TW202204501A - Resin composition, wiring board and method for producing conductive pattern - Google Patents

Abstract

The present invention provides a resin composition which is capable of forming a pattern that achieves a good balance between adhesion and good dispersibility (i. e. good conductivity in cases where the resin composition contains conductive particles) even if the pattern is a fine pattern. A resin composition which contains fine particles, a compound (B) that has a structure represented by general formula (1) and a functional group that produces an amino group by means of heat, and a binder resin (C), wherein the fine particles are composed of an organic pigment (F) or inorganic particles (G) that have coating layers containing carbon. (In general formula (1), X represents an Si, Ti or Zr atom; each of R1 to R3 independently represents 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 from 1 to 6 carbon atoms; and the R1 to R3 moieties may be the same as or different from each other, provided that at least one of the moieties is a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group.).

Description

Resin composition, wiring board, and method for producing conductive pattern

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

In recent years, various types of displays such as televisions, mobile phones, car navigation, and electronic signboards have been developing in large-scale and high-definition displays. With the increase in size, the wiring length of the electronic wiring has increased, and from the viewpoint of maintaining power consumption, the electrical conductivity of the wiring has been improved, that is, the demand for lower resistance is increasing. In the case of high definition, since the cross-sectional area of the wiring becomes smaller when the electronic wiring is made finer, it becomes necessary to improve the electrical conductivity in order to make the wiring resistance the same.

As a method of forming a conductive pattern used in electronic wiring, a resin composition containing conductive particles and a binder resin is generally used, and after patterning on a substrate, the conductive particles are brought into contact with each other by heating to obtain a conductive pattern. method (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 believed that the screen printing method and the ink jet method are not suitable for forming fine patterns, and photolithography is suitable for forming fine patterns.

In this case, there is known a technique for improving the conductivity of electronic wiring by using conductive fine particles with a sufficiently small particle size to reduce the surface energy of the particles and promote the fusion of the conductive particles. As a resin composition using electroconductive fine particles having a sufficiently small particle size, a resin composition using surface-coated silver fine particles (Patent Document 2) can be mentioned. By using the surface-coated silver fine particles, the surface energy of the silver fine particles can be appropriately controlled.

On the other hand, the coloring patterns used in color filters and the like are similarly sought to be refined. 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. [Prior Art Literature] [Patent Literature]

Patent Document 1 Japanese Patent Laid-Open No. 2000-199954 Patent Document 2 Japanese Patent Application Laid-Open No. 2013-196997

[The problem to be solved by the invention]

However, in the resin composition using the surface-coated silver fine particles, there is a problem in that if the surface of the silver fine particles is heated by high temperature to promote the fusion of the surface of the silver fine particles in order to improve the conductivity, the adhesiveness to the base material is reduced. . On the other hand, in order to impart adhesion, there is a method of adding an adhesion improver having an amine group, but there is a problem in that the dispersibility of the silver fine particles in the resin composition is deteriorated and the electrical conductivity is lowered. Therefore, it is difficult to achieve both adhesion and conductivity improvement.

Moreover, even in the resin composition containing a coloring pigment, when the adhesion improver which has an amine group is added, the dispersibility of a pigment deteriorates, and there exists a subject that the storage stability falls.

The present invention was conceived in view of the shortcomings of the related prior art, and its object is to obtain a pattern excellent in dispersibility and adhesion, and in particular, to provide a resin composition which, in a resin composition containing conductive particles, is In order to improve electrical conductivity, the fusion of the surfaces of the silver fine particles is promoted, and the adhesion to the base material can also be maintained. By using such a resin composition, a pattern having both good dispersibility (that is, good conductivity in a resin composition containing conductive particles) and adhesiveness can be obtained. [means to solve the problem]

As a result of intensive research by the inventors of the present invention, it has been found that containing the compound (B) having a structure that improves adhesion to substrates and a functional group that generates an amine group by heat in a resin composition is extremely effective for solving the above-mentioned problems of.

That is, the present invention is a resin composition comprising: fine particles, a compound (B) having a structure represented by the general formula (1) and a functional group that generates an amine group by heat, and a binder resin (C) , the fine particles are organic pigments (F) or inorganic particles (G) having a coating layer containing carbon.

(In the general formula (1), X represents a Si, Ti or Zr atom. R ¹ to R ³ each independently represent a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, Isobutoxy or hydrocarbon group having 1 to 6 carbon atoms. R ¹ to R ³ may be the same or different, but at least one of them is hydroxyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy.) [Effect of Invention]

According to the resin composition of the present invention, even in a fine pattern, a pattern having both excellent dispersibility (that is, excellent conductivity in the resin composition containing conductive particles) and adhesion can be obtained.

[Form for carrying out the invention]

The resin composition of the present invention is characterized by comprising fine particles, a compound (B) having a structure represented by the general formula (1) and a functional group that generates an amine group by heat, and a binder resin (C), wherein the The fine particles are organic pigments (F) or inorganic particles (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.

系顏料；培林酮(perinone)系顏料；苝系顏料；硫靛藍系顏料；異吲哚啉系顏料；異吲哚啉酮系顏料；喹啉黃系顏料；士林(threne)系顏料；金屬錯合物系顏料等。Examples of organic pigments include colored organic pigments, and examples thereof include diketopyrrolopyrrole-based pigments; azo-based pigments such as azo, disazo, and polyazo; copper phthalocyanine, copper halide phthalocyanine, and metal-free phthalocyanine. Phthalocyanine pigments such as blue; anthraquinones such as amine anthraquinone, diamine dianthraquinone, allion pyrimidine, flavonoids, anthraquinone (anthanthrone), indanthrene, picanthrone, violanthrone, etc. pigment; quinacridone pigment; two 㗁

Pigments; Perinone pigments; Perylene pigments; Sulfindigo pigments; Isoindolinone pigments; Isoindolinone pigments; Quinoline yellow pigments; Threne pigments; Metal complex pigments, etc.

As an organic pigment, a black organic pigment, a color mixing organic pigment, etc. are mentioned, for example. Examples of black organic pigments include carbon black, perylene black, aniline black, benzofuranone-based pigments, and the like. Examples of color-mixing organic pigments include those obtained by mixing two or more pigments having colors such as red, blue, green, violet, yellow, magenta, and indigo, and making them pseudo-black. Two or more of these organic pigments may be contained. Among these pigments, carbon black is preferable from the viewpoint of further improving the light-shielding properties of the colored film and adjusting the electrical conductivity of the colored film.

Moreover, in this invention, in order to make the effect more remarkable, it is preferable that the surface of an organic pigment (F) is acid-processed. When the surface is acid-treated, the dispersion stability can be improved, and the adhesion to the substrate can be improved by the interaction with the compound (B). As a method of acid-treating the surface of carbon black, a method of oxidizing the surface by O ₃ (Japanese Patent Laid-Open No. 11-181326) and a method of wet oxidation of the surface (Japanese Patent No. 4464081) are known. Gazette), a method of surface modification by an organic group including a sulfonic acid group and other non-polymeric groups (International Publication No. 2006/044676), and the like.

In the resin composition of the present invention, the content ratio of the organic pigment (F) is preferably 10 to 70 mass % with respect to 100 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 mass % or less, the dispersion stability of the organic pigment (F) can be improved, and the adhesion to the substrate can be secured. The content ratio is preferably 60% by mass or less. Here, the total solid content means all the components excluding 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 simply referred to as "inorganic particles (G)"). The inorganic particles (G) are particles in which the surface is covered with, for example, a carbon compound or the like. Examples of carbon compounds include aromatic hydrocarbons, aliphatic hydrocarbons, or their oxides, nitrides, sulfides, phosphides, and the like. Among them, aromatic hydrocarbons, aliphatic hydrocarbons, or oxides thereof are preferred from the viewpoint of suppressing fusion of 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 surfaces of the inorganic particles (G) are covered with a coating layer containing carbon, fusion of the inorganic particles (G) at low temperatures can be suppressed, and resolution reduction and generation of residues due to particle coarsening can be suppressed. . Furthermore, adhesiveness can be improved by reacting with the functional group which generate|occur|produces an amine group by heat mentioned 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), Metal fine particles such as palladium (Pd), platinum (Pt), aluminum (Al), tungsten (W), or molybdenum (Mo). 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 preferred; from the viewpoint of enhancing conductivity, More preferably, they are fine particles of silver.

As a method of covering the surfaces of the inorganic particles with a coating layer containing carbon, for example, a method of bringing a reactive gas into contact with the inorganic particles by a thermoplasma method (Japanese Patent Laid-Open No. 2007-138287 ). It is preferable that the surface of the inorganic particle (G) is completely covered, but as long as the object of the present invention is achieved, it is acceptable that some particles are not completely covered.

The average thickness of the coating layer is preferably 0.1 to 10 nm. Within this range, fine pattern workability can be improved by suppressing fusion of 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 measured by the mass reduction of the inorganic particles (G) measured by a thermobalance. Assuming that this value is all caused by the combustion of carbon, the coating layer can be calculated from the particle size by setting the carbon density to 2.0. average thickness. Carbon is coated on the electroconductive particle whose particle diameter (Dp) is known by the average thickness A (micrometer), and let the number of objects of the electroconductive particle coated with carbon be n. When the mass first weighed in the thermobalance measurement is W ₁ (g), the mass after complete combustion of carbon is W ₂ (g), and the density of inorganic particles is ρ, if Dp and W are known ₂ , n can be calculated from the following formula. W ₂ =π/6×Dp ³ ρ×n Further, the average thickness A of the coating layer can be calculated from the following equation. W ₁ -W ₂ ={4/3×π(Dp/2+A) ³ -π/6×Dp ³ }×2.0×n The conductive particles (A) of the inorganic particles (G) form a coating containing carbon The type of material of the layer, the surface will be acidic or alkaline. The pH of the suspension in which the electroconductive particle (A) is suspended in water at a concentration of 1% by mass is preferably 4.0 to 10.0. This pH is determined as follows. After adding 0.3 g of conductive particles (A) to 2.7 g of pure water to prepare a suspension having a concentration of 1 mass %, the mixture was stirred for 5 minutes and left to stand for 15 minutes. The upper clear liquid of the obtained suspension was collected and measured with a pH meter. When the pH is 4.0 or more, since the carbon coating layer strongly interacts with the dispersant described later, even a small amount of the dispersant can be stably dispersed. When the pH is 10.0 or less, the reaction between the conductive particles (A) and the binder resin (C) can be suppressed, and the pH of the resin composition can be maintained in an appropriate range, thereby achieving good storage stability. In order to control the pH of the suspension of electroconductive particle (A), for example, when producing electroconductive particle (A) by the thermoplasma method, it can be achieved by changing the kind of reactive gas, and an introduction ratio.

The average primary particle diameter of the fine particles is preferably 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 size is 1 nm or more, the specific surface area of the particles can be reduced, and even a small amount of dispersing amount can be stably dispersed. Moreover, when the average primary particle diameter is 700 nm or less, a fine pattern can be formed. Here, the average primary particle diameter of the fine particles is calculated as an average value of particle diameters of 100 randomly selected primary particles using a scanning electron microscope. The particle diameter of each primary particle is calculated by measuring the major axis and minor axis of the primary particle from the average value.

In the resin composition of the present invention, the content ratio of the inorganic particles (G) is preferably 65 to 95% by mass relative to 100% by mass of the solid content. When the content ratio is 65 mass % or more, the remaining organic components do not hinder the contact of the inorganic particles (G), and the conductivity is further improved when the inorganic particles (G) are the conductive particles (A). The content ratio is preferably 75% by mass or more. On the other hand, when the content ratio is 95 mass % or less, the residual organic components can stabilize the dispersibility of the inorganic particles (G) in the resin composition, form fine patterns, and reduce residues on the substrate. The content ratio is preferably 85% by mass or less. Here, the total solid content means all the components excluding the solvent among the components contained in the resin composition.

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

The analysis method of all the components of the resin composition is as follows. (i) The resin composition was diluted with an organic solvent, ¹ H-NMR measurement, GC measurement, and GC/MS measurement were performed to investigate the approximate contents. (ii) The resin composition is extracted with an organic solvent and then centrifuged to separate the soluble component and the insoluble component. (iii) The above-mentioned insoluble components are extracted with a highly polar organic solvent, and then centrifuged, and further separated into soluble components and insoluble components. (iv) IR measurement, ¹ H-NMR measurement, and GC/MS measurement were performed on the mixed solution of the soluble components obtained in the above (ii) and (iii). The above mixture was further separated by GPC. The obtained isolate was subjected to IR measurement and ¹ H-NMR measurement. In addition, GC measurement, GC/MS measurement, pyrolysis GC/MS measurement, and MALDI/MS measurement are carried out on the isolate as necessary. (v) IR measurement or TOF-SIMS measurement is performed on the insoluble component obtained in the above (iii). When the presence of organic matter is confirmed, thermal cracking GC/MS or TPD/MS measurement is performed. (vi) The content rate of each component contained in the resin composition can be obtained by comprehensively judging the measurement results of the above (i), (iv) and (v). Among them, as the highly polar organic solvent used in the above (iii), chloroform, methanol, or the like is preferable.

[Compound (B) having a structure represented by the general formula (1) and a functional group that generates an amine 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 that generates an amine group by heat (hereinafter abbreviated as "compound (B)").

In the general formula (1), X represents a Si, Ti or Zr atom. R ¹ to R ³ each independently represent a hydroxyl 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. Each of R ¹ to R ³ may be the same or different, but at least one of them is hydroxy, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy.

Examples of the hydrocarbon group having 1 to 6 carbon atoms include aliphatic hydrocarbon groups. The aliphatic hydrocarbon group may be linear or branched, and may be partially or entirely cyclic. As a C1-C6 hydrocarbon group, 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, a cyclohexyl group, etc. are mentioned, for example. Among these, a methyl group, an ethyl group, or a propyl group is preferable from the viewpoint that the steric hindrance is small and the adhesion with the substrate is not hindered.

The compound (B) generates an amine group by heating in a temperature range of, for example, 100 to 300° C. for 5 to 120 minutes after patterning. The generated amine group interacts with the surface of the organic pigment (F) or the inorganic particle (G), whereby the structure represented by the general formula (1) interacts with the substrate to improve the adhesion between the pattern and the substrate. Adhesion was evaluated by a cross-cut test in accordance with JIS K5600-5-6 (1999). In addition, among R ¹ to R ³ , hydroxyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy are removed by heating to form silanol groups, silanols The groups are polycondensed with each other to generate a compound (E) having a structure represented by the general formula (2) and an amine group.

(In the general formula (2), Y represents a Si, Ti or Zr atom. R ⁴ to R ⁶ each independently represent a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isopropoxy group, and an isopropyl group. Butoxy group, hydrocarbon group having 1 to 6 carbon atoms, or bridging oxygen. R ⁴ to R ⁶ may be the same or different, but at least one of them is bridging oxygen.) On the other hand, since in the resin composition before heating, , there is no amine group in the compound (B), so the compound (B) does not react with the surface of the organic pigment (F) or the inorganic particle (G), and can exist stably. Therefore, during the storage of the resin composition, function inhibition due to viscosity change and deterioration of the dispersibility of the organic pigment (F) or inorganic particles (G) is prevented, and development residues do not occur in the coating film of the resin composition. As a result, the penetration rate of the substrate is reduced. In addition, pattern workability can be improved. Here, the heating for the purpose of generating the amine group and the heating for the purpose of imparting a pattern function to the resin composition can be simultaneously performed.

The central element X of the general formula (1) is preferably Si from the viewpoint of reactivity. On the other hand, as R ¹ to R ³ in the general formula (1), a methoxy group or an ethoxy group is preferable, and a methoxy group is more preferable from the viewpoint of the adhesiveness with the base material.

As a functional group which generates an amine group by heat, an amide group, an imine group, a urea group, and an isocyanate group can be mentioned. By using at least one of these functional groups, the stability of the resin composition and the coating film can be improved, and the adhesion to the heated substrate can be further improved. From the viewpoints of improving the dispersion stability of the organic pigment (F) and the inorganic particles (G) in the resin composition, further improving the conductivity, and suppressing residues, the urea group is particularly preferred.

Specific examples of the compound (B) include: 3-trimethoxysilyl-N-(1,3-dimethylbutylene)propylamine, 3-triethoxysilyl-N-(1,3-dimethylene) butylene)propylamine, 3-tripropoxysilyl-N-(1,3-dimethylbutylene)propylamine, 3-trimethoxysilyl-N-(benzylidene)propylamine, 3-triethyl Oxysilyl-N-(benzylidene)propylamine, 3-tripropoxysilyl-N-(benzylidene)propylamine, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxy Silane, 3-Isocyanatopropyltriethoxysilane and 3-Isocyanatopropyltrimethoxysilane. Among them, as the compound having a urea group, 3-ureidopropyltriethoxysilane and 3-ureidopropyltrimethoxysilane are more preferable. Particularly preferred is 3-ureidopropyltrimethoxysilane.

In the resin composition of the present invention, the content of the compound (B) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of 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). When the content is 0.1 part by mass or more, the adhesiveness can be further improved. The content of the compound (B) is more preferably 0.5 part by mass or more. On the other hand, when the content is 2.5 parts by mass or less, the conductivity can be further improved. The content of the compound (B) is more preferably 1.0 part 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). When the content is 0.5 parts by mass or more, the adhesiveness can be further improved. The content of the compound (B) is more preferably 1.0 part by mass or more. On the other hand, when the content is 10 parts by mass or less, the storage stability can be further improved. The content of the 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 the like, and is not particularly limited. As the binder resin (C), it is preferable to use, for example, cellulose-based resins such as ethyl cellulose and nitrocellulose, acetal-based resins such as polyvinyl butyral, butyl methacrylate, methyl methacrylate, and the like. Acrylic resins obtained by polymerizing methyl methacrylate and the like are particularly preferred from the viewpoint of ease of composition design. Here, the acrylic resin refers to a resin in which at least a (meth)acrylic monomer is copolymerized in the resin component. Here, as a (meth)acrylic-type monomer, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, Tertiary butyl (meth)acrylate, tertiary butoxycarbonyl (meth)acrylate, benzyl (meth)acrylate, methyladamantyl (meth)acrylate, cyclohexyl (meth)acrylate ester, tetrahydropyranyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylate 2-hydroxyethyl acrylate, isobornyl (meth)acrylate or phenyl (meth)acrylate.

As a copolymerization component other than a (meth)acrylic-type monomer, the compound which has 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, and p-hydroxystyrene, (meth)acrylamide, N-methylol (meth)acrylamide, N-vinylpyrrolidone and other amide-based unsaturated compounds, (meth)acrylonitrile, allyl alcohol, vinyl acetate , cyclohexyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-hydroxyethyl vinyl ether, or 4-hydroxybutyl vinyl ether base ether.

The binder resin (C) preferably has an acid dissociable group. The acid dissociable group is an organic group that is thermally oxidatively decomposed and released by the action of an acid under heating. When there is such an acid dissociable group, for example, in an acidic gas environment, by heating at 100-300° C., the acid dissociable group is easily thermally oxidized and decomposed and detached, and the cured product of the resin composition of the present invention will shrink. By increasing the particle ratio in the cured product, the function can be further improved. As a result, for example, when the fine particles are inorganic particles (G), it becomes easy to obtain desired electrical conductivity with a specific resistance of 10 to 1,000 μΩ·cm. In this case, when the photoacid generator and/or the thermal acid generator mentioned later are used together, this 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, since it is vaporized at a low temperature after detachment, large bubbles are not generated in the hardened product, and the contact of the fine particles is not prevented, so the function is further improved. The carbon number of 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 hardened product after dissociation and prevents the contact between the fine particles, so that the function is further improved. Moreover, even if bubbles generate|occur|produce in the said hardened material, it is easy to make it disappear by heating.

As an acid dissociable group, a tertiary butyl group, a tertiary butoxycarbonyl group, a benzyl group, a methyladamantyl group, or a tetrahydropyranyl group is mentioned, for example.

The binder resin (C) is preferably a resin obtained by copolymerizing 20 to 80 mol % of a compound having an acid dissociable group. In particular, when the binder resin (C) is an acrylic resin, the acrylic resin preferably contains 20 to 80 mol % of (meth)acrylate having an acid dissociable group as a monomer component.

It is preferable to use the resin composition of the present invention as a photosensitive resin composition because a fine wiring pattern can be formed. As a photosensitive resin composition, it is preferable to further have a photosensitizer (D) mentioned later, and it is preferable that a 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 sulfonic acid group, a phosphoric acid group, an acid anhydride group, and the like, and a carboxyl group is particularly preferred from the viewpoint of reactivity and versatility.

When the binder resin (C) is an acrylic resin having an alkali-soluble group, the ease of composition design is better. In the case where the binder resin (C) is an acrylic resin having an alkali-soluble group, the carboxyl group-containing compound that imparts the alkali-soluble copolymerization component includes, for example, (meth)acrylic acid, itonic acid, crotonic acid, Maleic or fumaric acid or their anhydrides.

The carboxylic acid equivalent of the binder resin (C) is preferably 50 to 1,000 g/mol. The carboxylic acid equivalent of the binder resin (C) can be calculated by measuring the acid value. In addition, the double bond equivalent of the binder resin (C) is preferably 150 to 10,000 g/mol in order to achieve both hardness and crack resistance 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 making the weight average molecular weight (Mw) in the above-mentioned range, excellent coating properties can be obtained, and the solubility in a developing solution at the time of pattern formation can also be improved.

When the resin composition of the present invention is used as the photosensitive resin composition, in order to increase the speed of the curing reaction by the exposure of the photosensitive resin composition, it is preferable that the binder resin (C) becomes a side chain Or a (meth)acrylic copolymer having a carbon-carbon double bond at the molecular end. As a functional group which has a carbon-carbon double bond, a vinyl group, an allyl group, or a (meth)acrylic group is mentioned, for example. In order to add such a functional group to the (meth)acrylic copolymer, there is a method as follows: a compound having a glycidyl group or an isocyanate group and a carbon-carbon double bond or a (meth)acryloyl chloride or Allyl chloride undergoes an addition reaction with a mercapto group, an amine group, a hydroxyl group or a carboxyl group in the (meth)acrylic copolymer.

Examples of compounds having glycidyl and carbon-carbon double bonds include glycidyl (meth)acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl Glycidyl ether, glycidyl crotonate or glycidyl isocrotonate. As a compound which has an isocyanate group and a carbon-carbon double bond, (meth)acryloyl isocyanate and (meth)acryloyloxyethyl isocyanate are 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 mass % when the solid content is set to 100 mass %. When it is 1 mass % or more, the viscosity of the resin composition suitable for coating can be adjusted, and when it is 30 mass % or less, the function can be further improved.

[Sensitizer (D)] When the resin composition of the present invention is used as a photosensitive resin composition, it is preferable to contain a photosensitizer (D) from the viewpoint of forming a fine pattern. When the photosensitizer (D) is contained, positive or negative photosensitivity can be imparted to the resin composition.

系化合物、有機過氧化物、咪唑系化合物、二茂鈦系化合物、三

系化合物、醯基膦氧化物化合物、醌化合物或肟酯系化合物，其中較佳為即使是少量添加也有高敏感度之肟酯系化合物，更佳為具有咔唑骨架的肟酯系化合物。As a photosensitizer (D), it is preferable to use a photopolymerization initiator, a photoacid generator, and a photobase generator. Examples of photopolymerization initiators include acetophenone-based compounds, benzophenone-based compounds, benzoin ether-based compounds, α-aminoalkyl phenyl ketone-based compounds, and 9-oxysulfur

series compounds, organic peroxides, imidazole series compounds, titanocene series compounds, three

system compounds, acylphosphine oxide compounds, quinone compounds, or oxime ester-based compounds, among them, oxime-ester-based compounds having high sensitivity even when added in small amounts are preferred, and oxime-ester-based compounds having a carbazole skeleton are more preferred.

Specific examples of the oxime ester-based compound without a carbazole skeleton include 1,2-propanedione-3-cyclopentane, 1-[4-(phenylthio)-2-(O-benzyl) As specific examples of oxime ester compounds having a carbazole skeleton , for example: 3-cyclopentyl ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O- Acetoxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetoxime), etc. .

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 relative to 100 parts by mass of the binder resin (C).

As a photoacid generator, a quinonediazide compound, a pernium salt, a phosphonium salt, a diazonium salt, an iodonium salt, etc. are mentioned, Among them, a quinonediazide compound is more preferable. The quinonediazide compound has a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group, and any of them can be preferably used. Examples of the quinonediazide sulfonic acid ester include those in which the sulfonic acid of quinonediazide is ester-bonded to the polyhydroxy compound, and the sulfonic acid of quinonediazide is bonded to the polyamine compound with sulfonamides. A quinonediazide sulfonic acid is bound to a polyhydroxy polyamine compound with an ester and/or a sulfonamide, and the like. 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 relative to 100 parts by mass of the binder resin (C).

As a photobase generator, an amide compound, an ammonium salt, etc. are mentioned.

Examples of the amide compound include 2-nitrophenylmethyl-4-methacryloxy piperidine-1-carboxylate, 2-nitrophenylmethyl-4-methacryloxy piperidine-1-carboxylate, 9-anthrylmethyl-N,N-dimethyl carbamate, 1-(anthrylmethyl-N,N-dimethyl carbamate), 1-(anthraquinone-2-yl)ethylimidazole carboxylate (1-( anthraquinone-2-yl) ethyl imidazole carboxylate), (E)-1-[3-(2-hydroxyphenyl)-2-propenyl] piperidine, etc.

Examples of the ammonium salt include 1,2-diisopropyl-3-[(bis(dimethylamino)methylene]guanidinium 2-(3-benzylphenyl)propanoate, (3-Fluorophenyl)boronic acid (Z)-{[bis(dimethylamino)methenyl]amino}-N-cyclohexylamino)methylammonium, n-butyltriphenylboronic acid 1,2- Dicyclohexyl-4,4,5,5-tetramethylbiguanidinium, etc.

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 relative to 100 parts by mass of the binder resin (C).

[Dispersant] The resin composition of the present invention may contain a dispersant. When a dispersant is contained, fine particles can be stably present in the resin composition.

As the dispersant, an amine-based dispersant is preferred. 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 the above are manufactured by BYK-Chemie Japan). ).

In order to further improve the dispersibility, the dispersant preferably has an acrylic block copolymer structure. As a commercially available amine-type dispersing agent which has an acrylic block copolymer structure, DISPERBYK (registered trademark) 2001, 2008, 2022, 2150, 6919, or 21116 is mentioned, for example.

In the resin composition of the present invention, the content of the dispersant is 100 parts by mass, preferably 1 to 10 parts by mass, based on 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 dispersing agent within this range, fine particles are well dispersed in the resin composition, and fine pattern processing is possible. In the case of the fine particle-based conductive particles (A), the conductive particles (A) are incorporated Contact and welding are performed in the middle, and higher functions can be obtained.

[Acrylic monomer] From the viewpoint of adjusting photosensitivity and improving pattern workability, the resin composition of the present invention may contain acrylic acid in the range where the fine particles are the conductive particles (A) within a range that does not hinder the contact and fusion of the conductive particles. monomer.

Examples of the acrylic monomer include trimethylolpropane tri(meth)acrylate, neotaerythritol tri(meth)acrylate, neotaerythritol penta(meth)acrylate, neotaerythritol Tetra(meth)acrylate, dipivalerythritol hexa(meth)acrylate or dipeptaerythritol penta(meth)acrylate or their alkyl-modified products, alkyl ether-modified products or Alkyl ester modified products.

The content of the acrylic monomer in the resin composition is preferably in the range of 10 to 200 parts by mass relative 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 acetate, cyclopentanone, cyclohexanone, γ-butyrolactone, ethyl acetate Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether Diethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol dimethyl ether, propylene glycol diacetate, 1,3-butanediol diacetate, cyclohexanol acetate, dimethylsulfoxide, methyl ethyl ketone, acetic acid Isobutyl, butyl acetate, propyl acetate, isopropyl acetate or acetone.

[polymerization inhibitor] The resin composition of the present invention may also contain a polymerization inhibitor. When a proper amount of polymerization inhibitor is included, the resolution after development will be improved. The polymerization inhibitor is not particularly limited, and well-known ones can be used, for example, di-tertiary butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzene Quinone, tertiary butylcatechol. Moreover, as a commercially available polymerization inhibitor, "IRGANOX 1010", "IRGANOX 245", (above, BASF make) etc. are mentioned.

系化合物。[Ultraviolet Absorber] The resin composition of the present invention may contain an ultraviolet absorber. When an ultraviolet absorber is contained, the light resistance of the obtained hardened|cured material will improve, and the resolution after image development will improve for the application which requires pattern processing. The ultraviolet absorber is not particularly limited, and well-known ones can be used, but from the viewpoints of transparency and non-coloring properties, benzotriazole-based compounds, benzophenone-based compounds, and triphenyl ketone-based compounds are preferably used.

series compounds.

[other particles] The resin composition of the present invention may contain particles other than the organic pigment (F) and the inorganic particles (G) in order to improve dispersibility and control conductivity. Examples of other particles include electroconductive particles without surface coating, metal oxide fine particles, or inorganic pigments.

The particle diameter of these other particles is preferably 1 to 100 nm. 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 the conductive particles (A), the conductivity can be further improved. On the other hand, when the particle size is 100 nm or less, the resolution of the pattern is improved, and a fine pattern can be formed.

[Thermal acid generator and photoacid generator] The resin composition of the present invention may contain a thermal acid generator. In the case where the binder resin (C) is a binder resin having an acid-dissociable group, the generated acid promotes the decomposition of the acid-dissociable group, so that the heat treatment temperature in air can be lowered. In addition, it does not matter if a photoacid generator is contained. The photoacid generator is as previously mentioned.

As a thermal acid generator of a compound that generates an acid by heat, for example, SI-150L, SI-160L, SI-180L, or SI-200 (all of the above are manufactured by Sanshin Chemical Industry Co., Ltd.), 4- Hydroxyphenyldimethyl strontium, benzyl-4-hydroxyphenylmethyl strontium, 2-methylbenzyl-4-hydroxyphenylmethyl strontium, 2-methylbenzyl-4-acetonitrile Phenylmethylsulfuric acid or 2-methylbenzyl-4-benzyloxyphenylmethylsulfuric acid or their mesylate, triflate, camphorsulfonate or p-toluenesulfonic acid Salt. Among them, it is preferable to use 4-hydroxyphenyl dimethyl strontium, benzyl-4-hydroxyphenylmethyl strontium, 2-methylbenzyl-4-hydroxyphenylmethyl strontium, 2-methyl sulfite Benzyl-4-acetonitrile or 2-methylbenzyl-4-benzyloxyphenylmethyl succinate or their mesylate, triflate, camphor Sulfonate or p-toluenesulfonate.

In the resin composition of the present invention, the content of the thermal acid generator is in order to promote the decomposition of the acid dissociable group in the binder resin (C) containing the acid dissociable group, and not prevent the contact of the inorganic particles (G) with each other, To obtain a higher function, the range of 1 to 50 parts by mass is preferable 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. It is preferable that the sensitizer is vaporized by heat treatment, or even if it remains in the cured product of the resin composition of the present invention, it is discolored by irradiation of light, from high resolution during pattern processing. From the viewpoint of light, it is more preferable to be discolored by light.

Examples of sensitizers that are vaporized by heat treatment or discolored by light irradiation include coumarins such as 3,3'-carbonylbis(diethylaminocoumarin), and 9,10-anthracene. Anthraquinone such as quinone, diphenyl ketone, 4,4'-dimethoxydiphenyl ketone, acetophenone, 4-methoxyacetophenone, or aromatic ketone such as benzaldehyde, or biphenyl, 1 ,4-dimethylnaphthalene, 9-phenanthrene, fentanyl, 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; manufactured by Kawasaki Chemical Co., Ltd.), 9,10-dipentoxyanthracene, 2-tris Condensed aromatics such as butyl-9,10-dibutoxyanthracene or 9,10-bis(trimethylsilylethynyl)anthracene.

The sensitizer vaporized by heat treatment is preferably one that is sublimated or evaporated by heat treatment, or one that sublimates or evaporates a thermal decomposition product generated by thermal decomposition. As the vaporization temperature of the sensitizer, it does not vaporize at the drying temperature, but is decomposed and vaporized at the time of thermal hardening, and when the fine particles are the conductive particles (A), in order to make the conductive particles contact and weld each other, it is preferably 150～300℃.

In the resin composition of the present invention, the content of the sensitizer is such that the sensitization effect of the photoacid generator to be sensitized is sufficient, the contact between the fine particles is not hindered, and a higher function is obtained, relative to 100 parts by mass of the binding agent. The agent resin (C) is preferably 0.001 to 20 parts by mass, more preferably 0.005 to 15 parts by mass.

[Pigments and/or dyes that absorb visible light] When the fine particles are the conductive particles (A), the resin composition of the present invention may contain pigments and/or dyes that absorb visible light within a range that does not prevent contact and fusion of the conductive particles. When the resin composition contains an inorganic pigment and/or dye that absorbs visible light, the visible light reflection of the pattern after heating can be suppressed. It is also preferable that the inorganic particles (G) are inorganic pigments.

系顏料、陰丹士林系顏料、碳黑或無機顏料。Examples of pigments that absorb visible light include lactamide-based pigments, perylene-based pigments, phthalocyanine-based pigments, isoindoline-based pigments, diamineanthraquinone-based pigments, and diamine-based pigments.

pigments, indanthrene pigments, carbon black or inorganic pigments.

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

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

系染料，於耐熱性、耐光性及可見光的吸收性上優良的黑色染料為較佳的，較佳為VALIFAST(註冊商標) Black 1888、VALIFAST(註冊商標) Black 3830、NUBIAN(註冊商標) Black PA-2802或OIL Black 860。Examples of dyes that absorb visible light include ferrocene-based dyes, perylene-based dyes, perylene-based dyes, triphenylmethane-based dyes, coumarin-based dyes, diphenylamine-based dyes, and quinacridone-based dyes , quinoline yellow dyes, phthalocyanine dyes or

It is a type of dye, preferably a black dye excellent in heat resistance, light resistance and visible light absorption, preferably VALIFAST (registered trademark) Black 1888, VALIFAST (registered trademark) Black 3830, NUBIAN (registered trademark) Black PA -2802 or OIL Black 860.

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

[Adhesion Improver] The resin composition of the present invention may further contain an adhesion improver in addition to the compound (B). Examples of the adhesion improver include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxy ring Hexyl) Ethyltrimethoxysilane, 3-Methylpropionyloxypropyltrimethoxysilane, 3-Methylpropionyloxypropyltriethoxysilane, 3-Propionyloxypropyltrimethoxysilane Silane coupling agent such as alkoxysilane or 3-propionyloxypropyltriethoxysilane.

[surfactant] The resin composition of the present invention may further contain a surfactant if necessary.

Examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, and cationic interfaces such as stearylamine acetate and lauryltrimethylammonium chloride. Active agents, amphoteric surfactants such as lauryl dimethyl amine oxide or lauryl carboxymethyl hydroxyethyl imidazolium betaine, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or sorbitan mono Nonionic surfactants such as stearate, fluorine-based surfactants, or polysiloxane-based surfactants.

In the resin composition of the present invention, the content of the surfactant is preferably 0.001 to 10% by mass relative to the entire composition in order to improve the coatability and uniformity of the coating film surface. When the content of the surfactant is 0.001 mass % or more, the coatability and the uniformity of the coating film surface are improved. The content of the surfactant is more preferably 0.01 mass % or more. On the other hand, when the content of the surfactant is 10 mass % or less, coating film defects such as sags and dents, and aggregation of particles can be suppressed.

It is preferable that the wiring board of this invention is equipped with the electroconductive pattern which consists of the hardened|cured material of the resin composition of this invention containing electroconductive particle (A). The base material of the wiring board of the present invention is preferably a transparent substrate. As a transparent substrate, a glass substrate and a resin film are mentioned. A glass substrate is preferable as a transparent substrate from the viewpoint of easy penetration of the developer during pattern formation and suppression of residues. As a glass substrate, the glass substrate containing a _SiO2 layer or a _SiO2 layer on the surface, an alkali-free glass substrate, etc. are mentioned. Examples of the resin film include those selected from the group consisting of polyimide, polyimide siloxane, polyether, polybenzoxazole, aromatic polyamide, polysiloxane, and epoxy resins. A film composed of at least one material, etc. A SiO ₂ layer may also be included on the surface of the resin film. By using these materials as a base material, it is possible to obtain a wiring board having high adhesion to the conductive pattern formed of the cured product of the resin composition of the present invention.

Moreover, the wiring board of this invention may have a thin film containing an organic component other than the electroconductive pattern which consists of the hardened|cured material of the resin composition of this invention. From the viewpoint of protecting the conductive pattern, the thin film containing the organic component is preferably formed on the upper portion of the conductive pattern. When there is a thin film containing an organic component, scratches due to 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 it as a member for a touch panel, the wiring which connects the touch sensor wiring and the touch sensor wiring arrange|positioned in a grid shape can be used. In addition, it is also preferable to form the touch sensor wiring and the routing wiring at the same time. The substrate of the wiring board of the present invention can also be used as a cover glass, and the wiring board of the present invention can also be pasted with a cover material through OCA.

In the wiring board of the present invention, the width of the conductive pattern is preferably 1 to 6 μm. When the width of the conductive pattern is 1 μm or more, it is less likely to be affected by defects due to foreign matter and the like, and a conductive pattern of a desired shape can be formed. On the other hand, when the width of the conductive pattern is 6 μm or less, it becomes difficult to visually recognize the wiring. The width of the conductive pattern is more preferably 4 μm or less.

The wiring board of the present invention preferably further has a black layer. When the black layer is provided, the reflection of the wiring pattern can be reduced, the reflection of external light can be suppressed, and the visibility of the wiring can be suppressed and the visibility can be greatly improved. As a method of forming the black layer, for example, after forming a wiring pattern, applying a black positive photosensitive composition to the entire surface, exposing through the wiring pattern from the substrate surface, leaving the upper part of the wiring pattern so that it can be exposed Dissolved in the developer, and then removed by development.

[Manufacturing method of resin composition] The resin composition of the present invention can be dispersed using a ball mill, a sand mill, a three-roller mill, a mild disperser, or a medium-free after mixing the fine particles, the compound (B), and the binder resin (C). Machine and other dispersing machines are produced. When it is desired to disperse the fine particles uniformly, it can also be produced by the following method: using a dispersing agent, a dispersion liquid prepared by dispersing fine particles in an organic solvent is prepared in advance, and this dispersion liquid is mixed with monomers, polymers, adhesives, etc. The solution of modifier, surfactant and polymerization inhibitor is mixed. In particular, in order to prevent the surface coating layer from being damaged, the dispersion liquid of the inorganic particles (G) having a carbon-containing coating layer is preferably dispersed using a mild disperser or a medium-less disperser, more preferably a medium-less disperser. . The dispersion liquid of inorganic particles (G) having a coating layer containing carbon was produced by using a mild disperser Nano Getter (registered trademark) (Ashizawa Finetech Co., Ltd.) or a high-pressure wet medium-less micronizing device Nanomizer (Nanomizer ( The inorganic particles (G) having a carbon-containing coating layer are dispersed in an organic solvent using a dispersing machine such as a carbon-containing coating layer.

[Manufacturing method of conductivity and colored pattern] The method for producing a conductive pattern of the present invention includes a coating step of applying the resin composition of the present invention on a substrate so as to have a desired pattern shape to obtain a coating film, and a drying step of drying the coating film to obtain a dry film and the heating step of heating the above-mentioned dry film to obtain a conductive film.

The manufacturing method of the electroconductive pattern of this invention includes the coating process of apply|coating the resin composition of this invention on a board|substrate so that it may become a desired pattern shape, and obtains a coating film.

As a base material used in a coating process, a silicon wafer, a ceramic substrate, or an organic type board|substrate is mentioned, for example. 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 substrate. As an organic-type board|substrate, an epoxy board|substrate, a polyetherimide resin board|substrate, a polyetherketone resin board|substrate, a polyamide-type resin board|substrate, a polyimide film, or a polyester film is mentioned, for example.

As a method of coating the resin composition of the present invention on the surface of a substrate, for example, the use of a spin coater, a bar coater, a knife coater, a roll coater, a die coater, a calender coater, or a Meniscus coater coating, screen printing, spray coating or dip coating.

The manufacturing method of the electroconductive pattern of this invention includes the drying process of drying a coating film to obtain a dry 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 drying temperature and time may be appropriately determined according to the composition of the resin composition and the film thickness of the dried coating film, and it is preferable to heat in a temperature range of 50 to 150° C. for 10 seconds to 30 minutes.

Among them, heating on a hot plate or a hot air dryer (oven) combined with drying under reduced pressure is preferable because it can dry and remove the solvent while suppressing thermal hardening of the resin contained in the coating film. It is preferable that it is 5-200Pa as a reaching pressure of drying under reduced pressure, and it is more preferable that it is 10-100Pa.

The manufacturing method of the electroconductive pattern of this invention includes the heating process of heating and drying a film to obtain a conductive film.

By heating the dried film of the resin composition to obtain conductivity, the compound (B) is made to have an amine group, and the compound (B) interacts with the coating layer of the inorganic particles (G) having a coating layer containing carbon, so that the compound (B) interacts with the coating layer of the inorganic particles (G) of the coating layer containing carbon. Adhesion is improved.

As a heating method in a heating step, the same method as a drying step is mentioned. The heating gas environment, temperature and time can be appropriately determined according to the composition of the resin composition and the film thickness of the heated coating film. More preferably, it is heated for 30 to 120 minutes at a temperature of 150 to 270°C, and still more preferably in a temperature range of 160 to 260°C.

Furthermore, it is also preferable that between the drying step and the heating step, an exposure step of exposing the dried film to obtain an exposed film and a development step of developing the exposed film to form a pattern are provided, and a photolithography method is used. to form a conductive pattern. In this case, since the compound (B) has no amine group and does not react with the inorganic particles (G) in the exposure step, an excellent pattern with good developer solubility and no development residue can be formed in the subsequent development step. After the pattern is formed, amine groups appear in the heating step, which can improve the adhesion to the substrate.

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

啉等的環狀胺類等的有機鹼類，也可對它們適當添加乙醇、γｰ丁內酯、二甲基甲醯胺或N-甲基-2-吡咯啶酮等的水溶性有機溶劑。Examples of the alkaline substance used in the alkaline developer in the developing step include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, or ammonia water. , primary amines such as ethylamine or n-propylamine, secondary amines such as diethylamine or di-n-propylamine, tertiary amines such as triethylamine or methyldiethylamine, tetramethylammonium hydroxide (TMAH ) tetraalkylammonium hydroxides, quaternary ammonium salts such as choline, alcoholamines such as triethanolamine, diethanolamine, monoethanolamine, dimethylamine ethanol or diethylamine ethanol, or pyrrole, piperidine, 1 ,8-Diazabicyclo[5.4.0]-7-undecene, 1,5-Diazabicyclo[4.3.0]-5-nonene or

Organic bases such as cyclic amines such as linoline, and water-soluble organic solvents such as ethanol, γｰbutyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be appropriately added to these .

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

When a conductive pattern is formed in a grid shape on a substrate, it can be used as a transparent conductive wiring included in a touch panel, a display panel such as a liquid crystal or an organic EL, a wearable product, or the like. [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 Synthesis Examples and Examples, the abbreviations used are as follows. AIBN: 2,2'-azobis(isobutyronitrile) TMAH: Tetramethylammonium hydroxide.

First, 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 without special surface treatment (MA-100 manufactured by Mitsubishi Chemical) [Inorganic particles (G) having a coating layer containing carbon] (A-1) Silver particles (manufactured by Nisshin Engineering Co., Ltd.) having an average thickness of the coating layer of 3 nm and a primary particle diameter of 50 nm. The pH of the suspension in water having a concentration of 1% by mass was 8.0.

(A-2) Silver particles (manufactured by Nisshin Engineering Co., Ltd.) having an average thickness of the coating layer of 3 nm and a primary particle diameter of 40 nm. The pH of the suspension in water with a concentration of 1% by mass was 4.5.

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

[Compound (B) having a structure represented by the general formula (1) and a functional group that generates an amine group by heat] (B-1) KBM-585: 3-Ureapropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) (B-2) KBE-585: 3-Ureapropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) (B-3) KBE-9007: 3-Isocyanatopropyltriethoxysilane (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) In a 500 ml flask, 2.0 g of AIBN and 50 g of PGMEA were added. Then, 38.7 g of methacrylic acid, 79.3 g of benzyl methacrylate, and 22.0 g of tricyclo[5.2.1.0(2,6)]dec-8-ester methacrylate were added and stirred at room temperature while stirring. After fully substituting nitrogen in the flask by bubbling, it was heated and stirred at 70° C. for 5 hours. Next, 21.3 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours. The obtained acrylic polymer solution was added to PGMEA so that the solid content concentration was 40 wt % to obtain a solution of binder resin (C-1). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 18,000.

(C-2) In a 500 ml flask, 1.5 g of AIBN and 50 g of PGMEA were added. Then, 38.7 g of methacrylic acid, 46.9 g of styrene, and 22.0 g of tricyclo[5.2.1.0(2,6)]dec-8-ester methacrylate were added and stirred at room temperature while bubbling After fully substituting nitrogen in the flask, it was heated and stirred at 70° C. for 5 hours. Next, 21.3 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours. The obtained acrylic polymer solution was added to PGMEA so that the solid content concentration became 40 wt % to obtain a solution of the binder resin (C-2). 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 BYK-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.).

[Photopolymerization initiator] NCI-831E (registered trademark) (oxime ester compound; manufactured by ADEKA Corporation).

[Acrylic monomer] LIGHT ACRYLATE (registered trademark) PE-3A (Kyoeisha Chemical Co., Ltd.).

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

[Positive photoresist] (P-1) Under a stream of dry nitrogen, 29.3 g (0.08 mol) of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF; manufactured by Central Glass Co., Ltd.), 1.24 g (0.005 mol) ear) 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 3.27g (0.03mol) of 3-aminophenol as a capping agent were dissolved in 150g of N-methyl- 2-pyrrolidone (NMP). 31.0 g (0.1 mol) of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (ODPA; manufactured by MANAC Co., Ltd.) was added together with 50 g of NMP, and the mixture was stirred at 20° C. for 1 hour. Next, stirring was carried out at 50°C for 4 hours. Then, 15 g of xylene was added, and the mixture was stirred at 150° C. for 5 hours while azeotroping water and xylene. After the stirring, the solution was put into 3 L of water, and the white precipitate was collected. 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.

In addition, under a stream of dry nitrogen, 15.3 g of TrisP-HAP (manufactured by Honshu Chemical Industry Co., Ltd.) and 40.3 g of 5-naphthoquinonediazidesulfonyl chloride were dissolved in 450 g of 1,4-dioxane. , set to room temperature. To this, 15.2 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the inside of the system did not reach 35°C or higher, but did not reach it. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was put into water. The precipitate deposited after that was dried with a vacuum dryer to obtain a quinonediazide compound.

The obtained 11.0 g of polyimide resin, 4.0 g of quinonediazide compound, 63.75 g of ethyl lactate, and 21.25 g of PGMEA were put into a 100-ml PP bottle and stirred. Next, filtering was performed with a 0.2 μm filter to obtain a positive photoresist (P-1).

[Substrate] (S-1) Glass substrate (TU060; manufactured by TOKEN Co., Ltd.) sputtered with SiO ₂ on the surface (S-2) Alkali-free glass substrate (OA-10G; manufactured by Nippon Electric Glass Co., Ltd.) (S-3 ) polyimide film (Neopulim; manufactured by Mitsubishi Gas Chemical Co., Ltd.).

Examples 1 to 14, Comparative Examples 1 to 3 <Evaluation of Conductivity> The resin composition 1 was spin-coated on the substrate (S-1) under the conditions of 300 rpm for 10 seconds and 500 rpm for 1 second using a spin coater (“1H-360S (trade name)” manufactured by MIKASA Co., Ltd.). A hot plate (“SCW-636 (trade name)” manufactured by Dainippon SCREEN Co., Ltd.) prebaked the substrate at 100° C. for 5 minutes to obtain a prebaked film with a film thickness of 1 μm. Then, by performing post-baking at 230° C. for 30 minutes (in air) using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), a solid film composed of the resin composition 1 was obtained. Using a spin coater (“1H-360S (trade name)” manufactured by MIKASA Co., Ltd.), a positive photoresist (P-1) was spin-coated on the obtained solid film at 300 rpm for 10 seconds and 1000 rpm for 5 seconds. The substrate was prebaked at 100° C. for 2 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon SCREEN Co., Ltd.) to obtain a prebaked film with a thickness of 1 μm. The prebaked film was exposed to light through a desired mask using a parallel lithography machine (“PLA-501F (trade name)” manufactured by Canon Inc.) using an ultra-high pressure mercury lamp as a light source. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), a 2.38 wt% TMAH aqueous solution was used for shower development (shower development) for 60 seconds, followed by washing with water for 30 seconds. Perform pattern processing. The photoresist was peeled off by immersing the obtained board|substrate in the iron (III) nitrate aqueous solution with a density|concentration of 55%, etching, exposing, and developing. Then, using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), it was baked at 230° C. for 30 minutes (in air) after application, and a volume resistivity evaluation pattern was obtained.

Resin compositions 2 to 17 were spin-coated on (S-1) to (S -3) On each substrate, the substrate was prebaked at 100° C. for 5 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon SCREEN Co., Ltd.) to obtain a prebaked film with a film thickness of 1 μm. The prebaked film was exposed to light through a desired mask using a parallel lithography machine (“PLA-501F (trade name)” manufactured by Canon Inc.) using an ultra-high pressure mercury lamp as a light source. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), it was subjected to shower development with a 0.07 wt % TMAH aqueous solution for 60 seconds, followed by washing with water for 30 seconds to perform patterning. Then, using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), it was applied at 230° C. for 30 minutes (in air) and post-baking was performed to obtain a volume resistivity evaluation pattern.

For the obtained volume resistivity evaluation pattern, the surface resistance value ρs (Ω/□) measured with a surface resistance measuring machine (Loresta (registered trademark)-FP; manufactured by Mitsubishi Oil & Chemical Co., Ltd.) and the surface roughness shape were measured. The volume resistivity (μΩ･cm) was calculated by multiplying the film thickness t (cm) measured with a meter (SURFCOM (registered trademark) 1400D; manufactured by Tokyo Seiki Co., Ltd.).

<Adhesion evaluation> Resin composition 1 was spin-coated on (S-1) at 300 rpm for 10 seconds and 500 rpm for 1 second using a spin coater (“1H-360S (trade name)” manufactured by MIKASA Co., Ltd.), and heated A board ("SCW-636 (trade name)" manufactured by Dainippon SCREEN Co., Ltd.) was prebaked on the substrate at 100° C. for 5 minutes to obtain a prebaked film with a film thickness of 1 μm. Then, using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), it was applied and baked at 230° C. for 30 minutes (in air) to obtain a solid film composed of the resin composition 1.

In addition, using a spin coater (“1H-360S (trade name)” manufactured by MIKASA Co., Ltd.), under the conditions of 300 rpm for 10 seconds and 500 rpm for 1 second, the resin compositions 2 to 17 were spin-coated to (S-1) to (S-1). (S-3) On each substrate, a hot plate (“SCW-636 (trade name)” manufactured by Dainippon SCREEN Co., Ltd.) was used to pre-bake the substrate at 100° C. for 5 minutes to obtain a pre-baked film with a film thickness of 1 μm . Using a parallel lithography machine (“PLA-501F (trade name)” manufactured by Canon Co., Ltd.) with an ultra-high pressure mercury lamp as a light source, the pre-baked film was exposed without passing through a mask. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), it was subjected to shower development with a 0.07 wt % TMAH aqueous solution for 60 seconds, followed by washing with water for 30 seconds. Then, using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), it was applied at 230° C. for 30 minutes (in air) and post-baked, to obtain a solid film composed of each of resin compositions 2 to 17.

The obtained solid film was evaluated for adhesion to the substrate. Specifically, according to JIS K5600-5-6 (1999), a 100-grid test was performed according to 6-stage evaluation of 5B to 0B (the larger the number, the higher the adhesion). Among them, when the adhesiveness is 2B or less, since there is a possibility of causing a failure of the touch panel due to peeling of the cured product, etc., the adhesiveness is preferably 3B or more, and more preferably 4B or more.

<Patternability evaluation> Using a spin coater (“1H-360S (trade name)” manufactured by MIKASA Co., Ltd.), the resin compositions 2 to 17 were spin-coated to (S-1) to (S -3) On each substrate, the substrate was prebaked at 100° C. for 5 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon SCREEN Co., Ltd.) to obtain a prebaked film with a film thickness of 1 μm. The prebaked film was exposed to light through a desired mask using a parallel lithography machine (“PLA-501F (trade name)” manufactured by Canon Inc.) using an ultra-high pressure mercury lamp as a light source. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), it was subjected to shower development with a 0.07 wt % TMAH aqueous solution for 60 seconds, followed by washing with water for 30 seconds to perform patterning. After exposure and development, the minimum pattern size after development was measured at the exposure amount to form a 5 μm line width and line spacing pattern with a width of 1:1 as the resolution. The exposure amount was measured with an I-line illuminometer.

<Evaluation of Residues on Substrates> The residues on the substrates were evaluated by transmittance evaluation on the unexposed portions of the substrates in which the volume resistivity evaluation patterns were formed with the resin compositions 2 to 17. Specifically, the transmittance at 400 nm before and after film formation was measured with a spectrophotometer (U-3410; manufactured by Hitachi, Ltd.) about the unexposed portion. Then, the transmittance before film formation was set to T ₀ and the transmittance after film formation was set to T, and the transmittance change 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 residues was sufficient.

(Example 1) 80.00 g of conductive particles (A-1) having a carbon-containing coating layer, 2.00 g of DISPERBYK21116, 100.00 g of PGMEA, and 100.00 g of DPM were mixed with a homogenizer at 1200 rpm for 30 minutes, and then used. It disperse|distributed by the high pressure wet medium-less micronizing apparatus Nanomizer (Nanomizer (stock)), and obtained the silver particle dispersion. To 282.00 g of this silver fine particle dispersion, 0.50 g of a compound (B-1) having a structure represented by the general formula (1) and a functional group that generates an amine group by heat, 43.75 g of a solid content concentration of 40 were mixed. Resin composition 1 was obtained by adding 73.75 g of PGMEA and 100.00 g of DPM to the mixture with respect to the binder resin (C-1) of % by mass, and stirring the mixture.

Table 1 shows the results of evaluation of electrical conductivity and adhesion.

(Example 2) First, 80.00 g of conductive particles (A-1) having a coating layer containing carbon, 2.00 g of DISPERBYK21116, 100.00 g of PGMEA, and 100.00 g of DPM were mixed with a homogenizer at 1200 rpm for 30 minutes. Furthermore, it disperse|distributed using a high pressure wet medium-less micronizing apparatus Nanomizer (Nanomizer (stock)), and obtained the silver particle dispersion. To 282.00 g of this silver fine particle dispersion, 0.50 g of a compound (B-1) having a structure represented by the general formula (1) and a functional group that generates an amine group by heat, 25.00 g of a solid content concentration of 40 Mass % of binder resin (C-1), 1.50 g of (D) NCI-831E of the sensitizer, and 6.00 g of PE-3A, 85.00 g of PGMEA and 100.00 g of DPM were added to this mixture and stirred, thereby Resin composition 2 was obtained.

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

(Examples 3 to 14 and Comparative Examples 1 to 3) In the same manner as in Example 2, photosensitive resin compositions 3 to 17 having the compositions described in Tables 1 to 2 were obtained, and the photosensitive resin compositions were subjected to the same procedures as in Example 2 on the substrates described in Tables 1 to 2 for each photosensitive resin composition. evaluation of. The evaluation results are shown in Tables 1 and 2.

(Examples 15 to 19, Comparative Examples 4 to 5) (Colored resin composition 1) 300 g of carbon black (TPK1227 manufactured by Cabot), 150 g of propylene glycol monomethyl ether acetate (PGMEA) 40% by weight solution of acrylic polymer (C-1), 37.5 g of "DISPERBYK" (registered trademark) LPN-21116 having a tertiary amine group and a quaternary ammonium salt as a polymer dispersant, and 1012.5 g of PGMEA were added to the tank and stirred with a homogenizer for 20 minutes to obtain a preliminary dispersion. The obtained preliminary dispersion liquid was supplied to a dispersing machine Ultra Apex Mill manufactured by Shougyo Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of 0.05 mmφ zirconia beads, and the dispersion was carried out at a rotational speed of 8 m/s for 3 hours to obtain Coloring material dispersion liquid Bk-1 with a solid content concentration of 25% by weight, coloring material/resin (weight ratio)=80/20.

To the carbon black dispersion liquid Bk-1 (822.6 g), a 40% by weight solution (344.5 g) of propylene glycol monomethyl ether acetate of the acrylic polymer (C-1) and Shin-Etsu Chemical ( KBM-585 (7.5g) manufactured by Co., Ltd., a 10% by weight solution (4.0g) of propylene glycol monomethyl ether acetate of polysiloxane-based surfactant was dissolved in propylene glycol monomethyl ether acetate (218.5g) The resulting solution was obtained to obtain a colored resin composition 1.

(Colored resin composition 2) 300 g of carbon black (TPK1227 manufactured by Cabot), 150 g of propylene glycol monomethyl ether acetate (PGMEA) 40% by weight solution of acrylic polymer (C-1), 37.5 g of "DISPERBYK" (registered trademark) LPN-21116 and 1012.5 g of PGMEA having a tertiary amine group and a quaternary ammonium salt of the polymer dispersant were added to the tank and stirred with a homogenizer for 20 minutes to obtain a preliminary dispersion. The obtained pre-dispersion liquid was supplied to a dispersing machine Ultra Apex Mill manufactured by Shou Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of 0.05 mmφ zirconia beads, and the dispersion was carried out at a rotational speed of 8 m/s for 3 hours to obtain Coloring material dispersion liquid Bk-1 with a solid content concentration of 25% by weight, coloring material/resin (weight ratio)=80/20.

To the carbon black dispersion liquid Bk-1 (822.6 g), a 40% by weight solution (117.3 g) of propylene glycol monomethyl ether acetate of the acrylic polymer (C-1) and dipivale as a polyfunctional monomer were added A 50% by weight solution (92.7 g) of tetraol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), ADEKA Co., Ltd. "ADEKA ARKLS" NCI- as a photopolymerization initiator 831 (11.6g), KBM-585 (7.5g) manufactured by Shin-Etsu Chemical Co., Ltd. as an adhesion improver, 10% by weight solution of propylene glycol monomethyl ether acetate as a polysiloxane-based surfactant (4.0g) Colored resin composition 2 was obtained by dissolving a solution in propylene glycol monomethyl ether acetate (218.5 g).

(Colored resin compositions 3 to 7) By the same method as the colored resin composition 2, colored resin compositions 3 to 7 having the compositions described in Table 3 were obtained.

<Storage stability evaluation> For the above-mentioned colored resin compositions 1 to 7, use a viscometer (RE105L manufactured by Toki Sangyo Co., Ltd.) to set the temperature at 25.0 ± 0.2°C, and at a rotational speed of 50 rpm, measure the viscosity of the colored resin composition when the coloring resin composition is prepared and put the colored resin composition in. The viscosity after standing at room temperature (30°C) for 1 week was calculated, and the viscosity change rate was calculated. When the viscosity change rate was 15% or more, the storage stability was judged to be poor.

<Adhesion evaluation> Colored resin composition 1 was spin-coated on (S-2) using a spin coater ("1H-DS (trade name)" manufactured by MIKASA Co., Ltd.), and a hot plate ("1H-DS (trade name)" manufactured by Dainippon SCREEN Co., Ltd.) was used. SCW-636 (trade name)") prebaked the substrate at 100°C for 10 minutes to obtain a prebaked film. Then, using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), it was applied and baked at 230° C. for 30 minutes (in air) to obtain a solid film of colored resin composition 1 having a thickness of 1.5 μm.

In addition, the coloring 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 then a hot plate (manufactured by Dainippon SCREEN) was used. Co., Ltd. "SCW-636 (trade name)") prebaked the substrate at 100° C. for 10 minutes to obtain a prebaked film. Using a photolithography machine (manufactured by Union Optical Co., Ltd.) with an ultra-high pressure mercury lamp as a light source, the pre-baked film was exposed without passing through the mask. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), it was subjected to shower development with a 0.045 mass % KOH aqueous solution for 60 seconds, followed by washing with water for 30 seconds. Then, using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), it was applied at 230° C. for 30 minutes (in air), and then baked for 30 minutes (in the air) to obtain coloring resin compositions 2 to 7 each having a thickness of 1.5 μm solid film.

The obtained solid film was evaluated for adhesion to the substrate. Specifically, according to JIS K5600-5-6 (1999), a 100-grid test was performed according to 6-stage evaluation of 5B to 0B (the larger the number, the higher the adhesion). Among them, when the adhesiveness is 2B or less, since there is a possibility of causing a failure of the touch panel due to peeling of the cured product, etc., the adhesiveness is preferably 3B or more, and more preferably 4B or more.

<Patternability evaluation> 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 a hot plate (manufactured by Dainippon SCREEN Co., Ltd.) was used. "SCW-636 (trade name)") was prebaked on the substrate at 100° C. for 10 minutes to obtain a prebaked film. The prebaked film was exposed through a desired mask using a photolithography machine (manufactured by Union Optical Co., Ltd.) with an ultra-high pressure mercury lamp as a light source. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), spray development was performed for 60 seconds with a 0.045 mass % KOH aqueous solution, followed by washing with water for 30 seconds to perform patterning. After exposure and development, the minimum pattern size after development was measured at the exposure amount to form a 5 μm line width and line spacing pattern with a width of 1:1 as the resolution. The exposure amount was measured with an I-line illuminometer.

The results of each evaluation are shown in Table 3.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 resin composition resin composition 1 Resin composition 2 Resin composition 3 Resin composition 4 Resin composition 5 Resin composition 6 Resin composition 7 Resin composition 8 Resin composition 9 Resin composition 10 composition Electroconductive particle with carbon-containing coating layer (A) [g] A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-2 A-1 80.0 80.0 80.0 80.0 80.0 80.0 80.0 80.0 80.0 70.0 Compound (B) [g] B-1 B-1 B-1 B-1 B-1 B-1 B-2 B-3 B-1 B-1 0.50 0.50 0.30 0.05 1.00 2.10 0.50 0.50 0.50 0.44 Binder resin (C) [g] C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 17.5 10.0 10.2 10.5 9.5 8.4 10.0 10.0 10.0 20.3 Sensitizer (D) [g] - 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Acrylic monomer [g] - 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 Dispersant [g] 2 2 2 2 2 2 2 2 2 1.75 Total solid content [g] 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Content [mass part] of compound (B) with respect to 100 mass parts of electroconductive particles (A) 0.63 0.63 0.38 0.06 1.25 2.63 0.63 0.63 0.63 0.63 substrate S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 Evaluation results patterning ResolutionL/S (μm) - 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.0 conductivity Volume resistivity (μΩ・cm) 30.0 30.0 25.0 20.0 35.0 45.0 30.0 50.0 35.0 40.0 residue on the substrate Transmission change (400 nm) - 0.4% 0.3% 0.1% 0.6% 0.9% 0.4% 1.0% 0.4% 0.4% adhesion 100 grid test 5B 5B 4B 3B 5B 5B 4B 5B 5B 5B

[Table 2] Example 11 Example 12 Example 13 Example 14 Comparative Example 1 Comparative Example 2 Comparative Example 3 resin composition Resin composition 11 Resin composition 12 Resin composition 13 Resin composition 14 Resin composition 15 Resin composition 16 Resin composition 17 composition Electroconductive particle with carbon-containing coating layer (A) [g] A-1 A-1 A-1 A-1 A-1 A-1 A-3 90.0 80.0 80.0 80.0 80.0 80.0 80.0 Compound (B) [g] B-1 B-1 B-1 B-1 - B'-4 B-1 0.56 0.50 0.50 0.50 0.50 0.50 Binder resin (C) [g] C-1 C-2 C-1 C-1 C-1 C-1 C-1 3.7 10.0 10.0 10.0 10.5 10.0 10.0 Sensitizer (D) [g] 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Acrylic monomer [g] 2.0 6.0 6.0 6.0 6.0 6.0 6.0 Dispersant [g] 2.25 2 2 2 2 2 2 Total solid content [g] 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Content [mass part] of compound (B) with respect to 100 mass parts of electroconductive particles (A) 0.63 0.63 0.63 0.63 - 0.63 0.63 substrate S-1 S-1 S-2 S-3 S-1 S-1 S-1 Evaluation results patterning ResolutionL/S (μm) 3.0 2.5 2.5 2.5 2.5 3.5 10.0 conductivity Volume resistivity (μΩ・cm) 15.0 35.0 30.0 30.0 20.0 80.0 30.0 residue on the substrate Transmission change (400 nm) 0.8% 0.4% 0.4% 0.6% 0.4% 3.5% 3.5% adhesion 100 grid test 5B 5B 5B 5B 0B 5B 0B

[table 3] Example 15 Example 16 Example 17 Example 18 Example 19 Comparative Example 4 Comparative Example 5 Colored resin composition Colored resin composition 1 Colored resin composition 2 Colored resin composition 3 Colored resin composition 4 Colored resin composition 5 Colored resin composition 6 Colored resin composition 7 composition Carbon black [g] F-1 F-1 F-2 F-1 F-1 F-1 F-1 164.5 164.5 164.5 164.5 164.5 164.5 164.5 Compound (B) [g] B-1 B-1 B-1 B-1 B-1 - B'-4 7.50 7.50 7.50 0.50 18.00 7.50 Binder resin (C) [g] C-1 C-1 C-1 C-1 C-1 C-1 C-1 137.8 79.8 79.8 79.8 79.8 79.8 79.8 Sensitizer (D) [g] - 11.6 11.6 11.6 11.6 11.6 11.6 Acrylic monomer [g] - 46.4 46.4 46.4 46.4 46.4 46.4 Dispersant [g] 25 25 25 25 25 25 25 Total solid content [g] 334.79 334.79 334.79 327.79 345.29 327.29 334.79 Content [mass part] with respect to 100 mass parts of particulate compound (B) 4.56 4.56 4.56 0.30 10.94 0.00 4.56 substrate S-2 S-2 S-2 S-2 S-2 S-2 S-2 Evaluation results storage stability Viscosity change rate (30℃×1 week) 5% 6% 8% 6% 14% 6% 25% patterning ResolutionL/S (μm) - 5um 5um 5um 10um 5um 10um adhesion 100 grid test 5B 5B 3B 3B 5B 0B 4B [Possibility of Industrial Use]

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

without.

without.

without.

Claims (20)

A resin composition comprising: particles, a compound (B) having a structure represented by the general formula (1) and a functional group that generates an amine group by heat, and a binder resin (C), wherein the particles are organic Pigment (F), or inorganic particles (G) having a coating layer containing carbon,

(In the general formula (1), X represents a Si, Ti or Zr atom; R ¹ to R ³ each independently represent a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isopropyl group Butoxy or hydrocarbon group with 1 to 6 carbon atoms; R ¹ to R ³ may be the same or different, but at least one of them is hydroxyl, methoxy, ethoxy, propoxy, isopropoxy, butyl oxy or isobutoxy). The resin composition of claim 1, wherein the fine particles are inorganic particles (G) having a coating layer containing carbon, and the inorganic particles (G) are conductive particles (A). The resin composition according to claim 2, wherein the pH of the suspension in water with a concentration of 1 mass % of the conductive particles (A) is 4.0 to 10.0. The resin composition of claim 1, wherein the particles have an average primary particle size of 1-700 nm. The resin composition according to claim 1, which contains 0.1 to 2.5 parts by mass of the compound (B) with respect to 100 parts by mass of the fine particles. The resin composition of claim 1, wherein the fine particles are inorganic particles (G) having a carbon-containing coating layer, and the inorganic particles (G) are inorganic pigments. The resin composition of claim 1, wherein the fine particles are organic pigments (F). The resin composition of claim 7, wherein the surface of the organic pigment (F) is acidic. The resin composition according to any one of claims 1 to 8, wherein the functional group for generating an amine group by heat is at least one selected from the group consisting of an amide group, an imide group, a urea group and an isocyanate group . The resin composition of claim 9, wherein the functional group that generates the amine group by heat is a urea group. The resin composition according to any one of claims 1 to 10, wherein the binder resin (C) has an acid dissociable group. The resin composition according to any one of claims 1 to 11, further comprising a photosensitizer (D), and the binder resin (C) has an alkali-soluble group. A wiring board provided with a conductive pattern composed of a cured product of the resin composition according to any one of claims 1 to 3. The wiring board of claim 13, which further has a black layer. The wiring substrate of claim 13 or 14, wherein the conductive pattern has a width of 1 to 6 μm. A touch panel having the wiring substrate according to any one of claims 13 to 15. A method of manufacturing a conductive pattern, comprising: A coating step of applying the resin composition according to any one of claims 1 to 3 on a substrate so as to form a desired pattern shape to obtain a coating film, The drying step of drying the coated film to obtain a dry film, A heating step of heating the dried film to obtain a conductive film. A method of manufacturing a conductive pattern, comprising: The coating step of coating the resin composition according to any one of claims 1 to 3 on a substrate to obtain a coating film, The drying step of drying the coated film to obtain a dry film, an exposure step of exposing the dried film to obtain an exposed film, the developing step of developing the exposed film to form a pattern, A heating step of heating the pattern to obtain a conductive film. The method for producing a conductive pattern according to claim 17 or 18, wherein the heating step of heating the pattern to obtain a conductive film is at 150-270°C. A conductive pattern comprising: conductive particles (A) having a coating layer containing carbon, a compound (E) having a structure represented by the general formula (2) and an amine group, and a binder resin (C), wherein the binder resin (C) has an alkali-soluble group,

(In the general formula (2), Y represents a Si, Ti or Zr atom; R ⁴ to R ⁶ each independently represent a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isopropyl group A butoxy group, a hydrocarbon group having 1 to 6 carbon atoms, or a bridging oxygen; each of R ⁴ to R ⁶ may be the same or different, but at least one of them is a bridging oxygen.