000.

(C-2)

1.5 g of AIBN and 50 g of PGMEA were added to a 500 ml flask. After that, 38.7 g of methacrylic acid, 46.9 g of styrene, and 22.0 g of tricyclo[5.2.1.0(2,6)]decan-8-ylmethacrylate were added, stirred at room temperature for a while, and the inside of the flask was bubbled. After sufficiently nitrogen-substituting with a ring, it heat-stirred at 70 degreeC for 5 hours. Then, 21.3 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90°C for 4 hours, and solid content in the obtained acrylic polymer solution. A solution of binder resin (C-2) was obtained by adding PGMEA to a concentration of 40 wt%. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 14,000.

[Dispersant]

DISPERBYK (registered trademark) 21116 (manufactured by Big Chemie Japan Co., Ltd.).

[solvent]

PGMEA: propylene glycol monomethyl ether acetate (manufactured by Sankyo Chemical Co., Ltd.)

DPM: Dipropylene glycol monomethyl ether (manufactured by Toho Chemical Industry Co., Ltd.).

[Photoinitiator]

NCI-831E (registered trademark) (oxime ester compound; manufactured by ADEKA Co., Ltd.).

[Acrylic monomer]

LIGHT ACRYLATE (registered trademark) PE-3A (manufactured by Kyoei Sha Chemical Co., Ltd.).

Dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.).

[Positive Photoresist]

(P-1)

Under a dry nitrogen stream, 29.3 g (0.08 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF; manufactured by Central Glass Co., Ltd.), 1,3-bis(3- 1.24 g (0.005 mol) of aminopropyl)tetramethyl disiloxane and 3.27 g (0.03 mol) of 3-aminophenol as a terminal blocker were dissolved in 150 g of N-methyl-2-pyrrolidone (NMP). To this, 31.0 g (0.1 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA; manufactured by Manac Co., Ltd.) was added together with 50 g of NMP, followed by stirring at 20°C for 1 hour. , and then stirred at 50°C for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150°C for 5 hours while azeotroping water with xylene. After completion of stirring, the solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80°C for 24 hours to obtain a polyimide resin.

Further, 15.3 g of TrisP-HAP (manufactured by Honshu Kagaku Kogyo Co., Ltd.) and 40.3 g of 5-naphthoquinonediazidesulfonylic acid chloride were dissolved in 450 g of 1,4-dioxane under a separate dry nitrogen stream, and brought to room temperature. did. 15.2 g of triethylamine mixed with 50 g of 1,4-dioxane was dropped here so that the inside of the system would not be 35°C or higher. After dripping, it stirred at 30 degreeC for 2 hours. The triethylamine salt was filtered off, and the filtrate was poured into water. Thereafter, the precipitated precipitate was dried in a vacuum dryer to obtain a quinonediazide compound.

11.0 g of obtained polyimide resins, 4.0 g of quinonediazide compounds, and 63.75 g of ethyl lactate and 21.25 g of PGMEA were added to a 100 ml PP bottle and stirred. Subsequently, filtration was performed with a 0.2 μm filter to obtain a positive photoresist (P-1).

[Board]

(S-1) Glass substrate on which SiO ₂ is sputtered (TU060; manufactured by TOKEN)

(S-2) Alkali-free glass substrate (OA-10G; manufactured by Nippon Denki Glass Co., Ltd.)

(S-3) A polyimide film (NEOPULIM; manufactured by Mitsubishi Gas Chemical Co., Ltd.).

Examples 1 to 14, Comparative Examples 1 to 3

<Evaluation of conductivity>

Regarding resin composition 1, (S-1) spin coat on a substrate using a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.) at 300 rpm for 10 seconds and at 500 rpm for 1 second under conditions of spin coating, It prebaked at 100 degreeC for 5 minutes using the hot plate ("SCW-636 (brand name)" by Dainippon Screen Seijo Co., Ltd.), and obtained the prebaked film of 1 micrometer thickness. Thereafter, a solid film made of the resin composition 1 was obtained by post-baking at 230°C for 30 minutes (in the air) using an oven ("IHPS-222"; manufactured by Espec Co., Ltd.). On the obtained solid film, positive type photoresist (P-1) was spin-coated using a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.) at 300 rpm for 10 seconds and at 1000 rpm for 5 seconds under the conditions, The substrate was prebaked at 100°C for 2 minutes using a hot plate ("SCW-636 (trade name)" manufactured by Dainippon Screen Seijo Co., Ltd.) to obtain a prebaked film having a film thickness of 1 µm. The prebaked film was exposed through a desired mask using a parallel light mask aligner ("PLA-501F (trade name)" manufactured by Canon Co., Ltd.) using an ultra-high pressure mercury lamp as a light source. Thereafter, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 2.38 wt% TMAH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds to perform pattern processing. The resulting substrate was etched by being immersed in a 55% concentration ferric nitrate aqueous solution, followed by exposing and developing to remove the resist. Then, the volume resistivity evaluation pattern was obtained by post-baking at 230 degreeC for 30 minutes (in the air) using an oven ("IHPS-222"; manufactured by Espec Co., Ltd.).

Regarding the resin compositions 2 to 17, each substrate (S-1) to (S-3) was coated with a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.) at 300 rpm for 10 seconds and 500 rpm for 1 second. Spin coating was performed under the conditions of a candle, and the substrate was prebaked at 100°C for 5 minutes using a hot plate ("SCW-636 (trade name)" manufactured by Dainippon Screen Seijo Co., Ltd.) to obtain a prebaked film having a film thickness of 1 µm. . The prebaked film was exposed to light through a desired mask using a parallel light mask aligner ("PLA-501F (trade name)" manufactured by Canon Co., Ltd.) using an ultra-high pressure mercury lamp as a light source. Thereafter, using an automatic developing device ("AD-1200 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 0.07 wt% TMAH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds to perform pattern processing. Then, the volume resistivity evaluation pattern was obtained by post-baking at 230 degreeC for 30 minutes (in the air) using an oven ("IHPS-222"; manufactured by Espec Co., Ltd.).

For the obtained volume resistivity evaluation pattern, the surface resistance value ρs (Ω/□) measured with a surface resistance meter (Loresta (registered trademark) -FP; manufactured by Mitsubishi Yuka Co., Ltd.) and a surface roughness shape meter (SURFCOM (registered trademark) 1400D) ; manufactured by Tokyo Seimitsu Co., Ltd.), and the volume resistivity (μΩ·cm) was calculated by measuring the film thickness t (cm) and multiplying both values.

<Evaluation of Adhesion>

Regarding resin composition 1, spin coating was performed on (S-1) using a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.) at 300 rpm for 10 seconds and at 500 rpm for 1 second, and the substrate was hot It prebaked at 100 degreeC for 5 minutes using the plate ("SCW-636 (brand name)" by Dainippon Screen Seijo Co., Ltd.), and obtained the prebaked film of 1 micrometer thickness. Thereafter, a solid film made of the resin composition 1 was obtained by post-baking at 230°C for 30 minutes (in the air) using an oven ("IHPS-222"; manufactured by Espec Co., Ltd.).

Regarding the resin compositions 2 to 17, a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.) was separately applied to each substrate (S-1) to (S-3) at 300 rpm for 10 seconds and at 500 rpm for 10 seconds. Spin coating was performed under the condition of 1 second, and the substrate was prebaked at 100°C for 5 minutes using a hot plate ("SCW-636 (trade name)" manufactured by Dainippon Screen Seijo Co., Ltd.) to obtain a prebaked film having a thickness of 1 µm. Got it. The prebaked film was exposed to light without going through a mask using a parallel light mask aligner ("PLA-501F (trade name)" manufactured by Canon Co., Ltd.) using an ultra-high pressure mercury lamp as a light source. Thereafter, using an automatic developing device ("AD-1200 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 0.07 wt% TMAH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds. Thereafter, a solid film composed of each of the resin compositions 2 to 17 was obtained by post-baking at 230° C. for 30 minutes (in the air) using an oven ("IHPS-222"; manufactured by Espec Co., Ltd.).

Adhesion to the substrate was evaluated for the obtained solid film. Specifically, in accordance with JIS K5600-5-6 (1999), a cross-cut test was conducted by six-step evaluation of 5B to 0B (the higher the number, the higher the adhesion). Moreover, since adhesiveness may cause operation defect of the touch panel by peeling of hardened|cured material, etc. if adhesiveness is 2B or less, it is preferable that adhesiveness is 3B or more, and it is more preferable that it is 4B or more.

<Evaluation of patternability>

Resin compositions 2 to 17 were applied on each substrate (S-1) to (S-3) at 300 rpm for 10 seconds and 500 rpm for 10 seconds using a spin coater ("1H-360S (trade name)" manufactured by Mikasa Co., Ltd.) Spin coating was performed under the conditions of a candle, and the substrate was prebaked at 100°C for 5 minutes using a hot plate ("SCW-636 (trade name)" manufactured by Dainippon Screen Seijo Co., Ltd.) to obtain a prebaked film having a film thickness of 1 µm. . The prebaked film was exposed to light through a desired mask using a parallel light mask aligner ("PLA-501F (trade name)" manufactured by Canon Co., Ltd.) using an ultra-high pressure mercury lamp as a light source. Thereafter, using an automatic developing device ("AD-1200 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 0.07 wt% TMAH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds to perform pattern processing. After exposure and development, the minimum pattern size after development was measured at an exposure amount to form a 5 μm line-and-space pattern with a width of 1:1, and it was determined as the resolution. The exposure amount was measured with an I-line illuminometer.

<Evaluation of residue on substrate>

The residue on the board|substrate was evaluated by the transmittance|permeability evaluation about the unexposed part of the board|substrate on which the volume resistivity evaluation pattern by the said resin compositions 2-17 was formed. Specifically, the transmittance at 400 nm of the unexposed portion before and after film formation was measured using a spectrophotometer (U-3410; manufactured by Hitachi Seisakusho Co., Ltd.). Then, when the transmittance before film formation was T ₀ and the transmittance after film formation was T, the change in transmittance represented by the formula (T ₀ -T)/T ₀ × 100 was calculated. When the transmittance change was 1.0% or less, it was judged that the effect of suppressing residue was sufficient.

(Example 1)

80.00 g of conductive particles having a coating layer containing carbon (A-1), 2.00 g of DISPERBYK 21116, 100.00 g of PGMEA, and 100.00 g of DPM were subjected to a mixing treatment at 1200 rpm for 30 minutes with a homogenizer, followed by a high-pressure wet process. It dispersed using the medialess atomization apparatus NANOMIZER (Nanomizer Co., Ltd.), and the silver particle dispersion was obtained. 0.50 g of a compound (B-1) having a structure represented by the general formula (1) and a functional group generating an amino group by heat with respect to 282.00 g of this silver fine particle dispersion, a binder resin (C-1) having a solid content concentration of 40% by mass The resin composition 1 was obtained by adding and stirring 73.75 g of PGMEA and 100.00 g of DPM to what mixed 43.75 g of .

Table 1 shows the results of conductivity and adhesion evaluation.

(Example 2)

First, 80.00 g of conductive particles having a coating layer containing carbon (A-1), 2.00 g of DISPERBYK 21116, 100.00 g of PGMEA, and 100.00 g of DPM were mixed with a homogenizer at 1200 rpm for 30 minutes, and further It dispersed using the high-pressure wet-media-less atomization apparatus NANOMIZER (Nanomizer Co., Ltd.), and the silver particle dispersion was obtained. 0.50 g of a compound (B-1) having a structure represented by the general formula (1) and a functional group generating an amino group by heat relative to 282.00 g of this silver fine particle dispersion, a binder resin (C-1) having a solid content concentration of 40% by mass The resin composition 2 was obtained by adding 85.00 g of PGMEA and 100.00 g of DPM to a mixture of 25.00 g and (D) 1.50 g of NCI-831E as a photosensitizer and 6.00 g of PE-3A, followed by stirring.

Table 1 shows the results of evaluation of patternability, conductivity, residue on substrate and adhesion.

(Examples 3 to 14 and Comparative Examples 1 to 3)

Photosensitive resin compositions 3 to 17 having the composition shown in Tables 1 and 2 were obtained in the same manner as in Example 2, and the same evaluation as in Example 2 was performed on the substrates shown in Tables 1 and 2 for each photosensitive resin composition. An evaluation result is shown in Tables 1-2.

(Examples 15 to 19, Comparative Examples 4 to 5)

(Colored resin composition 1)

300 g of carbon black whose surface is modified by sulfonic acid groups (TPK1227 manufactured by Cabot), 150 g of a 40% by weight solution of propylene glycol monomethyl ether acetate (PGMEA) of acrylic polymer (C-1), tertiary amino groups and quaternary ammonium salts as polymer dispersants 37.5 g of "DISPERBYK" (registered trademark) LPN-21116 and 1012.5 g of PGMEA were put into a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion. The obtained preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 0.05 mmφ zirconia beads at 75% by volume, and dispersion was performed at a rotational speed of 8 m/s for 3 hours to obtain a solid content concentration A colorant dispersion Bk-1 of 25% by weight and colorant/resin (weight ratio) = 80/20 was obtained.

A 40% by weight solution (344.5 g) of propylene glycol monomethyl ether acetate of acrylic polymer (C-1) in carbon black dispersion Bk-1 (822.6 g), KBM-585 manufactured by Shin-Etsu Chemical Co., Ltd. (7.5 g) as an adhesion improving agent ), a solution obtained by dissolving a 10% by weight solution (4.0 g) of propylene glycol monomethyl ether acetate of a silicone-based surfactant in propylene glycol monomethyl ether acetate (218.5 g) was added to obtain a colored resin composition 1.

(Colored resin composition 2)

300 g of carbon black whose surface is modified by a sulfonic acid group (TPK1227 manufactured by Cabot), 150 g of a 40% by weight solution of propylene glycol monomethyl ether acetate (PGMEA) of an acrylic polymer (C-1), a tertiary amino group and a quaternary ammonium salt as a polymer dispersant 37.5 g of "DISPERBYK" (registered trademark) LPN-21116 and 1012.5 g of PGMEA were put into a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion. The obtained preliminary dispersion was supplied to a dispersing machine Ultra Apex Mill manufactured by Kotobuki Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of 0.05 mmφ zirconia beads, and dispersion was performed at a rotational speed of 8 m/s for 3 hours to obtain a solid content concentration A colorant dispersion Bk-1 of 25% by weight and colorant/resin (weight ratio) = 80/20 was obtained.

A 40% by weight solution (117.3 g) of propylene glycol monomethyl ether acetate of acrylic polymer (C-1) in carbon black dispersion Bk-1 (822.6 g), dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.) as a polyfunctional monomer ) DPHA) propylene glycol monomethyl ether acetate 50% by weight solution (92.7 g), ADEKA Co., Ltd. "ADEKA ARKLS" NCI-831 (11.6 g) as a photopolymerization initiator, Shin-Etsu Chemical Co., Ltd. KBM as an adhesive improver -585 (7.5g), a solution obtained by dissolving a 10% by weight solution of propylene glycol monomethyl ether acetate (4.0 g) of a silicone surfactant in propylene glycol monomethyl ether acetate (218.5 g) was added to obtain a colored resin composition 2.

(Colored resin compositions 3 to 7)

Colored resin composition 3-7 of the composition of Table 3 was obtained in the same way as in colored resin composition 2.

<Storage stability evaluation>

For the above colored resin compositions 1 to 7, the viscosity immediately after preparation of the colored resin composition and the viscosity after leaving the colored resin composition at room temperature (30 ° C.) for 1 week were measured at a temperature of 25.0 ± 0.2 ° C. with a viscometer (RE105L manufactured by Toki Sangyo). It was set, measured at a rotational speed of 50 rpm, and the viscosity change rate was calculated. The thing with a viscosity change rate of 15% or more was judged to be unsatisfactory in storage stability.

<Evaluation of Adhesion>

The colored resin composition 1 was spin-coated on (S-2) using a spin coater (manufactured by Mikasa Co., Ltd. "1H-DS (trade name)"), and the substrate was placed on a hot plate (manufactured by Dainippon Screen Seijo Co., Ltd.). It prebaked at 100 degreeC for 10 minutes using "SCW-636 (brand name)", and obtained the prebaked film. Thereafter, a solid film made of the colored resin composition 1 having a thickness of 1.5 μm was obtained by post-baking at 230 ° C. for 30 minutes (in the air) using an oven (“IHPS-222”; manufactured by Espec Co., Ltd.).

For the colored resin compositions 2 to 7, spin-coating was performed on a separate (S-2) using a spin coater (“1H-DS (trade name)” manufactured by Mikasa Co., Ltd.), and the substrate was placed on a hot plate (Dainippon Screen Seijo). Co., Ltd. product "SCW-636 (trade name)") was prebaked at 100°C for 10 minutes to obtain a prebaked film. The prebaked film was exposed to light using a mask aligner (manufactured by Union Kogaku Co., Ltd.) and using an ultra-high pressure mercury lamp as a light source without passing through a mask. Thereafter, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was carried out with a 0.045% by mass KOH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds. Thereafter, by post-baking at 230°C for 30 minutes (in the air) using an oven ("IHPS-222"; manufactured by Espec Co., Ltd.), the thickness of each of the colored resin compositions 2 to 7 is 1.5 µm. A solid film of

Adhesion to the substrate was evaluated for the obtained solid film. Specifically, in accordance with JIS K5600-5-6 (1999), a cross-cut test was conducted by six-step evaluation of 5B to 0B (the higher the number, the higher the adhesion). Moreover, since adhesiveness may cause operation defect of the touch panel by peeling of hardened|cured material, etc. if adhesiveness is 2B or less, it is preferable that adhesiveness is 3B or more, and it is more preferable that it is 4B or more.

<Evaluation of patternability>

The colored resin compositions 2 to 7 were spin-coated on (S-2) using a spin coater ("1H-DS (trade name)" manufactured by Mikasa Co., Ltd.), and the substrate was placed on a hot plate (Dainippon Screen Seijo) Co., Ltd. product "SCW-636 (trade name)") was prebaked at 100°C for 10 minutes to obtain a prebaked film. The prebaked film was exposed to light through a desired mask using a mask aligner (manufactured by Union Kogaku Co., Ltd.) using an ultra-high pressure mercury lamp as a light source. Thereafter, using an automatic developing device ("AD-1200 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 0.045% by mass KOH aqueous solution for 60 seconds, followed by rinsing with water for 30 seconds to pattern processing. After exposure and development, the minimum pattern size after development was measured at an exposure amount to form a 5 μm line-and-space pattern with a width of 1:1, and it was determined as the resolution. The exposure amount was measured with an I-line illuminometer.

The results of each evaluation are shown in Table 3.

The resin composition of the present invention can be suitably used for forming conductive patterns and colored patterns used in touch panels, displays, image sensors, organic electroluminescence lighting or solar cells, and the like.

Claims (20)

Contains fine particles, a compound (B) having a structure represented by Formula (1) and a functional group that generates an amino group by heat, and a binder resin (C),
The resin composition in which the fine particles are inorganic particles (G) having an organic pigment (F) or a coating layer containing carbon.

(In general formula (1), X represents Si, Ti or Zr atom. R ¹ to R ³ are each independently a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group. represents a group or a hydrocarbon group having 1 to 6 carbon atoms R ¹ to ^{R 3} may be the same or different, but at least one is a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group to be.) According to claim 1,
The resin composition wherein the fine particles are inorganic particles (G) having a coating layer containing carbon, and the inorganic particles (G) are conductive particles (A). According to claim 2,
The resin composition whose pH of the suspension of water of 1 mass % of the said electroconductive particle (A) concentration is 4.0-10.0. According to claim 1,
A resin composition wherein the average primary particle diameter of the fine particles is 1 to 700 nm. According to claim 1,
A resin composition containing 0.1 to 2.5 parts by mass of the compound (B) per 100 parts by mass of the fine particles. According to claim 1,
The resin composition according to claim 1 , wherein the fine particles are inorganic particles (G) having a coating layer containing carbon, and the inorganic particles (G) are inorganic pigments. According to claim 1,
A resin composition in which the fine particles are an organic pigment (F). According to claim 7,
The resin composition in which the surface of the said organic pigment (F) is acidic. According to any one of claims 1 to 8,
The resin composition in which the functional group which generates an amino group by the heat is at least one member selected from the group consisting of an amide group, an imine group, a ureido group and an isocyanate group. According to claim 9,
A resin composition in which the functional group that generates an amino group by the heat is a ureido group. According to any one of claims 1 to 10,
A resin composition in which the binder resin (C) has an acid dissociable group. According to any one of claims 1 to 11,
The resin composition which further has a photosensitizer (D), and the said binder resin (C) has an alkali-soluble group. A wiring board provided with a conductive pattern made of a cured product of the resin composition according to any one of claims 1 to 3. According to claim 13,
A wiring board further having a black layer. According to claim 13 or 14,
A wiring board wherein the width of the conductive pattern is 1 to 6 μm. A touch panel comprising the wiring board according to any one of claims 13 to 15. An application step of obtaining a coating film by applying the resin composition according to any one of claims 1 to 3 on a substrate so as to have a desired pattern shape;
A drying step of drying the coated film to obtain a dried film;
A method for producing a conductive pattern comprising a heating step of heating the dried film to obtain a conductive film. An application step of applying the resin composition according to any one of claims 1 to 3 on a substrate to obtain a coating film;
A drying step of drying the coated film to obtain a dried film;
An exposure step of exposing the dried film to obtain an exposure film;
A developing step of developing the exposure film to form a pattern;
A method for producing a conductive pattern comprising a heating step of heating the pattern to obtain a conductive film. According to claim 17 or 18,
The manufacturing method of the conductive pattern whose heating process which heats the said pattern and obtains a conductive film is 150-270 degreeC. Containing conductive particles (A) having a coating layer containing carbon, a compound (E) having a structure represented by Formula (2) and an amino group, and a binder resin (C),
A conductive pattern in which the binder resin (C) has an alkali-soluble group.

(In formula (2), Y represents a Si, Ti or Zr atom. R ⁴ to R ⁶ are each independently a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group. Represents a group, a hydrocarbon group having 1 to 6 carbon atoms, or a bridging oxygen. R ⁴ to R ⁶ may be the same or different, but at least one is a bridging oxygen.)