JP7173147B2 - Substrate with conductive layer and member for touch panel - Google Patents

Description

TECHNICAL FIELD The present invention relates to a substrate with a conductive layer, a member for a touch panel, and a touch panel.

Many of the current smartphones and tablet terminals use capacitive touch panels. The sensor substrate of the capacitive touch panel has wiring patterned with ITO (Indium Ti Oxide) or metal (silver, molybdenum, aluminum, etc.) on glass, and the intersection of the wiring is insulated with an insulating film. A multi-layer wiring structure in which a protective film is formed on the surface of wiring is common. In general, protective films and insulating films are often formed of photosensitive materials. In addition, from the viewpoint of higher sensitivity and higher resolution accompanying the increase in size of the touch panel, the development of a method of forming the wiring part with metal is progressing, and there is a demand for a photosensitive material that can form a fine pattern. .

As a photosensitive transparent material, a UV curable coating composition containing an alkali-soluble resin, a polymerizable monomer, a photopolymerization initiator and other additives is known, and a photosensitive resin composition for an insulating film of a touch panel has been disclosed. ing. (See Patent Documents 1 and 2, for example).

As a technique for improving the properties of these compositions, Patent Document 3 discusses mixing a cardo resin and an acrylic polymer at a specific ratio.

JP 2010-27033 A JP 2013-140229 A WO2017/159543

Multi-layer metal wiring tends to short-circuit due to the migration phenomenon in which metal ions move in the insulating layers between layers under high temperature and high humidity. is required. Patent Documents 1 and 2 describe that the obtained cured film is excellent in transparency. However, pattern workability and migration resistance under high temperature and high humidity conditions were not satisfied. Moreover, the cured film described in Patent Document 3 did not satisfy migration resistance.

The present invention provides a substrate with a conductive layer in which a conductive layer and an insulating layer are formed on a transparent substrate, wherein the photosensitive resin composition forming the insulating layer has excellent resolution and migration resistance under high temperature and high humidity. An object of the present invention is to provide a substrate with a conductive layer that is excellent in

The present inventors used a photosensitive resin composition in which an acrylic polymer having an alicyclic skeleton and an alkali-soluble group in a side chain and a compound having a specific structure are combined to form an insulating layer on a substrate with a conductive layer. It has been found that the objects of the present invention can be achieved by forming

That is, the substrate with a conductive layer of the present invention is a substrate with a conductive layer in which a conductive layer and an insulating layer are formed on a transparent substrate, and the insulating layer has (A) an alicyclic skeleton and an alkali-soluble group in a side chain. A cured film obtained by curing a photosensitive resin composition containing an acrylic polymer having a (B) photopolymerization initiator and (C) a compound having an unsaturated double bond, the (C) unsaturated double bond The substrate with a conductive layer includes a compound (C-1) in which the compound having a bond has a structure represented by the following general formula (1).

In general formula (1), R ¹ to R ⁶ each represent a hydrogen atom, a methacryloyl group, an acryloyl group or an organic group. Three or more of R ¹ to R ⁶ are methacryloyl groups or acryloyl groups. Also, n=0 to 10.

The substrate with a conductive layer of the present invention is a substrate with a conductive layer in which a conductive layer and an insulating layer are formed on a transparent substrate, and the insulating layer has excellent resolution and excellent migration resistance under high temperature and high humidity.

FIG. 3 is a top view showing the configuration of a laminated substrate used for evaluating migration resistance in Examples. FIG. 3 is a cross-sectional view showing the configuration of a laminated substrate used for evaluating migration resistance in Examples.

The substrate with a conductive layer of the present invention is a substrate with a conductive layer in which a conductive layer and an insulating layer are formed on a transparent substrate, wherein the insulating layer (A) has an alicyclic skeleton and an alkali-soluble group in its side chain. A cured film obtained by curing a photosensitive resin composition containing an acrylic polymer, (B) a photopolymerization initiator, and (C) a compound having an unsaturated double bond, wherein the (C) unsaturated double bond is The compound having a conductive layer is a substrate with a conductive layer containing a compound (C-1) having a structure represented by the general formula (1):
[Acrylic polymer (A)]
The photosensitive resin composition forming the insulating layer contains (A) an acrylic polymer having an alicyclic skeleton and an alkali-soluble group in a side chain (hereinafter referred to as acrylic polymer (A)).

By having an alicyclic skeleton in the acrylic polymer (A), it is possible to impart hydrophobicity to the insulating layer and improve migration resistance under high temperature and high humidity.

Here, the alicyclic skeleton is a hydrocarbon group that does not contain an aromatic ring structure, and includes monocyclic alicyclic skeletons and polycyclic alicyclic skeletons. Both a monocyclic alicyclic skeleton and a polycyclic alicyclic skeleton may be included. However, it does not need to be composed only of an alicyclic skeleton, and may partially contain a chain structure. From the viewpoint of improving migration resistance, a polycyclic alicyclic skeleton is preferred.

The acrylic polymer (A) preferably has a repeating unit represented by general formula (2) as a repeating unit having an alicyclic skeleton in its side chain.

In general formula (2), ^R7 represents a hydrogen atom or a methyl group.

The acrylic polymer (A) preferably has 0.1 to 10 mol % of repeating units represented by general formula (2) in all repeating units. When the content of the repeating unit represented by the general formula (2) is 0.1 mol % or more, the insulating layer is improved in hydrophobicity and further improved in migration resistance under high temperature and high humidity. It is more preferable to have 1 mol % or more, more preferably 2 mol % or more, of the repeating unit represented by the general formula (2). On the other hand, when the repeating unit represented by formula (2) is 10 mol % or less, a finer pattern can be formed.

Moreover, it is preferable that the acrylic polymer (A) has a repeating unit represented by the general formula (3).

In general formula ( ³ ), R8 represents a hydrogen atom or a methyl group. R ⁹ to R ¹³ each represent a hydrogen atom, an organic group having 1 to 6 carbon atoms or a hydroxyl group. R ⁹ to R ¹³ may be the same or different.

By having the repeating unit represented by the general formula (3) in the acrylic polymer (A), it is possible to prevent film roughness during alkali development and impart high transparency to the insulating layer. The acrylic polymer (A) preferably has 20 to 50 mol % of repeating units represented by general formula (3) in all repeating units. When the content of the repeating unit represented by formula (3) is 20 mol % or more, development properties are improved and finer patterns can be formed. It is more preferable to have 25 mol% or more, more preferably 30 mol% or more, of the repeating unit represented by the general formula (3). On the other hand, when the repeating unit represented by the general formula (3) is present in an amount of 50 mol % or less, the light resistance of the insulating layer is improved. More preferably, the acrylic polymer (A) contains 45 mol % or less of repeating units represented by general formula (3).

In general formula (3), the organic groups represented by R ⁹ to R ¹³ are preferably alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-pentyl and n-hexyl groups. is not limited to

When the acrylic polymer (A) has an alkali-soluble group, it is possible to impart pattern workability to the photosensitive resin composition and obtain an insulating layer with excellent resolution.

Here, the alkali-soluble group is a group selected from a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group and an acid anhydride group. A carboxyl group is particularly preferred from the viewpoint of reactivity and versatility.

The acrylic polymer (A) preferably has a repeating unit represented by the following general formula (4) as a repeating unit having an alkali-soluble group in its side chain.

In general formula (4), R ¹⁴ represents a hydrogen atom or a methyl group.

By having the repeating unit represented by the general formula (4), the acrylic polymer (A) can be imparted with pattern processability by alkali development. The acrylic polymer (A) preferably has 5 to 60 mol % of repeating units represented by the general formula (4) in all repeating units. When the content of the repeating unit represented by formula (4) is 5 mol % or more, development properties are improved and finer patterns can be formed. It is more preferable to have 10 mol % or more of repeating units represented by the general formula (4). On the other hand, when the repeating unit represented by the general formula (4) is contained in an amount of 60 mol % or less, the hydrophilicity of the resin composition is lowered, and pattern processing by alkali development is facilitated. More preferably, the acrylic polymer (A) contains 45 mol % or less of repeating units represented by general formula (4).

The acrylic polymer (A) preferably has a repeating unit represented by the following general formula (5).

In general formula (5), R ¹⁵ to R ¹⁶ each represent a hydrogen atom or a methyl group. R ¹⁵ to R ¹⁶ may be the same or different.

By having the repeating unit represented by the general formula (5), the acrylic polymer (A) exhibits negative photosensitivity and enables the formation of a fine pattern. The acrylic polymer (A) preferably has 5 to 60 mol % of repeating units represented by general formula (5) in all repeating units. Since the content of the repeating unit represented by the general formula (5) is 5 mol% or more, the degree of curing of the exposed area is improved, so that the difference in solubility in an alkaline developer between the exposed area and the unexposed area is reduced. It becomes large, and pattern formation becomes easy. It is more preferable to have 15 mol % or more of repeating units represented by the general formula (5). On the other hand, when the repeating unit represented by the general formula (5) is present in an amount of 60 mol % or less, the sensitivity due to exposure is moderately suppressed, thereby facilitating the formation of a fine pattern. More preferably, the acrylic polymer (A) contains 40 mol % or less of repeating units represented by the general formula (5).

By having both the repeating unit represented by the general formula (4) and the repeating unit represented by the general formula (5) in the acrylic polymer (A), it is possible to impart hydrophilicity and form a finer pattern. It is preferable because It is preferable that the repeating unit represented by the general formula (4) and the repeating unit represented by (5) are contained in a total of 40 to 60 mol % of all repeating units. By having a total of 40 mol% or more of the repeating unit represented by the general formula (4) and the repeating unit represented by (5), the hydroxyl group in the structure contributes to improve the development properties and form a finer pattern. can do. On the other hand, by having a total of 60 mol% or less of the repeating unit represented by the general formula (4) and the repeating unit represented by (5), in addition to being able to form a finer pattern, migration resistance is further improved.

The acrylic polymer (A) may have repeating units other than the repeating units represented by any of the general formulas (2) to (5). Examples of such repeating units include styrene, methyl (meth)acrylate, glycidyl (meth)acrylate, and the like.

The acrylic polymer (A) is obtained by radically polymerizing a monomer having an ethylenically unsaturated double bond. The repeating units represented by formulas (2) to (4) are obtained by radical polymerization of monomers forming each structure. Further, the repeating unit represented by the general formula (5) can be obtained by addition reaction of glycidyl (meth)acrylate to an acrylic polymer containing the repeating unit represented by the general formula (4).

The radical copolymerization catalyst is not particularly limited, and azo compounds such as azobisisobutyronitrile and organic peroxides such as benzoyl peroxide are generally used.

Further, the catalyst used for the addition reaction of glycidyl (meth)acrylate is not particularly limited, and known catalysts can be used. Amino catalysts such as benzylamine, tin catalysts such as tin (II) 2-ethylhexanoate and dibutyltin laurate, titanium catalysts such as titanium (IV) 2-ethylhexanoate, phosphorus catalysts such as triphenylphosphine Catalysts and chromium-based catalysts such as acetylacetonate chromium and chromium chloride are used.

The acrylic polymer (A) can also be obtained by polymerizing a polyfunctional (meth)acrylate compound and a polyhydric mercapto compound by Michael addition (β-position with respect to the carbonyl group).

The weight average molecular weight (Mw) of the acrylic polymer (A) is preferably 5,000 to 15,000 in terms of polystyrene measured by gel permeation chromatography (GPC). By setting the weight average molecular weight (Mw) to 5,000 or more, the sensitivity is improved, and oxidative deterioration of polymer molecule ends can be suppressed, thereby improving color characteristics. More preferably, the weight average molecular weight (Mw) is 7,000 or more. On the other hand, by setting the weight-average molecular weight (Mw) to 15,000 or less, finer patterns can be formed, and a transparent insulating layer can be formed. The weight average molecular weight (Mw) is more preferably 12,000 or less.

In the photosensitive resin composition for forming the insulating layer, the content of the acrylic polymer (A) is not particularly limited, and can be arbitrarily selected depending on the intended thickness of the insulating layer and the application. When the total solid content of the composition is 100% by mass, the content of the acrylic polymer (A) is generally 10% by mass or more and 70% by mass or less.

[Photoinitiator (B)]
The photosensitive resin composition forming the insulating layer contains a photopolymerization initiator (B). The photopolymerization initiator (B) decomposes and/or reacts with light (including ultraviolet rays and electron beams) to generate radicals. Specific examples include 1,2-propanedione-3-cyclopentane-1-[4-(phenylthio)-2-(O-benzoyloxime)], 3-cyclopentylethanone-1-[9-ethyl-6 -(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime) ], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) and the like. These can be used singly or in combination.

The content of the photopolymerization initiator (B) is not particularly limited, but is preferably 0.1 to 20% by mass when the total solid content of the photosensitive resin composition is 100% by mass. When the content of the photopolymerization initiator (B) is 0.1% by mass or more, photosensitivity can be imparted and a finer pattern can be formed. The content of the photopolymerization initiator (B) is more preferably 0.5% by mass or more. On the other hand, when the content of the photopolymerization initiator (B) is 20% by mass or less, yellowing due to photopolymerization initiator residues can be suppressed, so that a transparent insulating layer can be formed. The content of the photopolymerization initiator (B) is more preferably 15% by mass or less.

[Compound (C) having an unsaturated double bond]
The photosensitive resin composition forming the insulating layer contains a compound (C) having an unsaturated double bond, and includes a compound having a pentaerythritol skeleton as the compound (C) having an unsaturated double bond. A compound having an unsaturated double bond and a pentaerythritol skeleton is a compound (C-1) having a structure represented by the following general formula (1). A fine pattern can be formed by containing the compound (C-1).

In general formula (1), R ¹ to R ⁶ each represent a hydrogen atom, a methacryloyl group, an acryloyl group or an organic group. Three or more of R ¹ to R ⁶ are methacryloyl groups or acryloyl groups. Also, n=0 to 10. The organic groups of R ¹ to R ⁶ are preferably alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-pentyl and n-hexyl groups. is not limited to

Compound (C-1) preferably has n of 1 or more in general formula (1). In the general formula (1), when n is 1 or more, flexibility is imparted to the main chain skeleton, radical polymerizability is improved by improving the contact probability between molecules, and fine pattern formation is possible even when the exposure dose is small. becomes possible. Specific examples of the compound (C-1) are shown below, but are not limited thereto.

Examples of compounds in which n is 0 in the general formula (1) include pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. , Methoxylated pentaerythritol mono(meth)acrylate, Methoxylated pentaerythritol di(meth)acrylate, Methoxylated pentaerythritol tri(meth)acrylate, Methoxylated pentaerythritol tetra(meth)acrylate, Ethoxylated pentaerythritol mono(meth)acrylate , ethoxylated pentaerythritol di(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol mono(meth)acrylate, propoxylated pentaerythritol di(meth)acrylate , propoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, butoxylated pentaerythritol mono(meth)acrylate, butoxylated pentaerythritol di(meth)acrylate, butoxylated pentaerythritol tri(meth)acrylate , butoxylated pentaerythritol tetra(meth)acrylate and the like.

Examples of compounds in which n is 1 in the general formula (1) include dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra (Meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like.

Examples of compounds in which n is 2 or more in the general formula (1) include tripentaerythritol mono(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, and tripentaerythritol. Tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol mono(meth)acrylate , tetrapentaerythritol di(meth)acrylate, tetrapentaerythritol tri(meth)acrylate, tetrapentaerythritol tetra(meth)acrylate, tetrapentaerythritol penta(meth)acrylate, tetrapentaerythritol hexa(meth)acrylate, tetrapentaerythritol hepta (Meth)acrylate, tetrapentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, polypentaerythritol (meth)acrylate and the like. These can be used singly or in combination.

In the photosensitive resin composition forming the insulating layer, the content of the compound (C-1) is 0.01 to 5% by mass or less when the total solid content of the photosensitive resin composition is 100% by mass. Preferably. When the content of the compound (C-1) is 0.01% by mass or more, it becomes easy to obtain a favorable fine pattern from the viewpoint of photosensitivity. On the other hand, when the content of the compound (C-1) is 5% by mass or less, the hydrophilicity of the insulating layer becomes low, so that migration resistance under high temperature and high humidity conditions is further improved. From the viewpoint of resolution, the content of compound (C-1) is more preferably 3% by mass or less, still more preferably 2% by mass or less.

In addition, the photosensitive resin composition includes, as the compound (C) having an unsaturated double bond, a compound having an unsaturated double bond other than the compound (C-1) (hereinafter referred to as other compound (C)). may be contained, and the sensitivity of the resin composition can be adjusted.

The content of the other compound (C) is not particularly limited and can be arbitrarily selected depending on the desired application. % is preferred. By setting the content of the other compound (C) to 1% by mass or more, the sensitivity can be further improved. The content of the other compound (C) is more preferably 5% by mass or more, still more preferably 10% by mass or more. On the other hand, by setting the content of the other compound (C) to 30% by mass or less, it becomes possible to form a finer pattern. The content of other compound (C) is more preferably 20% by mass or less.

Compounds having two unsaturated double bonds include, for example, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, tris(2-hydroxyethyl)isocyanurate tri(meth) acrylates and the like. These can be used singly or in combination.

Furthermore, a polyfunctional allyl compound may be contained as the compound (C) having an unsaturated double bond. By containing a polyfunctional allyl compound, it is possible to further improve the migration resistance of the insulating layer under high temperature and high humidity conditions, and it is possible to obtain an insulating layer with a finer pattern, which contributes to improving the appearance during lamination processing. do. As the polyfunctional allyl compound, a compound represented by the following general formula (6) having an isocyanurate skeleton is preferred.

In general formula (6), l, m and n each independently represent an integer of 0 to 8. X1 and X2 represent an allyl group, and ^X3 represents ^a hydrogen atom ^, an allyl group, a fluoro group, a chloro group, a bromo group, an iodo group, a carboxyl group, an epoxy group, an acrylic group, a methacrylic group or an alkoxy group.

Examples of polyfunctional allyl compounds represented by formula (6) include, but are not limited to, the following compounds.

In the photosensitive resin composition that forms the insulating layer, the content of the polyfunctional allyl compound is not particularly limited and can be arbitrarily selected depending on the desired application. %, it is preferably 1 to 30% by mass or less. When the content of the polyfunctional allyl compound is 1% by mass or more, pattern thickening due to exposure can be suppressed, and a finer pattern can be formed. The content of the polyfunctional allyl compound is more preferably 5% by mass or more. On the other hand, when the content of the polyfunctional allyl compound is 30% by mass or less, thermosetting by heating can be accelerated and a film with a high degree of curing can be obtained. The content of the polyfunctional allyl compound is more preferably 20% by mass or less. These can be used singly or in combination.

[Colorant (D)]
The photosensitive resin composition forming the insulating layer preferably contains a coloring agent (D), and the b ^* value of the insulating layer can be adjusted. The b ^* value is a value according to the L ^* a ^* b ^* color system defined by the International Commission on Illumination 1976. By containing the coloring agent (D), the yellowness of the insulating layer can be reduced and the color can be improved. As is widely known, the L ^* value, a ^* value, and b ^* value in the L ^* a ^* b ^* color system are lightness, and the a ^* value and b ^* value are hue and chroma ^. represents degrees. Specifically, a positive a ^* value indicates a red hue, and a negative a* value indicates a green hue. A positive b ^* value indicates a yellow hue, and a negative b* value indicates a blue hue. For both the a ^* value and the b ^* value, the larger the absolute value, the higher the saturation of the color and the brighter the color, and the smaller the absolute value, the lower the saturation. Since the measured value of b ^* is neutral in the vicinity of 0, the color tone when observed is visually colorless, which is preferable. The b* value of the insulating layer can be measured by a reflection measurement method among the methods specified in JIS-Z8729:1994. More specifically, as described later, a photosensitive resin composition that forms an insulating layer on a glass substrate is cured to form a cured film, and the cured film is measured with a spectrophotometer (CM-2600d; Konica Minolta ( (manufactured by Co., Ltd.) to measure the reflectance of total reflected light and measure the reflection chromaticity b*.

Examples of the coloring agent (D) include pigments and dyes. Among them, pigments are preferable from the viewpoint of heat resistance and light resistance. A blue colorant is preferable from the viewpoint of reducing the yellowness of the insulating layer.

The coloring agent (D) preferably contains a metal complex. By using a metal complex, the yellow tint of the insulating layer can be further reduced by adding a very small amount. Examples of metal complexes include porphyrins, phthalocyanines, and compounds in which metals are coordinated to phthalocyanines at least partially having substituents. Examples of the substituent include halogen such as chlorine, sulfonic acid group, and amino group. Coordinating metals include, for example, copper, zinc, nickel, cobalt, and aluminum. Two or more of these metal complexes may be contained. As the metal complex, a copper complex of phthalocyanine is preferable because it suppresses the reaction between the colorant and other organic components, does not fade during high-temperature treatment in the process, and can further improve the color. More preferred are copper phthalocyanine sulfonate ammonium salt, copper phthalocyanine tertiary amine compound and copper phthalocyanine sulfonate amide compound. Colorant (D) can be detected by MASS spectral analysis or the like.

Examples of copper complexes of phthalocyanines include Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, etc. . Among them, Pigment Blue 15:1, which is a copper phthalocyanine blue pigment having an ε-type and α-type structure, is used from the viewpoint of improving light resistance, not discoloring even when exposed to sunlight, and maintaining a good appearance. Pigment Blue 15:6 and the like are preferred.

In the photosensitive resin composition forming the insulating layer, the content of the coloring agent (D) is 0.01 to 0.5% by mass or less when the total solid content of the photosensitive resin composition is 100% by mass. is preferably By setting the content of the coloring agent (D) to 0.01% by mass or more, the effect of the coloring agent (D) can be made sufficient, and the color of the insulating layer can be further improved. The content of the coloring agent (D) is more preferably 0.05% by mass or more. Also, by setting the content of the coloring agent (D) to 0.5% by mass or less, the absorption of the coloring agent (D) can be suppressed and the total light transmittance can be improved. The content of the coloring agent (D) is more preferably 0.4% by mass or less. The content of the coloring agent (D) can be quantified by TG-MASS.

[Polyfunctional epoxy compound]
The photosensitive resin composition forming the insulating layer may contain a polyfunctional epoxy compound. By containing a polyfunctional epoxy compound, it is possible to further improve the migration resistance of the insulating layer under high temperature and high humidity. Contributes to improving appearance during lamination processing. As the polyfunctional epoxy compound, a polyfunctional epoxy compound having an isocyanurate skeleton and/or a polyfunctional epoxy compound having 3 or more aromatic rings are preferred.

Examples of polyfunctional epoxy compounds having an isocyanurate skeleton include compounds having structures represented by any one of the following general formulas (7) to (12).

R ¹⁷ to R ²² each independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a substituent thereof represents

Examples of polyfunctional epoxy compounds having three or more aromatic rings include compounds having a structure represented by any one of the following general formulas (13) to (17).

R ²³ to R ²⁸ , R ²⁹ to R ³² , R ³³ to R ³⁶ , R ³⁷ to R ⁴⁰ and R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a fluorine atom, a methyl group, an ethyl group or a cyclohexyl group; show. o and p represent integers from 0 to 15;

Among these, compounds having structures represented by the structural formulas (7), (10), (11), (13) and (14) are particularly effective in improving migration resistance under high temperature and high humidity conditions. is.

In the photosensitive resin composition that forms the insulating layer, the content of the polyfunctional epoxy compound is not particularly limited and can be arbitrarily selected depending on the desired application. %, preferably 1% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 20% by mass or less. These can be used singly or in combination.

[Hindered amine light stabilizer]
The photosensitive resin composition forming the insulating layer may contain a hindered amine light stabilizer. By containing the hindered amine light stabilizer, it is possible to reduce the coloring of the insulating layer and improve the light resistance.

Hindered amine light stabilizers include, for example, compounds having structures represented by any of the following general formulas (18) to (22).

q, r, s and t each represents an integer of 0 to 15;

Among these, the hindered amine light stabilizer preferably has an unsaturated double bond because it is highly reactive and acts on curing. For example, compounds having a structure represented by the above structural formula (18) or (19) having an unsaturated double bond are particularly preferred.

In the photosensitive resin composition forming the insulating layer, the content of the hindered amine light stabilizer is not particularly limited, but is 0.01 mass when the total solid content of the photosensitive resin composition is 100 mass%. % or more and 10 mass % or less, more preferably 0.05 mass % or more and 5 mass % or less. These can be used singly or in combination.

[Silane coupling agent]
The photosensitive composition forming the insulating layer may contain a silane coupling agent. By containing the silane coupling agent, the adhesion between the substrate and the insulating layer is further improved.

Specific examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane. roxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propyl amine, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3, 4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3- oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic acid, and Nt-butyl-3-(3-trimethoxysilylpropyl)succinimide.

Among these, the silane coupling agent preferably contains nitrogen from the viewpoint of improving adhesion to the substrate. Since nitrogen acts as a catalyst for the condensation reaction between the silane coupling agent and the substrate surface, the adhesion is greatly improved.

Specific examples of nitrogen-containing silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-( 2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N -(vinylbenzyl)-(2-aminoethyl)-3-aminopropyltrimethoxysilane hydrochloride, N-(vinylbenzyl)-(2-aminoethyl)-3-aminopropyltriethoxysilane hydrochloride, tris-( trimethoxysilylpropyl)isocyanurate, tris-(triethoxysilylpropyl)isocyanurate, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3-trimethoxysilyl-N-(1, 3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3 -isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, Nt-butyl-3-(3-trimethoxysilylpropyl)succinimide, Nt-butyl-3-(3-triethoxysilylpropyl ) succinimide and the like.

Among these, 3-ureidopropyltriethoxysilane and 3-ureidopropyltrimethoxysilane are particularly preferred from the viewpoint of storage stability.

The amount of the silane coupling agent added is not particularly limited, but is preferably 0.1% by mass or more and 10% by mass or less when the total solid content of the photosensitive resin composition is 100% by mass. If the amount added is less than 0.1% by mass, the effect of improving adhesion is low. If the amount added is more than 10% by mass, the silane coupling agent undergoes a condensation reaction during storage, causing undissolved residue during development.

[Curing agent]
The photosensitive resin composition that forms the insulating layer may contain various curing agents that accelerate or facilitate curing of the resin composition. The curing agent is not particularly limited and known ones can be used. Specific examples include nitrogen-containing organic substances, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and their polymers, and methylolated melamine. derivatives, methylolated urea derivatives and the like. You may contain 2 or more types of these. Among them, metal chelate compounds, methylolated melamine derivatives, methylolated urea derivatives, and the like are preferably used in view of the stability of the curing agent, workability of the resulting coating film, and the like.

[Ultraviolet absorber]
The photosensitive resin composition forming the insulating layer may contain an ultraviolet absorber. By containing an ultraviolet absorber, the resulting insulating layer has improved light resistance, and in applications requiring pattern processing, resolution after development is improved. As the ultraviolet absorber, there is no particular limitation and known ones can be used, but benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds are preferably used in terms of transparency and non-coloring properties.

[Polymerization inhibitor]
The photosensitive resin composition forming the insulating layer may contain a polymerization inhibitor. By containing an appropriate amount of polymerization inhibitor, the resolution after development is improved. There are no particular limitations on the polymerization inhibitor, and known ones can be used. Examples thereof include di-t-butylhydroxytoluene, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone and t-butylcatechol. Commercially available polymerization inhibitors include "IRGANOX1010", "IRGANOX245", "IRGANOX3114", and "IRGANOX565" (manufactured by BASF).

[Surfactant]
The photosensitive resin composition forming the insulating layer may contain various surfactants such as various fluorine-based surfactants and silicone-based surfactants in order to improve flowability during application. The type of surfactant is not particularly limited. BYK-333 (trade name)” (manufactured by BYK-Chemie Japan Co., Ltd.) and other silicone-based surfactants, polyalkylene oxide-based surfactants, poly(meth)acrylate-based surfactants, and the like can be used. You may use 2 or more types of these.

[solvent]
The photosensitive resin composition forming the insulating layer may contain a solvent. The solvent preferably has a boiling point of 110 to 250°C under atmospheric pressure, more preferably 200°C or less. In addition, you may use multiple types of these solvents. If the boiling point is higher than 200° C., the amount of residual solvent in the film increases during the formation of the coating film, resulting in increased film shrinkage during curing, and good flatness cannot be obtained. On the other hand, if the boiling point is lower than 110° C., the coating film properties are deteriorated, such as the film surface becoming rough due to excessive drying during coating film formation. Therefore, it is preferable that the solvent having a boiling point of 200° C. or less under atmospheric pressure accounts for 50% by mass or more of the total solvent in the photosensitive resin composition.

Specific examples of solvents include ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, methoxymethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monopropyl ether. , ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, methyl lactate, cyclopentanone, cyclohexane, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, ethylene glycol diethyl ether , ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3 -methylbutanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, diacetone alcohol, ethyl lactate, butyl lactate , dimethylformamide, dimethylacetamide, γ-butyrolactone, N-methylpyrrolidone, cyclohexanone, cycloheptanone, diethylene glycol monobutyl ether, ethylene glycol dibutyl ether.

The content of the solvent is not particularly limited, and any amount can be used according to the coating method and the like. For example, when forming a film by spin coating, it is generally 50% by mass or more and 95% by mass or less of the entire photosensitive resin composition.

Additives such as a dissolution inhibitor, a stabilizer, and an antifoaming agent may be added to the photosensitive resin composition forming the insulating layer, if necessary.

The solid content concentration of the photosensitive resin composition forming the insulating layer is not particularly limited, and any amount of solvent or solute can be used according to the coating method or the like. For example, when forming a film by spin coating as described later, the solid content concentration is generally 5% by mass or more and 50% by mass or less. Here, the solid content is the photosensitive resin composition excluding the solvent.

Next, a representative method for producing a photosensitive resin composition for forming an insulating layer will be described. For example, an acrylic polymer (A), a photopolymerization initiator (B), a compound having an unsaturated double bond (C), a colorant (D) and other additives if necessary are added to any solvent and stirred. After dissolving, the resulting solution is filtered to obtain a photosensitive resin composition.

The insulating layer formed on the substrate with a conductive layer of the present invention is obtained by curing the photosensitive resin composition. The above photosensitive resin composition can be cured by a method described later.

Although the film thickness of the insulating layer is not particularly limited, it is preferably 0.1 to 15 μm. By setting the film thickness of the insulating layer to 0.1 μm or more, migration resistance under high temperature and high humidity is further improved. The film thickness of the insulating layer is more preferably 0.5 μm or more, more preferably 1.0 μm or more. On the other hand, by setting the film thickness of the insulating layer to 15 μm or less, a colorless and transparent film can be formed without yellowing. The film thickness of the insulating layer is more preferably 10 μm or less, more preferably 5.0 μm or less. The insulating layer preferably has a transmittance of 85% or more, more preferably 90% or more, 95% or more, or 97% or more per 2.0 μm film thickness. Here, the transmittance refers to the transmittance of light having a wavelength of 400 nm. Transmittance can be adjusted by selection of exposure dose and thermal cure temperature.

A method for manufacturing an insulating layer using a photosensitive resin composition will be described with an example.

The above photosensitive resin composition is applied onto a substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, or the like to form a coating film.

The coating film is pre-baked with a heating device such as a hot plate and an oven. Pre-baking is performed at a temperature of 50 to 150° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 15 μm.

After pre-baking, the coating film is exposed using an exposure machine such as a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (PLA). The exposure intensity is about 10 to 4000 J/m ² (converted to exposure amount of 365 nm wavelength), and the light is irradiated through a desired mask or not. The exposure light source is not limited, and UV rays such as g-line, h-line, and i-line, KrF (wavelength: 248 nm) laser, ArF (wavelength: 193 nm) laser, and the like can be used.

Next, the unexposed portion of the coating film is dissolved by development to obtain a negative pattern. As a developing method, it is preferable to immerse the coating film in a developer for 5 seconds to 10 minutes by a method such as showering, dipping, or puddle. A known alkaline developer can be used as the developer. Specific examples include alkali metal hydroxides, carbonates, phosphates, silicates, inorganic alkalis such as borates; amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine; tetramethylammonium hydroxide. , an aqueous solution containing one or more of quaternary ammonium salts such as choline. After development, the coating film is preferably rinsed with water. Subsequently, the coating film can be dried and baked in the range of 50 to 130°C.

Thereafter, this coating film is heated with a heating device such as a hot plate or an oven, preferably at 140 to 300° C. for about 15 to 90 minutes to obtain a cured film. The heating temperature is more preferably 200-250°C.

The substrate with a conductive layer of the present invention has a conductive layer and an insulating layer. The substrate with a conductive layer of the present invention may be produced by forming an insulating layer from a photosensitive resin composition by the method described above and then forming a conductive layer, or may be produced by forming a conductive layer on a substrate and then Alternatively, the insulating layer may be formed from the photosensitive resin composition by the method described above. In addition, the conductive layer can be manufactured by the same method as the manufacturing method of the insulating layer described above, using a solution containing a conductive material, which will be described later.

It is preferable that the substrate with a conductive layer of the present invention has a plurality of conductive layers and an insulating layer between the plurality of conductive layers. As described above, the insulating layer formed on the conductive layer-attached substrate of the present invention has ion migration resistance under high temperature and high humidity conditions, and thus can be particularly suitably used as an interlayer insulating film between a plurality of conductive layers.

The material of the metal wiring, that is, the conductive material contained in the conductive layer is not particularly limited. zinc), _ZnO2 and the like. Among these, silver having the lowest specific resistance value is preferable. Furthermore, the conductive layer preferably contains 60 to 95% by mass of silver in order to form a conductive layer with a low specific resistance value. When the specific resistance value is low, a highly sensitive touch panel can be produced. On the other hand, silver is particularly susceptible to ion migration under high temperature and high humidity conditions, but in the present invention, ion migration between conductive layers can be prevented by using the above insulating layer. Further, it is preferable that the primary particle size of silver is 10 to 200 nm because it is possible to form a finer wiring pattern. Further, the conductive layer preferably contains 5 to 35% by mass of an organic component having at least an alkali-soluble group. By containing an organic component having an alkali-soluble group, flexibility can be imparted to the wiring pattern, and a flexible touch panel can be produced. Examples of the alkali-soluble group include, but are not limited to, 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. A carboxyl group is particularly preferred from the viewpoint of reactivity and versatility. The organic component having an alkali-soluble group is not particularly limited. oxazole etc. can be mentioned.

The transparent substrate of the substrate with a conductive layer of the present invention includes a glass substrate provided with a _SiO2 layer on the surface, an alkali-free glass substrate, and a polyimide film polyimide, polyimidesiloxane, polyethersulfone, polybenzoxazole, aramid, polysulfone and epoxy. A substrate selected from the group consisting of films made of at least one resin selected from the group consisting of resins.

Adhesion with the insulating layer is improved by using a glass substrate provided with a SiO ₂ layer on the surface as the transparent substrate.

Adhesion to the insulating layer is improved by using a non-alkali glass substrate as the transparent substrate.

Adhesion with the insulating layer is improved by using the film as the transparent substrate. A SiO ₂ layer may be provided on the surface of the film. Since the film has heat resistance necessary for forming the insulating layer and has flexibility, a flexible touch panel can be produced. Among them, from the viewpoint of further improving heat resistance, it is preferable to use a film made of at least one resin selected from the group consisting of polyimide, polyimidesiloxane, polybenzoxazole and polysulfone.

The substrate with a conductive layer of the present invention can be used as a touch panel member. Here, the touch panel member has at least the conductive layer-attached substrate.

The touch panel of the present invention contains the substrate with a conductive layer of the present invention and a display device. The touch panel may further have a polarizing plate, a cover base material, an optical adhesive sheet, and the like as constituent elements, if necessary.

Display devices include liquid crystals, organic electroluminescence, micro LEDs, and the like. Examples of cover substrates include glass and films.

The order of configuration of the touch panel includes, from the bottom, a display device, an optical adhesive sheet, a substrate with a conductive layer, an optical adhesive sheet, a polarizing plate, an optical adhesive sheet, and a cover base material, but is not limited to this.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Note that Example 16 is currently a comparative example, and Examples 1-15 and 17-30 are examples of the present invention. Among the compounds used in Synthesis Examples and Examples, those using abbreviations are shown below.
AIBN: 2,2'-azobis(isobutyronitrile)
PGMEA: propylene glycol monomethyl ether acetate DAA: diacetone alcohol TMAH; tetramethylammonium hydroxide First, materials used in Examples and Comparative Examples are described.

[Acrylic polymer (A)]
Synthesis Example 1: Acrylic polymer (a1-1)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. Then, 34.4 g of methacrylic acid, 56.4 g of benzyl methacrylate, and 17.6 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 17.1 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-1). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 10,600.

Synthesis Example 2: Acrylic polymer (a1-2)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. Then, 39.9 g of methacrylic acid, 56.4 g of benzyl methacrylate, and 3.5 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 37.5 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution and heated with stirring at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-2). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 10,000.

Synthesis Example 3: Acrylic polymer (a1-3)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. Then, 31.0 g of methacrylic acid, 63.4 g of benzyl methacrylate, and 17.6 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 20.5 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-3). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 9,700.

Synthesis Example 4: Acrylic polymer (a1-4)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. Then, 41.3 g of methacrylic acid, 28.2 g of benzyl methacrylate, 17.6 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate, and 8.0 g of methyl methacrylate were charged. is. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 34.2 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution and heated with stirring at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-4). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 9,800.

Synthesis Example 5: Acrylic polymer (a1-5)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. Then, 51.6 g of methacrylic acid, 52.8 g of benzyl methacrylate, and 22.0 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 28.6 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-5). The weight average molecular weight Mw in terms of polystyrene measured by GPC method was 10,200.

Synthesis Example 6: Acrylic polymer (a1-6)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. Then, 31.0 g of methacrylic acid, 63.4 g of benzyl methacrylate, and 17.6 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 15.4 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution and heated with stirring at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-6). The weight average molecular weight Mw in terms of polystyrene measured by GPC method was 10,200.

Synthesis Example 7: Acrylic polymer (a1-7)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. Then, 67.1 g of methacrylic acid, 35.2 g of benzyl methacrylate, and 4.4 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 42.2 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-7). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 9,400.

Synthesis Example 8: Acrylic polymer (a1-8)
A 500 ml flask was charged with 0.5 g of AIBN and 50 g of PGMEA. Then, 34.4 g of methacrylic acid, 56.4 g of benzyl methacrylate, and 17.6 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 2 hours. Next, 17.1 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-8). The weight average molecular weight Mw in terms of polystyrene measured by GPC method was 3,000.

Synthesis Example 9: Acrylic polymer (a1-9)
A 500 ml flask was charged with 0.5 g of AIBN and 100 g of PGMEA. Then, 34.4 g of methacrylic acid, 56.4 g of benzyl methacrylate, and 17.6 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 4 hours. Next, 17.1 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-9). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 5,100.

Synthesis Example 10: Acrylic polymer (a1-10)
A 500 ml flask was charged with 1 g of AIBN and 70 g of PGMEA. Then, 34.4 g of methacrylic acid, 56.4 g of benzyl methacrylate, and 17.6 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 4 hours. Next, 17.1 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-10). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 8,000.

Synthesis Example 11: Acrylic polymer (a1-11)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. Then, 34.4 g of methacrylic acid, 56.4 g of benzyl methacrylate, and 17.6 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then the mixture was heated and stirred at 70° C. for 6 hours. Next, 17.1 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-11). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 11,800.

Synthesis Example 12: Acrylic polymer (a1-12)
A 500 ml flask was charged with 1.5 g of AIBN and 50 g of PGMEA. Then, 34.4 g of methacrylic acid, 56.4 g of benzyl methacrylate, and 17.6 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 17.1 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-12). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 14,500.

Synthesis Example 13: Acrylic polymer (a1-13)
A 500 ml flask was charged with 2.0 g of AIBN and 50 g of PGMEA. Then, 34.4 g of methacrylic acid, 56.4 g of benzyl methacrylate, and 17.6 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 17.1 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-13). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 20,000.
Synthesis Example 14: Acrylic polymer (a1-14)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. Then, 34.4 g of methacrylic acid, 42.3 g of benzyl methacrylate, and 35.2 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 17.1 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-14). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 9,700.

Synthesis Example 15: Acrylic polymer (a1-15)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. Then, 34.4 g of methacrylic acid, 33.3 g of styrene, and 17.6 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 17.1 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-15). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 10,000.

Synthesis Example 16: Acrylic polymer (a1-16)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. Then, 34.4 g of methacrylic acid, 17.6 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate, and 32.0 g of methyl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 17.1 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-16). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 11,500.

Synthesis Example 17: Acrylic polymer (a1-17)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. Then, 13.8 g of methacrylic acid, 98.7 g of benzyl methacrylate and 17.6 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 11.4 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1-17). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 9,400.

Synthesis Example 18: Cardo-based resin (a1-18)
"V-259ME (trade name)" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., which is a cardo-based resin PGMEA solution containing an ethylenically unsaturated group and a carboxyl group, has a solid content concentration of 45.6 wt%, measured by the GPC method. It is a product with a weight average molecular weight Mw of 3,500 in terms of polystyrene. 100 g of "V-259ME" was weighed, and 14.0 g of PGMEA was added and stirred. Thus, a solution of cardo-based resin (a1-18) having a solid concentration of 40 wt % was obtained.

Synthesis Example 19: Acrylic polymer (a1'-1)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. After that, 34.4 g of methacrylic acid and 70.5 g of benzyl methacrylate were charged. The mixture was stirred at room temperature for a while, the inside of the flask was sufficiently replaced with nitrogen by bubbling, and then heated and stirred at 70° C. for 5 hours. Next, 17.1 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90° C. for 4 hours. PGMEA was added to the polymer solution so that the solid content concentration was 40 wt % to obtain a solution of acrylic polymer (a1'-1). The weight average molecular weight Mw in terms of polystyrene measured by GPC method was 10,500.

Synthesis Example 20: Acrylic polymer (a1'-2)
A 500 ml flask was charged with 1 g of AIBN and 50 g of PGMEA. After that, 50.1 g of methyl methacrylate, 70.5 g of benzyl methacrylate, and 22.0 g of tricyclo[5.2.1.0(2,6)]decane-8-yl methacrylate were charged. Stir at room temperature for a while, replace the inside of the flask with nitrogen sufficiently by bubbling, heat and stir at 70 ° C. for 5 hours, add PGMEA to the obtained acrylic polymer solution so that the solid content concentration is 40 wt%, and add the acrylic polymer. A solution of (a1'-2) was obtained. The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 10,000.

[Photoinitiator (B)]
1,2-propanedione-3-cyclopentane-1-[4-(phenylthio)-2-(O-benzoyloxime)] ("PBG-305 (trade name)" manufactured by Kyoryoku Denshi Co., Ltd., hereinafter "PBG-305 ”.)
3-cyclopentyl ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) (PBG-304 ( product name)”, hereinafter referred to as “PBG-304”).

[Compound (C) having an unsaturated double bond]
Dendrimer-type polyfunctional acrylate (“SIRIUS-501 (trade name)” manufactured by Osaka Organic Chemical Industry Co., Ltd., hereinafter referred to as “SIRIUS-501”)
Dipentaerythritol hexaacrylate (“Kayarad” (registered trademark) DPHA (trade name), manufactured by Nippon Kayaku Co., Ltd., hereinafter referred to as “DPHA”).
Tripentaerythritol octaacrylate ("Viscoat #802 (trade name)" manufactured by Osaka Organic Chemical Industry Co., Ltd., hereinafter referred to as "Viscoat #802")
Fluorane acrylate (manufactured by Osaka Gas Chemicals Co., Ltd.) “EA-0250P (trade name)”, hereinafter referred to as “EA-0250P”. )
Triacryl isocyanurate ("M-315 (trade name)" manufactured by Kyoeisha Co., Ltd., hereinafter referred to as "M-315")
triallyl isocyanurate ("TAIC (trade name)" manufactured by Nippon Kasei Co., Ltd., hereinafter referred to as "TAIC");

[Colorant (D)]
Phthalocyanine copper compound “Pigment Blue 15:6” (manufactured by Dainichiseika Kogyo Co., Ltd.)
Phthalocyanine copper compound “Pigment Blue 15:1” (manufactured by Dainichiseika Kogyo Co., Ltd.)
Sodium alumino sulfosilicate (manufactured by Holiday).

[Polyfunctional epoxy compound]
9,9-bis(4-glycidyloxyphenyl)fluorene (“Ogsol PG-100 (trade name)” manufactured by Osaka Gas Chemicals Co., Ltd., hereinafter referred to as “PG-100”)
1,3,5-tris(4,5-epoxypentyl)isocyanuric acid (manufactured by Nissan Chemical Industries, Ltd., “TEPIC” (registered trademark)-VL (trade name), hereinafter “TEPIC-VL”)
Trifunctional epoxy compound (“TECHMORE VG3101L (trade name)” manufactured by Printec Co., Ltd., hereinafter referred to as “VG3101L”).

[Hindered amine light stabilizer]
2,2,6,6-tetramethyl-4-piperidine methacrylate (“ADEKA STAB LA-87 (trade name)” manufactured by ADEKA Corporation, hereinafter referred to as “LA-87”).

[Silane coupling agent]
3-glycidoxypropyltrimethoxysilane ("KBM-403 (trade name)" manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as "KBM-403")
[Polymerization inhibitor]
t-butyl catechol (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as "TBC")
[Surfactant]
Silicone surfactant ("BYK-333 (trade name)" manufactured by BYK-Chemie Japan Co., Ltd., hereinafter referred to as "BYK-333")
[solvent]
PGMEA ("PGM-AC (trade name)" manufactured by Kuraray Trading Co., Ltd.)
DAA ("DAA" manufactured by Mitsubishi Chemical Corporation).

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

[Photosensitive silver ink material]
Using the following photosensitive silver ink materials, lamination workability with a conductive layer and migration resistance at high temperature and high humidity were evaluated. A method for producing a photosensitive silver ink material is shown below.

<Preparation of photosensitive silver ink material>
First, with respect to 80.00 g of conductive fine particles (manufactured by Nisshin Engineering Co., Ltd.), 4.06 g of DISPERBYK21116 (manufactured by BYK-Chemie Japan Co., Ltd.), and 196.14 g of PGMEA , with a homogenizer at 1200 rpm for 30 minutes. Further, the mixed solution was dispersed using a mill-type dispersing machine filled with zirconia beads to obtain a silver particle dispersion. 7.31 g of PGMEA and 23.25 g of DAA are added to 63.28 g of this fine silver particle dispersion mixed with 4.40 g of acrylic polymer (a1-2), 0.41 g of OXE-02 and 1.30 g of DPHA. and stirred to prepare a photosensitive silver ink (α).

Next, the production of cured films/substrates and evaluation methods performed in Examples and Comparative Examples will be described.

<Patterning of photosensitive resin composition and preparation of cured film>
The photosensitive resin composition was spin-coated on the substrate using a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.) at an arbitrary number of rotations to form a coating film. The substrate on which the coating film was formed was prebaked at 100° C. for 2 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.) to prepare a prebaked film. The pre-baked film was exposed through a desired mask using a parallel light mask aligner ("PLA-501F (trade name)" manufactured by Canon Inc.) with an ultra-high pressure mercury lamp as a light source. After that, using an automatic developing device ("AD-2000 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 0.07 wt% TMAH aqueous solution for 60 seconds to remove the unexposed portion of the pre-baked film. Then, it was rinsed with water for 30 seconds and patterned.

If necessary, the patterned substrate was post-baked at 230° C. for 60 minutes (in the air) using an oven ("IHPS-222 (trade name)" manufactured by Espec Co., Ltd.) to prepare a cured film. .

<Preparation of conductive pattern of silver ink material (α)>
After the silver ink material (α) was spin-coated on the substrate using a spin coater at a predetermined number of revolutions, it was pre-baked at 100° C. for 2 minutes using a hot plate to prepare a pre-baked film. Using a parallel light mask aligner and using an ultra-high pressure mercury lamp as a light source, the pre-baked film was exposed through a desired mask. Thereafter, using an automatic developing device, shower development was performed with a 0.07 wt % TMAH aqueous solution for 60 seconds to remove the unexposed portion of the pre-baked film, followed by rinsing with water for 30 seconds for patterning.

The patterned substrate was post-baked in an oven at 230° C. for 60 minutes (in the air) to form a conductive film.

<Production of laminated substrate>
A laminated substrate shown in FIGS. 1 and 2 was produced using the photosensitive resin composition and the silver ink material (α). The substrate 1 is a glass substrate with _SiO2 sputtered on the surface, an alkali-free glass substrate, or a polyimide film. The conductive pattern layers 2 and 4 are conductive pattern layers formed by the method described above using the silver ink material (α). The insulating layers 3 and 5 are insulating layers formed by the above method using a photosensitive resin composition. A conductive pattern 2 is formed on a substrate 1, and an insulating layer 3 is formed on the upper surface of the conductive pattern 2 so as to protect the conductive pattern 2. FIG. A conductive pattern layer 4 is formed on the insulating layer 3 so as to be perpendicular to the conductive pattern 2 , and an insulating layer 5 is formed thereon to protect the conductive pattern 4 . The conductive patterns 2 and 4 each consist of five conductive patterns of 30 μm×4 cm in length, and terminals for resistance value measurement are provided at both ends. The patterning is such that the insulating layers 3 and 5 above the terminals of the conductive patterns 2 and 4 are removed when the insulating layers 3 and 5 are formed so that the terminals are exposed. The conductive pattern layers 2 and 4 and the insulating layers 3 and 5 were each post-baked using an oven.

(1) Pattern workability evaluation Using a non-alkali glass substrate (OA-10; manufactured by Nippon Electric Glass Co., Ltd.) as a base material, photosensitivity is obtained according to the above <Pattern processing of photosensitive resin composition and preparation of cured film>. Pattern workability evaluation of the photosensitive resin composition was performed by forming a pattern of the resin composition. The film thickness of the coating film of the photosensitive resin composition was adjusted to 2.5 μm after prebaking. As a mask for exposure, a grayscale mask for sensitivity measurement was used. A test was performed by changing the exposure dose, and the exposure dose at which a 30 μm line-and-space pattern having a width of 1:1 was formed after development (hereinafter referred to as the optimum exposure dose) was defined as the sensitivity. Also, the minimum pattern size after development at the optimum exposure dose was taken as the resolution. The smaller the sensitivity and resolution values, the better the pattern processability.

(2) Evaluation of cured film properties In the above <Preparation of laminated substrate>, a glass substrate with _SiO2 sputtered on the surface was used as a base material, and a laminated substrate with an insulating layer 3 was used. The colorless transparency (b ^* ) was measured.

Using an ultraviolet-visible spectrophotometer (“MultiSpec-1500 (trade name, manufactured by Shimadzu Corporation)”), only the substrate 1 was first measured, and the obtained ultraviolet-visible absorption spectrum was used as a reference. Next, the solid film portion of the insulating layer 3 of the laminated substrate is measured with a single beam, and the light transmittance per 2.0 μm thickness of the insulating layer 3 at a wavelength of 400 nm is obtained. rate.

In addition, using a spectrophotometer (CM-2600d; manufactured by Konica Minolta Co., Ltd.), after measuring only the substrate 1 as a blank, JIS-Z8729: 1994, JIS-Z8781-4: Based on 2013 Measure the reflectance of the total reflected light of each sample from the glass substrate side of the laminated substrate, and measure the color characteristic b ^* in the CIE (L ^* , a ^* , b ^* ) color space at 5 points in total at the center and 4 corners. The average value was taken as the color tone and evaluated according to the following criteria. 2 or more was set as the pass.
5: -1.5≤b ^* ≤0.5
4: −2.0≦b ^* <−1.5, or 0.5<b ^* ≦1.0
3: -2.5≤b ^* <-2.0, or 1.0<b ^* ≤1.5
2: −3.0≦b ^* <−2.5, or 1.5<b ^* ≦2.0
1: b ^* <−3.0 or b ^* >2.0.

(3) Reliability Evaluation In the above <Preparation of laminated substrate>, a glass substrate having a surface sputtered with SiO ₂ was used as a base material, and migration resistance under high temperature and high humidity conditions was evaluated. An insulation deterioration characteristic evaluation system "ETAC SIR13" (manufactured by Kusumoto Kasei Co., Ltd.) was used for the measurement. Electrodes were attached to the terminal portions of the conductive patterns 2 and 4, respectively, and the sample was placed in a high-temperature, high-humidity bath set at 85° C. and 85% RH. Five minutes after the environment in the tank was stabilized, a voltage was applied between the electrodes of the conductive patterns 2 and 4, and the change in insulation resistance over time was measured. A voltage of 5 V was applied using the conductive pattern 2 as a positive electrode and the conductive pattern 4 as a negative electrode, and the resistance value was measured at intervals of 5 minutes for 1000 hours. When the measured resistance value reached 10 5 Ω or less, it was determined that there was a short circuit due to poor insulation, and the printing pressure was stopped. Migration resistance was evaluated according to the following evaluation criteria. 2 or more was set as the pass.
5: Short circuit time 1000 hours or more 4: Short circuit time 700 hours or more and less than 1000 hours 3: Short circuit time 400 hours or more and less than 700 hours 2: Short circuit time 200 hours or more and less than 400 hours 1: Short circuit time less than 200 hours Using the above laminated substrate, the light resistance was evaluated by the following method. Using a light resistance tester (“Q-SUN Xenon Test Chamber Model Xe-1 (trade name, manufactured by Q-Lab Corporation)”), in an environment of 45 ° C., the irradiation amount at 340 nm is 0.60 W / m ² The amount of change in b ^* (hereinafter referred to as Δb ^* ) when continuously irradiated with light for 48 hours was evaluated according to the following criteria. The measurement of b ^* was performed in the same manner as in the above "(2) Evaluation of properties of cured film". 2 or more was set as the pass.
5: Δb ^* ≤ 1.0
4: 1.0 < Δb ^* ≤ 2.0
3: 2.0 < Δb ^* ≤ 3.0
2: 3.0<Δb ^* ≦5.0
1:5.0<Δb ^*
(Example 1)
Under a yellow light, PBG-305: 0.50 g as a photopolymerization initiator (B), LA-87: 0.50 g as a hindered amine light stabilizer, TBC as a polymerization inhibitor: 0.04 g, and PGMEA as a solvent. : 20.70 g, DAA: 37.50 g, BYK-333: 0.01 g as a surfactant was added and stirred. There, as a compound (C-1), SIRIUS-501: 1.25 g, as other compounds (C) having an unsaturated double bond, EA-0250P: 1.25 g, M-315: 2.90 g, TAIC: 4.40 g, PG-100: 2.70 g as a polyfunctional epoxy compound, KBM-403: 0.25 g as a silane coupling agent, 40 wt% PGMEA solution (a1-1) as acrylic polymer (A): 28. 00 g and stirred. Next, filtration was performed with a 0.20 μm filter to obtain a photosensitive resin composition. The resulting photosensitive resin composition was evaluated for (1) pattern workability, (2) cured film properties, and (3) reliability. The composition is shown in Table 1 and the evaluation results are shown in Table 4.

(Examples 2 to 18, 24 to 30, Comparative Examples 1 and 2, Reference Example 1)
By the same method as in Example 1, photosensitive resin compositions having the compositions shown in Tables 1 to 3 were obtained, and the same evaluation as in Example 1 was performed for each photosensitive resin composition. Evaluation results are shown in Tables 4-6. In Comparative Example 2, a pattern could not be formed in "(1) Evaluation of pattern processability".

(Example 19)
Under a yellow light, PBG-305: 0.50 g as a photopolymerization initiator (B), LA-87: 0.50 g as a hindered amine light stabilizer, TBC as a polymerization inhibitor: 0.04 g, and PGMEA as a solvent. : 20.70 g, DAA: 37.50 g, BYK-333: 0.01 g as a surfactant was added and stirred. There, as a compound (C-1), SIRIUS-501: 1.25 g, as other compounds (C) having an unsaturated double bond, EA-0250P: 1.25 g, M-315: 2.90 g, TAIC: 4.40 g, PG-100: 2.70 g as a polyfunctional epoxy compound, and KBM-403: 0.25 g as a silane coupling agent, 40 wt% PGMEA solution (a1-1) as acrylic polymer (A): 28 .00 g and Pigment Blue 15:6: 0.01 g as a coloring agent (D) were added and stirred. Next, filtration was performed with a 0.20 μm filter to obtain a photosensitive resin composition. The resulting photosensitive resin composition was evaluated for (1) pattern workability, (2) cured film properties, and (3) reliability. The composition is shown in Table 2 and the evaluation results are shown in Table 5.

(Examples 20-23)
By the same method as in Example 19, photosensitive resin compositions having the compositions shown in Tables 2 and 3 were obtained, and the same evaluation as in Example 19 was performed for each photosensitive resin composition. Evaluation results are shown in Tables 5 and 6.

Although the use of the substrate with a conductive layer of the present invention is not particularly limited, it is preferably used as, for example, members for touch panels, members for displays, members for transparent antennas, and the like.

1: Base material 2: Conductive pattern 3: Insulating layer 4: Conductive pattern 5: Insulating layer

Claims (13)

A substrate with a conductive layer comprising a conductive layer and an insulating layer formed on a transparent substrate, wherein the insulating layer comprises (A) an acrylic polymer having an alicyclic skeleton and an alkali-soluble group in a side chain, and (B) photopolymerization initiation. A cured film obtained by curing a photosensitive resin composition containing an agent and (C) a compound having an unsaturated double bond, wherein the (C) compound having an unsaturated double bond is represented by the following general formula (1) When the total solid content of the photosensitive resin composition is 100% by mass, the compound (C-1) is 0.4 in the total solid content. Substrate with a conductive layer containing ~5% by mass:

In general formula (1), R ¹ to R ⁶ represent a methacryloyl group or an acryloyl group; R ¹ to R ⁶ may be the same or different; and n is 1 or 2. . The substrate with a conductive layer according to claim 1, wherein the compound (C-1) is contained in an amount of 0.4 to 3% by mass based on the total solid content of the photosensitive resin composition being 100% by mass. 3. The substrate with a conductive layer according to claim 1, wherein said conductive layer contains silver. 4. The substrate with a conductive layer according to claim 3, wherein said conductive layer contains 60 to 95 mass % of said silver. The substrate with a conductive layer according to any one of claims 1 to 4, wherein the conductive layer contains an organic component having an alkali-soluble group. 6. The substrate with a conductive layer according to any one of claims 1 to 5, wherein the acrylic polymer (A) contains 2 to 10 mol% of repeating units having an alicyclic skeleton in a side chain in all repeating units. The substrate with a conductive layer according to any one of claims 1 to 6, wherein the repeating unit having an alicyclic skeleton in the side chain is a repeating unit represented by the following general formula (2):

In general formula (2), ^R7 represents a hydrogen atom or a methyl group. The substrate with a conductive layer according to any one of claims 1 to 7, wherein the acrylic polymer (A) has a repeating unit represented by the following general formula (3):

^In general formula (3), R ⁸ represents a hydrogen atom or a methyl group; R ⁹ to R ¹³ represent a hydrogen atom, an organic group having 1 to ⁶ carbon atoms or a hydroxyl group; There may be or may be different. 9. The substrate with a conductive layer according to claim 8, wherein the acrylic polymer (A) contains 20 to 50 mol % of repeating units represented by the general formula (3) in all repeating units. Any one of claims 1 to 9, wherein the acrylic polymer (A) has repeating units represented by the following general formula (4) and repeating units represented by (5) in a total of 40 to 60 mol% of all repeating units. or the substrate with a conductive layer according to:

In general formula (4), R ¹⁴ represents a hydrogen atom or a methyl group;

In general formula (5), R ¹⁵ to R ¹⁶ each represent a hydrogen atom or a methyl group; R ¹⁵ to R ¹⁶ may be the same or different. The substrate with a conductive layer according to any one of claims 1 to 10, wherein the insulating layer further contains a coloring agent (D). The substrate with a conductive layer according to any one of claims 1 to 11, wherein the substrate with a conductive layer has a plurality of conductive layers, and the insulating layer is provided between the plurality of conductive layers. A touch panel member comprising the substrate with a conductive layer according to any one of claims 1 to 12.

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