WO2021193354A1

WO2021193354A1 - Resin composition, wiring board and method for producing conductive pattern

Info

Publication number: WO2021193354A1
Application number: PCT/JP2021/011087
Authority: WO
Inventors: 日比野利保; 此島陽平; 三井博子; 山舖有香; 井上欣彦
Original assignee: 東レ株式会社
Priority date: 2020-03-27
Filing date: 2021-03-18
Publication date: 2021-09-30
Also published as: JP7095803B2; KR20220158678A; JPWO2021193354A1; CN115210322B; CN115210322A; TW202204501A

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

Method for manufacturing resin composition, wiring board and conductive pattern

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

In recent years, various displays such as TVs, mobiles, car navigation systems, and digital signage have become larger and have higher definition. As the size of the electronic wiring increases, the length of the electronic wiring increases. Therefore, from the viewpoint of maintaining power consumption, there is an increasing demand for improving the conductivity of the wiring, that is, reducing the resistance. As for high definition, as the electronic wiring is miniaturized, the wiring cross-sectional area becomes smaller, so it is necessary to increase the conductivity in order to make the wiring resistance equivalent.

As a method of forming a conductive pattern used for electronic wiring, a pattern is formed on a substrate using a resin composition containing conductive particles and a binder resin, and then the conductive particles are brought into contact with each other by heating. , A method of obtaining a conductive pattern is common (Patent Document 1). Examples of the method for forming a pattern on a substrate include a screen printing method, an inkjet method, and a photolithography method. Among them, the screen printing method and the inkjet method are not suitable for forming fine patterns, and the photolithography method is said to be suitable for forming fine patterns.

Here, there is known a technique of reducing the surface energy of particles by using conductive fine particles having a sufficiently small particle size, promoting fusion of the conductive particles, and increasing the conductivity of electronic wiring. Examples of the resin composition using conductive fine particles having a sufficiently small particle size include a resin composition using surface-coated silver fine particles (Patent Document 2). 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 for color filters and the like are also required to have high definition. The coloring pattern is formed by the same method as the conductive pattern using a coloring pigment-containing resin composition containing a pigment and a binder resin.

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

However, in the resin composition using the surface-coated silver fine particles, if the fusion of the silver fine particles surface is promoted by high-temperature heating or the like in order to increase the conductivity, there is a problem that the adhesion to the base material is lowered. there were. On the other hand, there is a method of adding an adhesion improver having an amino group in order to impart adhesion, but there is a problem that the dispersibility of silver fine particles in the resin composition is deteriorated and the conductivity is lowered. Therefore, it has been difficult to achieve both adhesion and improved conductivity.

Further, also in the color pigment-containing resin composition, when an adhesion improver having an amino group is added, there is a problem that the dispersibility of the pigment is deteriorated and the storage stability is lowered.

The present invention has been devised in view of the drawbacks of the prior art, and an object of the present invention is to obtain a pattern having excellent dispersibility and adhesion, and in particular, a resin composition containing conductive particles. In the present invention, it is an object of the present invention to provide a resin composition capable of maintaining adhesion with a base material even if fusion of the surface of silver fine particles is promoted in order to increase conductivity. By using such a resin composition, it is possible to obtain a pattern having both good dispersibility (that is, good conductivity in a resin composition containing conductive particles) and adhesion.

As a result of diligent studies, the present inventors have found that it is extremely effective to include the compound (B) having a structure that enhances the adhesion to the substrate and a functional group that produces an amino group by heat in the resin composition in order to solve the above-mentioned problems. I found that.

That is, the present invention contains fine particles, a compound (B) having a structure represented by the general formula (1) and a functional group that produces an amino group by heat, and a binder resin (C), and the fine particles are organic pigments ( F) or a resin composition which is an inorganic particle (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 are independently hydroxy groups, methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups and isobutoxy groups, respectively. Alternatively, it indicates a hydrocarbon group having 1 to 6 carbon atoms. R ¹ to R ³ may be the same or different, but at least one is a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy. Group, butoxy group or isobutoxy group.)

According to the resin composition of the present invention, it is possible to obtain a pattern having both good dispersibility (that is, good conductivity in a resin composition containing conductive particles) and adhesion even in a fine pattern. It becomes.

The resin composition of the present invention contains fine particles, a compound (B) having a structure represented by the general formula (1) and a functional group that produces an amino group by heat, and a binder resin (C). It is characterized by being an organic pigment (F) or an inorganic particle (G) having a coating layer containing carbon.

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

Organic pigments include colored organic pigments, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo, polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine; aminoanthraquinone, Anthraquinone pigments such as diaminodianthraquinone, antrapyrimidine, flavantron, antoanthron, indantron, pyranthron, biolantron; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; isoindolin pigments; Examples thereof include isoindolinone-based pigments; quinophthalone-based pigments; slene-based pigments; and metal complex-based pigments.

Examples of organic pigments include black organic pigments and mixed color organic pigments. Examples of the black organic pigment include carbon black, perylene black, aniline black, and benzofuranone pigments. Examples of the mixed color organic pigment include those obtained by mixing two or more kinds of pigments having colors such as red, blue, green, purple, yellow, magenta, and cyan to make a pseudo black color. Two or more of these organic pigments may be contained. Among these, carbon black is preferable from the viewpoint of further improving the light-shielding property of the colored film and adjusting the conductivity of the colored film.

Further, in the present invention, in order to make the effect more remarkable, it is preferable that the surface of the organic pigment (F) is acid-treated. Since the surface is acid-treated, the dispersion stability is improved, and the adhesion to the base material can be improved by the interaction with the compound (B). As a method for acid treating the surface of carbon black, a method of oxidizing the surface by _{O 3} (JP-A-11-181326 discloses) a method for wet oxidation treatment of the surface (Japanese Patent No. 4,464,081), and sulfonic acid groups, etc. A method of surface modification with an organic group composed of a non-polymer group (International Publication No. 2006/044676) and the like are known.

In the resin composition of the present invention, the content ratio of the organic pigment (F) is preferably 10 to 70% by mass with respect to 100% by mass of the solid content. When the content ratio is 10% by mass or more, a coating having a coloring power can be formed with a thin film. The content ratio is preferably 20% by mass or more. On the other hand, when the content ratio is 70% by mass or less, the dispersion stability of the organic pigment (F) can be improved and the adhesion to the base material can be ensured. 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, may be simply referred to as "inorganic particles (G)"). The inorganic particles (G) are particles whose surface is coated with, for example, a carbon compound. Examples of carbon compounds include aromatic hydrocarbons, aliphatic hydrocarbons, or oxides, nitrides, sulfides, phosphides, and the like thereof. Among these, aromatic hydrocarbons, aliphatic hydrocarbons or oxides thereof are preferable from the viewpoint of being able to suppress fusion of inorganic particles (G) at low temperatures. By containing the inorganic particles (G), various functions such as conductivity and light-shielding property can be imparted to the cured product of the resin composition of the present invention. Further, since the surface of the inorganic particles (G) is coated with a coating layer containing carbon, fusion of the inorganic particles (G) at a low temperature is suppressed, the resolution is lowered due to the coarsening of the particles, and residue is generated. Can be suppressed. Further, the adhesion can be improved by reacting with a functional group that produces an amino group by heat described later.

Examples of the inorganic particles (G) include conductive particles (A). Examples of the conductive particles include gold (Au), silver (Ag), copper (Cu), nickel (Ni), tin (Sn), bismuth (Bi), lead (Pb), zinc (Zn), and palladium ( Examples thereof include metal fine particles such as Pd), platinum (Pt), aluminum (Al), tungsten (W) and 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 preferable, and silver is preferable from the viewpoint of improving conductivity. It is more preferable that the fine particles of.

Examples of the method of coating the surface of the inorganic particles with a coating layer containing carbon include a method of contacting the reactive gas with the inorganic particles by a thermal plasma method (Japanese Patent Laid-Open No. 2007-138287). The surface of the inorganic particles (G) is preferably completely coated, but as long as this object is achieved, it is permissible for some particles to be incompletely coated.

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

For the average thickness of the coating layer, measure the mass loss of the inorganic particles (G) by a hot balance, and assume that all the values are due to the combustion of carbon. It can be calculated as 0. Conductive particles having a known particle size (Dp) are coated with carbon having an average thickness of A (μm), and the number of carbon-coated conductive particles is defined as n. Assuming that the mass first weighed in the hot balance measurement is W ₁ (g), the mass after completely burning carbon is W ₂ (g), and the density of inorganic particles is ρ, Dp and W are derived from the following equations. _{If 2} is known, n can be calculated.
W ₂ = π / 6 × Dp ³ ρ × n
Then, the average thickness A of the coating layer can be calculated from the following formula.
W _1- W ₂ = {4/3 x π (Dp / 2 + A) ^3- π / 6 x Dp ³ } x 2.0 x n
The surface of the conductive particles (A), which are the inorganic particles (G), may be acidic or basic depending on the type of material forming the coating layer containing carbon. The pH of the suspension in which the conductive particles (A) are suspended in water at a concentration of 1% by mass is preferably 4.0 to 10.0. This pH is measured as follows. 0.3 g of conductive particles (A) is added to 2.7 g of pure water to prepare a suspension having a concentration of 1% by mass, and then the mixture is stirred for 5 minutes and allowed to stand for 15 minutes. The supernatant of the obtained suspension is collected and measured using a pH meter. When the pH is 4.0 or more, the carbon coating layer strongly interacts with the dispersant described later, so that stable dispersion can be achieved even with a small dispersant content. When the pH is 10.0 or less, the reaction between the conductive particles (A) and the binder resin (C) can be suppressed, the pH of the resin composition can be kept in an appropriate range, and the storage stability can be improved. .. In order to control the pH of the suspension of the conductive particles (A), for example, when the conductive particles (A) are produced by the thermal plasma method, the type and introduction ratio of the reactive gas should be changed. Can be achieved with.

The average primary particle size of the fine particles is preferably 1 to 700 nm. In particular, the average primary particle size of the conductive particles (A) is preferably 1 to 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 dispersant can be stably dispersed. Further, when the average primary particle size is 700 nm or less, a fine pattern can be formed. Here, the average primary particle size of the fine particles is calculated from the average value of the particle sizes of 100 primary particles randomly selected using a scanning electron microscope. The particle size of each primary particle is calculated from the average value obtained by measuring the major axis and minor axis of each primary particle.

In the resin composition of the present invention, the content ratio of the inorganic particles (G) is preferably 65 to 95% by mass with respect to 100% by mass of the solid content. When the content ratio is 65% by mass or more, the residual organic component does not interfere with the contact between 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% by mass or less, the residual organic component can stabilize the dispersibility of the inorganic particles (G) in the resin composition and form a fine pattern on the substrate. The residue can be reduced. 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) to the total solid content can be calculated by quantitatively analyzing all the components of the resin composition. The ratio of each component described later can also be calculated by the same method.

The method for analyzing all the components of the resin composition is as follows.
(I) The resin composition is diluted with an organic solvent, and ^{1 1} H-NMR measurement, GC measurement and GC / MS measurement are carried out to examine the outline thereof.
(Ii) After extracting the resin composition with an organic solvent, centrifugation is performed to separate the soluble component and the insoluble component.
(Iii) The insoluble component is extracted with a highly polar organic solvent and then centrifuged to further separate the soluble component and the insoluble component.
^{(Iv) IR measurement, 1} H-NMR measurement and GC / MS measurement are performed on the mixed solution of the soluble components obtained in (ii) and (iii) above. Further, the above mixed solution is separated by GPC. IR measurement and ¹ H-NMR measurement are performed on the obtained sample. Further, for the preparative material, GC measurement, GC / MS measurement, thermal decomposition GC / MS measurement and MALDI / MS measurement are performed as necessary.
(V) IR measurement or TOF-SIMS measurement is performed on the insoluble component obtained in (iii) above. If it is confirmed that organic matter is present, thermal decomposition GC / MS or TPD / MS measurement is performed.
(Vi) The content of each component contained in the resin composition can be determined by comprehensively judging the measurement results of (i), (iv) and (v) above. The highly polar organic solvent used in (iii) above is preferably chloroform, methanol or the like.

[Compound (B) having a functional group that produces an amino group by heat and a structure represented by the general formula (1)]
The resin composition of the present invention may be referred to as a compound (B) having a structure represented by the following general formula (1) and a functional group that produces an amino group by heat (hereinafter, simply referred to as "compound (B)". ) Is contained.

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

Examples of the hydrocarbon group having 1 to 6 carbon atoms include an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be linear or branched, and may be partially or wholly cyclic. Examples of the hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group and a cyclohexyl group. Among these, a methyl group, an ethyl group or a propyl group is preferable from the viewpoint of having less steric hindrance and not hindering adhesion to the substrate.

After forming a pattern, compound (B) is heated in a temperature range of, for example, 100 to 300 ° C. for 5 to 120 minutes to form an amino group. The generated amino group interacts with the surface of the organic pigment (F) or the inorganic particle (G), and the structure represented by the general formula (1) interacts with the base material, so that the pattern and the base material adhere to each other. Is improved. Adhesion conforms to JIS K5600-5-6 (1999) and can be evaluated by a cross-cut test. Further, among the R 1 ^~ R ^3, hydroxy group, a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, butoxy group, isobutoxy group desorbed to produce a silanol group by heating, silanol groups are polycondensed As a result, the compound (E) having the structure represented by the general formula (2) and an amino group is produced.

(In the general formula (2), Y represents a Si, Ti or Zr atom. R ⁴ to R ⁶ are independently hydroxy groups, methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups and isobutoxy groups, respectively. , A hydrocarbon group having 1 to 6 carbon atoms or cross-linked oxygen. R ⁴ to R ⁶ may be the same or different, but at least one is cross-linked oxygen.)
On the other hand, since the amino group does not exist in the compound (B) in the resin composition before heating, the compound (B) does not react with the surface of the organic pigment (F) or the inorganic particles (G) and can exist stably. .. Therefore, during storage of the resin composition, functional inhibition due to viscosity change and deterioration of dispersibility of the organic pigment (F) or inorganic particles (G) is prevented, and the substrate is permeated by the development residue in the coating film of the resin composition. Does not cause a decrease in rate. Moreover, the pattern workability can be improved. Here, heating for the purpose of generating an amino group and heating for the purpose of imparting a function to the resin composition pattern can be performed at the same time.

The central element X of the general formula (1) is preferably Si from the viewpoint of reactivity. ^{Further, R 1} to R ³ of the general formula (1) are preferably a methoxy group or an ethoxy group, and more preferably a methoxy group, from the viewpoint of adhesion to the base material.

Examples of the functional group that produces an amino group by heat include an amide group, an imine group, a ureido group and an isocyanate group. By using at least one of these functional groups, the stability of the resin composition and the coating film can be enhanced, and the adhesion to the substrate after heating can be further improved. A ureido group is particularly preferable from the viewpoint of enhancing the dispersion stability of the organic pigment (F) and the inorganic particles (G) of the resin composition, further improving the conductivity, and suppressing the residue.

Specifically, the compound (B) is 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine. , 3-Tripropoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-trimethoxysilyl-N- (phenylmethylene) propylamine, 3-triethoxysilyl-N- (phenylmethylene) propylamine , 3-Tripropoxysilyl-N- (phenylmethylene) propylamine, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-isocyanuppropyltriethoxysilane and 3-isocyanuppropyltrimethoxysilane. .. Of these, 3-ureidopropyltriethoxysilane and 3-ureidopropyltrimethoxysilane are more preferable as the compound having a ureido group. 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 the fine particles. In particular, it is preferably 0.1 to 2.5 parts by mass with respect to 100 parts by mass of the conductive particles (A). When the content is 0.1 part by mass or more, the adhesion can be further improved. The content of compound (B) is more preferably 0.5 parts by mass or more. On the other hand, when the content is 2.5 parts by mass or less, the conductivity can be further improved. The content of 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 adhesion can be further improved. The content of 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 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), for example, a cellulosic resin such as ethyl cellulose or nitrocellulose, an acetal resin such as polyvinyl butyral, an acrylic resin obtained by polymerizing butyl methacrylate, methyl methacrylate or the like is preferably used. However, an acrylic resin is particularly preferable from the viewpoint of ease of composition design. Here, the acrylic resin refers to a resin obtained by copolymerizing at least a (meth) acrylic monomer with a resin component. Here, examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, and tert. -Butoxycarbonyl (meth) acrylate, benzyl (meth) acrylate, methyladamantyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl ( Examples thereof include meta) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, isobonyl (meth) acrylate or phenyl (meth) acrylate.

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

The binder resin (C) preferably has an acid dissociative group. The acid dissociable group is an organic group that is thermally oxidatively decomposed and desorbed by the action of an acid under heating. By having such an acid dissociable group, for example, by heating at 100 to 300 ° C. in an acidic atmosphere, the acid dissociative group is easily thermally oxidatively decomposed and desorbed, and the resin composition of the present invention is cured. The material can be shrunk to increase the proportion of fine particles in the cured product and further improve its function. As a result, for example, when the fine particles are inorganic particles (G), it becomes easy to obtain a desired conductivity having a specific resistance of 10 to 1,000 μΩ · cm. In this case, when a photoacid generator and / or a thermoacid generator, which will be described later, are used in combination, the effect becomes even more remarkable.

The acid dissociative group is preferably an organic group having 4 to 15 carbon atoms. Since the acid dissociative group has 4 or more carbon atoms, it vaporizes at a low temperature after desorption, so that the function is further improved without generating large bubbles in the cured product and hindering the contact between the fine particles. .. The acid dissociative group preferably has 6 or more carbon atoms. On the other hand, when the acid dissociative group has 15 or less carbon atoms, the dissociative group does not remain in the cured product after desorption and does not interfere with the contact between the fine particles, and the function is further improved. Further, even if bubbles are generated in the cured product, they can be easily eliminated by heating.

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

The binder resin (C) is preferably a resin obtained by copolymerizing 20 to 80 mol% of a compound having an acid dissociative group. In particular, when the binder resin (C) is an acrylic resin, it is preferable that the (meth) acrylic acid ester having an acid dissociative group is contained in the acrylic resin in an amount of 20 to 80 mol% 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. In order to obtain a photosensitive resin composition, it is preferable to further have a photosensitive agent (D) described later and the binder resin (C) to have an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, an acid anhydride group and the like, but the carboxyl group is particularly preferable from the viewpoint of reactivity and versatility. ..

It is preferable that the binder resin (C) is an acrylic resin having an alkali-soluble group from the viewpoint of ease of composition design. When the binder resin (C) is an acrylic resin having an alkali-soluble group, examples of the compound containing a carboxyl group, which is a copolymerization component that imparts alkali solubility, include (meth) acrylic acid, itaconic acid, and crotonic acid. , Maleic acid or fumaric acid or acid anhydrides thereof.

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

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

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

Examples of the compound having a glycidyl group and a carbon-carbon double bond include glycidyl (meth) acrylate, allyl glycidyl ether or glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonate or glycidyl isocrotonate. Examples of the compound having an isocyanate group and a carbon-carbon double bond include (meth) acryloyl isocyanate and (meth) acryloyloxyethyl isocyanate.

In the resin composition of the present invention, the content of the binder resin (C) is preferably in the range of 1 to 30% by mass when the solid content is 100% by mass. When it is 1% by mass or more, the viscosity of the resin composition suitable for coating can be adjusted, and when it is 30% by mass or less, the function can be further improved.

[Photosensitizer (D)]
When the resin composition of the present invention is used as a photosensitive resin composition, it preferably contains a photosensitive agent (D) from the viewpoint of forming a fine pattern. By containing the photosensitizer (D), it is possible to impart positive or negative photosensitivity to the resin composition.

As the photosensitizer (D), a photopolymerization initiator, a photoacid generator, and a photobase generator are preferably used. Examples of the photopolymerization initiator include acetphenone compounds, benzophenone compounds, benzoin ether compounds, α-aminoalkylphenone compounds, thioxanthone compounds, organic peroxides, imidazole compounds, titanosen compounds, and triazine compounds. , Acylphosphine oxide compound, quinone compound or oxime ester compound, but an oxime ester compound having high sensitivity even when added in a small amount is preferable, and an oxime ester compound having a carbazole skeleton is more preferable.

Specific examples of the oxime ester compound having no carbazole skeleton include 1,2-propanedione-3-cyclopentane, 1- [4- (phenylthio) -2- (O-benzoyloxime)], 1,2. -Octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] and the like, and specific examples of the oxime ester compound having a carbazole skeleton include 3-cyclopentylethaneone, 1-[. 9-Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), etanone, 1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazole-3-yl]-, 1- (0-acetyloxime) and the like can be mentioned.

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

Examples of the photoacid generator include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts and the like, but quinone diazide compounds are more preferable. The quinone diazide compound includes a compound having a 5-naphthoquinone diazidosulfonyl group and a compound having a 4-naphthoquinone diazidosulfonyl group, and any of these is preferably used. The quinonediazide sulfonic acid ester is a polyhydroxy compound with quinonediazide sulfonic acid bonded by an ester, a polyamino compound with quinonediazide sulfonic acid bonded with a sulfonamide, and a polyhydroxypolyamino compound with quinonediazide sulfonic acid bonded with an ester bond and /. Alternatively, those bonded with a sulfonamide may be mentioned. In the resin composition of the present invention, the content of the photoacid generator is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the binder resin (C).

Examples of the photobase generator include amide compounds and ammonium salts.

Examples of the amide compound include 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate, 9-anthrylmethyl-N, N-dimethylcarbamate, 1- (anthraquinone-2yl) ethylimidazole carboxylate, and the like. Examples thereof include (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine.

Examples of the ammonium salt include 1,2-diisopropyl-3- (bisdimethylamino) methylene) guanidium 2- (3-benzoylphenyl) propionate, (Z)-{[bis (dimethylamino) methylidene] amino} -N. -Cyclohexylamino) metaniminium tetrakis (3-fluorophenyl) borate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate and the like.

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

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

As the dispersant, amine-based ones are preferable. Examples of commercially available amine-based dispersants include DISPERBYK (registered trademark) 142, 145, 161, 167, 180, 2001, 2008, 2022, 2150, 6919 or 21116 (all manufactured by Big Chemie Japan). Be done.

In order to further improve the dispersibility, the dispersant preferably has an acrylic block copolymer structure. Examples of commercially available amine-based dispersants having an acrylic block copolymer structure include DISPERBYK® 2001, 2008, 2022, 2150, 6919 or 21116.

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

[Acrylic monomer]
From the viewpoint of adjusting the photosensitive performance and improving the pattern processability, the resin composition of the present invention uses an acrylic monomer, and when the fine particles are conductive particles (A), contact and fuse the conductive particles with each other. It may be contained within a range that does not inhibit it.

Examples of the acrylic monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate or dipentaerythritol hexa (meth) acrylate. Examples thereof include pentaerythritol penta (meth) acrylate or an alkyl-modified product thereof, an alkyl ether-modified product or an alkyl ester-modified product thereof.

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

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

[Polymerization inhibitor]
The resin composition of the present invention may contain a polymerization inhibitor. By containing an appropriate amount of the polymerization inhibitor, the resolution after development is improved. The polymerization inhibitor is not particularly limited and known ones can be used. Examples thereof include dit-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone and t-butylcatechol. .. Examples of commercially available polymerization inhibitors include "IRGANOX 1010", "IRGANOX 245", (all manufactured by BASF) and the like.

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

[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 the dispersibility and control the conductivity. Examples of other particles include conductive particles or metal oxide fine particles or inorganic pigments which are not surface-coated.

The particle size of these other particles is preferably 1 to 100 nm. When the particle size is 1 nm or more, the use of a dispersant for stabilizing dispersion can be reduced, and when the fine particles are conductive particles (A), the conductivity can be further improved. On the other hand, when the particle size is 100 nm or less, the resolution of the pattern is improved and a fine pattern can be formed. Twice

[Thermal acid generator and photoacid generator]
The resin composition of the present invention may contain a thermoacid generator. When the binder resin (C) is a binder resin having an acid dissociable group, the generated acid promotes the decomposition of the acid dissociable group, and the heat treatment temperature in air can be lowered. Further, a photoacid generator may be contained. The photoacid generator is as described above.

Examples of the thermoacid generator, which is a compound that generates acid by heat, include SI-150L, SI-160L, SI-180L or SI-200 (all manufactured by Sanshin Chemical Industry Co., Ltd.), 4- Hydroxyphenyldimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium or 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium Alternatively, these methane sulfonates, trifluoromethane sulfonates, camphor sulfonates or p-toluene sulfonates can be mentioned. Among them, 4-hydroxyphenyldimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium or 2-methylbenzyl-4-benzoyloxy. Phenylmethyl sulfonium or these methane sulfonates, trifluoromethane sulfonates, camphor sulfonates or p-toluene sulfonates can be preferably used.

In the resin composition of the present invention, the content of the thermoacid generator promotes the decomposition of the acid dissociable group in the binder resin (C) having the acid dissociative group, and causes the inorganic particles (G) to come into contact with each other. The range is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the binder resin (C) in order to obtain higher functions without hindering.

[Sensitizer]
When the resin composition of the present invention contains a photoacid generator, the resin composition may further contain a sensitizer. The sensitizer is preferably one that vaporizes by heat treatment, or one that fades by light irradiation even when it remains in the cured product of the resin composition of the present invention, and from the viewpoint of high resolution in pattern processing, light Those that fade with irradiation are more preferable.

Examples of the sensitizer that vaporizes by heat treatment or fades by light irradiation include coumarin such as 3,3'-carbonylbis (diethylaminocoumarin), anthracene such as 9,10-anthracene, benzophenone, and 4,4'. -Aromatic ketones such as dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone or benzaldehyde or biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene, triphenylene, pyrene, anthracene, 9-phenylanthracene, 9-methoxyanthracene , 9,10-diphenylanthracene, 9,10-bis (4-methoxyphenyl) anthracene, 9,10-bis (triphenylsilyl) anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9, 10-Dipropoxyanthracene (DPA; manufactured by Kawasaki Kasei Co., Ltd.), 9,10-dibutoxyanthracene (DBA; manufactured by Kawasaki Kasei Co., Ltd.), 9,10-dipentaoxyanthracene, 2-t-butyl-9 , 10-Dibutoxyanthracene or 9,10-bis (trimethylsilylethynyl) anthracene and other condensed aromatics.

As the sensitizer that vaporizes by heat treatment, it is preferable that the thermal decomposition product sublimates, evaporates or thermally decomposes by heat treatment sublimates or evaporates. As the vaporization temperature of the sensitizer, it does not vaporize at the drying temperature, but decomposes and vaporizes during thermosetting, and when the fine particles are conductive particles (A), the conductive particles are brought into contact with each other and fused to each other. It is preferably 150 to 300 ° C.

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

[Pigments and / or dyes that absorb visible light]
The resin composition of the present invention contains a pigment and / or a dye that absorbs visible light within a range that does not hinder the contact and fusion of the conductive particles when the fine particles are the conductive particles (A). It doesn't matter. Since the resin composition contains an inorganic pigment and / or a 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.

Examples of pigments that absorb visible light include lactam pigments, perylene pigments, phthalocyanine pigments, isoindoline pigments, diaminoanthraquinone pigments, dioxazine pigments, indantron pigments, carbon black or inorganic pigments. Be done.

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

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

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

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

[Adhesion improver]
The resin composition of the present invention may further contain an adhesion improver in addition to the compound (B). Examples of the adhesion improver include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxy. Examples thereof include silane coupling agents such as silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxysilane.

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

Examples of the surfactant include an anionic surfactant such as ammonium lauryl sulfate or polyoxyethylene alkyl ether sulfate triethanolamine, a cationic surfactant such as stearylamine acetate or lauryltrimethylammonium chloride, lauryldimethylamine oxide or lauryl. Amphoteric surfactants such as carboxymethylhydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or sorbitan monostearate, fluorosurfactants or silicone surfactants Can be mentioned.

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

The wiring substrate of the present invention preferably has a conductive pattern made of a cured product of the resin composition of the present invention containing the conductive particles (A). The base material of the wiring board of the present invention is preferably a transparent board. Examples of the transparent substrate include a glass substrate and a resin film. The transparent substrate is preferably a glass substrate from the viewpoint that the developing solution easily permeates during pattern formation and suppresses the residue. Examples of the glass substrate _{include a glass substrate containing two} layers of SiO or _two layers of SiO on the surface, a non-alkali glass substrate, and the like. Examples of the resin film include a film made of at least one selected from the group consisting of polyimide, polyimidesiloxane, polyethersulfone, polybenzoxazole, aramid, polysulfone and epoxy resin. The surface of the resin film may contain _{two layers of SiO.} By using these as a base material, it is possible to obtain a wiring board having high adhesion to a conductive pattern made of a cured product of the resin composition of the present invention.

Further, the wiring board of the present invention may have a film containing an organic component in addition to a conductive pattern made of a cured product of the resin composition of the present invention. From the viewpoint of protecting the conductive pattern, it is preferable that the film containing an organic component is formed on the upper part of the conductive pattern. By having a film containing an organic component, it is possible to prevent scratches due to an external force or the like, and a highly reliable wiring board can be obtained.

Further, the wiring board of the present invention can be suitably used as a member for a touch panel. When used as a touch panel member, it can be used for routing wiring that connects the touch sensor wiring arranged in a mesh shape and the touch sensor wiring. Further, it is also preferable to form the touch sensor wiring and the routing wiring at the same time. The base material of the wiring substrate of the present invention may be used as the cover glass, or the cover material may be bonded onto the wiring substrate of the present invention via 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 not easily affected by defects caused by foreign substances and the like, and a conductive pattern having a desired shape can be formed. On the other hand, when the width of the conductive pattern is 6 μm or less, 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. By having the black layer, the reflectance of the wiring pattern can be reduced to suppress the reflection of external light, and the visibility of the wiring can be suppressed to greatly improve the visibility. As a method for forming the black layer, after forming the wiring pattern, a black positive photosensitive composition is applied to the entire surface and exposed from the base material surface via the wiring pattern, so that the developing solution can be used leaving the upper part of the wiring pattern. Examples thereof include a method of melting and removing by development.

[Manufacturing method of resin composition]
The resin composition of the present invention is prepared by mixing fine particles, compound (B), and binder resin (C), and then using a ball mill, a sand grinder, a three-roll mill, a mild disperser, a medialess disperser, or the like. Manufactured using. If you want to disperse the fine particles uniformly, use a dispersant to prepare a dispersion in which the fine particles are dispersed in an organic solvent in advance, and use this dispersion as a monomer, polymer, adhesion improver, surfactant, and polymerization inhibitor. It may be produced by a method of mixing with a solution containing an agent or the like. In particular, the dispersion liquid of the inorganic particles (G) having a coating layer containing carbon is preferably dispersed using a mild disperser or a medialess disperser in order to prevent the surface coating layer from being damaged, and is medialess. It is more preferable to disperse using a disperser. The dispersion liquid of the inorganic particles (G) having a coating layer containing carbon is, for example, a mild disperser Nanogetter (registered trademark) (Ashizawa Finetech Co., Ltd.) or a high-pressure wet medialess atomizer Nanomizer (Namizer Co., Ltd.). ) Or the like, and inorganic particles (G) having a coating layer containing carbon are dispersed in an organic solvent.

[Manufacturing method of conductive and colored patterns]
The method for producing a conductive pattern of the present invention includes a coating step of applying the resin composition of the present invention on a substrate so as to have a desired pattern shape to obtain a coating film, and drying the coating film to form a dry film. The drying step of obtaining the drying film and the heating step of heating the dried film to obtain a conductive film are provided.

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.

Examples of the base material used in the coating step include a silicon wafer, a ceramic substrate, and an organic substrate. Examples of the ceramic substrate include soda glass, soda glass obtained _{by sputtering SiO 2} on the surface, non-alkali glass, glass substrate such as borosilicate glass or quartz glass, alumina substrate, aluminum nitride substrate or silicon carbide substrate. Examples of the organic substrate include an epoxy substrate, a polyetherimide resin substrate, a polyetherketone resin substrate, a polysulfone resin substrate, a polyimide film or a polyester film.

Examples of the method of applying the resin composition of the present invention on the surface of the base material include coating using a spin coater, bar coater, blade coater, roll coater, die coater, calendar coater or meniscus coater, screen printing, and spray coating. Alternatively, a dip coat may be mentioned.

The method for producing a conductive pattern of the present invention includes a drying step of drying a coating film to obtain a dried film.

Examples of the drying method in the drying step include a hot plate, a hot air dryer (oven), vacuum drying, vacuum drying, and drying by infrared irradiation.

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

Above all, it is preferable to use both heating with a hot plate or a hot air dryer (oven) and vacuum drying together because the solvent can be dried and removed while suppressing the thermosetting of the resin contained in the coating film. The ultimate pressure for vacuum drying is preferably 5 to 200 Pa, more preferably 10 to 100 Pa.

The method for producing a conductive pattern of the present invention includes a heating step of heating a dry film to obtain a conductive film.

By heating the dry film of the resin composition, conductivity is obtained, and at the same time, the compound (B) has an amino group and interacts with the coating layer of the inorganic particles (G) having a coating layer containing carbon. Therefore, the adhesion with the base material is improved.

Examples of the heating method in the heating process include the same as in the drying process. The atmosphere, temperature and time of heating may be appropriately determined depending on the composition of the resin composition and the film thickness of the coating film to be heated, but heating in air in a temperature range of 100 to 300 ° C. for 5 to 120 minutes. Is preferable. 150 to 270 ° C. is more preferable, and heating in the temperature range of 160 to 260 ° C. for 30 to 120 minutes is more preferable.

Further, between the above-mentioned drying step and heating step, an exposure step of exposing the dry film to obtain an exposure film and a development step of developing the exposure film to form a pattern are provided, and a conductive pattern is formed by a photolithography method. It is also preferable to form. In this case, since the compound (B) does not have an amino group and does not react with the inorganic particles (G) in the exposure step, it is possible to form a good pattern having good developer solubility and no development residue in the subsequent developing step. .. After the pattern is formed, an amino group is expressed in the heating step, and the adhesion to the substrate can be improved.

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

Examples of the alkaline substance used in the alkaline developing solution in the developing step include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate or aqueous ammonia, ethylamine or n-propyl. Primary amines such as amines, secondary amines such as diethylamine or di-n-propylamine, tertiary amines such as triethylamine or methyldiethylamine, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH) , Tertiary ammonium salts such as choline, triethanolamine, diethanolamine, monoethanolamine, alcohol amines such as dimethylaminoethanol or diethylaminoethanol, or pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7- Examples include organic alkalis such as undecene, 1,5-diazabicyclo [4,3,0] -5-nonane or cyclic amines such as morpholin, and these include ethanol, γ-butyrolactone, dimethylformamide or N-methyl-. 2-A water-soluble organic solvent such as pyrrolidone may be added as appropriate.

Further, in order to obtain a better conductive pattern, it is also preferable to add 0.01 to 1% by mass of a surfactant such as a non-ionic surfactant to these alkaline developers.

If the conductive pattern is formed in a mesh shape on the substrate, it can be used as a transparent conductive wiring provided in a touch panel, a display panel such as a liquid crystal display or an organic EL, a wearable terminal, or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Among the compounds used in the synthesis examples and examples, those using abbreviations are shown below.
AIBN: 2,2'-azobis (isobutyronitrile)
TMAH: Tetramethylammonium hydroxide.

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

[Organic pigment (F)]
(F-1) Carbon black (TPK1227 manufactured by Cabot) whose surface is modified with a sulfonic acid group.

(F-2) Carbon black without special surface treatment (MA-100 manufactured by Mitsubishi Chemical Corporation)
[Inorganic particles (G) having a coating layer containing carbon]
(A-1) Silver particles having an average thickness of 3 nm and a primary particle size of 50 nm (manufactured by Nisshin Engineering Co., Ltd.). The pH of a suspension of water with a concentration of 1% by mass is 8.0.

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

(A-3) Silver particles with a primary particle size of 200 nm (product name: DJA03N; manufactured by Toyo Kagaku Kogyo Co., Ltd.). The pH of a suspension of water with a concentration of 1% by mass is 5.0. No coating layer containing carbon.

[Compound (B) having a functional group that produces an amino group by heat and a structure represented by the general formula (1)]
(B-1) KBM-585: 3-ureidopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
(B-2) KBE-585: 3-ureidopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
(B-3) KBE-9007: 3-Isocyanatepropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
(B'-4) KBE-903: 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.).

[Binder resin (C)]
(C-1)
2.0 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. 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)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture 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, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain the obtained acrylic. PGMEA was added to the polymer solution so that the solid content concentration became 40 wt% to obtain a solution of the binder resin (C-1). The polystyrene-equivalent weight average molecular weight Mw measured by the GPC method was 18,000.

(C-2)
1.5 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 38.7 g of methacrylic acid, 46.9 g of styrene, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, and the mixture was stirred at room temperature for a while and inside the flask. Was sufficiently replaced with nitrogen by bubbling, and then 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, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain the obtained acrylic. PGMEA was added to the polymer solution so that the solid content concentration became 40 wt% to obtain a solution of the binder resin (C-2). The polystyrene-equivalent weight average molecular weight Mw measured by the GPC method was 14,000.

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

[solvent]
PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Sankyo Chemical Co., Ltd.)
DPM: Dipropylene glycol monomethyl ether (manufactured by Toho Chemical Industry Co., Ltd.).

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

[Acrylic monomer]
Light acrylate (registered trademark) PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.).

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

[Positive photoresist]
(P-1)
2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF; manufactured by Central Glass Co., Ltd.) 29.3 g (0.08 mol), 1,3-bis (3) under a dry nitrogen stream. 1.24 g (0.005 mol) of -aminopropyl) tetramethyldisiloxane, 3.27 g (0.03 mol) of 3-aminophenol as an end-capping agent to 150 g of N-methyl-2-pyrrolidone (NMP) Dissolved. To this, 31.0 g (0.1 mol) of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA; manufactured by Manac Co., Ltd.) was added together with 50 g of NMP, and the mixture was stirred at 20 ° C. for 1 hour. Then, the mixture was stirred 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 azeotropically boiling water with xylene. After the stirring was completed, the solution was poured into 3 L of water to collect a white precipitate. This 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.

Separately, under a dry nitrogen stream, 15.3 g of TrisP-HAP (manufactured by Honshu Chemical Industry Co., Ltd.) and 40.3 g of 5-naphthoquinonediazidosulfonyl acid chloride were dissolved in 450 g of 1,4-dioxane to bring the temperature to room temperature. .. Here, 15.2 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system did not rise above 35 ° C. After the dropping, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was added to water. Then, the precipitated precipitate was dried in a vacuum dryer to obtain a quinonediazide compound.

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

[substrate]
(S-1) _{Glass substrate with SiO 2} sputtered on the surface (TU060; manufactured by TOKEN)
(S-2) Non-alkali glass substrate (OA-10G; manufactured by Nippon Electric Glass Co., Ltd.)
(S-3) Polyimide film (Neoprim; manufactured by Mitsubishi Gas Chemical Company, Inc.).

Examples 1 to 14, Comparative Examples 1 to 3
<Evaluation of conductivity>
The resin composition 1 is spun on the (S-1) substrate 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. After coating, the substrate was prebaked at 100 ° C. for 5 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.) to obtain a prebaked film having a film thickness of 1 μm. Then, using an oven (“IHPS-222”; manufactured by ESPEC CORPORATION), post-baking was performed at 230 ° C. for 30 minutes (in the air) to obtain a solid film made of the resin composition 1. On the obtained solid film, a positive photoresist (P-1) was applied using a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.) at 300 rpm for 10 seconds and at 1000 rpm for 5 seconds. The substrate was spin-coated with a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.) at 100 ° C. for 2 minutes to obtain a prebaked film having a film thickness of 1 μm. The prebake film was exposed using a parallel light mask aligner (“PLA-501F (trade name)” manufactured by Canon Inc.) using an ultrahigh pressure mercury lamp as a light source and through a desired mask. After that, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 2.38 wt% TMAH aqueous solution for 60 seconds, then rinsed with water for 30 seconds, and pattern processing was performed. Was done. The obtained substrate was etched by immersing it in a ferric nitrate aqueous solution having a concentration of 55%, and the resist was peeled off by exposure and development. Then, using an oven (“IHPS-222”; manufactured by ESPEC CORPORATION), post-baking was performed at 230 ° C. for 30 minutes (in air) to obtain a volume resistivity evaluation pattern.

For the resin compositions 2 to 17, a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.) was used on each of the substrates (S-1) to (S-3) at 300 rpm for 10 seconds. , Spin-coated at 500 rpm for 1 second, and prebaked the substrate using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.) at 100 ° C. for 5 minutes to obtain a film thickness of 1 μm. A prebake film was obtained. The prebake film was exposed using a parallel light mask aligner (“PLA-501F (trade name)” manufactured by Canon Inc.) using an ultrahigh pressure mercury lamp as a light source and through a desired mask. After that, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 0.07 wt% TMAH aqueous solution for 60 seconds, then rinsed with water for 30 seconds, and pattern processing was performed. Was done. Then, using an oven (“IHPS-222”; manufactured by ESPEC CORPORATION), post-baking was performed at 230 ° C. for 30 minutes (in air) to obtain a volume resistivity evaluation pattern.

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

<Adhesion evaluation>
The resin composition 1 is spin-coated on (S-1) 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. Then, the substrate was prebaked at 100 ° C. for 5 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.) to obtain a prebaked film having a film thickness of 1 μm. Then, using an oven (“IHPS-222”; manufactured by ESPEC CORPORATION), post-baking was performed at 230 ° C. for 30 minutes (in the air) to obtain a solid film made of the resin composition 1.

Separately, for the resin compositions 2 to 17, a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.) was used on each of the substrates (S-1) to (S-3) at 300 rpm for 10 Spin coat at 500 rpm for 1 second, and prebak the substrate using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.) at 100 ° C. for 5 minutes to achieve a film thickness of 1 μm. Pre-baked film was obtained. The prebake film was exposed using a parallel light mask aligner (“PLA-501F (trade name)” manufactured by Canon Inc.) using an ultrahigh pressure mercury lamp as a light source and without using a mask. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 0.07 wt% TMAH aqueous solution for 60 seconds, and then rinse with water for 30 seconds. Then, using an oven (“IHPS-222”; manufactured by ESPEC CORPORATION), post-baking is performed at 230 ° C. for 30 minutes (in the air) to make the resin compositions 2 to 17 solid. A membrane was obtained.

The obtained solid film was evaluated for its adhesion to the substrate. Specifically, a cross-cut test was conducted in accordance with JIS K5600-5-6 (1999) by a 6-grade evaluation of 5B to 0B (the larger the number, the higher the adhesion). If the adhesion is 2B or less, the touch panel may malfunction due to peeling of the cured product. Therefore, the adhesion is preferably 3B or more, and more preferably 4B or more.

<Evaluation of patterning property>
Resin compositions 2 to 17 are applied onto the substrates (S-1) to (S-3) at 300 rpm for 10 seconds using a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.). Spin-coat at 500 rpm for 1 second, pre-bake the substrate using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.) at 100 ° C. for 5 minutes, and pre-bake with a film thickness of 1 μm. A film was obtained. The prebake film was exposed using a parallel light mask aligner (“PLA-501F (trade name)” manufactured by Canon Inc.) using an ultrahigh pressure mercury lamp as a light source and through a desired mask. After that, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 0.07 wt% TMAH aqueous solution for 60 seconds, then rinsed with water for 30 seconds, and pattern processing was performed. Was done. After exposure and development, the minimum pattern size after development at the exposure amount for forming a line-and-space pattern of 5 μm in a width of 1: 1 was measured and used as the resolution. The amount of exposure was measured with an I-line illuminometer.

<Evaluation of residue on substrate>
The residue on the substrate was evaluated by the transmittance evaluation of the unexposed portion of the substrate on which the volume resistivity evaluation pattern formed by the above resin compositions 2 to 17 was formed. Specifically, for the unexposed portion, the transmittance at 400 nm before and after the film formation was measured using a spectrophotometer (U-3410; manufactured by Hitachi, Ltd.). Then, when the transmittance before film formation was T ₀ and the transmittance after film formation was T, the change in transmittance represented by _{the formula (T 0} −T) / T _{0 × 100 was calculated.} When the change in transmittance was 1.0% or less, it was judged that the effect of suppressing the residue was sufficient.

(Example 1)
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 are mixed with a homogenizer at 1200 rpm for 30 minutes, and further. , High-pressure wet medialess atomizer Nanomizer (Namizer Co., Ltd.) was used for dispersion to obtain a silver particle dispersion. A binder having a structure represented by the general formula (1) and a compound (B-1) having a functional group that produces an amino group by heat, 0.50 g, and a solid content concentration of 40% by mass, based on 282.00 g of this silver fine particle dispersion. A resin composition 1 was obtained by adding 73.75 g of PGMEA and 100.00 g of DPM to a mixture of 43.75 g of the resin (C-1) and stirring the mixture.

Table 1 shows the results of conductivity and adhesion evaluation.

(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. Further, the silver particle dispersion was obtained by dispersing using a high-pressure wet medialess atomizer nanomizer (Namogenizer Co., Ltd.). A binder having a structure represented by the general formula (1) and a compound (B-1) having a functional group that produces an amino group by heat, 0.50 g, and a solid content concentration of 40% by mass, based on 282.00 g of this silver fine particle dispersion. Add 85.00 g of PGMEA and 100.00 g of DPM to a mixture of 25.00 g of resin (C-1), 1.50 g of NCI-831E (D) photosensitizer, and 6.00 g of PE-3A, and stir. As a result, the resin composition 2 was obtained.

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

(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 shown in Tables 1 and 2 were obtained, and the respective photosensitive resin compositions were subjected to the same method as in Example 2 on the substrates shown in Tables 1 and 2. A similar evaluation was made. 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) whose surface was modified with a sulfonic acid group, 150 g of a 40 wt% solution of propylene glycol monomethyl ether acetate (PGMEA) of acrylic polymer (C-1), and a tertiary amino group as a polymer dispersant. 37.5 g of "DISPERBYK" (registered trademark) LPN-21116 having a quaternary ammonium salt and 102.5 g of PGMEA were charged into a tank, and the mixture was stirred with a homomixer for 20 minutes to obtain a preliminary dispersion. The obtained pre-dispersion liquid was supplied to the Ultra Apex Mill, a disperser manufactured by Kotobuki Kogyo Co., Ltd., equipped with a centrifuge separator filled with 75% by volume of 0.05 mmφ zirconia beads, and dispersed at a rotation speed of 8 m / s for 3 hours. Then, a colorant dispersion liquid Bk-1 having a solid content concentration of 25% by weight and a colorant / resin (weight ratio) = 80/20 was obtained.

Carbon black dispersion Bk-1 (822.6 g), propylene glycol monomethyl ether acetate 40 wt% solution (344.5 g) of acrylic polymer (C-1), KBM-manufactured by Shin-Etsu Chemical Co., Ltd. as an adhesion improver A solution prepared by dissolving 585 (7.5 g), a 10 wt% solution of a silicone-based surfactant propylene glycol monomethyl ether acetate (4.0 g) in propylene glycol monomethyl ether acetate (218.5 g) was added to form a colored resin composition. I got the thing 1.

(Colored Resin Composition 2)
300 g of carbon black (TPK1227 manufactured by Cabot) whose surface was modified with a sulfonic acid group, 150 g of a 40 wt% solution of propylene glycol monomethyl ether acetate (PGMEA) of acrylic polymer (C-1), and a tertiary amino group as a polymer dispersant. 37.5 g of "DISPERBYK" (registered trademark) LPN-21116 having a quaternary ammonium salt and 102.5 g of PGMEA were charged into a tank, and the mixture was stirred with a homomixer for 20 minutes to obtain a preliminary dispersion. The obtained pre-dispersion liquid was supplied to the Ultra Apex Mill, a disperser manufactured by Kotobuki Kogyo Co., Ltd., equipped with a centrifuge separator filled with 75% by volume of 0.05 mmφ zirconia beads, and dispersed at a rotation speed of 8 m / s for 3 hours. Then, a colorant dispersion liquid Bk-1 having a solid content concentration of 25% by weight and a colorant / resin (weight ratio) = 80/20 was obtained.

Carbon black dispersion Bk-1 (822.6 g), propylene glycol monomethyl ether acetate 40 wt% solution (117.3 g) of acrylic polymer (C-1), dipentaerythritol hexaacrylate as a polyfunctional monomer (Nippon Kayaku) Propylene glycol monomethyl ether acetate 50% by weight solution (92.7 g) of DPHA Co., Ltd., ADEKA Co., Ltd. "Adecacruise" NCI-831 (11.6 g) as a photopolymerization initiator, Shinetsu as an adhesion improver A solution prepared by dissolving KBM-585 (7.5 g) manufactured by Kagaku Co., Ltd. and a 10 wt% solution (4.0 g) of propylene glycol monomethyl ether acetate, a silicone-based surfactant, in propylene glycol monomethyl ether acetate (218.5 g). Was added to obtain a colored resin composition 2.

(Colored resin compositions 3 to 7)
Colored resin compositions 3 to 7 having the compositions shown in Table 3 were obtained in the same manner as in the colored resin composition 2.

<Evaluation of storage stability>
For the above colored resin compositions 1 to 7, the viscosity immediately after the preparation of the colored resin composition and the viscosity after the colored resin composition was left at room temperature (30 ° C.) for 1 week were measured by a viscometer (RE105L manufactured by Toki Sangyo Co., Ltd.). The temperature was set to 25.0 ± 0.2 ° C. and the measurement was performed at a rotation speed of 50 rpm, and the rate of change in viscosity was calculated. Those with a viscosity change rate of 15% or more were judged to have poor storage stability.

<Adhesion evaluation>
The colored resin composition 1 is spin-coated on (S-2) using a spin coater (“1H-DS (trade name)” manufactured by Mikasa Co., Ltd.), and the substrate is hot-plate (Dainippon Screen Mfg. Co., Ltd.). )), Prebaked at 100 ° C. for 10 minutes to obtain a prebaked film. Then, using an oven (“IHPS-222”; manufactured by ESPEC CORPORATION), post-baking is performed at 230 ° C. for 30 minutes (in air) to obtain a solid film composed of the colored resin composition 1 having a thickness of 1.5 μm. Got

The colored resin compositions 2 to 7 are separately spin-coated on (S-2) using a spin coater (“1H-DS (trade name)” manufactured by Mikasa Co., Ltd.), and the substrate is hot-plate (large). A prebaked film was obtained by prebaking at 100 ° C. for 10 minutes using "SCW-636 (trade name)" manufactured by Nippon Screen Mfg. Co., Ltd. The prebake film was exposed using a mask aligner (manufactured by Union Optical Co., Ltd.) using an ultra-high pressure mercury lamp as a light source and without using a mask. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 0.045 mass% KOH aqueous solution for 60 seconds, and then rinse with water for 30 seconds. Then, using an oven (“IHPS-222”; manufactured by ESPEC CORPORATION), post-baking is performed at 230 ° C. for 30 minutes (in the air), whereby the colored resin compositions 2 to 7 are composed of the respective resin compositions. A solid film having a thickness of 1.5 μm was obtained.

<Evaluation of patterning property>
The colored resin compositions 2 to 7 are spin-coated on (S-2) using a spin coater (“1H-DS (trade name)” manufactured by Mikasa Co., Ltd.), and the substrate is hot-plate (Dainippon Screen). A prebaked film was obtained by prebaking at 100 ° C. for 10 minutes using “SCW-636 (trade name)” manufactured by Mfg. Co., Ltd. The prebake film was exposed using a mask aligner (manufactured by Union Optical Co., Ltd.) using an ultra-high pressure mercury lamp as a light source and through a desired mask. After that, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), shower-develop with 0.045 mass% KOH aqueous solution for 60 seconds, then rinse with water for 30 seconds, and pattern. Processed. After exposure and development, the minimum pattern size after development at the exposure amount for forming a line-and-space pattern of 5 μm in a width of 1: 1 was measured and used as the resolution. The amount of exposure was measured with an I-line illuminometer.

The results of each evaluation are shown in Table 3.

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

Claims

It contains fine particles, a compound (B) having a structure represented by the general formula (1) and a functional group that produces an amino group by heat, and a binder resin (C).
A resin composition in which the fine particles are an 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 are independently hydroxy groups, methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups and isobutoxy groups, respectively. Alternatively, it indicates a hydrocarbon group having 1 to 6 carbon atoms. R 1 to R 3 may be the same or different, but at least one is a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy. Group, butoxy group or isobutoxy group.)
The resin composition according to claim 1, wherein the fine particles are inorganic particles (G) having a coating layer containing carbon, and the inorganic particles (G) are conductive particles (A).
The resin composition according to claim 2, wherein the pH of the suspension of the conductive particles (A) in water having a concentration of 1% by mass is 4.0 to 10.0.
The resin composition according to claim 1, wherein the average primary particle size of the fine particles is 1 to 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 according to claim 1, wherein the fine particles are inorganic particles (G) having a coating layer containing carbon, and the inorganic particles (G) are inorganic pigments.
The resin composition according to claim 1, wherein the fine particles are an organic pigment (F).
The resin composition according to 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 that produces an amino group by the heat is at least one selected from the group consisting of an amide group, an imine group, a ureido group and an isocyanate group.
The resin composition according to claim 9, wherein the functional group that produces an amino group by the heat is a ureido group.
The resin composition according to any one of claims 1 to 10, wherein the binder resin (C) has an acid dissociative group.
The resin composition according to any one of claims 1 to 11, further comprising a photosensitizer (D) and the binder resin (C) having an alkali-soluble group.
A wiring board provided with a conductive pattern made of a cured product of the resin composition according to any one of claims 1 to 3.
The wiring board according to claim 13, further having a black layer.
The wiring board according to claim 13 or 14, wherein the width of the conductive pattern is 1 to 6 μm.
A touch panel having the wiring board according to any one of claims 13 to 15.
A coating step of applying the resin composition according to any one of claims 1 to 3 on a substrate so as to have a desired pattern shape to obtain a coating film.
A drying step of drying the coating film to obtain a drying film, and
A heating step of heating the dry film to obtain a conductive film, and
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 onto a substrate to obtain a coating film, and a coating step.
A drying step of drying the coating film to obtain a drying film, and
An exposure step of exposing the dry film to obtain an exposure film, and
A developing step of developing the exposure film to form a pattern, and
A heating step of heating the pattern to obtain a conductive film,
A method of manufacturing a conductive pattern comprising.
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 150 to 270 ° C.
It contains conductive particles (A) having a coating layer containing carbon, a compound (E) having a structure represented by the general formula (2) and an amino group, and a binder resin (C).
A conductive pattern in which the binder resin (C) has an alkali-soluble group.

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