CN115685693A

CN115685693A - Method for manufacturing laminate including transparent conductive pattern and method for manufacturing touch panel

Info

Publication number: CN115685693A
Application number: CN202210902459.5A
Authority: CN
Inventors: 有富隆志
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2021-07-30
Filing date: 2022-07-28
Publication date: 2023-02-03

Abstract

The invention provides a method for manufacturing a laminated body containing a transparent conductive pattern, which can easily form the transparent conductive pattern with a desired shape. The method for manufacturing the laminate including the transparent conductive pattern includes: preparing a base material with a transparent conductive layer; forming a 1 st photosensitive composition layer on one surface of the substrate with the transparent conductive layer; exposing the 1 st photosensitive composition layer to light and developing the layer with a 1 st developing solution to form a 1 st resist pattern; forming a 2 nd photosensitive composition layer on the other surface of the substrate with the transparent conductive layer; exposing the 2 nd photosensitive composition layer, and developing with the 2 nd developing solution to form a 2 nd resist pattern, thereby obtaining a laminate; and a step of forming a transparent conductive pattern by bringing the laminate into contact with an etching solution, wherein the dissolution time of the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer in the 2 nd developing solution satisfies predetermined requirements.

Description

Method for manufacturing laminate including transparent conductive pattern and method for manufacturing touch panel

Technical Field

The present invention relates to a method for manufacturing a laminate including a transparent conductive pattern and a method for manufacturing a touch panel.

Background

A method of forming a pattern by photolithography using a laminate having layers to be etched on both surfaces of a base material is known. In recent years, there have been cases where the layers to be etched formed on both surfaces of the base material are patterned as independent patterns.

For example, in the field of touch panels, in order to manufacture wiring for touch sensors, a method of forming patterns of different shapes on both surfaces of a base material is used.

For example, patent document 1 discloses a pattern forming method in which a laminate including a substrate having layers to be etched on both surfaces of the substrate and transparent to an exposure wavelength and having a photosensitive resin layer on each layer to be etched is used as a laminate used in the pattern forming method.

Patent document 1: international publication No. 2019/022090

In patent document 1, when forming a pattern having a predetermined shape on both surfaces of a base material, double-sided exposure is performed. As a result of studies on the pattern forming method described in patent document 1, the present inventors have found that when the transparency of the substrate and the transparent conductive layer with respect to the exposure wavelength is high, a phenomenon (hereinafter, also referred to as "exposure fogging") occurs in which exposure light irradiated to expose one of the photosensitive resin layers transmits through the substrate and the transparent conductive layer and exposes the other photosensitive resin layer, and thus a resist pattern having a desired shape cannot be obtained.

When a desired resist pattern is not obtained due to exposure fogging, the formed transparent conductive pattern does not have a desired shape. If such a shape defect of the transparent conductive pattern occurs, the conductivity of the transparent conductive pattern may be reduced or the transparent conductive pattern may be broken.

Disclosure of Invention

Accordingly, an object of the present invention is to provide a method for manufacturing a laminate including a transparent conductive pattern, which can easily form a transparent conductive pattern having a desired shape.

Another object of the present invention is to provide a method for manufacturing a touch panel.

The present inventors have made intensive studies to solve the above problems, and as a result, the present invention has been completed. That is, the following configuration was found to solve the above problems.

[ 1 ] A method for producing a laminate comprising a transparent conductive pattern, comprising:

a step A1 of preparing a substrate with a transparent conductive layer, the substrate with the transparent conductive layer having a substrate transparent to an exposure wavelength, A1 st transparent conductive layer transparent to the exposure wavelength and disposed on one surface side of the substrate, and a 2 nd transparent conductive layer transparent to the exposure wavelength and disposed on the other surface side of the substrate;

A step A2 of forming a 1 st photosensitive composition layer on one surface of the substrate with the transparent conductive layer;

a step A3 of exposing the 1 st photosensitive composition layer to light and developing the layer with a 1 st developing solution to form a 1 st resist pattern;

a step A4 of forming a2 nd photosensitive composition layer on the other surface of the substrate with the transparent conductive layer;

a step A5 of exposing the 2 nd photosensitive composition layer to light and developing the layer with a2 nd developing solution to form a2 nd resist pattern, thereby obtaining a laminate A5; and

a step A6 of bringing the laminate A5 into contact with an etching solution to etch the 1 st transparent conductive layer and the 2 nd transparent conductive layer to form a 1 st transparent conductive pattern and a2 nd transparent conductive pattern,

when the 1 st photosensitive composition layer is a negative photosensitive composition layer and the 2 nd photosensitive composition layer is a negative photosensitive composition layer,

a dissolving time of an exposure film obtained by subjecting the 1 st photosensitive composition layer to full-surface exposure under the same exposure conditions as in the step A3 in the 2 nd developer is 2.0 times or more the dissolving time of the 2 nd photosensitive composition layer in the 2 nd developer;

When the 1 st photosensitive composition layer is a negative photosensitive composition layer and the 2 nd photosensitive composition layer is a positive photosensitive composition layer,

a dissolving time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to the entire surface exposure under the same exposure condition as the step A3 in the 2 nd developing solution is 2.0 times or more a dissolving time of the exposed film obtained by subjecting the 2 nd photosensitive composition layer to the entire surface exposure under the same exposure condition as the step A5 in the 2 nd developing solution;

when the 1 st photosensitive composition layer is a positive photosensitive composition layer and the 2 nd photosensitive composition layer is a positive photosensitive composition layer,

the dissolving time of the 1 st photosensitive composition layer in the 2 nd developing solution is 2.0 times or more the dissolving time of the exposed film obtained by exposing the entire surface of the 2 nd photosensitive composition layer to the 2 nd developing solution under the same exposure conditions as in the step A5 in the 2 nd developing solution;

when the 1 st photosensitive composition layer is a positive photosensitive composition layer and the 2 nd photosensitive composition layer is a negative photosensitive composition layer,

the dissolution time of the 1 st photosensitive composition layer in the 2 nd developing solution is 2.0 times or more the dissolution time of the 2 nd photosensitive composition layer in the 2 nd developing solution.

[ 2 ] A method for producing a laminate comprising a transparent conductive pattern according to [ 1 ], wherein,

when the 1 st photosensitive composition layer is a negative photosensitive composition layer,

a dissolving time of an exposed film obtained by subjecting the 1 st photosensitive composition layer to full-surface exposure under the same exposure conditions as in the step A3 in the 2 nd developing solution is 100 seconds or more;

when the 1 st photosensitive composition layer is a positive photosensitive composition layer,

the dissolution time of the 1 st photosensitive composition layer in the 2 nd developing solution is 100 seconds or more.

[ 3 ] A method for producing a laminate including a transparent conductive pattern, comprising:

a step B1 of preparing a substrate with a transparent conductive layer, the substrate with the transparent conductive layer having a substrate transparent to an exposure wavelength and a 1 st transparent conductive layer transparent to the exposure wavelength and disposed on one surface side of the substrate;

a step B2 of forming a 1 st photosensitive composition layer on the 1 st transparent conductive layer;

a step B3 of exposing the 1 st photosensitive composition layer to light and developing the layer with the 1 st developing solution to form a 1 st resist pattern and obtain a laminate B3;

a step B4 of forming a 2 nd transparent conductive layer transparent to an exposure wavelength on a surface side of the substrate opposite to the 1 st transparent conductive layer side in the laminate B3;

A step B5 of forming a 2 nd photosensitive composition layer on the surface of the 2 nd transparent conductive layer;

a step B6 of exposing the 2 nd photosensitive composition layer to light and developing the layer with a 2 nd developing solution to form a 2 nd resist pattern, thereby obtaining a laminate B6; and

a step B7 of bringing the laminate B6 into contact with an etching solution to etch the 1 st transparent conductive layer and the 2 nd transparent conductive layer to form a 1 st transparent conductive pattern and a 2 nd transparent conductive pattern,

a dissolving time of an exposure film obtained by subjecting the 1 st photosensitive composition layer to full-surface exposure under the same exposure conditions as in the step B3 in the 2 nd developer is 2.0 times or more the dissolving time of the 2 nd photosensitive composition layer in the 2 nd developer;

a dissolving time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to the entire surface exposure under the same exposure condition as in the step B3 in the 2 nd developer is 2.0 times or more a dissolving time of the exposed film obtained by subjecting the 2 nd photosensitive composition layer to the entire surface exposure under the same exposure condition as in the step B6 in the 2 nd developer;

the dissolving time of the 1 st photosensitive composition layer in the 2 nd developing solution is 2.0 times or more the dissolving time of the exposed film obtained by exposing the entire surface of the 2 nd photosensitive composition layer to the same exposure conditions as in the step B6 in the 2 nd developing solution;

the dissolving time of the 1 st photosensitive composition layer in the 2 nd developing solution is 2.0 times or more the dissolving time of the 2 nd photosensitive composition layer in the 2 nd developing solution.

[ 4 ] the method for producing a laminate comprising a transparent conductive pattern according to [ 3 ], wherein,

a dissolving time of an exposed film obtained by subjecting the 1 st photosensitive composition layer to full-surface exposure under the same exposure conditions as in the step B3 in the 2 nd developing solution is 100 seconds or more;

The dissolving time of the 1 st photosensitive composition layer in the 2 nd developing solution is 100 seconds or more.

[ 5 ] the method for producing a laminate comprising a transparent conductive pattern according to any one of [ 1 ] to [ 4 ], wherein,

at least one of the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer is formed using a transfer film including a temporary support and a photosensitive composition layer.

[ 6 ] A method for producing a laminate comprising a transparent conductive pattern according to any one of [ 1 ] to [ 5 ], wherein,

the transmittance of the base material with respect to the exposure wavelength is 50% or more.

[ 7 ] the method for producing a laminate comprising a transparent conductive pattern according to any one of [ 1 ] to [ 6 ], wherein,

at least one of the 1 st transparent conductive layer and the 2 nd transparent conductive layer includes at least 1 selected from a metal nanowire and a metal nanoparticle.

[ 8 ] the method for producing a laminate comprising a transparent conductive pattern according to any one of [ 1 ] to [ 7 ], wherein,

at least one of the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer has an absorbance of 0.7 or less at an exposure wavelength.

[ 9 ] the method for producing a laminate comprising a transparent conductive pattern according to any one of [ 1 ] to [ 8 ], wherein,

at least one of the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer has an absorbance of 0.4 or less at an exposure wavelength.

[ 10 ] the method for producing a laminate comprising a transparent conductive pattern according to any one of [ 1 ] to [ 9 ], wherein,

at least one of the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer contains a polymerizable compound and a polymerization initiator.

[ 11 ] the method for producing a laminate comprising a transparent conductive pattern according to any one of [ 1 ] to [ 10 ], wherein,

the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer are photosensitive composition layers having the same composition.

A method for manufacturing a touch panel, comprising the method for manufacturing a laminate comprising a transparent conductive pattern according to any one of [ 1 ] to [ 11 ].

Effects of the invention

According to the present invention, it is possible to provide a method for manufacturing a laminate including a transparent conductive pattern, which can easily form a transparent conductive pattern having a desired shape.

The present invention can also provide a method for manufacturing a touch panel.

Drawings

Fig. 1 is a schematic diagram showing an example of the structure of a transfer film.

Detailed Description

The present invention will be described in detail below.

The following constituent elements may be described in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

The meanings of the respective descriptions in the present specification are shown below.

In the present specification, the numerical range expressed by the term "to" refers to a range including numerical values before and after the term "to" as a lower limit value and an upper limit value.

In the numerical ranges recited in the stepwise manner, the upper limit or the lower limit recited in a certain numerical range may be replaced with the upper limit or the lower limit recited in another stepwise manner. In the numerical ranges described in the present specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the values shown in the examples.

The term "step" includes not only an independent step but also a step that can achieve the intended purpose of the step even when the step is not clearly distinguished from other steps.

Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values obtained as follows: TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation) were used as columns, THF (tetrahydrofuran) was used as an eluent, a differential refractometer was used as a detector, polystyrene was used as a standard substance, and polystyrene was used as a standard substance measured by a Gel Permeation Chromatography (GPC) analyzer in conversion.

Unless otherwise specified, the molecular weight of the compound having a molecular weight distribution is a weight average molecular weight (Mw).

Unless otherwise specified, the content of the metal element is a value measured by an Inductively Coupled Plasma (ICP: inductively Coupled Plasma) spectroscopic analyzer.

"(meth) acrylic acid" is a concept including both acrylic acid and methacrylic acid, and "(meth) acryloyloxy" is a concept including both acryloyloxy and methacryloyloxy.

"alkali-soluble" means that the solubility in 100g of a 1 mass% aqueous solution of sodium carbonate at 22 ℃ is 0.1g or more. That is, "alkali-soluble resin" refers to a resin satisfying the above solubility.

"Water-soluble" means that the solubility in 100g of water having a pH of 7.0 at a liquid temperature of 22 ℃ is 0.1g or more. That is, the "water-soluble resin" refers to a resin satisfying the above solubility.

The "solid component" of the composition means a component of the composition layer (for example, the photosensitive composition layer, the intermediate layer, and the thermoplastic resin layer) formed from the composition, and when the composition contains a solvent (for example, an organic solvent, water, and the like), the composition means all components except the solvent. In addition, if the component is a component forming the composition layer, even a liquid component is considered as a solid component.

In the present specification, the "exposure wavelength" refers to the wavelength of light irradiated to the photosensitive composition layer (the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer) when the photosensitive composition layer is exposed to light. For example, when the photosensitive composition layer is exposed to light through a filter having wavelength selectivity, the wavelength of light before passing through the filter does not belong to the exposure wavelength. Here, "wavelength selectivity" refers to a property of transmitting light in a specific wavelength range. In the present specification, the wavelength of Light and the intensity of Light are measured by a known spectroscope (for example, RPS900-R, manufactured by International Light Technologies).

In the present specification, the term "dominant wavelength" refers to the wavelength of the light having the highest intensity among the exposure lights irradiated to the photosensitive composition layers (the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer). For example, when the light irradiated to the photosensitive composition layer has a wavelength of 365nm and a wavelength of 436nm, and the intensity of the light having the wavelength of 365nm is larger than the intensity of the light having the wavelength of 436nm, the main wavelength of the exposure light is 365nm. In the present specification, "exposure light" refers to light for exposing the photosensitive composition layer.

In the present specification, unless otherwise specified, "transparent" means that the transmittance at the main wavelength in the exposure wavelength is 30% or more. The transmittance is preferably 50% or more, more preferably 60% or more, further preferably 80% or more, and particularly preferably 90% or more. The upper limit is less than 100% in many cases. The transmittance is measured by a known transmittance measuring instrument (for example, V-700 series manufactured by JASCO Corporation).

In this specification, unless otherwise specified, the "maximum absorption wavelength" can be calculated from the obtained absorption spectrum by measuring the absorbance in the wavelength range of 200 to 800nm with an ultraviolet-visible spectrophotometer UV-1800 (manufactured by SHIMADZU CORPORATION).

In the present specification, the "negative photosensitive composition layer" refers to a photosensitive composition layer in which the solubility of an exposed portion in a developer is reduced by exposure. The "positive photosensitive composition layer" refers to a photosensitive composition layer in which the solubility of an exposed portion in a developing solution is improved by exposure.

The method for producing a laminate including a transparent conductive pattern according to the present invention includes the production method of embodiment 1 and the production method of embodiment 2 described below.

First, embodiment 1 will be described, and embodiment 2 will be described later.

< embodiment 1 >

Embodiment 1 of the present invention is a method for manufacturing a laminate including a transparent conductive pattern, including the steps of:

a step A1 of preparing a substrate with a transparent conductive layer, the substrate with the transparent conductive layer having a substrate transparent to an exposure wavelength, A1 st transparent conductive layer transparent to the exposure wavelength and disposed on one surface side of the substrate, and a2 nd transparent conductive layer transparent to the exposure wavelength and disposed on the other surface side of the substrate;

a step A2 of forming a1 st photosensitive composition layer on one surface of a substrate having a transparent conductive layer;

a step A3 of exposing the 1 st photosensitive composition layer to light and developing the layer with a1 st developing solution to form a1 st resist pattern;

a step A4 of forming a2 nd photosensitive composition layer on the other surface of the substrate having the transparent conductive layer;

a step A5 of exposing the 2 nd photosensitive composition layer to light and developing the layer with a2 nd developing solution to form a2 nd resist pattern to obtain a laminate A5; and

a step A6 of bringing the laminate A5 into contact with an etching solution to etch the 1 st transparent conductive layer and the 2 nd transparent conductive layer to form a1 st transparent conductive pattern and a2 nd transparent conductive pattern,

the dissolution time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to full-surface exposure under the same exposure conditions as in the step A3 in the 2 nd developing solution is 2.0 times or more the dissolution time of the 2 nd photosensitive composition layer in the 2 nd developing solution,

the dissolution time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to the entire surface exposure under the same exposure conditions as in the step A3 in the 2 nd developing solution is 2.0 times or more the dissolution time of the exposed film obtained by subjecting the 2 nd photosensitive composition layer to the entire surface exposure under the same exposure conditions as in the step A5 in the 2 nd developing solution,

the dissolving time of the 1 st photosensitive composition layer in the 2 nd developing solution is 2.0 times or more the dissolving time of the exposed film obtained by exposing the entire surface of the 2 nd photosensitive composition layer to the 2 nd developing solution under the same exposure conditions as in the step A5 in the 2 nd developing solution,

Hereinafter, the requirement relating to the dissolution time when the 1 st photosensitive composition layer is a negative photosensitive composition layer is also referred to as "requirement AX", and the requirement relating to the dissolution time when the 1 st photosensitive composition layer is a positive photosensitive composition layer is also referred to as "requirement AY".

The mechanism by which the shape of the transparent conductive pattern on the laminate including the transparent conductive pattern manufactured by the manufacturing method of embodiment 1 is as well as the design is good is not clear, but the present inventors presume that it is as follows.

In embodiment 1, after the 1 st resist pattern is formed in the steps A2 and A3, the 2 nd resist pattern is formed in the steps A4 and A5, that is, the 1 st resist pattern and the 2 nd resist pattern are sequentially formed, whereby the 1 st and 2 nd resist patterns having desired shapes can be easily obtained without causing exposure fogging. When the 2 nd resist pattern is formed by performing exposure and development successively while satisfying the requirement AX or the requirement AY, the 1 st resist pattern is less likely to be deformed by swelling or dissolution by the developer, and therefore the 1 st and 2 nd resist patterns having desired shapes can be obtained. By obtaining a resist pattern having a desired shape, the shape defect of the transparent conductive pattern to be formed is less likely to occur.

The steps A1 to A6 included in the manufacturing method of embodiment 1 will be described below. The requirement AX and the requirement AY are also described. The transfer film that can be used in steps A2 and A4 will be described later.

Hereinafter, the case where the defective shape of the formed transparent conductive pattern is less likely to occur is also referred to as "the effect of the present invention is more excellent".

[ Process A1]

The step A1 is a step of preparing a substrate with a transparent conductive layer, which includes a substrate transparent to an exposure wavelength, A1 st transparent conductive layer transparent to the exposure wavelength and disposed on one surface side of the substrate, and a2 nd transparent conductive layer transparent to the exposure wavelength and disposed on the other surface side of the substrate.

The substrate with the transparent conductive layer can be obtained by performing step A1.

The step of preparing a substrate with a transparent conductive layer comprises: a substrate preparation step of manufacturing a substrate transparent to an exposure wavelength; a1 st transparent conductive layer forming step of forming a1 st transparent conductive layer on one surface of a base material; and a2 nd transparent conductive layer forming step of forming a2 nd transparent conductive layer on the other surface of the base material.

The substrate preparation step, the 1 st transparent conductive layer forming step, and the 2 nd transparent conductive layer forming step will be described in detail below.

(base Material preparation Process)

In the substrate preparation step, a substrate transparent to the exposure wavelength is prepared.

The substrate is not particularly limited as long as it is transparent to the exposure wavelength, and is preferably a substrate such as a film or a sheet having at least 2 surfaces.

The term "transparent" as used herein means that the transmittance at the exposure wavelength is 30% or more. The transmittance at the exposure wavelength of the base material is preferably 50% or more, more preferably 80% or more, and further preferably 90% or more. The upper limit is not particularly limited, but is less than 100% in many cases.

The total light transmittance of the substrate is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. The upper limit is preferably less than 100%.

Examples of the substrate include a resin substrate (e.g., a resin film) and a glass substrate. The resin substrate is preferably a resin substrate that transmits visible light. Preferable components of the resin base material that transmits visible light include, for example, polyamide resins, polyethylene terephthalate resins, polyethylene naphthalate resins, cycloolefin resins, polyimide resins, and polycarbonate resins. More preferable components of the resin substrate that transmits visible light include, for example, polyamide, polyethylene terephthalate (PET), cycloolefin polymer (COP), polyethylene naphthalate (PEN), polyimide, and polycarbonate.

Among the above substrates, a polyamide film, a polyethylene terephthalate film, a cycloolefin polymer film, a polyethylene naphthalate film, a polyimide film, or a carbonate film is preferable, and a polyethylene terephthalate film or a cycloolefin polymer film is more preferable.

Examples of the base material include resin base materials, glass base materials, and semiconductor base materials other than those described above, and the base material described in paragraph [0140] of international publication No. 2018/155193.

The thickness of the substrate is not limited. The thickness of the substrate is preferably 10 to 200. Mu.m, more preferably 20 to 120. Mu.m, and still more preferably 20 to 100. Mu.m.

The thickness of the substrate was measured by the following method. A cross section in a direction perpendicular to the main surface of the transparent substrate (i.e., in the thickness direction) was observed by a Scanning Electron Microscope (SEM). From the obtained observation image, the thickness of the transparent substrate was measured at 10 points. The average thickness of the transparent substrate was obtained by arithmetically averaging the measured values.

(1 st Process for Forming transparent conductive layer)

In the 1 st transparent conductive layer forming step, the 1 st transparent conductive layer is formed on one surface of the base material.

The 1 st transparent conductive layer formed will be described below.

The 1 st transparent conductive layer is not particularly limited as long as it is transparent to an exposure wavelength and has conductivity.

The term "transparent" as used herein means that the transmittance at the exposure wavelength is 30% or more. The transmittance of the 1 st transparent conductive layer at the exposure wavelength is preferably 50% or more, more preferably 80% or more, and further preferably 90% or more. The upper limit is not particularly limited, and is less than 100% in many cases.

The total light transmittance of the 1 st transparent conductive layer is preferably 80% or more, more preferably 90% or more, and further preferably 95% or more. The upper limit is not particularly limited, and is less than 100% in many cases.

The volume resistivity of the 1 st transparent conductive layer is preferably less than 1X 10 ⁶ Omega cm, more preferably less than 1X 10 ⁴ Omega cm. The lower limit is not particularly limited, and is 1X 10 ^-6 Omega cm or more, 1X 10 ^-3 More often than Ω cm. The volume resistivity can be measured by using a known resistivity meter (e.g., resistance tester EC-80p, napson CORPORATION, etc.).

The material constituting the 1 st transparent conductive layer is not particularly limited, and preferably contains a conductive material. Examples of the conductive material include metals, metal compounds, carbon materials, conductive polymers, and the like.

The 1 st transparent conductive layer preferably contains a metal or a metal compound in view of more excellent conductivity.

Examples of the element contained In the metal or the metal compound include titanium (Ti), chromium (Cr), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), molybdenum (Mo), palladium (Pd), silver (Ag), indium (In), tin (Sn), tungsten (W), platinum (Pt), and gold (Au).

The metal may be any 1 of single metals and alloys. The metal preferably contains 1 or more elements selected from copper, silver, platinum, and gold, and more preferably contains silver.

For example, the metal compound includes a metal oxide containing the above element and oxygen. Examples of the metal oxide include Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), zinc oxide (ZnO), and IGZO (registered trademark; an oxide semiconductor containing indium (In), gallium (Ga), zinc (Zn), and oxygen (O)), and ITO is preferable In terms of more excellent transparency.

The form of the metal is not particularly limited, and from the viewpoint of excellent transparency and conductivity of the 1 st transparent conductive layer, a metal mesh, metal nanoparticles, or metal nanowires are preferable, and metal nanoparticles or metal nanowires are more preferable.

Examples of the metal nanoparticles include metal nanoparticles such as copper nanoparticles, silver nanoparticles, platinum nanoparticles, and gold nanoparticles, and silver nanoparticles are preferable.

Examples of the metal nanowire include a copper nanowire, a silver nanowire, a platinum nanowire, and a gold nanowire, and a silver nanowire is preferable.

The form of the metal compound is not particularly limited, and a dense layer is preferably formed by the metal compound in view of excellent conductivity.

Among the above, the 1 st transparent conductive layer preferably contains metal nanoparticles or metal nanowires from the viewpoint of excellent transparency and conductivity.

The average thickness of the 1 st transparent conductive layer is preferably 0.001 to 1000. Mu.m, more preferably 0.005 to 15 μm, and still more preferably 0.01 to 10 μm, from the viewpoint of more excellent conductivity and film formability. The average thickness of the 1 st transparent conductive layer can be obtained according to a method following the method for measuring the average thickness of the base material described above.

The method for forming the 1 st transparent conductive layer on the surface of the substrate is not particularly limited, and a known method can be used. Among them, from the viewpoint of productivity and film thickness controllability, a method of forming the 1 st transparent conductive layer by applying a liquid containing a conductive material onto a base material and drying the liquid is preferable. The coating method is not particularly limited, and a known method can be used.

Before the coating, the substrate is preferably pretreated.

The 1 st transparent conductive layer may be disposed on the entire substrate or may be disposed on a part of the substrate.

Further, the substrate may have a routing wire or a layer for routing wire in a portion where the 1 st transparent conductive layer is not formed.

As a material of the routing wire, metal is preferable.

Examples of the metal include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, and alloys of these metals in combination, with copper, molybdenum, aluminum, or titanium being preferred, and copper being more preferred.

(second transparent conductive layer Forming Process)

In the 2 nd transparent conductive layer forming step, the 2 nd transparent conductive layer is formed on the other surface of the base material.

The 2 nd transparent conductive layer may be formed simultaneously with the 1 st transparent conductive layer or may be formed sequentially.

The definition and preferred embodiments of the 2 nd transparent conductive layer are the same as those of the 1 st transparent conductive layer, and thus, the description thereof is omitted.

The 1 st transparent conductive layer and the 2 nd transparent conductive layer may be composed of the same composition or different compositions, but are preferably composed of the same composition.

The 1 st transparent conductive layer and the 2 nd transparent conductive layer may be the same thickness or different thicknesses, and preferably the same thickness.

[ Process A2]

The step A2 is a step of forming a 1 st photosensitive composition layer on one surface of the substrate with the transparent conductive layer.

By performing the step A2, a laminate A2 in which the 1 st photosensitive composition layer is formed on one surface of the substrate with the transparent conductive layer can be obtained. The 1 st photosensitive composition layer may be formed on the surface of the 1 st transparent conductive layer or on the surface of the 2 nd transparent conductive layer.

The formation of the 1 st photosensitive composition layer will be described in detail below.

(formation of the No. 1 photosensitive composition layer)

The method for forming the 1 st photosensitive composition layer is not particularly limited as long as the 1 st photosensitive composition layer is formed on one surface of the substrate with the transparent conductive layer, and a method using a transfer film and a method of applying a photosensitive composition described later are exemplified. Among these, a method using a transfer film is preferable. More specifically, the following method is preferred: a transfer film including a temporary support and a photosensitive composition layer is prepared, and the transfer film is bonded to a substrate with a transparent conductive layer so that the photosensitive composition layer side of the transfer film faces the conductive layer of the substrate with the transparent conductive layer.

The transfer film is a film having at least a temporary support and a photosensitive composition layer. The release film may have an intermediate layer between the temporary support and the photosensitive composition layer. The transfer film will be described in detail in the subsequent stage.

The method of bonding the substrate with the transparent conductive layer and the transfer film is preferably performed while applying pressure and heat with a roller or the like. The pressure at the time of pressurization is often 1000 to 10000N/m in line pressure. The temperature during the heating is usually 40 to 130 ℃.

In the method of laminating the substrate with the transparent conductive layer and the transfer film, for example, a laminator, a vacuum laminator, and an automatic cutting laminator can be used. The method of bonding the substrate with the transparent conductive layer and the transfer film may be performed in a roll-to-roll manner according to the material of the substrate with the transparent conductive layer.

The temporary support may be peeled off after the step A2, or may be peeled off after the step A3.

In view of more excellent suppression of the unevenness in the cross-sectional shape of the 1 st resist pattern and the line width of the resist pattern, which will be described later, the absorbance of the 1 st photosensitive composition layer formed at the exposure wavelength is preferably 0.8 or less, more preferably 0.7 or less, still more preferably 0.5 or less, and particularly preferably 0.4 or less. The lower limit is not particularly limited, and is 0.05 or more, preferably 0.1 or more.

The absorbance of the 1 st photosensitive composition layer can be calculated from the absorption spectrum obtained by measuring the absorbance in the wavelength range of 200 to 800nm with an ultraviolet-visible spectrophotometer UV-1800 (manufactured by SHIMADZU CORPORATION).

When the absorbance of the 1 st photosensitive composition layer in the transfer film is measured, the absorbance of the 1 st photosensitive composition layer can be calculated by subtracting the absorbance of the temporary support of the transfer film from the absorbance of the transfer film.

[ Process A3]

The step A3 is a step of exposing the 1 st photosensitive composition layer to light and developing the layer with the 1 st developing solution to form a 1 st resist pattern.

By performing step A3, a laminate A3 in which the 1 st resist pattern is formed on one surface of the substrate with the transparent conductive layer can be obtained.

The step of forming the 1 st resist pattern includes a 1 st exposure step of exposing the 1 st photosensitive composition layer and a 1 st development step of developing the 1 st photosensitive composition layer with a 1 st developer.

The 1 st exposure step and the 1 st development step will be described in detail below.

(the 1 st Exposure step)

In the 1 st exposure step, pattern exposure is performed to form a 1 st resist pattern of a desired shape.

The "pattern exposure" is a pattern exposure method, and refers to exposure in which an exposed portion and a non-exposed portion are present. The positional relationship between the exposed portion (exposed area) and the unexposed portion (unexposed area) in the pattern exposure can be appropriately adjusted.

The exposure direction may be from the 1 st photosensitive composition layer side or the side opposite to the 1 st photosensitive composition layer side (substrate side).

The 1 st photosensitive composition layer exposed in the 1 st exposure step has a change in solubility in a developer between an exposed portion and an unexposed portion. For example, when the 1 st photosensitive composition layer is a positive photosensitive composition layer, the exposed portion of the 1 st photosensitive composition layer has higher solubility in a developer than the unexposed portion. On the other hand, for example, when the 1 st photosensitive composition layer is a negative photosensitive composition layer, the exposed portion of the 1 st photosensitive composition layer has a lower solubility in a developer than the unexposed portion.

Examples of the exposure method include known methods.

Specifically, a method using a photomask is given. For example, by disposing a photomask between the 1 st photosensitive composition layer and the exposure light source, the 1 st photosensitive composition layer can be pattern-exposed through the photomask. By pattern-exposing the 1 st photosensitive composition layer, exposed portions and unexposed portions can be formed on the 1 st photosensitive composition layer.

In the exposure step, it is preferable to perform exposure by bringing the 1 st photosensitive composition layer into contact with a photomask (hereinafter, also referred to as "contact exposure") from the viewpoint of further improving the resolution.

In the exposure step, in addition to the contact exposure, a proximity exposure, a lens-based or mirror-based projection exposure method, or a direct exposure method using an exposure laser or the like may be used.

The lens projection exposure system can use an exposure machine having a Numerical Aperture (NA) of an appropriate lens according to the resolution and the depth of focus. The direct exposure method may be a method of directly drawing on the photosensitive composition layer, or a method of performing reduction projection exposure on the photosensitive composition layer through a lens. The exposure may be performed under the atmospheric air, reduced pressure or vacuum, or may be performed by adding a liquid such as water between the exposure light source and the 1 st photosensitive composition layer.

In the step A2, when the 1 st photosensitive composition layer is formed using a transfer film, the 1 st exposure step may be performed after the temporary support is peeled off, or the photosensitive composition layer may be exposed through the temporary support. When the photosensitive composition layer is exposed by contact exposure, it is preferable to expose the 1 st photosensitive composition layer through the temporary support in order to avoid contamination of the photomask and influence of foreign matter adhering to the photomask on the exposure. When the 1 st photosensitive composition layer is exposed through the temporary support, it is preferable to perform the 1 st developing step described later after peeling off the temporary support.

The exposure light used in the 1 st exposure step is not particularly limited as long as it can change the solubility of the 1 st photosensitive composition layer in the developer. The dominant wavelength of the exposure light is usually 10 to 450nm, preferably 300 to 450nm, more preferably 350 to 450nm. "dominant wavelength" refers to the wavelength at which the intensity is greatest.

Examples of the exposure light source include various lasers, light Emitting Diodes (LEDs), ultra-high pressure mercury lamps, and metal halide lamps.

The exposure amount is preferably 5 to 200mJ/cm ² More preferably 10 to 200mJ/cm ² . The exposure is determined according to the illumination of the light source and the exposure time. The exposure amount can be measured using a known optical meter.

Examples of the light source, the exposure amount, and the exposure method include paragraphs [0146] to [0147] of International publication No. 2018/155193, which are incorporated herein by reference.

In the exposure step, the photosensitive composition layer may be exposed without using a photomask.

In the case where the photosensitive composition layer is exposed without using a photomask (hereinafter, also referred to as "maskless exposure"), the 1 st photosensitive composition layer can be exposed by, for example, a direct writing apparatus.

The direct imaging device is a device capable of directly imaging with active energy rays.

Examples of the exposure light source in the maskless exposure include a laser beam (e.g., a semiconductor laser, a gas laser, a solid-state laser, etc.) and a short-arc mercury lamp (e.g., an ultra-high pressure mercury lamp, etc.) capable of emitting light having a wavelength of 350 to 410 nm.

The exposure wavelength is as described above. The exposure amount can be determined by the illuminance of the light source and the moving speed of the laminate. The traced pattern can be controlled by a computer.

(1 st developing step)

The 1 st developing step is a step of developing the 1 st photosensitive composition layer exposed to light to form a 1 st resist pattern.

For example, when the 1 st photosensitive composition layer is a positive photosensitive composition layer, the exposed portion of the 1 st photosensitive composition layer is removed by a developing solution in the 1 st developing step. On the other hand, for example, when the 1 st photosensitive composition layer is a negative photosensitive composition layer, in the 1 st developing step, the unexposed portion of the 1 st photosensitive composition layer is removed by the developing solution.

As the developing method, for example, a known method can be used.

Specifically, a method using a developer is mentioned.

Examples of the developer include those described in Japanese patent application laid-open No. 5-072724 and International publication No. 2015/093271, paragraph [0194 ].

As the developer, an alkaline aqueous solution is preferable.

Examples of the basic compound (a compound which is dissolved in water and exhibits basicity) contained in the basic aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

The temperature of the developing solution is preferably 20 to 40 ℃.

As the development method, for example, a known method can be used. Examples of the development method include spin immersion development, shower and spin development, and immersion development.

As the developing method, the developing method described in paragraph [0195] of International publication No. 2015/093271 is preferable.

Further, a step of further exposing the 1 st resist pattern obtained in the 1 st developing step (hereinafter, also referred to as a "post-exposure step") and/or a step of heating (hereinafter, also referred to as a "post-baking step") may be provided.

When the method of manufacturing the laminate includes both the post-exposure step and the post-baking step, it is preferable to perform the post-baking step after performing the post-exposure step.

The exposure amount in the post-exposure step is preferably 100 to 5000mJ/cm ² More preferably 200 to 3000mJ/cm ² 。

The temperature of the post-baking in the post-baking step is preferably 80 to 250 ℃, more preferably 90 to 160 ℃.

The time for the post-baking in the post-baking step is preferably 1 to 180 minutes, and more preferably 10 to 60 minutes.

[ Process A4]

The step A4 is a step of forming a 2 nd photosensitive composition layer on the other surface of the substrate with the transparent conductive layer.

By performing the step A4, a laminate A4 in which the 1 st resist pattern is formed on one surface of the substrate with the transparent conductive layer and the 2 nd photosensitive composition layer is formed on the other surface of the substrate with the transparent conductive layer can be obtained.

The method for forming the 2 nd photosensitive composition layer and the preferred embodiment thereof are the same as those for forming the 1 st photosensitive composition layer, and therefore, the description thereof will be omitted. The method of forming the 1 st photosensitive composition layer may be the same as or different from the method of forming the 2 nd photosensitive composition layer, and is preferably the same from the viewpoint of simplification of the process. Therefore, the 2 nd photosensitive composition layer is preferably formed using a transfer film.

The 1 st photosensitive composition layer and the 2 nd photosensitive composition layer to be formed may be composed of the same composition or may be composed of different compositions, but are preferably composed of the same composition. The 1 st photosensitive composition layer and the 2 nd photosensitive composition layer to be formed may have the same thickness or different thicknesses, and preferably have the same thickness.

[ Process A5]

The step A5 is a step of exposing the 2 nd photosensitive composition layer to light and developing the layer with the 2 nd developing solution to form a 2 nd resist pattern, thereby obtaining a laminate A5.

By performing step A5, a laminate A5 in which the 1 st resist pattern is formed on one surface of the substrate with the transparent conductive layer and the 2 nd resist pattern is formed on the other surface of the substrate with the transparent conductive layer can be obtained.

The step of forming the 2 nd resist pattern includes a 2 nd exposure step of exposing the 2 nd photosensitive composition layer and a 2 nd development step of developing with a 2 nd developer.

The method of the 2 nd exposure step and its preferred embodiment are the same as those of the 1 st exposure step, and therefore, the description thereof is omitted.

The method and preferred embodiment of the 2 nd developing step are the same as those of the 1 st developing step, and therefore, the description thereof will be omitted.

[ requirements AX ]

When the 1 st photosensitive composition layer is a negative photosensitive composition layer and the 2 nd photosensitive composition layer is a negative photosensitive composition layer, the dissolution time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to the full-surface exposure under the same exposure condition as the step A3 in the 2 nd developer is 2.0 times or more the dissolution time of the 2 nd photosensitive composition layer in the 2 nd developer, and when the 1 st photosensitive composition layer is a negative photosensitive composition layer and the 2 nd photosensitive composition layer is a positive photosensitive composition layer, the dissolution time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to the full-surface exposure under the same exposure condition as the step A3 in the 2 nd developer is 2.0 times or more the dissolution time of the exposed film obtained by subjecting the 2 nd photosensitive composition layer to the full-surface exposure under the same exposure condition as the step A5 in the 2 nd developer.

Hereinafter, the dissolution time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to the entire surface exposure under the same exposure conditions (exposure amount, exposure time, etc.) as those in the step A3 in the 2 nd developer is also referred to as "dissolution time AX1". When the 2 nd photosensitive composition layer is a negative photosensitive composition layer, the dissolution time of the 2 nd photosensitive composition layer in the 2 nd developer is also referred to as "dissolution time AX2". When the 2 nd photosensitive composition layer is a positive photosensitive composition layer, the dissolution time of the exposed film obtained by subjecting the 2 nd photosensitive composition layer to full-surface exposure under the same exposure conditions as in the step A5 in the 2 nd developer is also referred to as "dissolution time AX3".

The dissolution time AX1 is measured by the following method.

The 2 nd developing solution was supplied by a shower method to an exposed film obtained by exposing the 1 st photosensitive composition layer to light over the entire surface under the same exposure conditions (exposure amount, exposure time, etc.) as in the step A3 in a state where the exposed film was exposed. The supply of the developer by the shower method was performed using a 25 ℃ 1.0 mass% sodium carbonate aqueous solution, and was performed under a condition that the developer spray pressure was adjusted to 0.15MPa by a Full Cone (Full Cone) nozzle (h.ikeuchi co., ltd.).

Samples in which the supply time of the developing solution was changed were prepared in the above-described procedure, and the surfaces of the samples were observed with an optical microscope. As a result of the observation, the supply time of the developer of the sample in which the residue of the exposed film derived from the 1 st photosensitive composition layer was not found for the first time was defined as the dissolution time AX1.

The dissolution time AX2 is measured by the following method.

The 2 nd photosensitive composition layer is not exposed to light and the 2 nd photosensitive composition layer is exposed to light, through the spray method to the 2 nd photosensitive composition layer supply the 2 nd developing solution. The conditions for supplying the developer by the shower method are set to be the same as the dissolution time AX1.

Samples in which the supply time of the developing solution was changed were prepared in the above-described procedure, and the surfaces of the samples were observed with an optical microscope. As a result of the observation, the supply time of the developer of the sample in which the residue derived from the 2 nd photosensitive composition layer was not found for the first time was defined as the dissolution time AX2.

The dissolution time AX3 is measured by the following method.

The 2 nd developing solution was supplied by a shower method to an exposed film obtained by subjecting the 2 nd photosensitive composition layer to full-surface exposure under the same exposure conditions (exposure amount, exposure time, and the like) as in the step A5 in a state where the exposed film was exposed. The conditions for supplying the developer by the shower method are the same as the dissolution time AX1.

Samples in which the supply time of the developing solution was changed were prepared in the above-described procedure, and the surfaces of the samples were observed with an optical microscope. As a result of the observation, the supply time of the developer of the sample in which the residue of the exposed film derived from the 2 nd photosensitive composition layer was not found for the first time was defined as the dissolution time AX3.

From the viewpoint of further improving the effect of the present invention, the dissolution time AX1 is preferably 60 seconds or more, more preferably 100 seconds or more, and further preferably 150 seconds or more. The upper limit is not particularly limited, and is 600 seconds or less, but from the viewpoint of the removability of the resist pattern, 450 seconds or less is preferable, and 350 seconds or less is more preferable.

From the viewpoint of further improving the effect of the present invention, the dissolution time AX2 is preferably 100 seconds or less, more preferably 60 seconds or less, and further preferably 30 seconds or less. The lower limit is not particularly limited, and may be 1 second or more, preferably 5 seconds or more, and more preferably 10 seconds or more.

From the viewpoint of further improving the effect of the present invention, the dissolution time AX3 is preferably 100 seconds or less, more preferably 60 seconds or less, and further preferably 30 seconds or less. The lower limit is not particularly limited, and may be 1 second or more, preferably 5 seconds or more, and more preferably 10 seconds or more.

The requirement AX is that the dissolution time AX1 is 2.0 times or more the dissolution time AX2 when the 1 st photosensitive composition layer is a negative photosensitive composition layer and the 2 nd photosensitive composition layer is a negative photosensitive composition layer. From the viewpoint of further improving the effect of the present invention, the dissolution time AX1 is preferably more than 2.5 times, and more preferably more than 3.0 times the dissolution time AX 2. The upper limit is not particularly limited, and the dissolution time AX1 is preferably 50 times or less, more preferably 40 times or less, and further preferably 30 times or less of the dissolution time AX 2.

Further, the requirement AX requires that the dissolution time AX1 be 2.0 times or more the dissolution time AX3 when the 1 st photosensitive composition layer is a negative photosensitive composition layer and the 2 nd photosensitive composition layer is a positive photosensitive composition layer. From the viewpoint of further improving the effect of the present invention, the dissolution time AX1 is preferably more than 2.5 times, more preferably more than 3.0 times the dissolution time AX 3. The upper limit is not particularly limited, and the dissolution time AX1 is preferably 50 times or less, more preferably 40 times or less, and further preferably 30 times or less of the dissolution time AX 3.

The dissolution time AX1 can be controlled by the type and content of the component used in the 1 st photosensitive composition layer, the thickness of the 1 st photosensitive composition layer, the type of the 2 nd developing solution, and the like. Preferred embodiments of the kind and content of the component used for the 1 st photosensitive composition layer and the thickness of the 1 st photosensitive composition layer will be described in detail in a section of a transfer film in a subsequent stage.

The dissolution time AX2 and the dissolution time AX3 can be controlled by the type and content of the component used for the 2 nd photosensitive composition layer, the thickness of the 2 nd photosensitive composition layer, the type of the 2 nd developing solution, and the like. Preferred embodiments of the kind and content of the component used for the 2 nd photosensitive composition layer and the thickness of the 2 nd photosensitive composition layer will be described in detail in a portion of a transfer film in a subsequent stage.

[ requirements AY ]

When the 1 st photosensitive composition layer is a positive photosensitive composition layer and the 2 nd photosensitive composition layer is a positive photosensitive composition layer, the dissolution time of the 1 st photosensitive composition layer in the 2 nd developer is 2.0 times or more the dissolution time of the 2 nd developer of an exposure film obtained by full-face exposure of the 2 nd photosensitive composition layer under the same exposure conditions as in the step A5, and when the 1 st photosensitive composition layer is a positive photosensitive composition layer and the 2 nd photosensitive composition layer is a negative photosensitive composition layer, the dissolution time of the 1 st photosensitive composition layer in the 2 nd developer is 2.0 times or more the dissolution time of the 2 nd photosensitive composition layer in the 2 nd developer.

Hereinafter, the dissolution time of the 1 st photosensitive composition layer in the 2 nd developing solution is also referred to as "dissolution time AY1". When the 2 nd photosensitive composition layer is a positive photosensitive composition layer, the dissolution time of the exposed film obtained by subjecting the 2 nd photosensitive composition layer to full-surface exposure under the same exposure conditions as in the step A5 in the 2 nd developer is also referred to as "dissolution time AY2". When the 2 nd photosensitive composition layer is a negative photosensitive composition layer, the dissolution time of the 2 nd photosensitive composition layer in the 2 nd developing solution is also referred to as "dissolution time AY3".

The dissolution time AY1 is measured by the following method.

The 1 st photosensitive composition layer is exposed without exposing the 1 st photosensitive composition layer, and the 2 nd developing solution is supplied to the 1 st photosensitive composition layer by a shower method. The supply of the developer by the shower method was performed using a 25 ℃ 1.0 mass% sodium carbonate aqueous solution, and was performed under a condition that the developer spray pressure was adjusted to 0.15MPa by a Full Cone (Full Cone) nozzle (h.ikeuchi co., ltd.).

Samples in which the supply time of the developing solution was changed were prepared in the above-described procedure, and the surfaces of the samples were observed with an optical microscope. As a result of the observation, the supply time of the developer of the sample in which the residue of the exposed film derived from the 1 st photosensitive composition layer was not found for the first time was defined as the dissolution time AY1.

The dissolution time AY2 is measured by the following method.

The 2 nd developing solution was supplied by a shower system to an exposed film obtained by exposing the 2 nd photosensitive composition layer over the entire surface under the same exposure conditions (exposure amount, exposure time, etc.) as in the step A5 in a state where the exposed film was exposed. The conditions for supplying the developer by the shower method are the same as the dissolution time AY 1.

Samples were prepared in which the supply time of the developing solution was changed in the above-described procedure, and the surface of each sample was observed with an optical microscope. As a result of the observation, the supply time of the developer of the sample in which the residue derived from the 2 nd photosensitive composition layer was not found for the first time was defined as the dissolution time AY2.

The dissolution time AY3 is measured by the following method.

The 2 nd photosensitive composition layer is exposed without exposing the 2 nd photosensitive composition layer, and the 2 nd developing solution is supplied to the 2 nd photosensitive composition layer by a shower method. The conditions for supplying the developer by the shower method are the same as the dissolution time AY 1.

Samples were prepared in which the supply time of the developing solution was changed in the above-described procedure, and the surface of each sample was observed with an optical microscope. As a result of the observation, the supply time of the developer of the sample in which the residue of the exposed film derived from the 2 nd photosensitive composition layer was not found for the first time was defined as the dissolution time AY3.

From the viewpoint of further improving the effect of the present invention, the dissolution time AY1 is preferably 60 seconds or longer, more preferably 100 seconds or longer, and further preferably 150 seconds or longer. The upper limit is not particularly limited, and is 600 seconds or less, but from the viewpoint of the removability of the resist pattern, 450 seconds or less is preferable, and 350 seconds or less is more preferable.

From the viewpoint of further improving the effect of the present invention, the dissolution time AY2 is preferably 100 seconds or less, more preferably 60 seconds or less, and further preferably 30 seconds or less. The lower limit is not particularly limited, and may be 1 second or more, preferably 5 seconds or more, and more preferably 10 seconds or more.

From the viewpoint of further improving the effect of the present invention, the dissolution time AY3 is preferably 100 seconds or less, more preferably 60 seconds or less, and further preferably 30 seconds or less. The lower limit is not particularly limited, and may be 1 second or more, preferably 5 seconds or more, and more preferably 10 seconds or more.

When the requirement AY is that the 1 st photosensitive composition layer is a positive photosensitive composition layer and the 2 nd photosensitive composition layer is a positive photosensitive composition layer, the dissolution time AY1 is required to be 2.0 times or more of the dissolution time AY 2. From the viewpoint of further improving the effect of the present invention, the dissolution time AY1 is preferably more than 2.5 times, and more preferably more than 3.0 times the dissolution time AY 2. The upper limit is not particularly limited, and the dissolution time AY1 is preferably 50 times or less, more preferably 40 times or less, and still more preferably 30 times or less the dissolution time AY 2.

Further, the requirement AY requires that the dissolution time AY1 be 2.0 times or more the dissolution time AY3 when the 1 st photosensitive composition layer is a positive photosensitive composition layer and the 2 nd photosensitive composition layer is a negative photosensitive composition layer. From the viewpoint of further improving the effect of the present invention, the dissolution time AY1 is preferably more than 2.5 times, and more preferably more than 3.0 times the dissolution time AY 3. The upper limit is not particularly limited, and the dissolution time AY1 is preferably 50 times or less, more preferably 40 times or less, and still more preferably 30 times or less the dissolution time AY 3.

The dissolution time AY1, the dissolution time AY2, and the dissolution time AY3 can be controlled by the same method as the dissolution time AX1, the dissolution time AX2, and the dissolution time AX 3.

[ Process A6]

The step A6 is a step of forming a 1 st transparent conductive pattern and a 2 nd transparent conductive pattern by bringing the laminate A5 into contact with an etching solution and etching the 1 st transparent conductive layer and the 2 nd transparent conductive layer.

By performing the step A6, a laminate A6 in which the 1 st transparent conductive pattern and the 1 st resist pattern are formed in this order from the substrate side on one surface of the substrate and the 2 nd transparent conductive pattern and the 2 nd resist pattern are formed in this order from the substrate side on the other surface of the substrate can be obtained. The laminate A6 obtained in the step A6 may be a laminate A6' in which the 2 nd transparent conductive pattern and the 1 st resist pattern are formed in this order from the substrate side on one surface of the substrate, and the 1 st transparent conductive pattern and the 2 nd resist pattern are formed in this order from the substrate side on the other surface of the substrate.

The following describes the etching (etching step) of the 1 st transparent conductive layer and the 2 nd transparent conductive layer in detail.

(etching Process)

And a step of etching the 1 st transparent conductive layer and the 2 nd transparent conductive layer in the region of the laminate A5 where the 1 st resist pattern and the 2 nd resist pattern are not arranged.

Specifically, the 1 st resist pattern and the 2 nd resist pattern are used as an etching resist to perform etching treatment on the 1 st transparent conductive layer and the 2 nd transparent conductive layer.

As a method of the etching treatment, for example, a known etching method can be cited.

Specifically, the method described in paragraphs [0209] to [0210] of Japanese patent application laid-open No. 2017-120435, the method described in paragraphs [0048] to [0054] of Japanese patent application laid-open No. 2010-152155, and dry etching such as wet etching and plasma etching by immersing in an etching solution can be mentioned.

The etching solution used for wet etching may be an acidic or alkaline etching solution, as appropriate, depending on the object to be etched.

Examples of the acidic etching solution include an acidic aqueous solution containing at least 1 acidic compound, and an acidic mixed aqueous solution of an acidic compound and at least 1 selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate.

The acidic compound (compound which is dissolved in water and exhibits acidity) contained in the acidic aqueous solution is preferably at least 1 selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, fluoric acid, oxalic acid, and phosphoric acid.

Examples of the alkaline etching solution include an alkaline aqueous solution containing at least 1 kind of alkaline compound and an alkaline mixed aqueous solution of an alkaline compound and a salt (e.g., potassium permanganate).

As the basic compound (a compound which exhibits basicity when dissolved in water) contained in the basic aqueous solution, for example, at least 1 selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (for example, tetramethylammonium hydroxide) is preferable.

In the etching step, the etching treatment of the 1 st transparent conductive layer and the 2 nd transparent conductive layer may be performed simultaneously or sequentially. In view of further improving the productivity, it is preferable to simultaneously perform the etching treatment of the 1 st transparent conductive layer and the 2 nd transparent conductive layer.

The position and size of the pattern formed on the substrate obtained by the method for producing a laminate are not particularly limited, and a thin line shape is preferable.

Specifically, the line width of the pattern is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit is preferably 1.0 μm or more.

[ Process A7]

The method for producing a laminate including a transparent conductive pattern according to embodiment 1 of the present invention may include a step A7 of removing the remaining 1 st resist pattern and 2 nd resist pattern.

By performing the step A7, a laminate A7 in which the 1 st transparent conductive pattern is formed on one surface of the base material and the 2 nd transparent conductive pattern is formed on the other surface of the base material can be obtained.

As a method of removing the residual pattern, for example, a method of removing by chemical treatment is exemplified, and a method of removing using a removing liquid is preferable.

Examples of the method of removing the residual pattern include a method of removing the residual pattern by a known method such as a spray method, a shower method, or a spin-on immersion method using a removing liquid.

Examples of the removing solution include a solution obtained by dissolving at least 1 basic compound in water, dimethyl sulfoxide, and N-methylpyrrolidone.

Examples of the basic compound (a compound which exhibits basicity when dissolved in water) include basic inorganic compounds such as sodium hydroxide and potassium hydroxide, and basic organic compounds such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

The temperature of the removal solution is preferably 30 to 80 ℃ and more preferably 50 to 80 ℃.

A preferred embodiment of the removal method includes a method in which the substrate having the pattern to be removed is immersed in a removal liquid under stirring at a liquid temperature of 50 to 80 ℃ for 1 to 30 minutes.

< embodiment 2 >

Embodiment 2 of the present invention is a method for manufacturing a laminate including a transparent conductive pattern, including the steps of:

a step B1 of preparing a substrate with a transparent conductive layer, the substrate with the transparent conductive layer including a substrate transparent to an exposure wavelength and a 1 st transparent conductive layer transparent to the exposure wavelength and disposed on one surface side of the substrate;

a step B3 of exposing the 1 st photosensitive composition layer to light and developing the layer with a 1 st developing solution to form a 1 st resist pattern and obtain a laminate B3;

A step B6 of exposing the 2 nd photosensitive composition layer to light and developing the layer with a 2 nd developing solution to form a 2 nd resist pattern and obtain a laminate B6; and

the dissolution time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to the entire surface exposure under the same exposure conditions as in the step B3 in the 2 nd developing solution is 2.0 times or more the dissolution time of the 2 nd photosensitive composition layer in the 2 nd developing solution,

the dissolution time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to the entire surface exposure under the same exposure conditions as in the step B3 in the 2 nd developing solution is 2.0 times or more the dissolution time of the exposed film obtained by subjecting the 2 nd photosensitive composition layer to the entire surface exposure under the same exposure conditions as in the step B6 in the 2 nd developing solution,

the dissolving time of the 1 st photosensitive composition layer in the 2 nd developing solution is 2.0 times or more the dissolving time of the exposed film obtained by exposing the entire surface of the 2 nd photosensitive composition layer to the 2 nd developing solution under the same exposure conditions as in the step B6 in the 2 nd developing solution,

Hereinafter, the requirement relating to the dissolution time when the 1 st photosensitive composition layer is a negative photosensitive composition layer is also referred to as "requirement BX", and the requirement relating to the dissolution time when the 1 st photosensitive composition layer is a positive photosensitive composition layer is also referred to as "requirement BY".

The mechanism of the excellent conductivity of the transparent conductive pattern in the laminate including the transparent conductive pattern produced by the production method of embodiment 2 is not clear, but the present inventors presume as follows.

In embodiment 2, by successively forming the 1 st resist pattern and the 2 nd resist pattern in the same manner as in embodiment 1 described above, the 1 st and 2 nd resist patterns having a desired shape can be easily obtained without causing exposure fogging. BY satisfying the requirement BX or the requirement BY, the 1 st and 2 nd resist patterns having desired shapes can be obtained as in the above-described embodiment 1.

The steps B1, B2, B3, B4, B5, B6, and B7 of the manufacturing method of embodiment 2 will be described below. The requirement BX and the requirement BY will also be described. The transfer film that can be used in steps B2 and B5 will be described later.

[ Process B1]

The step B1 is a step of preparing a substrate with a transparent conductive layer, which has a substrate transparent to an exposure wavelength and a 1 st transparent conductive layer transparent to the exposure wavelength and disposed on one surface side of the substrate.

By performing the step B1, a substrate with the 1 st transparent conductive layer can be obtained.

The substrate with the 1 st transparent conductive layer prepared in step B1 is the same as the substrate with the transparent conductive layer prepared in step Al, except that the 2 nd transparent conductive layer is not included, and therefore, the description thereof is omitted.

[ Process B2]

The step B2 is a step of forming a 1 st photosensitive composition layer on the 1 st transparent conductive layer.

By performing the step B2, a laminate B2 in which the 1 st transparent conductive layer and the 1 st photosensitive composition layer are formed on one surface of the substrate in this order from the substrate side can be obtained.

The step B2 is performed by the same method as the step A2, and therefore, the description thereof is omitted.

[ Process B3]

The step B3 is a step of exposing the 1 st photosensitive composition layer to light and developing the layer with the 1 st developing solution to form a 1 st resist pattern and obtain a laminate B3.

By performing the step B3, a laminate B3 in which the 1 st transparent conductive layer and the 1 st resist pattern are formed on one surface of the substrate in this order from the substrate side can be obtained.

The step B3 is performed by the same method as the step A3, and therefore, the description thereof is omitted.

[ Process B4]

Step B4 is a step of forming a2 nd transparent conductive layer transparent to the exposure wavelength on the surface side of the substrate opposite to the 1 st transparent conductive layer side in the laminate B3.

By performing step B4, a laminate B4 in which the 1 st transparent conductive layer and the 1 st resist pattern are formed in this order from the substrate side on one surface of the substrate and the 2 nd transparent conductive layer is formed on the other surface of the substrate can be obtained.

In the step A2, when the 1 st photosensitive composition layer is formed on the surface of the 1 st transparent conductive layer, the laminate A3 obtained in the step A3 is the same as the laminate B4.

The step B4 is the same as the step A1 in the method for forming the 1 st transparent conductive layer, and therefore, the description thereof is omitted.

[ Process B5]

The step B5 is a step of forming a2 nd photosensitive composition layer on the surface of the 2 nd transparent conductive layer.

By performing the step B5, a laminate B5 in which the 1 st transparent conductive layer and the 1 st resist pattern are formed in this order from the substrate side on one surface of the substrate and the 2 nd transparent conductive layer and the 2 nd photosensitive composition layer are formed in this order from the substrate side on the other surface of the substrate can be obtained.

In the step A2, when the 1 st photosensitive composition layer is formed on the surface of the 1 st transparent conductive layer, the laminate A4 obtained in the step A4 is the same as the laminate B5.

The step B5 is performed by the same method as the step A4, and therefore, the description thereof is omitted.

[ Process B6]

The step B6 is a step of exposing the 2 nd photosensitive composition layer to light and developing the layer with the 2 nd developing solution to form a2 nd resist pattern, thereby obtaining a laminate B6.

By performing the step B5, a laminate B6 in which the 1 st transparent conductive layer and the 1 st resist pattern are formed in this order from the substrate side on one surface of the substrate and the 2 nd transparent conductive layer and the 2 nd resist pattern are formed in this order from the substrate side on the other surface of the substrate can be obtained.

In the step A2, when the 1 st photosensitive composition layer is formed on the surface of the 1 st transparent conductive layer, the laminate A5 obtained in the step A5 is the same as the laminate B6.

The step B6 is performed by the same method as the step A5, and therefore, the description thereof is omitted.

[ Condition BX ]

When the 1 st photosensitive composition layer is a negative photosensitive composition layer and the 2 nd photosensitive composition layer is a negative photosensitive composition layer, the dissolution time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to the full-surface exposure under the same exposure condition as the step B3 in the 2 nd developer is 2.0 times or more the dissolution time of the 2 nd photosensitive composition layer in the 2 nd developer, and when the 1 st photosensitive composition layer is a negative photosensitive composition layer and the 2 nd photosensitive composition layer is a positive photosensitive composition layer, the dissolution time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to the full-surface exposure under the same exposure condition as the step B3 in the 2 nd developer is 2.0 times or more the dissolution time of the exposed film obtained by subjecting the 2 nd photosensitive composition layer to the full-surface exposure under the same exposure condition as the step B6 in the 2 nd developer.

Hereinafter, the dissolution time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to the entire surface exposure under the same exposure conditions as in the step B3 in the 2 nd developing solution is also referred to as "dissolution time BX1". When the 2 nd photosensitive composition layer is a negative photosensitive composition layer, the dissolution time of the 2 nd photosensitive composition layer in the 2 nd developing solution is also referred to as "dissolution time BX2". When the 2 nd photosensitive composition layer is a positive photosensitive composition layer, the dissolution time of the exposed film obtained by subjecting the 2 nd photosensitive composition layer to full-surface exposure under the same exposure conditions as in the step B6 in the 2 nd developer is also referred to as "dissolution time BX3".

The dissolution time BX1 is measured by the following method.

The 2 nd developing solution was supplied by a shower system to an exposed film obtained by exposing the 1 st photosensitive composition layer to light over the entire surface under the same exposure conditions (exposure amount, exposure time, etc.) as in the step B3 in a state where the exposed film was exposed. The supply of the developer by the shower system was performed by using a 1.0 mass% sodium carbonate aqueous solution at 25 ℃ through a Full Cone (Full Cone) nozzle (h.ikeuchi co., ltd. System) under a condition that the developer spray pressure was adjusted to 0.15 MPa.

Samples in which the supply time of the developing solution was changed were prepared in the above-described procedure, and the surfaces of the samples were observed with an optical microscope. As a result of the observation, the supply time of the developer of the sample in which the residue of the exposed film derived from the 1 st photosensitive composition layer was not found for the first time was defined as the dissolution time BX1.

The dissolution time BX2 is measured by the following method.

The 2 nd photosensitive composition layer is not exposed to light and the 2 nd photosensitive composition layer is exposed to light, through the spray method to the 2 nd photosensitive composition layer supply the 2 nd developing solution. The conditions for supplying the developer by the shower method are the same as the dissolution time BX1.

Samples in which the supply time of the developing solution was changed were prepared in the above-described procedure, and the surfaces of the samples were observed with an optical microscope. As a result of the observation, the supply time of the developer of the sample in which the residue derived from the 2 nd photosensitive composition layer was not found for the first time was defined as the dissolution time BX2.

The dissolution time BX3 is measured by the following method.

The 2 nd developing solution was supplied by a shower method to an exposed film obtained by subjecting the 2 nd photosensitive composition layer to full-surface exposure under the same exposure conditions (exposure amount, exposure time, and the like) as in the step B6 in a state where the exposed film was exposed. The conditions for supplying the developer by the shower method are the same as the dissolution time BX1.

Samples in which the supply time of the developing solution was changed were prepared in the above-described procedure, and the surfaces of the samples were observed with an optical microscope. As a result of the observation, the supply time of the developer of the sample in which the residue of the exposed film derived from the 2 nd photosensitive composition layer was not found for the first time was defined as the dissolution time BX3.

From the viewpoint of further improving the effect of the present invention, the dissolution time BX1 is preferably 60 seconds or more, more preferably 100 seconds or more, and further preferably 150 seconds or more. The upper limit is not particularly limited, but 600 seconds or less is mentioned, and from the viewpoint of the removability of the resist pattern, 450 seconds or less is preferable, and 350 seconds or less is more preferable.

From the viewpoint of further improving the effect of the present invention, the dissolution time BX2 is preferably 100 seconds or less, more preferably 60 seconds or less, and further preferably 30 seconds or less. The lower limit is not particularly limited, and may be 1 second or more, preferably 5 seconds or more, and more preferably 10 seconds or more.

From the viewpoint of further improving the effect of the present invention, the dissolution time BX3 is preferably 100 seconds or less, more preferably 60 seconds or less, and further preferably 30 seconds or less. The lower limit is not particularly limited, and may be 1 second or more, preferably 5 seconds or more, and more preferably 10 seconds or more.

The requirement BX is that when the 1 st photosensitive composition layer is a negative photosensitive composition layer and the 2 nd photosensitive composition layer is a negative photosensitive composition layer, the dissolution time BX1 is required to be 2.0 times or more the dissolution time BX 2. From the viewpoint of further improving the effect of the present invention, the dissolution time BX1 is preferably more than 2.5 times, and more preferably more than 3.0 times the dissolution time BX 2. The upper limit is not particularly limited, and the dissolution time BX1 is preferably 50 times or less, more preferably 40 times or less, and further preferably 30 times or less of the dissolution time BX 2.

Further, the requirement BX is that when the 1 st photosensitive composition layer is a negative photosensitive composition layer and the 2 nd photosensitive composition layer is a positive photosensitive composition layer, the dissolution time BX1 is required to be 2.0 times or more the dissolution time BX 3. From the viewpoint of further improving the effect of the present invention, the dissolution time BX1 is preferably more than 2.5 times, and more preferably more than 3.0 times the dissolution time BX 3. The upper limit is not particularly limited, and the dissolution time BX1 is preferably 50 times or less, more preferably 40 times or less, and further preferably 30 times or less of the dissolution time BX 3.

The dissolution time BX1, the dissolution time BX2, and the dissolution time BX3 can be controlled by the same method as the dissolution time AX1, the dissolution time AX2, and the dissolution time AX 3.

[ requirement BY ]

When the 1 st photosensitive composition layer is a positive photosensitive composition layer and the 2 nd photosensitive composition layer is a positive photosensitive composition layer, the dissolution time of the 1 st photosensitive composition layer in the 2 nd developer is 2.0 times or more the dissolution time of the 2 nd developer of an exposure film obtained by full-face exposure of the 2 nd photosensitive composition layer under the same exposure conditions as in the step B5, and when the 1 st photosensitive composition layer is a positive photosensitive composition layer and the 2 nd photosensitive composition layer is a negative photosensitive composition layer, the dissolution time of the 1 st photosensitive composition layer in the 2 nd developer is 2.0 times or more the dissolution time of the 2 nd photosensitive composition layer in the 2 nd developer.

Hereinafter, the dissolution time of the 1 st photosensitive composition layer in the 2 nd developing solution is also referred to as "dissolution time BY1". When the 2 nd photosensitive composition layer is a positive photosensitive composition layer, the dissolution time of the exposed film obtained BY exposing the entire surface of the 2 nd photosensitive composition layer to the same exposure conditions as in the step B6 in the 2 nd developing solution is also referred to as "dissolution time BY2". When the 2 nd photosensitive composition layer is a negative photosensitive composition layer, the dissolution time of the 2 nd photosensitive composition layer in the 2 nd developing solution is also referred to as "dissolution time BY3".

The dissolution time BY1 is measured BY the following method.

Samples were prepared in which the supply time of the developing solution was changed in the above-described procedure, and the surface of each sample was observed with an optical microscope. As a result of the observation, the supply time of the developer of the sample in which the residue of the exposed film derived from the 1 st photosensitive composition layer was not found for the first time was defined as the dissolution time BY1.

The dissolution time BY2 is measured BY the following method.

The 2 nd developing solution was supplied by a shower method to an exposed film obtained by subjecting the 2 nd photosensitive composition layer to full-surface exposure under the same exposure conditions (exposure amount, exposure time, and the like) as in the step B6 in a state where the exposed film was exposed. The conditions for supplying the developer BY the shower method are the same as the dissolution time BY1.

Samples were prepared in which the supply time of the developing solution was changed in the above-described procedure, and the surface of each sample was observed with an optical microscope. As a result of the observation, the supply time of the developer of the sample in which the residue derived from the 2 nd photosensitive composition layer was not found for the first time was defined as the dissolution time BY2.

The dissolution time BY3 is measured BY the following method.

The 2 nd photosensitive composition layer is exposed without exposing the 2 nd photosensitive composition layer, and the 2 nd developing solution is supplied to the 2 nd photosensitive composition layer by a shower method.

The 2 nd developing solution was supplied by a shower method to an exposed film obtained by subjecting the 2 nd photosensitive composition layer to full-surface exposure under the same exposure conditions (exposure amount, exposure time, and the like) as in the step B6 in a state where the exposed film was exposed. The conditions for supplying the developer BY the shower method are the same as the dissolution time BY 1.

Samples in which the supply time of the developing solution was changed were prepared in the above-described procedure, and the surfaces of the samples were observed with an optical microscope. As a result of the observation, the supply time of the developer of the sample in which the residue derived from the exposed film of the 2 nd photosensitive composition layer was not found for the first time was defined as the dissolution time BY3.

From the viewpoint of further improving the effect of the present invention, the dissolution time BY1 is preferably 60 seconds or more, more preferably 100 seconds or more, and further preferably 150 seconds or more. The upper limit is not particularly limited, but 600 seconds or less is mentioned, and from the viewpoint of the removability of the resist pattern, 450 seconds or less is preferable, and 350 seconds or less is more preferable.

From the viewpoint of further excellent effects of the present invention, the dissolution time BY2 is preferably 100 seconds or less, more preferably 60 seconds or less, and further preferably 30 seconds or less. The lower limit is not particularly limited, and may be 1 second or more, preferably 5 seconds or more, and more preferably 10 seconds or more.

From the viewpoint of further improving the effect of the present invention, the dissolution time BY3 is preferably 100 seconds or less, more preferably 60 seconds or less, and further preferably 30 seconds or less. The lower limit is not particularly limited, and may be 1 second or more, preferably 5 seconds or more, and more preferably 10 seconds or more.

The requirement BY requires that the dissolution time BY1 be 2.0 times or more the dissolution time BY2 when the 1 st photosensitive composition layer is a positive photosensitive composition layer and the 2 nd photosensitive composition layer is a positive photosensitive composition layer. From the viewpoint of further improving the effect of the present invention, the dissolution time BY1 is preferably more than 2.5 times, and more preferably more than 3.0 times the dissolution time BY 2. The upper limit is not particularly limited, and the dissolution time BY1 is preferably 50 times or less, more preferably 40 times or less, and further preferably 30 times or less the dissolution time BY 2.

In the requirement BY, when the 1 st photosensitive composition layer is a positive photosensitive composition layer and the 2 nd photosensitive composition layer is a negative photosensitive composition layer, the dissolution time BY1 is required to be 2.0 times or more the dissolution time BY 3. From the viewpoint of further improving the effect of the present invention, the dissolution time BY1 is preferably more than 2.5 times, and more preferably more than 3.0 times the dissolution time BY 3. The upper limit is not particularly limited, and the dissolution time BY1 is preferably 50 times or less, more preferably 40 times or less, and further preferably 30 times or less of the dissolution time BY 3.

The dissolution time BY1, dissolution time BY2, and dissolution time BY3 can be controlled BY the same method as the dissolution time AX1, dissolution time AX2, and dissolution time AX 3.

[ Process B7]

Step B7 is a step of forming the 1 st transparent conductive pattern and the 2 nd transparent conductive pattern by bringing the laminate B6 into contact with an etching solution and etching the 1 st transparent conductive layer and the 2 nd transparent conductive layer.

The laminate A6 obtained in the step A6 is the same as the laminate B7.

The step B7 is performed by the same method as the step A6, and therefore, the description thereof is omitted.

[ Process B8]

The method for producing a laminate including a transparent conductive pattern according to embodiment 2 of the present invention may include a step B8 of removing the remaining 1 st resist pattern and 2 nd resist pattern.

By performing the step B8, a laminate A7 in which the 1 st transparent conductive pattern is formed on one surface of the base material and the 2 nd transparent conductive pattern is formed on the other surface of the base material can be obtained.

The laminate B8 obtained in the step B8 is the same as the laminate A7.

The step B8 is performed by the same method as the step A7, and therefore, the description thereof is omitted.

< uses of the laminate >

The laminate including the transparent conductive pattern manufactured by the manufacturing method of the present invention can be applied to various apparatuses. Examples of the device including the laminate include an input device, preferably a touch panel, and more preferably an electrostatic capacitance type touch panel. The input device can be applied to, for example, a display device such as an organic EL (organic electroluminescence) display device or a liquid crystal display device.

The method for producing a laminate of the present invention can be applied to production of a conductive film such as a transparent heater, a transparent antenna, an electromagnetic shield, and a light-adjusting film; manufacturing a printed circuit board and a semiconductor package; the fabrication of posts and pins for interconnection between semiconductor chips and packages; manufacturing a metal mask; and (3) manufacturing Tape base materials such as COF (Chip on Film) and TAB (Tape Automated Bonding).

Hereinafter, transfer films preferably used in the steps A2 and A4 and the steps B2 and B5 will be described.

< transfer film >

The transfer film is a transfer film that has a temporary support and a photosensitive composition layer and that performs an exposure step of pattern-exposing the photosensitive composition layer.

The transfer film may have other layers in addition to the photosensitive composition layer described later.

Examples of the other layer include an intermediate layer and a thermoplastic resin layer described below. The transfer film may have another member (e.g., a protective film) described later.

Examples of the embodiment of the transfer film include the following configurations (1) to (3).

Among them, the transfer film preferably has an intermediate layer, more preferably the following structure (2) or structure (3), and further preferably structure (2).

(1) "temporary support/photosensitive composition layer/protective film"

(2) "temporary support/intermediate layer/photosensitive composition layer/protective film"

(3) "temporary support/thermoplastic resin layer/intermediate layer/photosensitive composition layer/protective film"

The photosensitive composition layer in each of the above structures is preferably a negative photosensitive composition layer described later or a colored resin layer described later.

From the viewpoint of suppressing the generation of bubbles in the bonding step, the maximum width of the waviness of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 60 μm or less. The lower limit is preferably 0 μm or more, more preferably 0.1 μm or more, and further preferably 1 μm or more.

The maximum width of the moire of the transfer film was measured in the following procedure.

The transfer film was cut into a size of 20cm in the vertical direction by 20cm in the horizontal direction in the direction perpendicular to the main surface, thereby preparing a sample. When the transfer film has a protective film, the protective film is peeled from the transfer film. Next, on a stage having a smooth and horizontal surface, the sample is allowed to stand so that the surface of the temporary support body faces the stage. After standing, the surface of the sample is scanned by a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) within a range of 10cm square from the center of the sample to obtain a three-dimensional surface image, and the minimum depression height is subtracted from the maximum projection height observed in the obtained three-dimensional surface image. The above operation was performed for 10 samples, and the arithmetic average value thereof was taken as the maximum width of the moire of the transfer film.

In the case where the photosensitive composition layer of the transfer film further includes another composition layer (for example, a photosensitive composition layer, an intermediate layer, a thermoplastic resin layer, and the like) on the side opposite to the temporary support, the total thickness of the other composition layers is preferably 0.1 to 30%, more preferably 0.1 to 20%, based on the thickness of the photosensitive composition layer.

From the viewpoint of more excellent adhesion, the transmittance of light having a wavelength of 365nm of the photosensitive composition layer is preferably 10% or more, more preferably 30% or more, and further preferably 50% or more. The upper limit is preferably 99.9% or less, more preferably 99.0% or less.

An example of an embodiment of the transfer film will be described.

The transfer film 10 shown in fig. 1 includes a temporary support 11, a composition layer 17 including an intermediate layer 13 and a photosensitive composition layer 15, and a protective film 19 in this order.

The transfer film 10 shown in fig. 1 is a system having the intermediate layer 13 and the protective film 19, but may not have the intermediate layer 13 and the protective film 19.

In fig. 1, the layers other than the protective film 19 that can be disposed on the temporary support 11 (for example, the photosensitive composition layer, the intermediate layer, and the thermoplastic resin layer) are also referred to as "composition layers".

The transfer film may further include a thermoplastic resin layer in addition to the above-described layer. The thermoplastic resin layer is preferably disposed between the temporary support 11 and the intermediate layer 13.

Hereinafter, the transfer film will be described in detail with respect to each member and each component.

Further, the following description of the constituent elements may be made in accordance with a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[ temporary support ]

The transfer film has a temporary support.

The temporary support is a member for supporting the photosensitive composition layer, and is finally removed by a peeling treatment.

The temporary support may have 1 of a single-layer structure and a multilayer structure.

As the temporary support, a film is preferable, and a resin film is more preferable. Further, as the temporary support, a film which has flexibility and does not significantly deform, shrink, or stretch under pressure or under pressure and heat, and a film which does not have deformation such as wrinkles or scratches is also preferable.

Examples of the film include a polyethylene terephthalate film (e.g., a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film, and a polyethylene terephthalate film is preferable.

The temporary support is preferably high in transparency in view of enabling pattern exposure through the temporary support. Specifically, the transmittance of the temporary support at a wavelength of 365nm is preferably 60% or more, and more preferably 70% or more. The upper limit is preferably less than 100%.

The temporary support is preferably low in haze from the viewpoint of pattern formability when pattern exposure is performed through the temporary support and transparency of the temporary support. Specifically, the haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and still more preferably 0.1% or less. The lower limit is preferably 0% or more.

In view of pattern formability in pattern exposure through the temporary support and transparency of the temporary support, the number of particles, foreign matters, and defects in the temporary support is preferably small. Specifically, the number of particles (for example, particles having a diameter of 1 μm), foreign matters and defects in the temporary support is preferably 50 particles/10 mm ² Hereinafter, more preferably 10/10 mm ² Hereinafter, more preferably 3/10 mm ² Below, particularly preferably less than 1/10 mm ² . The lower limit is preferably 0 per 10mm ² The above.

The thickness of the temporary support is preferably 5 to 200. Mu.m, more preferably 5 to 150. Mu.m, still more preferably 5 to 50 μm, and particularly preferably 5 to 25 μm, from the viewpoint of easy handling and versatility.

The thickness of the temporary support was calculated as an average value at arbitrary 5 points measured by cross-sectional observation based on SEM (Scanning Electron Microscope).

The temporary support may have a fine particle-containing layer (lubricant layer) on one or both surfaces of the temporary support in terms of handling properties.

The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm.

The thickness of the lubricant layer is preferably 0.05 to 1.0. Mu.m.

In order to improve the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support that is in contact with the photosensitive composition layer may be subjected to a surface modification treatment.

Examples of the surface modification treatment include treatment by UV irradiation, corona discharge, plasma, and the like.

The exposure amount in UV irradiation is preferably 10 to 2000mJ/cm ² More preferably 50 to 1000mJ/cm ² 。

The lamp output and the illuminance are not particularly limited as long as the exposure amount is within the above range.

Examples of the light source for UV irradiation include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, and a Light Emitting Diode (LED) that emit light in a wavelength band of 150 to 450 nm.

Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.

Further, examples of the temporary support include paragraphs [0017] to [0018] in Japanese patent laid-open No. 2014-085643, paragraphs [0019] to [0026] in Japanese patent laid-open No. 2016-027363, paragraphs [0041] to [0057] in International publication No. 2012/081680, and paragraphs [0029] to [0040] in International publication No. 2018/179370, which are incorporated herein.

Examples of commercially available temporary supports include registered trademarks of Lumirror16KS40 and LumirFor16FB40 (both of which are TORAY INDUSTRIES, INC.); COSMOSHINE a4100, COSMOSHINE a4300 and COSMOSHINE a8300 (made by TOYOBO co.

[ photosensitive composition layer ]

The transfer film has a photosensitive composition layer. The photosensitive composition layer can be the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer.

In a display device (for example, an organic EL display device, a liquid crystal display device, and the like) including a touch panel such as a capacitive output device, a conductive pattern such as an electrode pattern of a sensor corresponding to a visual recognition unit, a peripheral wiring portion, and a wiring for extracting the wiring portion is provided inside the touch panel. Generally, in the formation of a patterned layer, the following method is widely employed: a method in which a photosensitive composition layer is provided on a substrate using a transfer film or the like, and the photosensitive composition layer is exposed to light through a mask having a desired pattern and then developed. Therefore, the photosensitive composition layer is preferably a negative photosensitive composition layer. When the photosensitive composition layer is a negative photosensitive composition layer, the pattern formed corresponds to a cured film.

The photosensitive composition layer preferably contains a resin described later and a polymerizable compound described later, and more preferably contains a resin described later, a polymerizable compound described later, and a polymerization initiator described later. Further, the photosensitive composition layer preferably contains an alkali-soluble resin as a resin to be described later. That is, the photosensitive composition layer preferably contains a resin including an alkali-soluble resin and a polymerizable compound.

The photosensitive composition layer preferably contains 10.0 to 90.0 mass% of a resin, 5.0 to 70.0 mass% of a polymerizable compound, and 0.01 to 20.0 mass% of a polymerization initiator, based on the total mass of the photosensitive composition layer.

Hereinafter, each component that the photosensitive composition layer may contain will be described.

(resin)

The photosensitive composition layer may contain a resin.

As the resin, an alkali-soluble resin is preferable.

As the resin, an alkali-soluble resin contained in a thermoplastic resin layer described later can be used.

The resin preferably contains a structural unit derived from a monomer having an aromatic hydrocarbon group, from the viewpoint of suppressing thickening of the line width and deterioration of the resolution when the focus position is shifted during exposure.

Examples of the aromatic hydrocarbon group include a phenyl group which may have a substituent and an aralkyl group which may have a substituent.

The content of the structural unit derived from the monomer having an aromatic hydrocarbon group is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, and further preferably 30.0% by mass or more, based on the total mass of the resin. The upper limit is preferably 80.0% by mass or less, more preferably 60.0% by mass or less, and further preferably 55.0% by mass or less, based on the total mass of the resin. When the photosensitive composition layer contains a plurality of resins, the mass average value of the content of the structural unit derived from the monomer having an aromatic hydrocarbon group is preferably within the above range.

Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, and the like), a monomer having an aralkyl group or styrene is preferable, and styrene is more preferable.

When the monomer having an aromatic hydrocarbon group is styrene, the content of the structural unit derived from styrene is preferably 10.0 to 80.0% by mass, more preferably 20.0 to 60.0% by mass, and still more preferably 30.0 to 55.0% by mass, based on the total mass of the resin. When the photosensitive composition layer contains a plurality of resins, the mass average value of the content of the structural unit having an aromatic hydrocarbon group is preferably within the above range.

Examples of the aralkyl group include a phenylalkyl group which may have a substituent (excluding a benzyl group) and a benzyl group which may have a substituent, and a benzyl group which may have a substituent is preferable.

Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate and the like.

Examples of the monomer having a benzyl group include (meth) acrylates having a benzyl group such as benzyl (meth) acrylate and chlorobenzyl (meth) acrylate; the vinyl monomer having a benzyl group such as vinylbenzyl chloride and vinylbenzyl alcohol is preferably a (meth) acrylate having a benzyl group, and more preferably benzyl (meth) acrylate.

When the monomer having an aromatic hydrocarbon group is benzyl (meth) acrylate, the content of the structural unit derived from benzyl (meth) acrylate is preferably 10.0 to 90.0% by mass, more preferably 20.0 to 80.0% by mass, and still more preferably 30.0 to 70.0% by mass, based on the total mass of the resin.

The resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group, at least 1 kind of the following 1 st monomer and/or at least 1 kind of the following 2 nd monomer.

The resin not containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably obtained by polymerizing at least 1 kind of the following 1 st monomer, and more preferably by polymerizing at least 1 kind of the 1 st monomer with at least 1 kind of the following 2 nd monomer.

The 1 st monomer is a monomer having a carboxyl group in the molecule.

Examples of the 1 st monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half-ester, and (meth) acrylic acid is preferable.

The content of the structural unit derived from the 1 st monomer is preferably 5.0 to 50.0% by mass, more preferably 10.0 to 40.0% by mass, and still more preferably 10.0 to 30.0% by mass, based on the total mass of the resin.

When the content is 5.0 mass% or more, excellent developability, control of edge meltability, and the like can be achieved. When the content is 50.0 mass% or less, high resolution of the resist pattern, control of the Tailing (Tailing) shape, and high chemical resistance of the resist pattern can be achieved.

The 2 nd monomer is a monomer which is not acidic (has no acidic group) and has a polymerizable group in the molecule.

The polymerizable group has the same meaning as the polymerizable group of the polymerizable compound described later, and the preferable embodiment is also the same.

Examples of the 2 nd monomer include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; esters of vinyl alcohol such as vinyl acetate; (meth) acrylonitrile.

Among them, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, or n-butyl (meth) acrylate is preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is more preferable.

The content of the structural unit derived from the 2 nd monomer is preferably 1.0 to 80.0% by mass, more preferably 1.0 to 60.0% by mass, and still more preferably 1.0 to 50.0% by mass, based on the total mass of the resin.

The resin may have any 1 of a linear structure, a branched structure, and an alicyclic structure in a side chain.

By using a monomer containing a group having a branched structure in a side chain or a monomer containing a group having an alicyclic structure in a side chain, a branched structure or an alicyclic structure can be introduced into a side chain of a resin. The group having an alicyclic structure may be any 1 of monocyclic and polycyclic groups.

"side chain" refers to a group of atoms branching from the main chain. The "main chain" refers to a relatively longest bonding chain in a molecule of a polymer compound constituting a resin.

Examples of the monomer having a group having a branched structure in a side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, and tert-octyl (meth) acrylate.

Among them, isopropyl (meth) acrylate, isobutyl (meth) acrylate, or tert-butyl methacrylate is preferable, and isopropyl methacrylate or tert-butyl methacrylate is more preferable.

Examples of the monomer containing a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Further, a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms is exemplified.

Specific examples thereof include (bicyclo [ 2.2.1 ] heptyl-2) - (meth) acrylate, 1-adamantyl- (meth) acrylate, 2-adamantyl- (meth) acrylate, 3-methyl-1-adamantyl- (meth) acrylate, 3, 5-dimethyl-1-adamantyl- (meth) acrylate, 3-ethyladamantyl- (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl- (meth) acrylate, 3,5, 8-triethyl-1-adamantyl- (meth) acrylate, 3, 5-dimethyl-8-ethyl-1-adamantyl- (meth) acrylate, 2-methyl-2-adamantyl- (meth) acrylate, 2-ethyl-2-adamantyl- (meth) acrylate, 3-hydroxy-1-adamantyl- (meth) acrylate, octahydro-4, 7-menthoide-5-yl- (meth) acrylate, octahydro-4, 7-menthoide-1-ylmethyl- (meth) acrylate, 1-menthyl- (meth) acrylate, (tris-hydroxy-decyloxy) acrylate, and (tris-cyclodecyl) acrylate, 6, 6-trimethyl-bicyclo [ 3.1.1 ] heptyl- (meth) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [ 4.1.0 ] heptyl- (meth) acrylate, (norbornyl (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate.

Among them, cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate, 1 adamantyl- (meth) acrylate, 2 adamantyl- (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl- (meth) acrylate, or tricyclodecanyl (meth) acrylate is preferable, and cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate, 2-adamantyl- (meth) acrylate, or tricyclodecanyl (meth) acrylate is more preferable.

The resin may have a polymerizable group. When the resin has a polymerizable group, the resin preferably contains a structural unit having a polymerizable group, and more preferably contains a structural unit having an ethylenically unsaturated group in a side chain.

The polymerizable group includes polymerizable groups of polymerizable compounds described later, preferably an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

Further, the polymerizable group is preferably a polymerizable group capable of undergoing a polymerization reaction with the polymerizable group of the polymerizable compound.

The resin containing a structural unit having a polymerizable group is preferably obtained by reacting a resin containing a structural unit derived from the 1 st monomer with the 3 rd monomer.

The 3 rd monomer is a monomer having 2 or more polymerizable groups in the molecule, and preferably a monomer having 2 polymerizable groups in the molecule.

Examples of the polymerizable group include polymerizable groups of polymerizable compounds described below. Among these, the 3 rd monomer preferably has 2 polymerizable groups, more preferably has an ethylenically unsaturated group and a cationically polymerizable group, and further preferably has an acryloyl group or a methacryloyl group and an epoxy group.

Examples of the 3 rd monomer include glycidyl (meth) acrylate.

As the structural unit having a polymerizable group, a structural unit represented by the formula (P) is preferable.

[ chemical formula 1]

In the formula (P), R ^P Represents a hydrogen atom or a methyl group. L is ^P Represents a 2-valent linking group.

P represents a polymerizable group.

R ^P Represents a hydrogen atom or a methyl group.

As R ^P Preferably a hydrogen atom.

L ^P Represents a 2-valent linking group.

As the above-mentioned 2-valent linking group, for example, examples thereof include-CO-, -O- ] -S-, -SO ₂ -、-NR ^N A hydrocarbon group and a combination thereof. R is ^N Represents a substituent.

Examples of the hydrocarbon group include an alkylene group, a cycloalkylene group, and an arylene group.

The alkylene group may be linear or branched. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 3 to 5 carbon atoms. The above alkylene group may have a hetero atom, and a methylene group in the above alkylene group may be substituted with a hetero atom. The heteroatom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, and more preferably an oxygen atom.

The cycloalkylene group may be a single ring or a polycyclic ring. The carbon number of the cycloalkylene group is preferably 3 to 20, more preferably 5 to 10, and still more preferably 6 to 8.

The arylene group may be a single ring or a polycyclic ring. The arylene group preferably has 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10 carbon atoms. As the above arylene group, phenylene group is preferable.

The above cycloalkylene group and the above arylene group may have a hetero atom as a ring member atom. The hetero atom is preferably an oxygen atom, a sulfur atom or a nitrogen atom, and more preferably an oxygen atom.

The hydrocarbon group may further have a substituent.

Examples of the substituent include a halogen atom (e.g., fluorine atom), a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and an alkenyl group, and a hydroxyl group is preferable.

As L ^P An alkylene group which may have a hetero atom is preferable.

P represents a polymerizable group.

The polymerizable group is as described above.

Examples of the structural unit having a polymerizable group include the following structural units.

[ chemical formula 2]

When the resin contains a structural unit having a polymerizable group, the content of the structural unit having a polymerizable group is preferably 5.0 to 70.0% by mass, more preferably 10.0 to 50.0% by mass, even more preferably 15.0 to 40.0% by mass, and particularly preferably 20.0 to 40.0% by mass, based on the total mass of the resin, from the viewpoint of further excellent effects of the present invention.

Examples of the method for introducing a polymerizable group into a resin include a method in which an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic anhydride are reacted with a group such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group of the resin.

Preferred examples of the method for introducing a polymerizable group into a resin include the following methods: after the 1 st monomer is synthesized by polymerization, a part of the carboxyl group derived from the structural unit of the 1 st monomer of the obtained resin is subjected to a polymer reaction with the 3 rd monomer (preferably glycidyl (meth) acrylate), thereby introducing a polymerizable group (preferably a (meth) acryloyloxy group) into the resin. The reaction temperature of the polymer reaction is preferably 80 to 110 ℃. The polymerization reaction is preferably carried out using a catalyst, and more preferably using an ammonium salt (tetraethylammonium bromide).

The reaction temperature in the above polymerization reaction is preferably 70 to 100 ℃ and more preferably 80 to 90 ℃. In the above polymerization reaction, a polymerization initiator is preferably used, and as the polymerization initiator, an azo-based initiator is more preferably used, and as the polymerization initiator, V-601 (manufactured by FUJIFILM Wako Pure Chemical Corporation) or V-65 (manufactured by FUJIFILM Wako Pure Chemical Corporation) is more preferably used.

As the resin, a resin containing a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, a structural unit derived from styrene, or a structural unit derived from benzyl methacrylate, and a resin containing a structural unit derived from methacrylic acid and a structural unit derived from styrene are preferable, and a resin further containing a structural unit having a polymerizable group is more preferable.

In the above, it is also preferable to set the content of each constituent unit to the above-described preferred embodiments.

The Tg of the resin is preferably 60 to 135 ℃, more preferably 70 to 115 ℃, still more preferably 75 to 105 ℃, and particularly preferably 80 to 100 ℃.

From the viewpoint of further improving the effect of the present invention, the acid value of the resin is preferably 220mgKOH/g or less, more preferably 200mgKOH/g or less, still more preferably 190mgKOH/g or less, and particularly preferably 170mgKOH/g or less. From the viewpoint of further improving the effect of the present invention, the lower limit is preferably 10mgKOH/g or more, more preferably 50mgKOH/g or more, still more preferably 70mgKOH/g or more, and particularly preferably 90mgKOH/g or more.

The "acid value (mgKOH/g)" means the mass (mg) of potassium hydroxide required for neutralizing 1g of the sample. For example, the acid value can be in accordance with JIS K0070: 1992.

The acid value of the resin can be adjusted by the kind of the structural unit contained in the resin and/or the content of the structural unit containing an acid group.

The weight average molecular weight of the resin is preferably 5,000 to 500,000, more preferably 10,000 to 100,000, still more preferably 10,000 to 60,000, and particularly preferably 20,000 to 50,000.

When the weight average molecular weight is 500,000 or less, the resolution and the developability can be improved. When the weight average molecular weight is 5,000 or more, the properties of the developed aggregates and the properties of the unexposed film such as the edge meltability and the chipping property of the transfer film can be controlled. The "edge meltability" refers to a degree that the photosensitive composition layer easily protrudes from an end face of a roll when the transfer film is wound into a roll. The term "swarf property" means the degree of scattering of swarf when an unexposed film is cut with a knife. If the chips adhere to the upper surface of the transfer film, the chips are transferred to a mask in a subsequent exposure step or the like, resulting in a defective product.

The degree of dispersion of the resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

The photosensitive composition layer may contain other resins in addition to the above-mentioned resin.

Examples of the other resin include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine and polyalkylene glycols.

The resin can be used alone in 1, can also use more than 2.

When 2 or more kinds of resins are used, it is preferable to use 2 kinds of resins containing structural units derived from a monomer having an aromatic hydrocarbon group in a mixture, or to use a resin containing structural units derived from a monomer having an aromatic hydrocarbon group in a mixture with a resin not containing structural units derived from a monomer having an aromatic hydrocarbon group. In the latter case, the content of the resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably 50.0% by mass or more, more preferably 70.0% by mass or more, further preferably 80.0% by mass or more, and particularly preferably 90.0% by mass or more, based on the total mass of the resin. The upper limit is preferably 100.0 mass% or less with respect to the total mass of the resin.

The content of the resin is preferably 10.0 to 90.0% by mass, more preferably 20.0 to 80.0% by mass, still more preferably 30.0 to 70.0% by mass, and particularly preferably 40.0 to 60.0% by mass, based on the total mass of the photosensitive composition layer. When the content of the resin is 90.0 mass% or less with respect to the total mass of the photosensitive composition layer, the development time can be controlled. When the content of the resin is 10.0% by mass or more based on the total mass of the photosensitive composition layer, the edge melting resistance can be improved.

Examples of a method for synthesizing a resin include a method in which an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile is added to a solution obtained by diluting the above-mentioned monomer with a solvent such as acetone, methyl ethyl ketone, and isopropyl alcohol, and the mixture is heated and stirred. The synthesis may be performed while dropping a part of the mixture in the reaction solution. After the completion of the reaction, a solvent may be further added to adjust the concentration to a desired level.

Examples of the method for synthesizing the resin include bulk polymerization, suspension polymerization, and emulsion polymerization, in addition to the above.

(polymerizable Compound)

The photosensitive composition layer may contain a polymerizable compound having a polymerizable group.

The "polymerizable compound" is a compound which is polymerized by the action of a polymerization initiator described later, and is a compound different from the resin.

The polymerizable group of the polymerizable compound may be a group participating in polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; a group having a cationically polymerizable group such as an epoxy group or an oxetanyl group.

Among these, the polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.

The polymerizable compound is preferably a compound having 1 or more ethylenically unsaturated groups (hereinafter, also referred to as "ethylenically unsaturated compound"), and more preferably a compound having 2 or more ethylenically unsaturated groups in the molecule (hereinafter, also referred to as "polyfunctional ethylenically unsaturated compound"), from the viewpoint of more excellent photosensitivity of the photosensitive composition layer.

In addition, the number of ethylenically unsaturated groups in the molecule of the ethylenically unsaturated compound is preferably 1 to 6, more preferably 1 to 3, even more preferably 2 to 3, and particularly preferably 3, from the viewpoint of further improving resolution and peelability.

The polymerizable compound may have an alkyleneoxy group.

The alkyleneoxy group is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group from the viewpoint of further improving the effect of the present invention. The number of addition of alkyleneoxy groups to the polymerizable compound is preferably 2 to 30, more preferably 2 to 20 per molecule.

From the viewpoint that the balance between the photosensitivity and the resolution and the peelability of the photosensitive composition layer is more excellent, the polymerizable compound preferably contains a 2-functional or 3-functional ethylenically unsaturated compound having 2 or 3 ethylenically unsaturated groups in the molecule, and more preferably contains a 3-functional ethylenically unsaturated compound having 3 ethylenically unsaturated groups in 1 molecule.

The content of the 2-functional ethylenically unsaturated compound is preferably 20.0% by mass or more, more preferably more than 40.0% by mass, further preferably 55.0% by mass or more, and particularly preferably 90.0% by mass or more, based on the total mass of the polymerizable compound, from the viewpoint of excellent peelability. The upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less. That is, all of the polymerizable compounds contained in the photosensitive composition layer may be 2-functional ethylenically unsaturated compounds.

The content of the 3-functional ethylenically unsaturated compound is preferably 10.0% by mass or more, and more preferably 20.0% by mass or more, based on the total mass of the polymerizable compound. The upper limit is preferably 100.0% by mass or less, more preferably 80.0% by mass or less, and still more preferably 50.0% by mass or less. That is, all of the polymerizable compounds contained in the photosensitive composition layer may be 3-functional ethylenically unsaturated compounds.

The ethylenically unsaturated compound is preferably a (meth) acrylate compound having a (meth) acryloyl group as a polymerizable group.

Polymerizable compound B1-

The photosensitive composition layer preferably further contains a polymerizable compound B1 having an aromatic ring and 2 ethylenically unsaturated groups.

Among the polymerizable compounds, the polymerizable compound B1 is a 2-functional ethylenically unsaturated compound having 1 or more aromatic rings in the molecule.

Examples of the aromatic ring of the polymerizable compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring; aromatic heterocycles such as a thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring; the condensed rings are preferably aromatic hydrocarbon rings, and more preferably benzene rings. The aromatic ring may have a substituent.

The polymerizable compound B1 may have 1 or 2 or more aromatic rings.

The polymerizable compound B1 preferably has a bisphenol structure in order to improve resolution by suppressing swelling of the photosensitive composition layer by the developer.

Examples of the bisphenol structure include a bisphenol a structure derived from bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), a bisphenol F structure derived from bisphenol F (2, 2-bis (4-hydroxyphenyl) methane), and a bisphenol B structure derived from bisphenol B (2, 2-bis (4-hydroxyphenyl) butane), and the bisphenol a structure is preferred.

Examples of the polymerizable compound B1 having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure.

The bisphenol structure may have 2 polymerizable groups directly bonded to both ends thereof or may have 1 or more alkyleneoxy groups bonded to both ends thereof. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of alkyleneoxy groups (preferably ethyleneoxy groups) added to the bisphenol structure is preferably 2 to 30, more preferably 2 to 20 per molecule.

Examples of the polymerizable compound B1 having a bisphenol structure include paragraphs [0072] to [0080] of Japanese patent application laid-open No. 2016-224162, which are incorporated herein by reference.

The polymerizable compound B1 is preferably a 2-functional ethylenically unsaturated compound having a bisphenol a structure, and more preferably 2, 2-bis (4- ((meth) acryloyloxyalkyloxy) phenyl) propane.

Examples of the 2, 2-bis (4- ((meth) acryloyloxyalkyl) phenyl) propane include ethoxylated bisphenol a dimethacrylate (BPE series, SHIN-namura CHEMICAL Co., ltd. Manufactured), such as 2, 2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane (FA-324m, showa Denko Materials Co., ltd. Manufactured), 2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane, and 2, 2-bis (4- (methacryloyloxypentaethoxy) phenyl) propane (fan-namura CHEMICAL Co., ltd. Manufactured), 2-bis (4- (methacryloyloxydodecaethoxytetrapropoxy) phenyl) propane (FA-3200my, showa Denko Materials Co., ltd. Manufactured), and ethoxylated (10) bisphenol a diacrylate (estde a-BPE-10, SHIN-Denko CHEMICAL Co., ltd. Manufactured), and ethoxylated (10) bisphenol a diacrylate (estde a-BPE-10, SHIN-naemica Co., ltd. Manufactured).

As the polymerizable compound B1, a compound represented by the formula (B1) is also preferable.

[ chemical formula 3]

In the formula (B1), R ₁ And R ₂ Each independently represents a hydrogen atom or a methyl group.

A represents a vinyl group. B represents a propenyl group. n1 and n3 each independently represent an integer of 1 to 39. n1+ n3 represents an integer of 2 to 40. n2 and n4 each independently represent an integer of 0 to 29. n2+ n4 represents an integer of 0 to 30.

The arrangement of the structural units of- (A-O) -and- (B-0) -may be 1 kind of random or block. In the case of a block, any 1 of- (A-0) -and- (B-O) -may be on the bisphenyl side.

N1+ n2+ n3+ n4 is preferably 2 to 20, more preferably 2 to 16, and still more preferably 4 to 12. N2+ n4 is preferably 0 to 10, more preferably 0 to 4, further preferably 0 to 2, particularly preferably 0.

The content of the polymerizable compound B1 is preferably 10.0% by mass or more, more preferably 20.0% by mass or more, and further preferably 25.0% by mass or more, based on the total mass of the photosensitive composition layer, from the viewpoint of further excellent resolution. The upper limit is preferably 70.0 mass% or less, more preferably 60.0 mass% or less, from the viewpoint of transferability and edge melting (a phenomenon in which the photosensitive composition bleeds out from the end of the transfer member).

From the viewpoint of further improving the resolution, the content of the polymerizable compound B1 is preferably 40.0% by mass or more, more preferably 50.0% by mass or more, further preferably 55.0% by mass or more, and particularly preferably 60.0% by mass or more, based on the total mass of the polymerizable compounds. The upper limit is preferably 100.0% by mass or less, more preferably 99.0% by mass or less, further preferably 95.0% by mass or less, particularly preferably 90.0% by mass or less, and most preferably 85.0% by mass or less, based on the total mass of the polymerizable compound, from the viewpoint of peelability.

Other polymerizable compounds

The photosensitive composition layer may contain other polymerizable compounds in addition to the above compounds.

Examples of the other polymerizable compound include known polymerizable compounds.

Specifically, there may be mentioned a compound having 1 ethylenically unsaturated group in the molecule (monofunctional ethylenically unsaturated compound), a 2-functional ethylenically unsaturated compound having no aromatic ring, and an ethylenically unsaturated compound having 3 or more functions.

Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate.

Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.

Examples of the alkylene glycol di (meth) acrylate include tricyclodecane dimethanol diacrylate (A-DCP, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.), 1, 6-hexanediol diacrylate (A-HD-N, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.), ARONIX (registered trademark) M-220 (TOAGOSCO., manufactured by LTD.), ARONIX (registered trademark) M-240 (TOAGOSE I CO., manufactured by LTD), ARONIX (registered trademark) M-270 (TOAGOSEI CO., manufactured by TOLTD), ethylene glycol dimethacrylate, 1, 10-decanediol diacrylate and neopentyl glycol dimethacrylate (neopentyl glycol dimethacrylate).

Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and polypropylene glycol di (meth) acrylate.

Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide-and propylene oxide-modified urethane di (meth) acrylate. Further, commercially available urethane di (meth) acrylate includes, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., ltd.), UA-32P (manufactured by SHIN-NAKAMURA CHEMICAL Co., ltd.), and UA-1100H (manufactured by SHIN-NAKAMURA CHEMICAL Co., ltd.).

Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, and alkylene oxide-modified products thereof.

"(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. Also, "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

Examples of the alkylene oxide-modified product of the ethylenically unsaturated compound having 3 or more functional groups include caprolactone-modified (meth) acrylate compounds (e.g., nippon Kayaku Co., ltd., kayarad (registered trademark) DPCA-20 and SHIN-NAKAMURA CHEMICAL Co., ltd., A-9300-1CL, manufactured by Ltd.), ethoxylated trimethylolpropane triacrylate (e.g., TOMOE ENGINEERING CO., SR454, SR499, and SR502, manufactured by LTD), alkylene oxide-modified (meth) acrylate compounds (e.g., nippon Kayaku Co., ltd., katrad RP-1040, SHIN-NAKAMURA chemcal co., ATM-35E, a-9300, DAICEL-allex LTD., EBECRYL (registered trademark) 135, etc., ethoxylated glyceryl triacrylate (SHIN-NAKAMURA chemcal co., a-GLY-9E, etc., LTD., product a-GLY-9E, etc.), aronium (registered trademark) T0-2349 (toagii c0., LTD., product), ARONIX m-520 (toagiei c0., product LTD), and ARONIX m-510 (toagisei c0., product LTD).

The polymerizable compound may be a polymerizable compound having an acid group (e.g., a carboxyl group). The acid groups may form anhydride groups.

Examples of the polymerizable compound having an acid group include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI co., ltd.), ARONIX (registered trademark) M-520 (manufactured by TOAGOSEI co., ltd.), and ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI c0., ltd.).

Examples of the polymerizable compound having an acid group include polymerizable compounds having an acid group described in paragraphs [0025] to [0030] of Japanese patent application laid-open No. 2004-239942.

The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and still more preferably 300 to 2,200.

The viscosity of the polymerizable compound at 25 ℃ is preferably 1 to 10000 mPas, more preferably 5 to 3000 mPas, and still more preferably 10 to 1500 mPas.

When 2 or more polymerizable compounds are used, the difference (absolute value) between the viscosity at 25 ℃ of the polymerizable compound a having the highest viscosity and the viscosity at 25 ℃ of the polymerizable compound B having the lowest viscosity among the 2 or more polymerizable compounds is preferably 250 to 5000mPa · s, more preferably 500 to 2500Pa · s, and still more preferably 900 to 1000Pa · s.

Examples of the method for measuring the viscosity include the following methods.

The measurement was carried out using a vibratile viscometer (VM-10A, manufactured by SEKONIC). Specifically, the polymerizable compound (20 mL) was transferred to a vessel and allowed to stand at room temperature (25. + -. 2 ℃ C.) for 30 minutes. After that, the detection terminal was inserted into the container of the polymerizable compound, and then the power was turned on to read the value of the viscosity after 30 seconds.

The content of the polymerizable group in the polymerizable compound is preferably 1.0mmol/g or more, more preferably 2.0mmol/g or more, and still more preferably 2.4mmol/g or more, from the viewpoint of further improving the effect of the present invention. The upper limit is preferably 10.0mmol/g or less. The content of the polymerizable group may be defined as the content of a double bond.

When the photosensitive composition layer contains a plurality of polymerizable compounds, the content of the polymerizable group in all the polymerizable compounds contained is preferably the above-described preferred embodiment. For example, all of the polymerizable compounds preferably have a polymerizable group of 2.4mmol/g or more.

The "content of the polymerizable group" means an equivalent (mol) of the polymerizable group contained in 1g of the polymerizable compound.

The polymerizable compound may be used alone in 1 kind, or may be used in 2 or more kinds.

Among them, from the viewpoint of further improving the effect of the present invention, 3 or more polymerizable compounds are preferably used, and 3 are more preferably used.

When 3 kinds of polymerizable compounds are used, at least 1 of the 3 kinds is preferably the polymerizable compound B1, and more preferably at least 2 of the 3 kinds is the polymerizable compound B1.

The content of the polymerizable compound is preferably 10.0 to 70.0% by mass, more preferably 15.0 to 70.0% by mass, and still more preferably 20.0 to 70.0% by mass, based on the total mass of the photosensitive composition layer.

The mass ratio of the content of the polymerizable compound to the content of the resin (content of the polymerizable compound/content of the resin) is preferably 0.10 to 2.00, more preferably 0.50 to 1.50, and further preferably 0.70 to 1.10 in terms of more excellent effects of the present invention.

The photosensitive composition layer preferably further contains the polymerizable compound B1 and an ethylenically unsaturated compound having a functionality of 3 or more.

The mass ratio of the content of the polymerizable compound B1 to the content of the ethylenically unsaturated compound having a functionality of 3 or more (content of the polymerizable compound B1/content of the ethylenically unsaturated compound having a functionality of 3 or more) is preferably 1.0 to 5.0, more preferably 1.2 to 4.0, and further preferably 1.5 to 3.0.

(polymerization initiator)

The photosensitive composition layer may contain a polymerization initiator.

Examples of the polymerization initiator include known polymerization initiators depending on the form of the polymerization reaction. Specifically, a thermal polymerization initiator and a photopolymerization initiator are mentioned.

The polymerization initiator may be any 1 of a radical polymerization initiator and a cationic polymerization initiator.

The photosensitive composition layer preferably contains a photopolymerization initiator.

The photopolymerization initiator is a compound that starts polymerization of a polymerizable compound upon receiving active light such as ultraviolet light, visible light, and X-ray. Examples of the photopolymerization initiator include known photopolymerization initiators.

Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator, and a photo radical polymerization initiator is preferable.

Examples of the photo radical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylphenone structure, a photopolymerization initiator having an α -hydroxyalkylphenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

The photo radical polymerization initiator preferably contains at least 1 selected from 2,4, 5-triarylimidazole dimers and derivatives thereof in view of photosensitivity, visibility of exposed portions and unexposed portions, and resolution. In addition, 2,4, 5-triarylimidazole dimers and 2,4, 5-triarylimidazole structures in the derivatives thereof may be the same or different.

Examples of the derivatives of the 2,4, 5-triarylimidazole dimer include a 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, a 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and a 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.

Examples of the photo-radical polymerization initiator include those described in paragraphs [0031] to [0042] of Japanese patent application laid-open No. 2011-095716 and paragraphs [0064] to [0081] of Japanese patent application laid-open No. 2015-014783.

Examples of the photo radical polymerization initiator include ethyl Dimethylaminobenzoate (DBE), benzoin methyl ether, anisole (p, p '-dimethoxybenzyl), TAZ-110 (Midori Kagaku Co., ltd., manufactured by Ltd.), benzophenone, 4' -bis (diethylamino) benzophenone, TAZ-111 (Midori Kagaku Co., ltd., ltd.), 1- [4- (phenylthio) ] -1, 2-octanedione-2- (0-benzoyloxime) (IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime) (IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF) 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (Omnirad 379EG, IGM Resins B.V.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinylpropan-1-one (Omnirad 907, IGM Resins B.V.), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-hydroxy-1- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2 Methylpropan-1-one (Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (Omnirad 369, manufactured by IGMResins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resins B.V.), 2-dimethoxy-1, 2-diphenylethan-1-one (Omnirad 651, manufactured by IGM Resins B.V.), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO H, manufactured by IGM Resins B.V.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (Omnirad B.V.), SH-series 2,4, 6-trimethylbenzoyl) phenylphosphine oxide (Omnir II.V.), 2-bis (Lunar-DK-4, 4-chlorophenyl-photopolymerization initiator (L.V), 5,5' -Tetraphenylbis-imidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (B-CIM manufactured by Hampford), 2- (O-chlorophenyl) -4, 5-diphenylimidazole dimer (BCTB manufactured by Tokyo Chemical Industry Co., ltd.), 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (O-benzoyloxime) (TR-PBG- 305, changzzhou Tronly New Electronic Materials Co., manufactured by LTD.), 1, 2-propanedione, 3-cyclohexyl-1- [ 9-ethyl-6- (2-furancarbonyl) -9H-carbazol-3-yl ] -,2- (O-acetoxime) (TR-PBG-326, changzzhou Tronly New Electronic Materials Co., manufactured by LTD.) and 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (O-benzoyl oxime) (TR-PBG-391, changzzhou Tronly New Electronic Materials Co., manufactured by LTD).

The photo cation polymerization initiator (photo acid generator) is a compound that receives active light to generate an acid. The photo cation polymerization initiator is preferably a compound which generates an acid by being sensitive to active light having a wavelength of 300nm or more (preferably, a wavelength of 300 to 450 nm). Further, even if the photo cation polymerization initiator is a photo cation polymerization initiator which does not directly induce the active light having the wavelength of 300nm or more, it can be preferably used in combination with a sensitizer as long as it is a compound which generates an acid by inducing the active light having the wavelength of 300nm or more by using the sensitizer in combination.

The photo cation polymerization initiator is preferably a photo cation polymerization initiator generating an acid having a pKa of 4 or less, more preferably a photo cation polymerization initiator generating an acid having a pKa of 3 or less, and still more preferably a photo cation polymerization initiator generating an acid having a pKa of 2 or less. The lower limit is preferably-10.0 or more.

Examples of the photo cation polymerization initiator include an ionic photo cation polymerization initiator and a nonionic photo cation polymerization initiator.

Examples of the ionic photo-cationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

Examples of the ionic photo-cationic polymerization initiator include ionic photo-cationic polymerization initiators described in paragraphs [0114] to [0133] of Japanese patent application laid-open No. 2014-085643.

Examples of the nonionic photocationic polymerization initiator include trichloromethyl s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.

Examples of the trichloromethyl-s-triazine, diazomethane compounds and imide sulfonate compounds include those described in paragraphs [0083] to [0088] of Japanese patent laid-open publication No. 2011-221494.

Examples of the oxime sulfonate compound include compounds described in paragraphs [0084] to [0088] of International publication Nos. 2018/179640.

The polymerization initiator may be used alone in 1 kind, or may be used in 2 or more kinds.

The content of the polymerization initiator (preferably, photopolymerization initiator) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the photosensitive composition layer. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less, based on the total mass of the photosensitive composition layer.

(pigments)

The photosensitive composition layer may contain a dye (hereinafter, also referred to as "dye N") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400 to 780nm during development and a maximum absorption wavelength that changes by an acid, an alkali, or a radical, in view of visibility of an exposed portion and a non-exposed portion and visibility and resolution of a pattern after development.

Although the detailed mechanism is not clear, when the dye N is contained, the adhesion to the adjacent layer (for example, the intermediate layer) is improved and the resolution is further excellent.

The "dye" changes in the maximum absorption wavelength by an acid, an alkali, or a radical "may mean any of a method in which a dye in a colored state is decolorized by an acid, an alkali, or a radical, a method in which a dye in a decolorized state is colored by an acid, an alkali, or a radical, and a method in which a dye in a colored state is changed to a colored state of another color.

Specifically, the dye N may be any 1 of a compound that develops color by changing from a decolored state by exposure and a compound that develops color by changing from a colored state by exposure. In the above case, the dye may be one that changes the state of coloration or decoloration by generating an acid, a base, or a radical in the photosensitive composition layer by exposure and acting, or may be one that changes the state (for example, pH) in the photosensitive composition layer by changing the acid, the base, or the radical. Further, the dye may be a dye which changes the state of color development or decoloration by being directly stimulated by an acid, an alkali, or a radical without exposure.

Among them, the pigment N is preferably a pigment whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a pigment whose maximum absorption wavelength is changed by a radical, from the viewpoint of visibility and resolution of an exposed portion and a non-exposed portion.

In view of the visibility and resolution of the exposed portions and the unexposed portions, the photosensitive composition layer preferably contains both a dye whose maximum absorption wavelength as the dye N is changed by a radical and a photo-radical polymerization initiator. The dye N is preferably a dye that develops color by an acid, an alkali, or a radical, in view of visibility of the exposed portion and the unexposed portion.

As a color developing mechanism of the dye N, for example, there is a method of adding a photo radical polymerization initiator, a photo cation polymerization initiator (photo acid generator) or a photo base generator to the photosensitive composition layer, and developing a color by a radical, an acid or a base generated from the photo radical polymerization initiator, the photo cation polymerization initiator or the photo base generator after exposure, a radical reactive dye, an acid reactive dye or a base reactive dye (for example, leuco dye).

The maximum absorption wavelength in the wavelength range of 400 to 780nm in the color development of the dye N is preferably 550nm or more, more preferably 550 to 700nm, and still more preferably 550 to 650nm, from the viewpoint of the visibility of the exposed portion and the unexposed portion.

The dye N may have 1 or 2 or more maximum absorption wavelengths in the wavelength range of 400 to 780nm in the case of color development. When the dye N has 2 or more maximum absorption wavelengths in the wavelength range of 400 to 780nm during color development, the maximum absorption wavelength having the highest absorbance among the 2 or more maximum absorption wavelengths may be 450nm or more.

The maximum absorption wavelength of the dye N can be measured as follows: under atmospheric conditions, using a spectrophotometer: UV3100 (manufactured by SHIMADZU CORPORATION) measures the transmission spectrum of a solution containing dye N (liquid temperature 25 ℃) in the range of 400 to 780nm, and detects a wavelength at which the light intensity becomes extremely small (maximum absorption wavelength).

Examples of the dye which develops color or is decolored by exposure include colorless compounds.

Examples of the dye decolorized by exposure to light include a leuco compound, a diarylmethane dye, an oxazine dye, a xanthene dye, an imidonaphthoquinone dye, an azomethine dye, and an anthraquinone dye.

The dye N is preferably a colorless compound in view of visibility of an exposed portion and a non-exposed portion.

Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane-based dye), a leuco compound having a spiropyran skeleton (spiropyran-based dye), a leuco compound having a fluoran skeleton (fluorane-based dye), a leuco compound having a diarylmethane skeleton (diarylmethane-based dye), a leuco compound having a rhodamine lactam skeleton (rhodamine lactam-based dye), a leuco compound having an indolylphthalide skeleton (indolylphthalide-based dye), and a leuco compound having a leuco auramine skeleton (leuco auramine-based dye).

Among them, triarylmethane-based dyes and fluorane-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) and fluorane-based dyes are more preferable.

The colorless compound preferably has a lactone ring, a sudane (sulfene) ring, or a sultone ring in view of visibility of an exposed portion and a non-exposed portion. Thus, the lactone ring, sudantin ring or sultone ring of the colorless compound can be reacted with the radical generated from the photo radical polymerization initiator or the acid generated from the photo cation polymerization initiator to change the colorless compound into a closed ring state and decolorize it or to change the colorless compound into an open ring state and develop it. The colorless compound is preferably a compound having a lactone ring, a sudan ring, or a sultone ring, and the lactone ring, the sudan ring, or the sultone ring develops color by radical or acid ring opening, and more preferably a compound having a lactone ring, and the lactone ring develops color by radical or acid ring opening.

Examples of the dye N include dyes and leuco compounds.

Examples of the dye include brilliant GREEN, ethyl violet, methyl GREEN, crystal violet, basic fuchsin, methyl violet 2B, quinaldine RED, rose bengal, m-aniline yellow, thymol BLUE, xylenol BLUE, methyl orange, p-methyl RED, congo RED, benzo RED violet 4B, α -naphthyl RED, nile BLUE 2B, nile BLUE a, methyl violet, malachite GREEN, coupled fuchsin, victoria pure BLUE-naphthalene sulfonate, victoria pure BLUE BOH (manufactured by Hodogaya Chemical CO., LTD.), OIL BLUE #603 (manufactured by 0RIENT Chemical INDUSTRIES CO., LTD.), OIL PINK #312 (organic Chemical INDUSTRIES c 0.), LTD, manufactured by LTD), OIL R ED 5B (ORIENT CHEMICAL INDUSTRIES CO., manufactured by LTD), OIL SCARLET #308 (ORIENT CHEMICAL INDUSTRIES CO., manufactured by LTD), OIL RED OG (ORIENT CHEMICAL INDUSTRIES CO., manufactured by LTD), OIL RED RR (ORIENT CHEMICAL INDUSTRIES CO., manufactured by LTD), OIL GREEN #502 (ORIENT CHEMICAL INDUSTRIES CO., manufactured by LTD), spilon BEH spectral (Hodogaya Chemical Co., manufactured by Ltd.), m-cresol purple, cresol RED, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylamino phenylmenadione, 2-carboxy anilino-4-p-diethylamino phenylnaphthoquinone, 2-carboxy amino-4-p-stearyl-p-stearido, n-bis (hydroxyethyl) amino-phenylimino naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazoline, and 1-beta-naphthalene-4-p-binaphthyl diethylaminophenylimino-5-pyrazoline.

Examples of the colorless compound include p, p' -hexamethyltriaminotriphenylmethane (colorless crystal violet), pergascript Blue SRB (manufactured by Ciba-Geigy AG), crystal violet lactone, malachite green lactone, benzoyl leuco methylene Blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) aminofluoran, 2-anilino-3-methyl-6- (N-ethyl-p-toluidine) fluoran, 3, 6-dimethoxyfluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran, 3- (N, N-diethylamino) -6-methyl-7-xylenylfluoran, 3- (N, N-diethylamino) -6-methyl-7-chlorofluoran, 3- (N, N-diethylamino) -6-methoxy-7-aminofluoran, 3- (N, N-diethylamino) -7- (4-chloroanilino) fluoran, 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N-diethylamino) -7, 8-benzofluorane, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6-methyl-7-xylenylfluorane, 3-piperidine-6-methyl-7-anilinofluorane, 3-pyrrolidine-6-methyl-7-anilinofluorane, 3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminobenzephthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-aza) -4-phthalide, 3- (3 ' -diethylamino) -6-methyl-1 ' -diphenylamino) -3 ' -diphenylphthalide, and 3' -bis (1-ethyl-2-methylindol-3 ' -diphenylphthalide), 9' - [9H ] xanthen-3-one.

The dye N is preferably a dye whose maximum absorption wavelength changes by a radical, and more preferably a dye that develops color by a radical, from the viewpoint of being excellent in visibility of an exposed portion and a non-exposed portion, visibility of a pattern after development, and resolution.

As the pigment N, leuco crystal violet, crystal violet lactone, brilliant green or victoria pure blue-naphthalene sulfonate is preferable.

The pigment N may be used alone in 1 kind or in 2 or more kinds.

The content of the dye N is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, even more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 1% by mass, based on the total mass of the photosensitive composition layer, from the viewpoint of excellent visibility of the exposed portion and the unexposed portion, and visibility of the pattern after development and resolution.

The content of the pigment N is a content of the pigment when all the pigment N included in the total mass of the photosensitive composition layer is in a colored state. Hereinafter, a method for quantifying the content of pigment N will be described by taking a pigment that develops color by a radical as an example.

A solution prepared by dissolving pigment N (0.001 g) in 100mL of methyl ethyl ketone and a solution prepared by dissolving pigment N (0.01 g) in 100mL of methyl ethyl ketone were prepared. To each of the obtained solutions, a photoradical polymerization initiator (Irgacure OXE01, manufactured by basf japan ltd.) was added and 365nm light was irradiated, thereby generating radicals and bringing all the dye N into a colored state. Then, the absorbance of each solution at a liquid temperature of 25 ℃ was measured by a spectrophotometer (UV 3100, manufactured by SHIMADZU CORPORATION) under an atmospheric environment to prepare a calibration curve.

Next, the absorbance of the solution in which all the dyes were developed was measured in the same manner as described above except that the photosensitive composition layer (3 g) was dissolved in methyl ethyl ketone instead of the dye N. The content of the pigment N contained in the photosensitive composition layer was calculated from the absorbance of the obtained solution containing the photosensitive composition layer according to the calibration curve. The "photosensitive composition layer (3 g)" has the same meaning as 3g of the total solid content in the photosensitive composition.

(thermally crosslinkable Compound)

The photosensitive composition layer may contain a thermally crosslinkable compound in terms of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.

The thermally crosslinkable compound having an ethylenically unsaturated group described later is regarded as a thermally crosslinkable compound, not as a polymerizable compound.

Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds, and the blocked isocyanate compounds are preferred in terms of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.

Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when the resin and/or the polymerizable compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film tends to decrease, and the function tends to be enhanced when the film obtained by curing the photosensitive composition layer is used as a protective film.

The "blocked isocyanate compound" refers to a compound having a structure in which an isocyanate group of an isocyanate is protected with a blocking agent.

The dissociation temperature of the blocked isocyanate compound is preferably 100 to 160 ℃ and more preferably 130 to 150 ℃.

Examples of the method for measuring the dissociation temperature of the blocked isocyanate compound include the following methods: the dissociation degree is determined as the temperature of the endothermic peak accompanying the deprotection reaction of the blocked isocyanate compound by D SC (Differential scanning calorimetry) analysis using a Differential scanning calorimeter (for example, DSC6200, manufactured by Seiko Instruments inc.).

Examples of the blocking agent having a dissociation temperature of 100 to 160 ℃ include an active methylene compound such as malonic diester and an oxime compound.

Examples of the malonic diester include dimethyl malonate, diethyl malonate, di-n-butyl malonate, and di-2-ethylhexyl malonate.

Examples of the oxime compound include compounds having a structure represented by-C (= N-OH) -in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime.

Among these, oxime compounds are preferred as the blocking agent having a dissociation temperature of 100 to 160 ℃ in view of storage stability.

The blocked isocyanate compound preferably has an isocyanurate structure in order to improve the brittleness of the film and to improve the adhesion force to the transfer target.

The blocked isocyanate compound having an isocyanurate structure is protected by isocyanurating hexamethylene diisocyanate, for example.

Among them, as the blocked isocyanate compound having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is preferable from the following points: compared with a compound having no oxime structure, the dissociation temperature can be adjusted to a preferable range more easily and development residue can be reduced.

The blocked isocyanate compound may have a polymerizable group.

The polymerizable group is, for example, the same as the polymerizable group of the polymerizable compound, and the preferable embodiment is also the same.

Examples of the blocked isocyanate compound include Karenz series (registered trademark) (manufactured by SHOWA DENKO K.K.) such as AOI-BM, MOI-BM and MOI-BP; end capped Duranate series (registered trademark) such as TPA-B80E and WT32-B75P (manufactured by Asahi Kasei Corporation).

The blocked isocyanate compound is preferably the following compound.

[ chemical formula 4]

The heat-exchange compound may be used alone in 1 kind, or may be used in 2 or more kinds.

The content of the thermally crosslinkable compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition layer.

(pigment)

The photosensitive composition layer may contain a pigment.

When the photosensitive composition layer contains a pigment, it corresponds to the colored resin layer.

In a liquid crystal display window of a recent electronic device, a cover glass having a black frame-shaped light shielding layer formed on a peripheral edge portion of a back surface of a transparent glass substrate or the like is sometimes attached to protect the liquid crystal display window. A colored resin layer can be used to form such a light-shielding layer.

The pigment may be appropriately selected depending on the desired hue, and examples thereof include a black pigment, a white pigment, and a color pigment other than black and white, and in the case of forming a black pattern, the pigment is preferably a black pigment.

Black pigments

Examples of the black pigment include known black pigments (e.g., organic pigments and inorganic pigments).

Among them, carbon black, titanium oxide, titanium carbide, iron oxide, or graphite is preferable as the black pigment from the viewpoint of optical density, and carbon black is more preferable. As the carbon black, surface-modified carbon black in which at least a part of the surface is coated with a resin is preferable in view of surface resistance.

The particle diameter (number average particle diameter) of the black pigment is preferably 0.001 to 0.1. Mu.m, more preferably 0.01 to 0.08. Mu.m, from the viewpoint of dispersion stability.

The "particle diameter" refers to the diameter of a circle when the area of the pigment particle is determined from a photographic image of the pigment particle taken by an electron microscope and a circle having the same area as the area of the pigment particle is assumed. The "number average particle diameter" is an average value obtained by obtaining the above particle diameter for any 100 particles and averaging the obtained 100 particle diameters.

Examples of the self-color pigment include inorganic pigments and white pigments described in paragraphs [0015] and [0114] of Japanese patent application laid-open No. 2005-007765.

As the inorganic pigment, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferable, titanium oxide or zinc oxide is more preferable, titanium oxide is further preferable, rutile-type or anatase-type titanium oxide is particularly preferable, and rutile-type titanium oxide is most preferable.

The surface of the titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic matter treatment, or 2 or more of these treatments may be performed. This suppresses the catalytic activity of titanium oxide, and improves heat resistance and light fading.

In view of reducing the thickness of the photosensitive composition layer after heating, at least one of the alumina treatment and the zirconia treatment is preferably performed as the surface treatment of the titanium oxide surface, and more preferably both the alumina treatment and the zirconia treatment are performed.

When the photosensitive composition layer is a colored resin layer, the photosensitive composition layer preferably further contains a color pigment other than a black pigment and a white pigment from the viewpoint of transferability.

The particle diameter (number average particle diameter) of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of more excellent dispersibility. The lower limit is preferably 10nm or more.

<xnotran> , , BO ( : color Index (, "C.I.".) 42595), O (C.I.41000), HB (C.I.26150), MONOLITF GT (C.I. 12), GR (C.I. 17), HR (C.I. 83), FBB (C.I. 146), HOSTAPERM E5B (C.I. 19), FBH (C.I. 11), FASTEL PINKB SPRA (C.I. 81), (C.I. 15), MONOLITE FAST BLACK B (C.I. 1) , C.I. 97, C.I. 122, C.I. 149, C.I. 168, C.I. 177, C.I. 180, C.I. 192, C.I. 215, C.I. 7, C.I. 15:1, C.I. 15:4, C.I. 22, C.I. 60, C.I. 64 C.I. 23, C.I. 177. </xnotran>

The pigment may be used alone in 1 kind, or in 2 or more kinds.

The content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, further preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10 to 35% by mass, based on the total mass of the photosensitive composition layer.

When the photosensitive composition layer contains a pigment other than a black pigment (for example, a white pigment, a color pigment, or the like), the content of the pigment other than a black pigment is preferably 30% by mass or less, more preferably 1 to 20% by mass, and still more preferably 3 to 15% by mass, based on the total mass of the black pigment.

When the photosensitive composition layer contains a black pigment, the black pigment (preferably, carbon black) is preferably introduced into the photosensitive composition in the form of a pigment dispersion.

The dispersion can be prepared by the following method: a mixture obtained by mixing a black pigment and a pigment dispersant in advance is added to an organic solvent (or a carrier) and dispersed with a dispersing machine. The pigment dispersant may be selected depending on the pigment and the solvent, and for example, a commercially available dispersant can be used.

The "carrier" refers to a portion of a medium for dispersing a pigment when used as a pigment dispersion liquid. The carrier is in a liquid state and contains a binder component for holding the black pigment in a dispersed state and a solvent component (organic solvent) for dissolving and diluting the binder component.

Examples of the dispersing machine include known dispersing machines such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill.

Further, the fine grinding may be performed by mechanical grinding and utilizing a frictional force. Examples of the dispersing machine and the fine pulverization include those described in "encyclopedia of pigment" (manufactured by Bingpo, first edition, bingshu shop, 2000, 438, 310).

(other additives)

The photosensitive composition layer may contain other additives as needed, in addition to the above components.

Examples of the other additives include radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, surfactants, plasticizers, heterocyclic compounds (e.g., triazole), pyridines (e.g., isonicotinamide), and purine bases (e.g., adenine).

Examples of the other additives include metal oxide particles, a chain transfer agent, an antioxidant, a dispersant, an acid amplifier, a development accelerator, conductive fibers, an ultraviolet absorber, a thickener, a crosslinking agent, an organic or inorganic anti-settling agent, and paragraphs [0165] to [0184] of jp 2014-085643 a, which are incorporated herein.

The other additives may be used alone in 1 kind, or in 2 or more kinds.

Inhibitors of free radical polymerization

Examples of the radical polymerization inhibitor include the thermal polymerization inhibitors described in paragraph [0018] of Japanese patent No. 4502784, and phenothiazine, phenoxazine, or 4-methoxyphenol is preferable.

Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine, and nitrosophenylhydroxylamine aluminum salt is preferable from the viewpoint of not impairing the sensitivity of the photosensitive composition layer.

The content of the radical polymerization inhibitor is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0.02 to 2.0% by mass, based on the total mass of the photosensitive composition layer.

The content of the radical polymerization inhibitor is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0.01 to 1.0% by mass, based on the total mass of the polymerizable compounds.

-benzotriazoles-

Examples of benzotriazoles include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-methylbenzotriazole and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.

-carboxybenzotriazoles-

Examples of the carboxybenzotriazole include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole and N- (N, N-di-2-ethylhexyl) aminovinyl carboxybenzotriazole.

Specific examples of the carboxybenzotriazole include CBT-1 (manufactured by JOOOKU CHEMICAL CO., LTD).

The total content of the radical polymerization inhibitor, the benzotriazole compound and the carboxybenzotriazole compound is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is further excellent. On the other hand, when the content is 3% by mass or less, the sensitivity is maintained and the dye discoloration is suppressed more excellently.

Sensitizer

Examples of the sensitizer include known sensitizers, dyes, and pigments.

Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2, 4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthylimine compounds, triarylamine compounds, and aminoacridine compounds.

The content of the sensitizer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer, from the viewpoint of enhancing the curing rate by enhancing the sensitivity to a light source and balancing the polymerization rate and the chain transfer.

Surfactants-

Examples of the surfactant include surfactants described in paragraphs [0017] of Japanese patent No. 4502784 and paragraphs [0060] to [0071] of Japanese patent application laid-open No. 2009-237362.

The surfactant is preferably a nonionic surfactant, a fluorine surfactant, or a silicone surfactant.

Examples of the fluorine-based surfactant include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41-LM, R-O1, R-40, R-LM, RS-43, TF-6, RS-90, R-94 and DS-19521 (manufactured by DS Corporation); fluorad FC430, FC431 and FC171 (manufactured by Sumitomo 3M Limited); surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393 and KH-40 (manufactured by AGC Inc.); polyFox PF636, PF656, PF6320, PF6520 and PF7002 (manufactured by OMNOVA Solutions Inc.); ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (manufactured by Neos Corporation).

Further, as the fluorine-based surfactant, the following acrylic compounds are also preferable: has a molecular structure containing a functional group containing a fluorine atom, and when heated, a part of the functional group containing a fluorine atom is cleaved and the fluorine atom is volatilized.

Examples of such fluorine-based surfactants include MEGAFACE DS series (The Chemical Daily Co., ltd. (22/2/2016) and NIKKEI BUSIN ESS DAILY (23/2/2016)) manufactured by DIC Corporation

Further, as the fluorine-based surfactant, a copolymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound is preferably used.

As the fluorine-based surfactant, a block polymer can also be used.

The fluorine-containing surfactant is preferably a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups).

Further, examples of the fluorine-based surfactant include fluoropolymers having an ethylenically unsaturated group in a side chain, such as MEGAFACE RS-101, RS-102, RS-718K and RS-72-K (see above, DIC Corporation).

As the fluorine-based surfactant, surfactants derived from alternative materials to compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are preferable from the viewpoint of improving environmental compatibility.

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, ethoxylates and propoxylates thereof (e.g., glycerin propoxylate and glycerin ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; PLURONIC L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF corporation); TETRONIC 304, 701, 704, 901, 904 and 150R1 (manufactured by BASF corporation); solsperse 20000 (manufactured by The Lubrizol Corp corporation); NCW-101, NCW-1001, and NCW-1002 (hereinafter, manufactured by FUJIFILM Wako Pure Chemical Corporation); PIONI D-6112, D-6112-W and D-6315 (TAKEMOTO OIL & FAT Co., manufactured by Ltd.); OLFINE E1010, surfynol104, 400 and 440 (above, manufactured by Nissin Chemical Industry co., ltd.).

Examples of the silicone surfactant include a linear polymer having siloxane bonds, a structural unit having a hydrophilic group in a side chain, a polymer having a structural unit having a siloxane bond-containing group in a side chain, and a modified siloxane polymer having an organic group introduced into a side chain and/or a terminal.

Among these, a polymer having a structural unit having a hydrophilic group in a side chain and a structural unit having a siloxane bond-containing group in a side chain is preferable. The polymer exemplified as the silicone surfactant may be a random copolymer or a block copolymer.

The structural unit having a hydrophilic group in a side chain is preferably a structural unit derived from a compound represented by the following formula.

[ chemical formula 5]

In the above formula, R ⁴ Represents a hydrogen atom or a methyl group.

In the above formula, R ⁵ Represents a hydrogen atom or a methyl group.

In the formula, n represents an integer of 1 to 4. m represents an integer of 1 to 100.

The structural unit having a siloxane bond-containing group in a side chain is preferably a structural unit derived from a compound represented by the following formula.

[ chemical formula 6]

In the formula, R independently represents an alkyl group having 1 to 3 carbon atoms.

In the above formula, R ¹ Represents a hydrogen atom or a methyl group.

In the above formula, L ¹ Represents a single bond or a 2-valent linking group. L is ¹ The 2-valent linking group represented is preferably an organic linking group containing a carbon atom. As L ¹ Examples of the 2-valent linking group include an alkylene group having 1 to 50 carbon atoms and an oxyalkylene group having 1 to 50 carbon atoms.

As the structural unit having a siloxane bond-containing group in a side chain, a structural unit derived from a compound represented by the following formula is also preferable.

[ chemical formula 7]

In the above formula, R ⁶ Represents a hydrogen atom or a methyl group.

In the above formula, R ⁷ Represents a 2-valent linking group. R is ⁷ The 2-valent linking group represented is preferably an organic linking group containing a carbon atom. As R ⁷ Examples of the 2-valent linking group include alkylene groups having 1 to 10 carbon atoms.

In the above formula, R ⁸ Represents an alkyl group having 1 to 4 carbon atoms.

In the above formula, n represents an integer of 5 to 50.

Specific examples of the silicone surfactant include DOWNSIL 8032ADDITIVE, TORAY SILICON DC3PA, TORAY SILICON SH7PA, TORAY SILICON DC11PA, TORAY SILICON SH21PA, TORAY SILICON SH28PA, TORAY SILICON SH29PA, TORAY SILICON SH30PA, and TORAY SILICON SH8400 (Dow Corning Toray Co., ltd.; mentioned above); x-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002 (Shin-Etsu Silicone Co., ltd.); f-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (manufactured by Momentive performance Materials Inc.); BYK307, BYK323, and BYK330 (manufactured by BYK-Chemie GmbH).

The content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and still more preferably 0.05 to 0.8% by mass, based on the total mass of the photosensitive composition layer.

Examples of the plasticizer and the heterocyclic compound include compounds described in paragraphs [0097] to [0103] and paragraphs [0111] to [0118] of International publication No. 2018/179640.

(impurities)

The photosensitive composition layer may contain impurities.

Examples of the impurities include metal impurities or ions thereof, halide ions, residual organic solvents, residual monomers, and water.

Metal impurities and halide ions-

Examples of the metal impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, ions thereof, and halide ions.

Among them, sodium ions, potassium ions, and halide ions are preferably contained in the following amounts from the viewpoint of easy contamination.

The metal impurities are compounds different from the particles (for example, metal oxide particles) that can be contained in the transfer film.

The content of the metal impurities is preferably 80 mass ppm or less, more preferably 10 mass ppm or less, and further preferably 2 mass ppm or less, with respect to the total mass of the photosensitive composition layer. The lower limit is preferably 1 mass ppb or more, more preferably 0.1 mass ppm or more, with respect to the total mass of the photosensitive composition layer.

Examples of the method for adjusting the content of impurities include a method of selecting a raw material having a small content of impurities as a raw material of the photosensitive composition layer; a method for preventing impurities from being mixed in the process of forming the photosensitive composition layer; and a cleaning and removing method.

For example, the content of impurities can be determined by a known method such as ICP emission spectrometry, atomic absorption spectrometry, or ion chromatography.

Residual organic solvent-

Examples of the residual organic solvent include benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, and hexane.

The content of the residual organic solvent is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and further preferably 4 mass ppm or less, with respect to the total mass of the photosensitive composition layer. The lower limit is preferably 10 mass ppb or more, more preferably 100 mass ppb or more, with respect to the total mass of the photosensitive composition layer.

As a method for adjusting the content of the residual organic solvent, a method for adjusting drying conditions in a method for producing a transfer film to be described later can be mentioned. The content of the residual organic solvent can be quantified by a known method such as gas chromatography.

Residual monomers-

The photosensitive composition layer may contain a residual monomer of each structural unit of the resin.

The content of the residual monomer is preferably 5000 mass ppm or less, more preferably 2000 mass ppm or less, and still more preferably 500 mass ppm or less, based on the total mass of the resin, from the viewpoint of pattern formability and reliability. The lower limit is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, with respect to the total mass of the resin.

From the viewpoint of pattern formability and reliability, the residual monomer in each structural unit of the alkali-soluble resin is preferably 3000 mass ppm or less, more preferably 600 mass ppm or less, and still more preferably 100 mass ppm or less, with respect to the total mass of the photosensitive composition layer. The lower limit is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, with respect to the total mass of the photosensitive composition layer.

The residual amount of the monomer in synthesizing the alkali-soluble resin by a polymer reaction is also preferably within the above range. For example, when the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably in the above range.

Examples of the method for adjusting the content of the residual monomer include the above-mentioned methods for adjusting the content of impurities.

The amount of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.

The content of water in the photosensitive composition layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoint of improving reliability and laminatability.

(characteristics of photosensitive composition layer)

The thickness (film thickness) of the photosensitive composition layer is usually 0.1 to 300. Mu.m, preferably 0.2 to 100. Mu.m, more preferably 0.5 to 50 μm, still more preferably 0.5 to 30 μm, particularly preferably 1 to 20 μm. This can improve the developability of the photosensitive composition layer, and can improve the resolution.

The content of the polymerizable group contained in the photosensitive composition layer is preferably 1.0mmol/g or more, more preferably 2.0mmol/g or more, and further preferably 3.0mmol/g or more from the viewpoint of further excellent effects of the present invention. The upper limit is preferably 10.0mmol/g or less. The content of the polymerizable group may be defined as the content of a double bond.

The acid value of the photosensitive composition layer is preferably 10 to 150mgKOH/g, more preferably 40 to 120mgKOH/g, still more preferably 50 to 120mgKOH/g, particularly preferably 50 to 100mgKOH/g, most preferably 60 to 100mgKOH/g.

Examples of the method of measuring the acid value include a method of measuring the acid value in the resin and a method of calculating the acid value from the content of the resin having a known acid value.

[ intermediate layer ]

The transfer film may have an intermediate layer between the temporary support and the photosensitive composition layer.

For example, when the thermoplastic resin layer is not present, the intermediate layer is preferably disposed between the temporary support and the photosensitive composition layer, or when the thermoplastic resin layer is present, the intermediate layer is preferably disposed between the thermoplastic resin layer and the photosensitive composition layer.

Examples of the intermediate layer include a water-soluble resin layer and an oxygen barrier layer having an oxygen barrier function, which is described as a "separation layer" in japanese patent laid-open No. 5-072724.

The intermediate layer is preferably an oxygen barrier layer, and more preferably an oxygen barrier layer which exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1 mass% aqueous solution of sodium carbonate at 22 ℃), from the viewpoint of improving the sensitivity at the time of exposure and reducing the time load of the exposure machine to improve the productivity.

Hereinafter, each component that the intermediate layer may contain will be described.

(Water-soluble resin)

The intermediate layer may contain a water-soluble resin.

Examples of the water-soluble resin include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, polyether resins, gelatin, and polyamide resins.

Examples of the cellulose resin include water-soluble cellulose derivatives.

Examples of the water-soluble cellulose derivative include hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, methyl cellulose, and ethyl cellulose.

Examples of the polyether resin include polyethylene glycol, polypropylene glycol, alkylene oxide (alkylene oxide) adducts thereof, and vinyl ether resins.

Examples of the polyamide resin include an acrylamide resin, a vinyl amide resin, and an acrylamide resin.

Examples of the water-soluble resin include a copolymer of (meth) acrylic acid and a vinyl compound, preferably a copolymer of (meth) acrylic acid and allyl (meth) acrylate, and more preferably a copolymer of methacrylic acid and allyl methacrylate.

When the water-soluble resin is a copolymer of (meth) acrylic acid and a vinyl compound, the composition ratio (% by mol of (meth) acrylic acid/% by mol of vinyl compound) is preferably 90/10 to 20/80, more preferably 80/20 to 30/70.

The weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and still more preferably 10,000 or more. The upper limit is preferably 200,000 or less, more preferably 100,000 or less, and still more preferably 50,000 or less.

The dispersibility of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.

The water-soluble resin may be used alone in 1 kind, or may be used in 2 or more kinds.

The content of the water-soluble resin is preferably 50% by mass or more, and more preferably 70% by mass or more, based on the total mass of the intermediate layer. The upper limit is preferably 100% by mass or less, more preferably 99.9% by mass or less, still more preferably 99.8% by mass or less, and particularly preferably 99% by mass or less, based on the total mass of the intermediate layer.

(other Components)

The intermediate layer may contain other components in addition to the above-described resin.

As the other component, a polyhydric alcohol, an alkylene oxide adduct of a polyhydric alcohol, a phenol derivative, or an amide compound is preferable, and a polyhydric alcohol, a phenol derivative, or an amide compound is more preferable.

Examples of the polyhydric alcohols include glycerin, diglycerin, and diethylene glycol.

The number of hydroxyl groups of the polyhydric alcohol is preferably 2 to 10.

Examples of the polyol alkylene oxide adduct include compounds obtained by adding ethyleneoxy groups, propyleneoxy groups, and the like to the above polyols.

The average addition number of alkyleneoxy groups is preferably 1 to 100, more preferably 2 to 50, and further preferably 2 to 20.

Examples of the phenol derivative include bisphenol a and bisphenol S.

Examples of the amide compound include N-methylpyrrolidone.

The intermediate layer preferably contains at least 1 selected from the group consisting of water-soluble cellulose derivatives, polyols, polyol oxide adducts, polyether resins, phenol derivatives, and amide compounds.

The molecular weight of the other component is preferably less than 5,000, more preferably 4,000 or less, further preferably 3,000 or less, particularly preferably 2,000 or less, most preferably 1,500 or less. The lower limit is preferably 60 or more.

The other components may be used alone in 1 kind, or in 2 or more kinds.

The content of the other component is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more, based on the total mass of the intermediate layer. The upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

(impurities)

The intermediate layer may contain impurities.

Examples of the impurities include impurities contained in the photosensitive composition layer.

The thickness of the intermediate layer is preferably 3.0 μm or less, more preferably 2.0 μm or less.

The lower limit is preferably 1.0 μm or more.

[ thermoplastic resin layer ]

The transfer film may have a thermoplastic resin layer.

The thermoplastic resin layer is preferably disposed between the temporary support and the photosensitive composition layer when the intermediate layer is not present, and is preferably disposed between the temporary support and the intermediate layer when the intermediate layer is present.

When the transfer film has the thermoplastic resin layer, the following property to the transfer target body in the bonding step of the transfer film and the transfer target body is improved, and the mixing of air bubbles between the transfer film and the transfer target body can be suppressed. As a result, the adhesion to a layer (for example, a temporary support) adjacent to the thermoplastic resin layer is improved.

Examples of the thermoplastic resin layer include paragraphs [0189] to [0193] of Japanese patent application laid-open No. 2014-085643, which are incorporated herein.

Hereinafter, each component that the thermoplastic resin layer may contain will be described.

(thermoplastic resin)

The thermoplastic resin layer may comprise a thermoplastic resin.

As the thermoplastic resin, an alkali-soluble resin is preferable.

Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine and polyalkylene glycols.

As the alkali-soluble resin, the alkali-soluble resin contained in the photosensitive composition layer described above may also be used.

As the alkali-soluble resin, an acrylic resin is preferable in terms of developability and adhesion to adjacent layers.

The "acrylic resin" refers to a resin containing at least 1 structural unit selected from a structural unit derived from (meth) acrylic acid, a structural unit derived from a (meth) acrylate ester, and a structural unit derived from (meth) acrylamide.

In the acrylic resin, the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylamide is preferably 30% by mass or more, and more preferably 50% by mass or more, based on the total mass of the acrylic resin. The upper limit is preferably 100% by mass or less with respect to the total mass of the acrylic resin.

Among these, the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic ester is preferably 30 to 100% by mass, and more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.

As the alkali-soluble resin, a resin having an acid group is preferable.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and a phosphonic acid group, and a carboxyl group is preferable.

The alkali-soluble resin preferably contains a structural unit having an acid group, more preferably contains a structural unit having a carboxyl group, and further preferably contains an acrylic resin having a structural unit derived from (meth) acrylic acid from the viewpoint of developability and adhesion to an adjacent layer.

The acid value of the alkali-soluble resin is preferably 60mgKOH/g or more in view of developability. The upper limit is preferably 300mgKOH/g or less, more preferably 250mgKOH/g or less, still more preferably 200mgKOH/g or less, and particularly preferably 150mgKOH/g or less.

Among these, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60mgKOH/g or more, and more preferably an acrylic resin having a carboxyl group having an acid value of 60mgKOH/g or more.

The acrylic resin having a carboxyl group and an acid value of 60mgKOH/g or more can be suitably selected from known resins, for example.

Specifically, there are paragraphs [0025] of Japanese patent application laid-open No. 2011-095716, paragraphs [0033] to [0052] of Japanese patent application laid-open No. 2010-237589, and paragraphs [0053] to [0068] of Japanese patent application laid-open No. 2016-224162.

The content of the structural unit having a carboxyl group is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 12 to 30% by mass, based on the total mass of the acrylic resin.

The alkali-soluble resin may have a polymerizable group.

The polymerizable group may be a group participating in polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; a group having a cationically polymerizable group such as an epoxy group or an oxetanyl group.

The weight average molecular weight of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and further preferably 20,000 to 50,000.

The thermoplastic resin may be used alone in 1 kind, or 2 or more kinds.

The content of the thermoplastic resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, still more preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of developability and adhesion to an adjacent layer.

(pigments)

The thermoplastic resin layer may contain a dye (hereinafter, also simply referred to as "dye B") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400 to 780nm during color development and a maximum absorption wavelength that changes by an acid, an alkali, or a radical.

Except for the following portions, the pigment B has the same meaning as the pigment N, and the preferable embodiment is also the same.

The dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoints of visibility and resolution of an exposed portion and a non-exposed portion.

In view of visibility and resolution of the exposed portion and the unexposed portion, the thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength of the dye B is changed by an acid and a compound which generates an acid by light, which will be described later.

The pigment B may be used alone or in combination of 1 or more.

The content of the dye B is preferably 0.2% by mass or more, more preferably 0.2 to 6.0% by mass, further preferably 0.2 to 5.0% by mass, and particularly preferably 0.25 to 3.0% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoint of the visibility of the exposed portion and the unexposed portion.

The "content of the coloring matter B" refers to a content of the coloring matter when all the coloring matter B contained in the thermoplastic resin layer is brought into a colored state. Hereinafter, a method for quantifying the content of pigment B will be described by taking a pigment that develops color by a radical as an example.

A solution prepared by dissolving pigment B (0.001 g) in 100mL of methyl ethyl ketone and a solution prepared by dissolving pigment B (0.01 g) in 100mL of methyl ethyl ketone were prepared. To each of the obtained solutions, a photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF Japan ltd.) was added and 365nm light was irradiated, thereby generating radicals and bringing all the dyes B into a colored state. Then, the absorbance of each solution at a liquid temperature of 25 ℃ was measured by a spectrophotometer (UV 3100, manufactured by SHIMADZU CORPORATION) under an atmospheric environment to prepare a calibration curve.

Next, the absorbance of the solution in which all the dyes were developed was measured in the same manner as described above except that the thermoplastic resin layer (3 g) was dissolved in methyl ethyl ketone instead of the dye B. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the pigment B contained in the thermoplastic resin layer was calculated from the calibration curve. The "thermoplastic resin layer (3 g)" has the same meaning as that of 3g of the total solid content in the thermoplastic resin composition.

(Compound generating acid, base or radical by light)

The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, also simply referred to as "compound C").

The compound C is preferably a compound that generates an acid, a base, or a radical upon receiving an active ray such as ultraviolet light or visible light.

Examples of the compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators).

Photoacid generators

The thermoplastic resin layer may contain a photoacid generator in view of resolution.

Examples of the photo-acid generator include a photo-cationic polymerization initiator that can be contained in the photosensitive composition layer, and preferred embodiments are the same except for the following points.

The photoacid generator preferably contains at least 1 compound selected from an onium salt compound and an oxime sulfonate compound from the viewpoint of sensitivity and resolution, and more preferably contains an oxime sulfonate compound from the viewpoint of sensitivity, resolution and adhesion.

As the photoacid generator, a photoacid generator having the following structure is also preferable.

[ chemical formula 8]

Photo radical polymerization initiator

The thermoplastic resin layer may contain a photo radical polymerization initiator.

The photo radical polymerization initiator may be, for example, a photo radical polymerization initiator contained in the photosensitive composition layer, and the same is preferred.

Photobase generators-

The thermoplastic resin composition may contain a photobase generator.

Examples of the photobase generator include known photobase generators.

Specific examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyloxime, [ [ (2, 6-dinitrobenzyl) oxy ] carbonyl ] cyclohexylamine, bis [ [ (2-nitrobenzyl) oxy ] carbonyl ] hexane 1, 6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, tris (triphenylmethylboronic acid) cobalt hexaammine (III), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2, 6-dimethyl-3, 5-diacetyl-4- (2-nitrophenyl) -1, 4-dihydropyridine and 2, 6-dimethyl-3, 5-diacetyl-4- (2, 4-dinitrophenyl) -1, 4-dihydropyridine.

The compound C may be used alone in 1 kind, or in 2 or more kinds.

The content of the compound C is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of visibility and resolution of an exposed portion and a non-exposed portion.

(plasticizer)

The thermoplastic resin layer may contain a plasticizer in terms of resolution, adhesion to an adjacent layer, and developability.

The molecular weight of the plasticizer is preferably smaller than the molecular weight (weight average molecular weight when an oligomer or polymer and having a molecular weight distribution) of the thermoplastic resin (preferably, alkali-soluble resin). Specifically, the molecular weight (weight average molecular weight) of the plasticizer is preferably 200 to 2,000.

The plasticizer is not particularly limited as long as it is a compound which is compatible with the alkali-soluble resin and exhibits plasticity.

From the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

As the plasticizer, a polyalkylene glycol compound is preferable.

From the viewpoint of resolution and storage stability, the plasticizer preferably contains a (meth) acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.

Examples of the (meth) acrylate compound include (meth) acrylate compounds which are polymerizable compounds that can be contained in the photosensitive composition layer.

In the transfer film, when the thermoplastic resin layer and the photosensitive composition layer are laminated in direct contact with each other (when the intermediate layer is not provided), it is preferable that both the thermoplastic resin layer and the photosensitive composition layer contain the same (meth) acrylate compound. When the thermoplastic resin layer and the photosensitive composition layer each contain the same (meth) acrylate compound, interlayer diffusion of the components is suppressed, and storage stability is improved.

When the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, the (meth) acrylate compound is preferably not polymerized in the exposed portion after exposure, also from the viewpoint of adhesion between the thermoplastic resin layer and the adjacent layer.

In addition, as the (meth) acrylate compound, a polyfunctional (meth) acrylate compound having 2 or more (meth) acryloyl groups in 1 molecule is preferable from the viewpoint of resolution of the thermoplastic resin layer, adhesion to an adjacent layer, and developability.

Further, as the (meth) acrylate compound, a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound is also preferable.

The plasticizer may be used alone in 1 kind, or may be used in 2 or more kinds.

The content of the plasticizer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 20 to 50% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of resolution of the thermoplastic resin layer, adhesion to an adjacent layer, and developability.

(sensitizer)

The thermoplastic resin layer may contain a sensitizer.

Examples of the sensitizer include sensitizers that can be contained in the photosensitive composition layer.

The sensitizer may be used alone in 1 kind, or may be used in 2 or more kinds.

The content of the sensitizer is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of improvement of sensitivity to a light source and visibility of exposed portions and unexposed portions.

(other additives)

The thermoplastic resin layer may contain other additives in addition to the above components.

Examples of the other additives include those which can be contained in the photosensitive composition layer.

(impurities)

The thermoplastic resin layer may contain impurities.

The thickness (layer thickness) of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to adjacent layers. From the viewpoint of developability and resolution, the upper limit is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 8 μm or less.

[ other parts ]

The transfer film may have other members in addition to the above-described members.

As the other member, for example, a protective film is given.

Examples of the protective film include a resin film having heat resistance and solvent resistance. Specific examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. As the protective film, a resin film made of the same material as the temporary support can be used.

Among them, as the protective film, a polyolefin film is preferable, and a polypropylene film or a polyethylene film is more preferable.

The thickness of the protective film is preferably 1 to 100. Mu.m, more preferably 5 to 50 μm, still more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm.

The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and preferably 100 μm or less from the viewpoint of relative inexpensiveness.

The number of fish eyes having a diameter of 80 μm or more contained in the protective film is preferably 5/m ² The following. The lower limit is preferably 0/m ² The above.

The term "fisheye" refers to a defect that when a material is hot-melted and formed into a film by a method such as kneading, extrusion, biaxial stretching, or casting, foreign matter, undissolved matter, or oxidation-degradation product of the material is taken into the film.

The number of particles having a diameter of 3 μm or more contained in the protective film is preferably 30 particles/mm ² Hereinafter, more preferably 10 pieces/mm ² Hereinafter, more preferably 5 pieces/mm ² The following. The lower limit is preferably 0/mm ² The above. In the case where the amount of the protective film is within the above range, defects caused by transfer of the unevenness caused by the particles contained in the protective film to the photosensitive composition layer or the conductive layer can be suppressed.

From the viewpoint of imparting winding properties, the arithmetic average roughness Ra of the surface of the protective film on the side opposite to the surface in contact with the photosensitive composition layer or the surface in contact therewith is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more. The upper limit is preferably less than 0.50. Mu.m, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.

< method for producing transfer film >

As a method for producing the transfer film, for example, a known method can be cited.

Examples of the method for manufacturing the transfer film 10 include a method including the steps of: a step of applying the intermediate layer-forming composition to the surface of the temporary support 11 to form a coating film, and further drying the coating film to form the intermediate layer 13; and a step of applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form the photosensitive composition layer 15.

Before the step of forming the intermediate layer 13, the following steps may be included: the composition for forming a thermoplastic resin layer is applied to the surface of the temporary support 11 to form a coating film, and the coating film is further dried to form a thermoplastic resin layer.

The transfer film 10 is manufactured by pressure-bonding a protective film 19 to the photosensitive composition layer 15 of the laminate manufactured by the above-described manufacturing method.

As a method for producing the transfer film, it is preferable to produce the transfer film 10 including the temporary support 11, the intermediate layer 13, the photosensitive composition layer 15, and the protective film 19 by including a step of providing the protective film 19 so as to contact a surface of the photosensitive composition layer 15 opposite to the temporary support 11 side.

Further, as a method for producing the transfer film, it is also preferable to produce the transfer film 10 including the temporary support 11, the thermoplastic resin layer, the intermediate layer 13, the photosensitive composition layer 15, and the protective film 19 by including a step of providing the protective film 19 so as to contact a surface of the photosensitive composition layer 15 opposite to the temporary support 11 side.

The transfer film 10 manufactured by the above-described manufacturing method can be wound up to manufacture and store a roll-shaped transfer film. The roll transfer film is directly provided in a roll form in a step of bonding to a substrate by a roll-to-roll method described later.

In addition, as a method for manufacturing the transfer film 10, after the photosensitive composition layer 15 and the intermediate layer 13 are formed on the protective film 19, a thermoplastic resin layer may be formed so as to be in contact with the surface of the intermediate layer 13 on the side opposite to the photosensitive composition layer.

[ photosensitive composition and method for Forming photosensitive composition layer ]

As a method for forming the photosensitive composition layer, a coating method using a photosensitive composition coating containing components (for example, a resin, a polymerizable compound, a polymerization initiator, and the like) included in the photosensitive composition layer and a solvent is preferable.

As a method for forming the photosensitive composition layer, for example, the following method is preferable: the photosensitive composition is applied to the intermediate layer to form a coating film, and the coating film is dried at a predetermined temperature as necessary to form a photosensitive composition layer. The amount of the residual solvent is adjusted by the drying treatment of the coating film.

The photosensitive composition preferably contains a component contained in the photosensitive composition layer and a solvent. The content of each component contained in the photosensitive composition layer is as described above.

The solvent is not particularly limited as long as it can dissolve or disperse components contained in the photosensitive composition layer other than the solvent.

Examples of the solvent include an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (e.g., methanol, ethanol, etc.), a ketone solvent (e.g., acetone, methyl ethyl ketone, etc.), an aromatic hydrocarbon solvent (e.g., toluene, etc.), an aprotic polar solvent (e.g., N-dimethylformamide, etc.), a cyclic ether solvent (e.g., tetrahydrofuran, etc.), an ester solvent (e.g., N-propyl acetate, etc.), an amide solvent, a lactone solvent, and a mixed solvent combining these solvents.

The solvent preferably comprises at least 1 selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent.

Among these solvents, a mixed solvent containing at least 1 selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least 1 selected from the group consisting of ketone solvents and cyclic ether solvents is more preferable, and a mixed solvent containing 3 selected from the group consisting of at least 1 selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, ketone solvents, and cyclic ether solvents is even more preferable.

Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (e.g., propylene glycol monomethyl ether acetate), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

Examples of the solvent include solvents described in paragraphs [0092] to [0094] of International publication No. 2018/179640 and solvents described in paragraph [0014] of Japanese patent application laid-open No. 2018-177889, and these contents are incorporated in the present specification.

The solvent may be used alone in 1 kind, or may be used in 2 or more kinds.

The content of the solvent is preferably 50 to 1900 parts by mass, more preferably 100 to 1200 parts by mass, and further preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive composition.

As a method for applying the photosensitive composition, for example, a known application method can be cited.

Specifically, there may be mentioned a printing method, a spray coating method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method and a die coating method (slit coating method).

As a method for drying the coating film of the photosensitive composition, heating drying and drying under reduced pressure are preferable.

The drying temperature is preferably 90 ℃ or higher, more preferably 100 ℃ or higher, and still more preferably 110 ℃ or higher. The upper limit is preferably 130 ℃ or lower, more preferably 120 ℃ or lower.

Further, as the drying method, a method of continuously changing the drying temperature may be used.

The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and still more preferably 60 seconds or more. The upper limit is preferably 600 seconds or less, more preferably 450 seconds or less, and further preferably 300 seconds or less.

Further, a protective film may be attached to the photosensitive composition layer to manufacture a transfer film.

As a method for attaching the protective film to the photosensitive composition layer, for example, a known method can be cited. Examples of the device for bonding the protective film to the photosensitive composition layer include known laminating machines such as a vacuum laminating machine and an automatic cutting laminating machine.

The laminator is preferably provided with an optional heatable roller such as a rubber roller, and can be pressurized and heated.

[ composition for Forming intermediate layer and method for Forming intermediate layer ]

As a method for forming the intermediate layer, a coating method of coating with a composition for forming an intermediate layer containing a component (for example, a water-soluble resin or the like) contained in the intermediate layer and a solvent is preferably used.

As a method for forming the intermediate layer, for example, the following method is preferable: the intermediate layer-forming composition is applied to the temporary support to form a coating film, and the coating film is dried at a predetermined temperature as necessary to form the intermediate layer. The amount of the residual solvent is adjusted according to the drying treatment of the coating film.

The composition for forming the intermediate layer preferably contains the components contained in the intermediate layer and a solvent.

The content of the components contained in the intermediate layer is as described above.

The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the intermediate layer.

The solvent is preferably at least 1 of the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and water-miscible organic solvent.

Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, glycerin, and mixed solvents of these, and alcohols having 1 to 3 carbon atoms, more preferably methanol or ethanol.

The solvent may be used alone in 1 kind, or may be used in 2 or more kinds.

The content of the solvent is preferably 50 to 2500 parts by mass, more preferably 50 to 1900 parts by mass, and still more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the intermediate layer-forming composition.

Examples of the method for forming the intermediate layer include a known coating method.

Specifically, slit coating, spin coating, curtain coating, and inkjet coating can be mentioned.

As a method for drying the coating film of the intermediate layer-forming composition, heating drying and drying under reduced pressure are preferable.

[ composition for Forming thermoplastic resin layer and method for Forming thermoplastic resin layer ]

As a method for forming the thermoplastic resin layer, a coating method in which a composition for forming a thermoplastic resin layer containing a component (for example, a thermoplastic resin or the like) contained in the thermoplastic resin layer and a solvent is coated is preferably used.

As a method for forming the thermoplastic resin layer, for example, the following method is preferable: the intermediate layer-forming composition is applied to the temporary support to form a coating film, and the coating film is dried at a predetermined temperature as necessary to form a thermoplastic resin layer. The amount of the residual solvent is adjusted by the drying treatment of the coating film.

The composition for forming a thermoplastic resin layer preferably contains a component contained in the thermoplastic resin layer and a solvent.

The content of the components contained in the thermoplastic resin layer is as described above.

The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer.

The solvent is the same as that contained in the photosensitive composition, and the preferred embodiment is the same.

The solvent may be used alone in 1 kind, or may be used in 2 or more kinds.

The content of the solvent is preferably 50 to 1900 parts by mass, and more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content of the thermoplastic resin layer forming composition.

Examples of the method for forming the thermoplastic resin layer include a known coating method.

Specific examples thereof include slit coating, spin coating, curtain coating, and inkjet coating.

The method of drying the coating film of the composition for forming a thermoplastic resin layer is preferably drying by heating or drying under reduced pressure.

When at least one of the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer is a positive photosensitive composition layer, a known positive photosensitive composition can be used to form the positive photosensitive composition layer by the above-described method.

As the positive photosensitive composition, a composition containing a polymer containing a repeating unit having a group whose hydrophilicity is increased by the action of an acid and a photoacid generator can be cited.

Examples

The present invention will be described in further detail below with reference to examples.

The materials, the amounts used, the ratios, the contents of the treatments, the procedures of the treatments, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. The scope of the invention should therefore not be construed in a limiting sense by the examples presented below.

< transfer film >

In the following examples and comparative examples, the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer were formed using transfer films. Hereinafter, a method for producing a transfer film will be described.

[ production of temporary support 1 ]

The temporary support 1 was produced in the following order.

(extrusion Molding)

Polyethylene terephthalate pellets in which a citric acid-chelated organic titanium complex described in Japanese patent No. 5575671 was used as a polymerization catalyst were dried to a water content of 50ppm or less, and then placed in a hopper of a single-shaft kneading extruder having a diameter of 30mm, and melted and extruded at 280 ℃. After passing the melt (melt) through a filter (pore size 2 μm), it was extruded from a die to a cooling roll at 25 ℃ to obtain an unstretched film. Further, the extruded melt was brought into close contact with a cooling roll by an electrostatic application method.

(stretching and formation of particle-containing layer)

(a) Longitudinal stretching

The unstretched film was stretched in the longitudinal direction (carrying direction) by passing it between 2 pairs of nip rolls having different peripheral speeds. The stretching was performed at a preheating temperature of 75 ℃, a stretching temperature of 90 ℃, a stretching magnification of 3.4 times, and a stretching speed of 1300%/sec.

(b) Coating of

On one surface of the longitudinally stretched film, a composition 1 for forming a particle-containing layer shown below was applied by a bar coater until the thickness was 40nm after film formation.

Preparation of composition 1 for Forming a particle-containing layer

The components were mixed in the following formulation to obtain composition 1 forming a particle-containing layer. After preparation of composition 1 forming the particle-containing layer, the membrane was filtered with a 6 μm filter (F20, manufactured by MAHLE Japan ltd.), and then degassed with 2 × 6RADIAL FLOW supprboic (manufactured by polypore international, inc.).

167 parts by mass of an acrylic polymer (AS-56FA, 27.5% by mass of solid content, manufactured by Daicel Miraizu Ltd.)

0.7 part by mass of a nonionic surfactant (NAROACTY CL95, sanyo Chemical Industries, ltd., solid content 100% by mass)

114.4 parts by mass of an anionic surfactant (RAPISOL A-90, manufactured by NOF CORPORATION, diluted with water to a solid content of 1% by mass)

7 parts by mass of a carnauba wax dispersion (Cellosol 524, chuKYO YUSHI CO., LTD., product of solid content 30% by mass) was added

20.9 parts by mass of a carbodiimide compound (CARBODILITE V-02-L2, nisshinbo co., ltd. System, diluted with water to a solid content of 10 mass%) was added

Flatting agent (SNOWTEX XL, manufactured by Nissan Chemical Corporation, solid content 40% by mass, average particle diameter 50 nm) 2.8 parts by mass

690.2 parts by mass of Water

(c) Stretching in transverse direction

The film subjected to the above-described longitudinal stretching and coating was subjected to transverse stretching using a tenter under the following conditions.

Transverse stretching conditions

Preheating temperature: 110 deg.C

Stretching temperature: 120 deg.C

Stretching ratio: 4.2 times of

Stretching speed: 50%/second

(Heat setting and Heat relaxation)

Next, the biaxially stretched film after the longitudinal stretching and the transverse stretching were finished was heat-set under the following conditions. After the heat setting, the width of the tenter was reduced, and the thermal relaxation was performed under the following conditions.

Heat-setting conditions

Heat setting temperature: 227 deg.C

Heat setting time: 6 seconds

Thermal relaxation conditions

Thermal relaxation temperature: 190 deg.C

Thermal relaxation rate: 4 percent

(Take-up)

After heat setting and heat relaxation, both ends were trimmed, and the ends were subjected to extrusion processing (knurling) with a width of 10mm, and then wound up with a tension of 40 kg/m. The width was 1.5m, and the roll length was 6300m. The obtained film roll was used as a temporary support 1.

The haze of the obtained temporary support 1 was 0.2. The haze was measured as a total haze using a haze meter (NIPPON DENSHOKU INDUSTRIES co., ltd., NDH 2000).

The heat shrinkage upon heating at 150 ℃ for 30 minutes was 1.0% in the MD (Machine Direction) and 0.2% in the TD (Transverse Direction) on the surface of the film.

The thickness of the particle-containing layer was 40nm as measured by a cross-sectional TEM image. The average particle diameter of the particles contained in the particle-containing layer was measured by a Transmission Electron Microscope (TEM) model HT-7700 manufactured by Hitachi High-Technologies Corporation, and found to be 50nm.

[ production of temporary support 2 ]

A temporary support 2 having a thermoplastic resin layer and a water-soluble resin layer was produced in the following order.

(preparation of thermoplastic resin composition)

Thermoplastic resin compositions were prepared by mixing the following components in the mass parts shown in table 1 below.

[ Table 1]

(production of Polymer)

The polymers described in table 1 were produced as follows.

In the following synthesis examples, the following abbreviations represent the following compounds, respectively.

MAA: methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

BzMA: benzyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

AA: acrylic acid (Tokyo Chemical Industry Co., ltd.)

PGMEA: propylene glycol monomethyl ether acetate (manufactured by SHOWA DHNKO K.)

V-601: dimethyl-2, 2' -azobis (2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

Synthesis of Polymer A-2

PGMEA (116.5 parts) was added to a three-necked flask and the temperature was raised to 90 ℃ under a nitrogen atmosphere. A solution prepared by adding BzMA (75.0 parts), MMA (10.0 parts), AA (15.0 parts) and V-601 (4.0 parts) to PGMEA (116.5 parts) was added dropwise over 2 hours to a three-necked flask maintained at 90 ℃. + -. 2 ℃. After the completion of the dropwise addition, the mixture was stirred at 90 ℃. + -. 2 ℃ for 2 hours, whereby polymer A-2 (solid content concentration: 40.0%) was obtained.

In table 1, abbreviations respectively represent the following compounds.

A-2: the above-mentioned Polymer A-2

B-1: a compound having a structure shown below (dye which develops color by acid)

[ chemical formula 9]

C-1: a compound having the structure shown below (photoacid generator, which is synthesized according to the method described in paragraph 0227 of Japanese patent application laid-open No. 2013-47765)

[ chemical formula 10]

D-3: NK ESTER A-DCP (Dicidol diacrylate, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.)

D-4:8UX-015A (multifunctional urethane acrylate Compound, manufactured by Taisei Fine Chemical Co., ltd.)

D-5: aronium TO-2349: polyfunctional acrylate compound having carboxyl group (TOAGOSEI C0., LTD. Manufactured)

E-1: MEGAFACE F552 (DIC Corporation)

F-1: phenothiazine (manufactured by FUJlFILM Wako Pure Chemical Corporation)

F-2: CBT-1: carboxybenzotriazole (JOHOKU CHEMICAL CO., LTD products)

MEK: methyl Ethyl Ketone (SANKYO CHEMICAL CO., LTD. Manufactured)

PGME: propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.)

PGMEA: propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.)

(preparation of Water-soluble resin composition 1)

The following components were mixed to prepare a water-soluble resin composition 1. The unit of the amount of each component is part by mass.

Ion exchange water: 38.12 parts by mass

Methanol (MITSUBISHI GAS CHEMICAL COMPANY, inc.): 57.17 parts by mass

Kuraray Poval PVA-205 (polyvinyl alcohol, kuraray co., ltd.): 3.22 parts by mass

Polyvinylpyrrolidone K-30 (NIPPON SHOKUBAI co., ltd.): 1.49 parts by mass

MEGAFACE F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0015 part by mass

(formation of thermoplastic resin layer and Water-soluble resin layer)

The prepared thermoplastic resin composition 1 was applied to the surface of the temporary support 1 opposite to the particle-containing layer using a slit-shaped nozzle until the width became 1.0m and the thickness became 2.0 μm, and the resultant was passed through a drying zone at 80 ℃ for 40 seconds, thereby obtaining a temporary support 1 with a thermoplastic resin layer.

The water-soluble resin composition 1 was applied to the thermoplastic resin layer of the temporary support 1 with a thermoplastic resin layer by using a slit nozzle until the application width became 1.0m and the thickness became 1.0 μm, and the resultant was passed through a drying zone at 80 ℃ for 40 seconds, thereby forming a water-soluble resin layer. This was used as a temporary support 2.

[ production of temporary support 3 ]

The temporary support 3 having the water-soluble resin layer was produced in the following order.

(preparation of Water-soluble resin composition 2)

The following components were mixed to prepare a water-soluble resin composition 2. The unit of the amount of each component is part by mass.

Cellulose resin (METOLOSE 60SH-03, shin-Etsu Chemical Co., ltd.): 3.5 parts of

Surfactant (MEGAFACE F-444, manufactured by DIC Corporation): 0.1 part

Pure water: 33.7 parts of

Methanol: 62.7 portions of

(formation of Water-soluble resin layer)

The water-soluble resin composition 2 was applied to a Lumiror (registered trademark) 16FB40 (polyethylene terephthalate film having a thickness of 16 μm, manufactured by TORAY INDUSTRIES, INC.) by using a slit nozzle in an amount of 2.0 μm in dry film thickness, followed by drying to form a water-soluble resin layer. This was used as a temporary support 3.

[ production of transfer film ]

Photosensitive compositions 1 to 10 shown below were prepared, compositions mixed with a solvent were obtained, and the obtained compositions were applied to the temporary support 1, 2, or 3 to produce a transfer film.

The following describes the details.

(photosensitive compositions 1 to 8)

Photosensitive compositions 1 to 8 were prepared using the components and formulations shown in table 2 below. The photosensitive composition layers 1 to 8 formed using the photosensitive compositions 1 to 8 are negative photosensitive composition layers.

In table 2, the numerical values shown in the columns of the respective components indicate the contents (parts by mass) of the respective components.

The details of each component in table 2 are as follows.

-resins-

Resin A1: a solution (solid content 30.0 mass%) containing a copolymer (Mw =60,000) of styrene/methacrylic acid/methyl methacrylate =52/29/19 (mass%)

Resin A2: solution (solid content 30.0 mass%) containing copolymer (Mw =40,000) of benzyl methacrylate/methacrylic acid =78/22 (mass%)

Resin A3: a solution (solid content 30.0 mass%) containing a copolymer (Mw =35,000) of styrene/methacrylic acid/methyl methacrylate =50/34/16 (mass%)

Further, mw means a weight average molecular weight.

The resin content in table 2 indicates the solid content of each resin.

Polymeric compounds

BPE-500: ethoxylated bisphenol A dimethacrylate, SHIN-NAKAMURA CHEMICAL Co., ltd

Dimethacrylate of polyethylene glycol obtained by adding ethylene oxide of 15 mol on average and propylene oxide of 2 mol on average to both ends of bisphenol A

M-270: ARONIXM-270 (polypropylene glycol diacrylate, TOAGOSEI co., ltd. Manufactured)

A-TMPT: trimethylolpropane triacrylate, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd

SR-454: ethoxylated (3) trimethylolpropane triacrylate, manufactured by Arkema s.a

A-9300-1CL: caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd

Polymerization initiators

B-CIM:2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazol (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (Kurogane Kasei Co., manufactured by Ltd.)

Additives-

SB-PI701:4,4' -bis (diethylamino) benzophenone (Sanyo Trading Co., ltd., manufactured by Ltd.)

Colorless crystal violet (Tokyo Chemical Industry Co., ltd.)

N-phenylglycine (Tokyo Chemical Industry Co., ltd.; manufactured by Ltd.)

Bright green (Tokyo Chemical Industry Co., ltd.)

CBT-1: carboxybenzotriazole (JOHOKU CHEMICAL CO., LTD products)

1: 1 (mass ratio) mixture of 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole

TDP-G: phenothiazine (Kawaguchi Chemical Industry Co., LTD. Product.)

Irganox245 (manufactured by BASF corporation)

N-nitrosophenylhydroxylamine aluminum salt (manufactured by FUJIFILM Wako Pure Chemical Corporation)

Phenidone (Tokyo Chemical Industry Co., ltd.)

F-552: MEGAFACE F-552; fluorine-based surfactant (manufactured by DIC Corporation)

[ Table 2]

-solvent-

A mixed solvent containing methyl ethyl ketone (60 parts by mass, manufactured by SANKYO CHEMICAL co., ltd.) and propylene glycol monomethyl ether acetate (40 parts by mass, manufactured by SHOWA DENKO k.k.) was prepared. The mixed solvent was mixed with each photosensitive composition until the solid content concentration of each photosensitive composition became 20 mass%. Then, the obtained mixed solution was filtered using a filter made of polytetrafluoroethylene having a pore size of 2 μm, thereby preparing a coating solution of each photosensitive composition.

(photosensitive composition 9)

The photosensitive composition 9 was prepared by using the components and the formulation shown below. The photosensitive composition layer 9 formed using the photosensitive composition 9 is a positive photosensitive composition layer.

The following polymer 1:9.59 parts of

Photoacid generators (the following compound a-1): 0.30 portion

Surfactant (surfactant C below): 0.01 part

Additives (the following compound D): 0.1 part of

Propylene glycol monomethyl ether acetate: 90.00 parts

Polymer 1: the following structural polymers (glass transition temperature 25 ℃ C. Weight average molecular weight 25,000. The numerical values in the following structural units are expressed in% by mass.)

[ chemical formula 11]

Compound A-1: structural compound shown in the following

[ chemical formula 12]

Surfactant C: the structural polymers shown below

[ chemical formula 13]

Compound D: structural compound shown in the following

[ chemical formula 14]

(photosensitive composition 10)

Each photosensitive composition 10 was prepared by using the components and formulation shown below. The photosensitive composition layer 10 formed using the photosensitive composition 10 is a positive photosensitive composition layer.

The following polymer 2:9.57 parts

Photoacid generators (the following compound a-2): 0.30 portion

Surfactant (surfactant C described above): 0.01 part

Additive (compound D above): 0.12 part of

Propylene glycol monomethyl ether acetate: 90.00 parts

Polymer 2: the structural compound shown below (glass transition temperature 90 ℃ C., weight average molecular weight 20,000. The numerical values in the following structural units are expressed in% by mass.)

[ chemical formula 15]

Compound A-2: structural compound shown in the following

[ chemical formula 16]

(application of photosensitive composition coating solution)

Production of the transfer film 1

The coating liquid of the photosensitive composition 1 containing the photosensitive composition 1 was applied to the surface of the temporary support 1 obtained in the above step on the side opposite to the particle-containing layer using a slit-shaped nozzle until the coating width became 1.0m and the thickness became 3.0 μm, and the coating liquid was passed through a drying zone at 100 ℃ for 60 seconds, thereby forming a photosensitive composition layer.

Next, a PET film (Lumirror (registered trademark) 16KS40, manufactured by INC) was pressure-bonded as a cover film on the photosensitive composition layer to produce a photosensitive transfer member, which was wound in a roll form to obtain a transfer film 1.

Production of transfer films 2 to 12

Transfer films 2 to 12 were obtained by using the temporary support and the coating liquid of the photosensitive composition shown in table 3 below and adjusting the thickness of the photosensitive composition layer after drying to be shown in table 3 in the same manner as the method for producing transfer film 1.

In Table 3, the absorbance at 365nm indicates the absorbance measured by the above-mentioned measurement method.

In table 3, with respect to the transfer films 1 to 10, the dissolution time of the exposed portion indicates the dissolution time when the 1 st photosensitive composition layer shown in the subsequent stage is exposed to light and developed with the 2 nd developer. The dissolution time was measured as described above. In the transfer films 11 to 12, the dissolution time of the exposed portion indicates the dissolution time when the 2 nd photosensitive resin layer shown in the subsequent stage is exposed to light and developed with the 2 nd developer.

In Table 3, the dissolution time of the unexposed portion shows the dissolution time when the photosensitive composition layer was developed with the 2 nd developer shown in the subsequent paragraph. The dissolution time was measured as described above.

[ Table 3]

< production of laminate comprising transparent conductive Pattern >

[ example 1]

(preparation of coating liquid for silver nanowire layer formation)

Additive liquid a was prepared in the following procedure.

Silver nitrate powder (0.51 g) was dissolved in 50mL of pure water. 1mol/L aqueous ammonia was added to the obtained liquid until the liquid became transparent. Then, pure water was added to the obtained liquid until the total amount of the liquid became 100mL, thereby preparing additive liquid a.

Then, 0.5G of glucose powder was dissolved in 140mL of pure water to prepare additive solution G.

Further, 0.5g of HTAB (hexadecyl-trimethylammonium bromide) powder was dissolved in 27.5mL of pure water, thereby preparing additive solution H.

After pure water (410 mL) was added to the three-necked flask, additive solution H (82.5 mL) and additive solution G (206 mL) were added to the flask via a funnel while stirring at 20 ℃. To the obtained liquid, additive solution A (206 mL) was added at a flow rate of 2.0 mL/min and a stirring speed of 800rpm (fluctuations per minute). After 10 minutes, 82.5mL of additive solution H was added to the obtained liquid. Thereafter, the temperature of the obtained liquid was raised to an internal temperature of 75 ℃ at 3 ℃ per minute. Thereafter, the stirring speed was reduced to 200rpm, and heating was performed for 5 hours, thereby obtaining a silver-containing nanowire liquid. After cooling the obtained silver nanowire-containing liquid, the liquid was placed in a stainless steel cup, and ultrafiltration was performed by an ultrafiltration apparatus in which an ultrafiltration module SIP1013 (manufactured by asahi kasei Corporation, molecular weight fraction 6, 000), a magnetic pump, and a stainless steel cup were connected to a silicone tube. At the point when the filtrate from the module reached 50mL, 950mL of distilled water was added to the stainless steel cup and washed. After repeating the above washing 10 times, the mixture was concentrated until the liquid volume reached 50mL.

In addition, the additive solution a, the additive solution G, and the additive solution H were repeatedly prepared in the above amounts and methods, and used for synthesizing silver nanowires.

The obtained concentrated solution was diluted with pure water and methanol (volume ratio of pure water to methanol: 60/40) to obtain a coating liquid for forming a silver nanowire layer.

(preparation of a substrate with a transparent conductive layer)

Next, a coating liquid for forming a silver nanowire layer was applied to one surface of a cycloolefin polymer film (substrate) having a thickness of 100 μm, the surface of which was subjected to corona discharge treatment, and dried, thereby forming a 1 st transparent conductive layer (silver nanowire layer). The coating amount of the coating liquid for forming a silver nanowire layer was set to an amount such that the wet film thickness became 20 μm. The layer thickness of the dried silver nanowire layer is 30nm, and the sheet resistance of the silver-containing nanowire layer is 60 omega/\9633. For the measurement of the sheet resistance, a resistance tester EC-80P (manufactured by NAPSON CORPORATION) of a noncontact eddy current system was used. The silver nanowires had a diameter of 17nm and a major axis length of 35 μm.

In the same manner as described above, the silver nanowire liquid was coated on the side of the cyclic olefin polymer film not coated with the silver nanowires and dried, thereby forming the 2 nd transparent conductive layer (silver nanowire layer). In this way, a substrate with a transparent conductive layer, which sequentially includes a silver nanowire layer, a cycloolefin polymer film, and a silver nanowire layer, was prepared.

(formation, exposure, and development of the 1 st photosensitive composition layer)

The transfer film 1 was bonded to the substrate with the transparent conductive layer by a roll-to-roll method using a vacuum laminator (MCK corporation, roll temperature: 100 ℃, line pressure: 1.0MPa, line speed: 0.5 m/min) to obtain a laminate. The obtained laminate comprises at least a substrate with a transparent conductive layer, a 1 st photosensitive composition layer, and a temporary support in this order.

The obtained laminate was subjected to pressure defoaming under conditions of 0.6MPa and 60 ℃ for 30 minutes using an autoclave apparatus.

Then, the temporary support was not peeled off, and the 1 st photosensitive composition layer was exposed to light using an ultrahigh pressure mercury lamp through a line and space pattern mask (duty ratio 1: 1, line width from 1 μm to 20 μm, stepwise changed at 1 μm intervals, pattern length 50mm, number of wires 10).

After the temporary support is peeled off, development is performed using the 1 st developer. For development, shower development was performed using the 1 st developer (1.0 mass% aqueous solution of sodium carbonate at 25 ℃). The developing time was 1.5 times as long as the dissolution time of the unexposed portion of the 1 st photosensitive composition layer in the development with the 1 st developing solution.

Through the above steps, a laminate having the 1 st resist pattern formed on one surface of the substrate with the transparent conductive layer was obtained.

The exposure amount at the time of the above exposure was adjusted so that the line width of the 1 st resist pattern obtained by development corresponding to the line-and-space pattern of 15 μm became 15 μm.

(formation, exposure, and development of the 2 nd photosensitive composition layer)

A laminate having a 1 st resist pattern formed on one surface of a substrate with a transparent conductive layer was laminated with a transfer film 1 on the surface of the transparent conductive layer opposite to the 1 st resist pattern by a roll-to-roll method using a vacuum laminator (MCK, roll temperature: 100 ℃, line pressure: 1.0MPa, line speed: 0.5 m/min) to obtain a laminate. The obtained laminate comprises at least a 1 st resist pattern, a substrate with a transparent conductive layer, a 2 nd photosensitive composition layer, and a temporary support in this order.

Next, without peeling the temporary support, the 2 nd photosensitive composition layer was exposed using an ultra-high pressure mercury lamp with the line and space pattern mask interposed therebetween.

After the temporary support is peeled off, development is performed using a 2 nd developer. For development, shower development was performed using the 2 nd developer (1.0 mass% aqueous sodium carbonate solution at 25 ℃). The developing time was 1.5 times as long as the dissolution time of the unexposed portions of the 2 nd photosensitive composition layer in the development with the 2 nd developer.

The exposure amount at the time of the exposure was adjusted so that the line width of the 2 nd resist pattern obtained by development corresponding to the line-and-space pattern of 15 μm became 15 μm.

Through the above steps, a laminate having the 1 st resist pattern, the substrate with the transparent conductive layer, and the 2 nd resist pattern in this order was obtained. The 1 st resist pattern and the 2 nd resist pattern have a resist pattern having a width of 15 μm at least in a partial region.

(etching of transparent conductive layer)

The laminate obtained in the above step was immersed in a 30% ferric nitrate aqueous solution at 35 ℃ for 25 seconds, and the transparent conductive layer (silver nanowire layer) was etched.

After the etching of the transparent conductive layer, the 1 st resist pattern and the 2 nd resist pattern were peeled off by a 10% aqueous sodium hydroxide solution.

Through the above steps, a substrate having transparent conductive patterns on both sides was obtained.

Examples 2 to 13 and comparative example 1

A substrate having transparent conductive patterns of examples 2 to 13 and comparative example 1 on both sides was obtained in the same manner as in example 1 except that the photosensitive composition layer 1 and the photosensitive composition layer 2 were formed using the transfer film shown in table 4 of the subsequent stage and the exposure amount and the development time were adjusted.

[ example 14]

In the same manner as in example 1, the coating liquid for forming a silver nanowire layer was applied to one surface of the substrate having a surface subjected to the corona discharge treatment and dried, thereby forming a 1 st transparent conductive layer (silver nanowire layer).

A transfer film 2 was bonded to the surface of the 1 st transparent conductive layer in the same manner as in example 1. Then, exposure and development were carried out in the same manner as in example 1, thereby obtaining a laminate having the 1 st transparent conductive layer and the 1 st resist pattern on one surface of the substrate from the substrate side.

In the same manner as in example 1, a 2 nd transparent conductive layer (silver nanowire layer) was formed on the surface of the other substrate of the laminate, and a 2 nd resist pattern was formed on the surface of the 2 nd transparent conductive layer in the same order as described above.

Through the above steps, a laminate having the 1 st resist pattern, the substrate with the transparent conductive layer, and the 2 nd resist pattern in this order was obtained. The transparent conductive layer was etched in the same manner as in example 1 to remove the 1 st resist pattern and the 2 nd resist pattern, thereby obtaining a substrate having transparent conductive patterns on both surfaces in example 14.

Comparative example 2

A transfer film 6 including the 1 st photosensitive composition layer was bonded to one surface of the substrate with the transparent conductive layer by a roll-to-roll method using a vacuum laminator (MCK, 100 ℃ C., line pressure: 1.0MPa, line speed: 0.5 m/min) to obtain a laminate.

In the same manner as in the above method, the transfer film 6 including the 2 nd photosensitive composition layer was bonded to the surface of the substrate with the transparent conductive layer on the laminate on the side opposite to the transfer film 6, to obtain a laminate.

The obtained laminate comprises at least a temporary support, a 1 st photosensitive composition layer, a substrate with a transparent conductive layer, a 2 nd photosensitive composition layer, and a temporary support in this order.

The obtained laminate was subjected to a pressure defoaming treatment for 30 minutes under conditions of 0.6MPa and 60 ℃.

Next, the temporary support is not peeled off, and the line and space pattern masks are arranged on both surfaces of the laminate. The 1 st photosensitive composition layer and the 2 nd photosensitive composition layer were simultaneously exposed from both sides with an ultrahigh pressure mercury lamp through masks disposed on both sides.

The exposed laminate was subjected to development and etching of the transparent conductive layer in the same order as in example 1, thereby obtaining a substrate having transparent conductive patterns on both sides of comparative example 2.

[ examples 15, 16, 18 and 19]

A substrate having transparent conductive patterns of examples 15, 16, 18 and 19 on both sides was obtained in the same manner as in example 1 except that the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer were formed using the transfer films shown in tables 5 to 7 of the subsequent stage and the exposure amount and the development time were adjusted.

[ example 17]

A substrate having transparent conductive patterns of example 17 on both sides was obtained in the same manner as in example 14 except that the photosensitive composition layer 1 and the photosensitive composition layer 2 were formed using the transfer films shown in table 5 at the subsequent stage, and the exposure amount and the development time were adjusted.

< evaluation >

[ defectiveness ]

The transparent conductive pattern corresponding to the pattern of 15 μm of the exposure mask on the substrate having the transparent conductive patterns on both sides obtained above was observed with an optical microscope for a defect state of the transparent conductive pattern, and evaluated according to the following criteria.

(reference for evaluation of defects)

A: no defect of the wiring pattern could be confirmed.

B: several defects of the wiring less than 25% of the width of the wiring were observed.

C: several wiring defects of 25% or more and less than 75% of the wiring width were observed.

D: a defect of 75% or more of the wiring width was observed.

E: a short circuit between the wirings was confirmed.

[ resist Pattern Cross-sectional shape ]

The cross-sectional shapes of portions of the 1 st resist pattern and the 2 nd resist pattern having a line width of 15 μm were observed with a Scanning Electron Microscope (SEM) with respect to the laminate before etching of the transparent conductive layer, and evaluated according to the following criteria.

(evaluation criteria for resist Pattern Cross-sectional shape)

A: the resist pattern is substantially rectangular, and the difference between the width of the resist pattern at the half thickness portion of the resist pattern and the pattern width of the upper surface is less than 0.2 [ mu ] m.

B: the resist pattern has a reverse tapered shape, and the difference between the width of the resist pattern in the half thickness portion of the resist pattern and the pattern width of the upper surface is 0.2 μm or more and less than 0.8 μm.

C: the resist pattern has a reverse tapered shape, and the difference between the width of the resist pattern in the half thickness portion of the resist pattern and the pattern width of the upper surface is 0.8 [ mu ] m or more.

[ resist Pattern linewidth unevenness ]

The laminate before etching of the transparent conductive layer was observed by SEM at the portions of the 1 st resist pattern and the 2 nd resist pattern having a line width of 15 μm, and the maximum value-minimum value of the line width (also referred to as "line width variation") in the length range of 100 μm was calculated and evaluated according to the following criteria.

(evaluation criteria for resist Pattern line Width unevenness)

A: the line width variation is less than 1.0 μm.

B: the variation value of the line width is more than 1.0 μm and less than 3.0 μm.

C: the line width variation is 3.0 μm or more.

The evaluation results of the examples and comparative examples are shown in tables 4 to 7.

In tables 4 to 7, the description of "double-sided substrate" in the column of the substrate indicates the case where the 1 st photosensitive composition layer was formed using a substrate having transparent conductive layers on both sides. On the other hand, the expression "single-sided substrate" indicates a case where the 1 st photosensitive composition layer is formed using a substrate having a transparent conductive layer on only one side.

In Table 4, "ratio of dissolution time" represents the ratio of the dissolution time of the exposed portions of the 1 st photosensitive composition layer to the dissolution time of the unexposed portions of the 2 nd photosensitive composition layer.

In Table 5, "ratio of dissolution time" represents the ratio of the dissolution time of the unexposed portions of the 1 st photosensitive composition layer to the dissolution time of the exposed portions of the 2 nd photosensitive composition layer.

In Table 6, "the ratio of dissolution times" indicates the ratio of the dissolution time of the exposed portion of the 1 st photosensitive composition layer to the dissolution time of the exposed portion of the 2 nd photosensitive composition layer.

In Table 7, "the ratio of dissolution times" represents the ratio of the dissolution time of the unexposed portion of the 1 st photosensitive composition layer to the dissolution time of the unexposed portion of the 2 nd photosensitive composition layer.

[ Table 4]

[ Table 5]

According to the comparison of the examples with the comparative example, it was confirmed that the transparent conductive pattern formed by the manufacturing method of the present invention is less likely to cause poor conduction.

From the comparison of examples 3 and 5, it was confirmed that when the dissolution time of the 1 st photosensitive composition layer in the 2 nd developing solution was 100 seconds or more, the suppression of the line width unevenness of the resist pattern was more excellent.

From comparison of examples 3, 9, and 10 with the other examples, it was confirmed that when the absorbance of at least one of the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer at the wavelength of light used for exposure was 0.7 or less, the resist pattern cross-sectional shape and the resist pattern line width unevenness were more excellent in suppression.

From comparison of examples 3, 8, 9 and 10 with the other examples, it was confirmed that when the absorbance of at least one of the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer at the wavelength of light used for exposure is 0.4 or less, the resist pattern cross-sectional shape and the resist pattern line width unevenness are more excellent in suppression.

From comparison of example 12 with other examples, it was confirmed that when the ratio of the dissolution times exceeds 2.5, the defect suppression property is more excellent.

Based on comparison of examples 3, 5, 7 and 12 with other examples, it was confirmed that the defect-inhibiting property is more excellent when the ratio of the dissolution times exceeds 3.0.

Further, from the results of table 5, it was confirmed that even when the 1 st photosensitive composition layer was a positive photosensitive composition layer and the 2 nd photosensitive composition layer was a positive photosensitive composition layer, the transparent conductive pattern formed by the manufacturing method of the present invention hardly causes a conduction failure.

From the results of table 6, it was confirmed that even when the 1 st photosensitive composition layer was a negative photosensitive composition layer and the 2 nd photosensitive composition layer was a positive photosensitive composition layer, the transparent conductive pattern formed by the manufacturing method of the present invention hardly causes poor conduction.

From the results of table 6, it was confirmed that even when the 1 st photosensitive composition layer was a positive photosensitive composition layer and the 2 nd photosensitive composition layer was a negative photosensitive composition layer, the transparent conductive pattern formed by the manufacturing method of the present invention hardly had poor conductivity.

In addition, even when the 1 st photosensitive composition layer is a negative photosensitive composition layer and the 2 nd photosensitive composition layer is a positive photosensitive composition layer, or the 1 st photosensitive composition layer is a positive photosensitive composition layer and the 2 nd photosensitive composition layer is a negative photosensitive composition layer, and the order of example 14 (i.e., using the single-sided substrate described in tables 4 to 7) is formed in the transparent conductive pattern having the transparent conductive patterns on both sides, the transparent conductive pattern formed by the manufacturing method of the present invention is difficult to cause poor conduction.

Description of the symbols

10-transfer film, 11-temporary support, 13-intermediate layer, 15-photosensitive composition layer, 17-composition layer, 19-protective film.

Claims

1. A method of manufacturing a laminate comprising a transparent conductive pattern, comprising:

a step A1 of preparing a substrate with a transparent conductive layer, the substrate having a substrate transparent to an exposure wavelength, A1 st transparent conductive layer transparent to the exposure wavelength and disposed on one surface side of the substrate, and a2 nd transparent conductive layer transparent to the exposure wavelength and disposed on the other surface side of the substrate;

a step A2 of forming a1 st photosensitive composition layer on one surface of the substrate with the transparent conductive layer;

a dissolution time of an exposed film obtained by subjecting the 1 st photosensitive composition layer to full-surface exposure under the same exposure conditions as in the step A3 in the 2 nd developing solution is 2.0 times or more the dissolution time of the 2 nd photosensitive composition layer in the 2 nd developing solution;

a dissolution time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to the entire surface exposure under the same exposure condition as the step A3 in the 2 nd developing solution is 2.0 times or more a dissolution time of the exposed film obtained by subjecting the 2 nd photosensitive composition layer to the entire surface exposure under the same exposure condition as the step A5 in the 2 nd developing solution;

the dissolution time of the 1 st photosensitive composition layer in the 2 nd developing solution is more than 2.0 times of the dissolution time of an exposed film obtained by performing whole surface exposure on the 2 nd photosensitive composition layer under the same exposure condition as the step A5 in the 2 nd developing solution;

the dissolving time of the 1 st photosensitive composition layer in the 2 nd developing solution is more than 2.0 times of the dissolving time of the 2 nd photosensitive composition layer in the 2 nd developing solution.

2. The method for manufacturing a laminate comprising a transparent conductive pattern according to claim 1,

a dissolution time of an exposed film obtained by subjecting the 1 st photosensitive composition layer to entire surface exposure under the same exposure conditions as in the step A3 in the 2 nd developing solution is 100 seconds or more;

3. A method of manufacturing a laminate comprising a transparent conductive pattern, comprising:

a step (B1) of preparing a substrate with a transparent conductive layer, the substrate with the transparent conductive layer having a substrate transparent to an exposure wavelength and a 1 st transparent conductive layer transparent to the exposure wavelength and disposed on one surface side of the substrate;

a dissolution time of an exposed film obtained by subjecting the 1 st photosensitive composition layer to full-surface exposure under the same exposure conditions as in the step B3 in the 2 nd developing solution is 2.0 times or more the dissolution time of the 2 nd photosensitive composition layer in the 2 nd developing solution;

a dissolution time of the exposed film obtained by subjecting the 1 st photosensitive composition layer to the entire surface exposure under the same exposure condition as in the step B3 in the 2 nd developing solution is 2.0 times or more a dissolution time of the exposed film obtained by subjecting the 2 nd photosensitive composition layer to the entire surface exposure under the same exposure condition as in the step B6 in the 2 nd developing solution;

the dissolution time of the 1 st photosensitive composition layer in the 2 nd developing solution is more than 2.0 times of the dissolution time of an exposed film obtained by performing whole surface exposure on the 2 nd photosensitive composition layer under the same exposure condition as the step B6 in the 2 nd developing solution;

4. The method for manufacturing a laminate comprising a transparent conductive pattern according to claim 3,

a dissolution time of an exposed film obtained by subjecting the 1 st photosensitive composition layer to full-surface exposure under the same exposure conditions as in the step B3 in the 2 nd developing solution is 100 seconds or more;

5. The method for manufacturing a laminated body including a transparent conductive pattern according to any one of claims 1 to 4,

6. The method for manufacturing a laminate comprising a transparent conductive pattern according to any one of claims 1 to 4,

the transmittance of the base material with respect to an exposure wavelength is 50% or more.

7. The method for manufacturing a laminated body including a transparent conductive pattern according to any one of claims 1 to 4,

8. The method for manufacturing a laminated body including a transparent conductive pattern according to any one of claims 1 to 4,

9. The method for manufacturing a laminated body including a transparent conductive pattern according to any one of claims 1 to 4,

10. The method for manufacturing a laminate comprising a transparent conductive pattern according to any one of claims 1 to 4,

11. The method for manufacturing a laminated body including a transparent conductive pattern according to any one of claims 1 to 4,

the 1 st photosensitive composition layer and the 2 nd photosensitive composition layer are photosensitive composition layers of the same composition.

12. A method for manufacturing a touch panel, comprising the method for manufacturing a laminate containing a transparent conductive pattern according to any one of claims 1 to 11.