CN115480451A - Laminate, substrate with transparent conductive layer, and pattern formation method - Google Patents

Abstract

The invention provides a laminated body which can obtain a pattern with excellent exposure fogging inhibition performance and excellent resolution. Another object of the present invention is to provide a substrate with a transparent conductive layer and a pattern forming method. The laminate comprises a 1 st composition layer, a 1 st transparent conductive layer, a substrate, a 2 nd transparent conductive layer and a 2 nd composition layer in this order, wherein the 1 st composition layer has a 1 st photosensitive layer, the 2 nd composition layer has a 2 nd photosensitive layer, and the laminate satisfies at least one of requirements 1 to 3.

Description

Laminate, substrate with transparent conductive layer, and pattern formation method

Technical Field

The present invention relates to a laminate, a substrate with a transparent conductive layer, and a pattern forming method.

Background

A patterning method is known in which a laminate having layers to be etched on both surfaces of a base material is used and patterning is performed by photolithography. 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, a method of forming patterns of different shapes on both surfaces of a base material is used to manufacture a touch sensor wiring.

For example, patent document 1 discloses a laminate having etched layers on both surfaces of a base material as a laminate used in the above-described pattern forming method.

Patent document 1: international publication No. 2019/022090

The present inventors have studied the laminate described in patent document 1, and as a result, have found that when both surfaces of a laminate having a transparent conductive layer and a composition layer (layer including a photosensitive layer) on 2 surfaces of a transparent substrate facing each other in this order from the transparent substrate side are exposed simultaneously or sequentially, the resolution of the obtained pattern is poor.

Further, it has been found that, when the conventional laminated body other than the above is simultaneously or sequentially exposed, there is a phenomenon (hereinafter, also referred to as "exposure fogging") in which exposure light of one photosensitive layer causes the other photosensitive layer to be also exposed.

That is, when both surfaces of the conventional laminate are exposed simultaneously or sequentially, it is difficult to achieve both the exposure fogging suppression property and the resolution of the obtained pattern.

Disclosure of Invention

Accordingly, an object of the present invention is to provide a laminate capable of obtaining a pattern having excellent exposure fogging suppression properties and also having excellent resolution. Another object of the present invention is to provide a substrate with a transparent conductive layer and a pattern forming method.

As a result of earnest results of the above problems, the present inventors have found that the above problems can be solved by the following configuration.

A laminate comprising a 1 st composition layer, a 1 st transparent conductive layer, a substrate, a 2 nd transparent conductive layer and a 2 nd composition layer in this order,

the 1 st composition layer has a 1 st photosensitive layer,

the 2 nd composition layer has a 2 nd photosensitive layer,

the laminate satisfies at least one of requirements 1 to 3.

Requirement 1: the above-mentioned substrate is a light-absorbing substrate comprising a light absorber having an absorption maximum wavelength in a range of 200 to 450nm in wavelength.

Requirement 2: the substrate is a transparent substrate, and the laminate further includes a layer containing the light absorbing agent between the 1 st photosensitive layer and the 2 nd photosensitive layer.

Requirement 3: the substrate has a minimum transmittance of 70% or more at a wavelength of 350 to 450nm, and the laminate further has a layer containing the light absorber between the 1 st photosensitive layer and the 2 nd photosensitive layer.

[ 2 ] the laminate according to [ 1 ], 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.

[ 3 ] the laminate according to [ 1 ] or [ 2 ], which satisfies at least one of the above requirement 2 and the above requirement 3,

the layer containing the light absorbing agent is disposed between the 1 st photosensitive layer and the 1 st transparent conductive layer or between the 2 nd photosensitive layer and the 2 nd transparent conductive layer.

[ 4 ] the laminate according to any one of [ 1 ] to [ 3 ], which satisfies at least one of the above requirement 2 and the above requirement 3,

a layer containing the light absorber is disposed between the 1 st transparent conductive layer and the transparent base material or between the 2 nd transparent conductive layer and the transparent base material.

[ 5 ] the laminate according to [ 1 ] or [ 2 ], which satisfies the above requirement 1.

[ 6 ] the laminate according to any one of [ 1 ] to [ 5 ], wherein,

at least one of the 1 st composition layer and the 2 nd composition layer has at least 1 selected from the group consisting of an intermediate layer and a thermoplastic resin layer.

[ 7 ] the laminate according to any one of [ 1 ] to [ 6 ], wherein,

the 1 st photosensitive layer and the 2 nd photosensitive layer include an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.

[ 8 ] the laminate according to any one of [ 1 ] to [ 7 ], wherein,

the 1 st photosensitive layer and the 2 nd photosensitive layer contain a heterocyclic compound.

[ 9 ] the laminate according to any one of [ 1 ] to [ 8 ], wherein,

the molecular weight of the light absorber is 20000 or less.

[ 10 ] A substrate with a transparent conductive layer, which comprises a 1 st transparent conductive layer, a substrate and a 2 nd transparent conductive layer in this order,

the transmittance of the base material at a wavelength of 550nm is 70% or more,

the transmittance of the base material at least 1 position in the wavelength 365nm, the wavelength 405nm and the wavelength 436nm is 20% or less.

[ 11 ] the substrate with a transparent conductive layer according to [ 10 ], 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.

[ 12 ] the substrate with a transparent conductive layer according to [ 10 ] or [ 11 ], wherein,

the above-mentioned substrate is a light-absorbing substrate comprising a light absorber having an absorption maximum wavelength in a range of 200 to 450nm in wavelength.

[ 13 ] the substrate with a transparent conductive layer according to [ 12 ], wherein,

the molecular weight of the light absorber is 20000 or less.

[ 14 ] A pattern forming method of subjecting the 1 st photosensitive layer and the 2 nd photosensitive layer in the laminate according to any one of [ 1 ] to [ 9 ] to exposure treatment and development treatment,

the pattern forming method includes:

exposing the 1 st photosensitive layer;

exposing the 2 nd photosensitive layer;

and a developing step of developing the exposed 1 st photosensitive layer and the exposed 2 nd photosensitive layer to form a pattern.

[ 15 ] the pattern forming method according to [ 14 ], wherein,

the step of exposing the 1 st photosensitive layer and the step of exposing the 2 nd photosensitive layer are performed simultaneously or sequentially.

Effects of the invention

According to the present invention, a laminate capable of obtaining a pattern having excellent exposure fogging suppression and excellent resolution can be provided. Further, according to the present invention, a substrate with a transparent conductive layer and a pattern forming method can be provided.

Detailed Description

The present invention will be described in detail below.

The following symbols in the present specification are given their meanings.

The numerical range represented by "to" means a range including numerical values described before and after "to" as a lower limit and an upper limit.

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 it is not clearly distinguished from other steps.

Unless otherwise specified, the hue is a value measured by a colorimeter (CR-221, minolta Co., ltd).

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

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 a composition layer (for example, a photosensitive layer, an intermediate layer, and a 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 when exposing the photosensitive layer (the 1 st photosensitive layer and the 2 nd photosensitive layer), and refers to the wavelength of light reaching the photosensitive layer. For example, when a photosensitive layer is exposed to light through a filter having wavelength selectivity, the wavelength of light before passing through the filter does not match the exposure wavelength. In addition, "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 "main wavelength" refers to a wavelength of light having the strongest intensity among wavelengths of light (i.e., exposure wavelengths) reaching the photosensitive layers (the 1 st photosensitive layer and the 2 nd photosensitive layer). For example, the light reaching the photosensitive layer has a wavelength of 365nm and a wavelength of 436nm, and in the case of exposure light having an intensity of 365nm which is greater than an intensity of 436nm, the dominant wavelength of the exposure light is 365nm. In the present specification, "exposure light" refers to light for exposing the photosensitive layer.

In the present specification, unless otherwise specified, "transparent" means that the transmittance at the main wavelength is 30% or more in the exposure wavelength. The transmittance is preferably 50% or more, more preferably 80% or more, and further 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).

[ laminate ]

The laminate of the present invention is a laminate comprising a 1 st composition layer, a 1 st transparent conductive layer, a substrate, a 2 nd transparent conductive layer and a 2 nd composition layer in this order,

the 1 st composition layer has a 1 st photosensitive layer,

the 2 nd composition layer has a 2 nd photosensitive layer,

the laminate satisfies at least one of requirements 1 to 3.

Requirement 1: the substrate is a light-absorbing substrate comprising a light absorber having a maximum absorption wavelength in the wavelength range of 200 to 450 nm.

Requirement 2: the substrate is a transparent substrate, and the laminate further has a layer containing the light absorbing agent (hereinafter, also referred to as a "light absorbing layer") between the 1 st photosensitive layer and the 2 nd photosensitive layer.

Requirement 3: the lowest transmittance of the substrate at a wavelength of 350 to 450nm is 70% or more, and the laminate further has a layer containing a light absorbing agent between the 1 st photosensitive layer and the 2 nd photosensitive layer.

Hereinafter, the 1 st composition layer and the 2 nd composition layer are also collectively referred to as "composition layers". The 1 st photosensitive layer and the 2 nd photosensitive layer are also collectively referred to as "photosensitive layers". The 1 st transparent conductive layer and the 2 nd transparent conductive layer are also collectively referred to as "transparent conductive layers". The substrate having a minimum transmittance at a wavelength of 350 to 450nm of 70% or more is also referred to as "specific substrate".

The details of the mechanism of action of the laminate of the present invention to exhibit the desired effect are not clear, but the present inventors presume as follows.

The laminate of the present invention is characterized by satisfying at least one of requirements 1 to 3. For example, when the laminate 1 satisfying the requirement 1 is irradiated with the 1 st exposure light from the side of the 1 st composition layer opposite to the light-absorbing substrate, the 1 st photosensitive layer in the 1 st composition is exposed to light. On the other hand, it is presumed that the 2 nd photosensitive layer in the 2 nd composition layer opposed to the 1 st composition layer absorbs a part or all of the 1 st exposure light by the light absorbing base material, and therefore exposure fogging can be suppressed because the 1 st exposure light is not easily sensitized. It is presumed that the same mechanism of action is excellent in the exposure fogging suppression property also in the laminate satisfying at least one of requirement 2 and requirement 3. The laminate of the present invention satisfying at least one of requirements 1 to 3 is also excellent in resolution.

Hereinafter, the case where at least one of the effects of the exposure fogging suppression property and the resolution is more excellent is also referred to as the case where the effect of the present invention is more excellent.

The components constituting the laminate of the present invention will be described in detail below.

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.

[ Condition 1 to Condition 3 ]

The laminate satisfies at least one of requirements 1 to 3.

Requirement 1: the substrate is a light-absorbing substrate comprising a light absorber having a maximum absorption wavelength in the wavelength range of 200 to 450 nm.

Requirement 2: the substrate is a transparent substrate, and the laminate further has a light-absorbing layer between the 1 st photosensitive layer and the 2 nd photosensitive layer.

Requirement 3: the lowest transmittance of the substrate at a wavelength of 350 to 450nm is 70% or more, and the laminate further has a layer containing a light absorbing agent between the 1 st photosensitive layer and the 2 nd photosensitive layer.

When the laminate satisfies requirement 1, the laminate may further include a light absorbing layer between the 1 st photosensitive layer and the 2 nd photosensitive layer.

A preferred embodiment of the light absorbing layer in the laminate satisfying requirement 1 is the same as the embodiment in which the transparent substrate in requirement 2 is referred to as a light absorbing substrate. For example, the "light absorbing layer" is preferably disposed between the 1 st transparent conductive layer and the transparent substrate. The expression "the light absorbing layer" may be referred to as "the light absorbing layer is preferably disposed between the 1 st transparent conductive layer and the light absorbing substrate. ".

When the laminate satisfies at least one of requirements 2 and 3, the light absorbing layer is preferably disposed between the 1 st photosensitive layer and the 1 st transparent conductive layer or between the 2 nd photosensitive layer and the 2 nd transparent conductive layer. Further, the light absorbing layer is preferably disposed between the 1 st transparent conductive layer and the transparent base material or the specific base material, or between the 2 nd transparent conductive layer and the transparent base material or the specific base material.

The stacked body may have 1 or 2 or more light absorbing layers.

When there are 2 or more light absorbing layers, all of the light absorbing layers may be disposed between the 1 st photosensitive layer and the transparent substrate or the specific substrate, or between the 2 nd photosensitive layer and the transparent substrate or the specific substrate, or one of the light absorbing layers may be disposed between the 1 st photosensitive layer and the transparent substrate or the specific substrate, or the other may be disposed between the 2 nd photosensitive layer and the transparent substrate or the specific substrate.

[ substrate ]

The laminate has a base material.

When the laminate satisfies requirement 1, the substrate is a light-absorbing substrate. When the laminate satisfies requirement 2, the substrate is a transparent substrate. When the laminate satisfies requirement 3, the substrate is a specific substrate.

The light-absorbing substrate is not particularly limited as long as it is a substrate containing a light absorber described later.

The transparent substrate is not particularly limited as long as it has a transmittance at the above-specified dominant wavelength.

The specific substrate is not particularly limited as long as the minimum transmittance at a wavelength of 350 to 450nm is 70% or more. The specific substrate has a minimum transmittance of 70% or more among transmittances at respective wavelengths in a range of 350 to 450 nm. In other words, the transmittance of the specific substrate is 70% or more at any wavelength in the range of 350 to 450 nm.

The minimum transmittance is preferably 80% or more, and more preferably 90% or more. The upper limit is less than 100% in many cases. The transmittance can be measured by a known transmittance measuring instrument (for example, V-700 series manufactured by JASCO Corporation).

The main material constituting the light-absorbing substrate, the transparent substrate and the specific substrate is not particularly limited, and examples thereof include resin and glass. Examples of the light-absorbing substrate, the transparent substrate, and the specific substrate include a resin substrate such as a resin film and a glass substrate.

Examples of the material of the resin base include polyamide resin, polyethylene terephthalate resin, polyethylene naphthalate resin, cycloolefin resin, polyimide resin, and polycarbonate resin.

The transparent substrate and the specific substrate are preferably resin films, more preferably polyamide films, polyethylene terephthalate films, cycloolefin films, polyethylene naphthalate films, polyimide films, or polycarbonate films, and still more preferably polyethylene terephthalate films.

When the light absorbing substrate is formed of a resin film, the light absorbing substrate is a resin film containing a predetermined light absorbing agent.

The average thickness of the light-absorbing substrate, the transparent substrate and the specific 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 average thickness of the base material such as the light-absorbing base material, the transparent base material, and the specific base material can be measured by the following method. Any 10 places of a cross section in a direction (thickness direction) perpendicular to the main surface of the substrate (light-absorbing substrate, transparent substrate, and specific substrate) were observed by a Scanning Electron Microscope (SEM). The average thickness of the base materials (light-absorbing base material, transparent base material, and specific base material) can be measured by measuring the thickness of each base material from the obtained observation image and arithmetically averaging the measured values.

The transmittance of the substrate (light-absorbing substrate, transparent substrate, and specific substrate) at a wavelength of 550nm is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. The upper limit is less than 100% in many cases.

When the substrate is a light-absorbing substrate, the light-absorbing substrate preferably has a transmittance of 20% or less, more preferably 10% or less, at least 1 point of the wavelengths 365nm, 405nm and 436nm. The lower limit is more than 0% in many cases. Further, at least one of the wavelength 365nm and the wavelength 436nm is also preferable as the above-described preferable mode of transmittance.

< light absorber >

The light absorber is a light absorber having a maximum absorption wavelength in the wavelength range of 200 to 450 nm.

The light absorber is preferably not included in the layers other than the light-absorbing substrate and the light-absorbing layer. In other words, the 1 st composition layer, the 2 nd composition layer, the 1 st transparent conductive layer, and the 2 nd transparent conductive layer preferably do not contain a light absorbing agent.

The maximum absorption wavelength of the light absorber is in the range of 200 to 450nm, preferably 300 to 450nm, more preferably 350 to 450nm, still more preferably 365nm, 405nm or 436nm, and particularly preferably 365nm or 436nm.

In addition, when the light absorber has a plurality of absorption maxima in the wavelength range of 200 to 450nm, the absorption maximum in the absorption maxima is preferably the above-mentioned preferred embodiment.

Examples of the light absorber include organic compounds, for example, benzotriazole compounds, benzophenone compounds, benzoate compounds, salicylate compounds, triazine compounds, cyanoacrylate compounds, carbon black, salicylate compounds, and benzoxazine compounds, and at least 1 selected from benzotriazole compounds and triazine compounds is preferable.

Examples of the benzotriazole compound include benzotriazole and a derivative thereof (substituted benzotriazole). More specifically, 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylethyl) phenol, 2- [ 5-chloro (2H) -benzotriazol-2-yl ] -4-methyl-6- (tert-butyl) phenol, 2- (2H-benzotriazol-yl) -4, 6-di-tert-amylphenol, 2- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol, and mixtures, modifications, polymers, and derivatives thereof can be cited.

Examples of the triazine compound include triazine and a derivative thereof (substituted triazine). More specifically, there may be mentioned 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ (hexyl) oxy ] -phenol, 2- [4- [ (2-hydroxy-3-dodecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- [ (2-hydroxy-3-tridecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2, 4-bis (2, 4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -s-triazine, and mixtures, modifications, polymers and derivatives thereof.

Examples of the benzophenone compound include benzophenone and a derivative thereof (substituted benzophenone).

Examples of the salicylate compound include metal salts of alkylsalicylic acids and derivatives thereof (metal salts of alkylsalicylic acids having substituents).

Examples of the cyanoacrylate compound include cyanoacrylate and a derivative thereof (a substituted cyanoacrylate).

Examples of the salicylate compound include compounds having a salicylate ester bond.

Examples of the benzoxazine compound include benzoxazines and derivatives thereof (substituted benzoxazines).

The light absorber is preferably a low molecular compound. Specifically, the molecular weight of the light absorber is preferably 20000 or less, more preferably 5000 or less, and further preferably 1000 or less. The lower limit is usually 50 or more.

The light absorbing agent may be used singly in 1 kind or 2 or more kinds.

The content of the light absorbing agent is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 10.0% by mass, and still more preferably 0.5 to 5.0% by mass, based on the total mass of the light absorbing substrate.

The content of the light absorbing agent is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 10.0% by mass, and still more preferably 1.0 to 5.0% by mass, based on the total mass of the light absorbing layer.

[ light-absorbing layer ]

The laminate has a light-absorbing layer when it satisfies at least one of requirements 2 and 3.

When the laminate satisfies requirement 1, the laminate may further include a light-absorbing layer.

The light absorbing layer is not particularly limited as long as it is a layer containing a light absorbing agent.

The light absorbing agent is the same as the light absorbing agent that the light absorbing substrate may contain, and preferably is the same.

Examples of the component contained in the light absorbing layer include components contained in the 1 st thermoplastic resin layer and the 2 nd thermoplastic resin layer described below.

The light absorbing layer preferably contains at least 1 selected from the group consisting of a light absorber, a resin, a polymerizable compound, a compound that generates an acid, a base, or a radical by light, and other additives. The resin, the polymerizable compound, the compound which generates an acid, a base or a radical by light, and other additives are the same as the respective components which can be contained in the 1 st thermoplastic resin layer and the 2 nd thermoplastic resin layer described later, and preferred embodiments are also the same.

The average thickness (layer thickness) of the light-absorbing layer is preferably 1 μm or more, more preferably 2 μm or more. 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.

The method of measuring the average thickness includes a method of measuring the average thickness of the base material.

[ layer of composition ]

The laminate has a 1 st composition layer and a 2 nd composition layer.

The structure of the composition layer is preferably, for example, the structures represented by (1) to (3), and more preferably the structure represented by (3).

The 1 st composition layer and the 2 nd composition layer may have the same structure or 1 of different structures, and preferably have the same structure.

For example, the 1 st composition layer and the 2 nd composition layer having the same structure means that the 1 st composition layer and the 2 nd composition layer have a layer structure represented by (1). For example, the 1 st composition layer and the 2 nd composition layer are different from each other means that the 1 st composition layer has a layer structure represented by (1) and the 2 nd composition layer has a layer structure represented by (3).

(1) (transparent conductive layer side)/photosensitive layer

(2) (transparent conductive layer side)/photosensitive layer/thermoplastic resin layer

(3) (transparent conductive layer side)/photosensitive layer/intermediate layer/thermoplastic resin layer

The photosensitive layer in each of the structures (1) to (3) may be any of 1 st photosensitive layer and 2 nd photosensitive layer. The transparent conductive layer side is the 1 st transparent conductive layer in the case where the photosensitive layer is the 1 st photosensitive layer, and is the 2 nd transparent conductive layer in the case where the photosensitive layer is the 2 nd photosensitive layer.

In the composition layer of the above (3), the intermediate layer may be formed into 2 layers. Specifically, the structure "photosensitive layer/intermediate layer a/intermediate layer B/thermoplastic resin layer" may be used. The intermediate layer a and the intermediate layer B may be the same or different.

The composition layer may be used as a resist or a wiring protective film. When the composition layer is used as a resist, the composition layer preferably has the structures (1) to (3) described above, for example. When the composition layer is used as a wiring protective film, the composition layer preferably has the structure of (1) above, for example.

Examples of the composition layer include embodiment 1 and embodiment 2, and embodiment 1 is preferred. Embodiment 1 is suitable for etching applications, and embodiment 2 is suitable for a wiring protective film.

Further, it is also preferable that at least one of the 1 st composition layer and the 2 nd composition layer has at least 1 kind selected from the group consisting of the intermediate layer and the thermoplastic resin layer.

< 1 st embodiment >

< photosensitive layer >

The composition layer of embodiment 1 has a 1 st photosensitive layer and a 2 nd photosensitive layer.

In addition, the 1 st photosensitive layer and the 2 nd photosensitive layer preferably do not contain a light absorbing agent.

The 1 st photosensitive layer and the 2 nd photosensitive layer may have the same structure or 1 of different structures, and preferably have the same structure. For example, the 1 st photosensitive layer and the 2 nd photosensitive layer have the same structure means that the 1 st photosensitive layer and the 2 nd photosensitive layer contain the same components and the contents thereof are also the same.

The photosensitive 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. Also, the above resin preferably includes an alkali-soluble resin.

The 1 st photosensitive 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 1 st photosensitive layer.

The 2 nd photosensitive 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 2 nd photosensitive layer.

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

(resin)

The photosensitive 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 line width and deterioration of resolution when a 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 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, a styrene dimer, a styrene trimer, and the like), preferably a monomer having an aralkyl group or styrene, and more preferably styrene.

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 further preferably 30.0 to 55.0% by mass, based on the total mass of the resin. When the photosensitive 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 benzyl chloride (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 85.0% by mass, and further preferably 30.0 to 85.0% 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 later-described 1 st monomer and/or at least 1 later-described 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 type of the 1 st monomer described later, and more preferably obtained by polymerizing at least 1 type of the 1 st monomer with at least 1 type of the 2 nd monomer described later.

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) acrylic esters 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 10.0 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 containing 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 (6-hydroxy-1-menthyl) acrylate, 3, 6-trimethylheptyl- (meth) acrylate, 3-trimethyl-1-menthyl) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [ 4.1.0 ] heptyl- (meth) acrylate, (norbornyl) 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 tricyclodecyl (meth) acrylate is preferable, and cyclohexyl (meth) acrylate, (norbornyl (meth) acrylate, (isobornyl (meth) acrylate, 2-adamantyl- (meth) acrylate, or tricyclodecyl (meth) acrylate is more preferable.

From the viewpoint of further improving the effect of the present invention, the resin preferably has a polymerizable group, more preferably contains a structural unit having a polymerizable group, and still 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.

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 still more preferably has an acryloyl group or a methacryloyl group and an epoxy group.

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

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, still 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.

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 reaction, 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 further 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 ℃.

The acid value of the resin is preferably 220mgKOH/g or less, more preferably less than 200mgKOH/g, and still more preferably less than 170mgKOH/g. The lower limit is preferably 10mgKOH/g or more, more preferably 50mgKOH/g or more, and still more preferably 70mgKOH/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 determined 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, and still more preferably 20,000 to 60,000.

When the weight average molecular weight is 500,000 or less, the resolution and 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 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 dispersity (Mw/Mn) of the resin is preferably 1.0 to 6.0, more preferably 1.0 to 4.0, and still more preferably 1.0 to 3.0.

The photosensitive 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 may be used alone in 1 or 2 or more.

The content of the resin 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 1 st photosensitive layer or the 2 nd photosensitive layer. When the content of the resin is 90.0 mass% or less with respect to the total mass of the photosensitive layer, the development time can be controlled. When the content of the resin is 10.0 mass% or more based on the total mass of the photosensitive layer, the edge melting resistance can be improved.

Examples of the method for synthesizing the 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 monomers with a solvent such as acetone, methyl ethyl ketone, or 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 reaction is completed, a solvent may be further added to adjust the concentration to a desired concentration.

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 layer may contain a polymerizable compound having a polymerizable group.

The "polymerizable compound" is a compound that 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.

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 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. The number of alkyleneoxy groups added to the polymerizable compound per molecule is preferably 2 to 30, more preferably 2 to 20.

From the viewpoint that the photosensitive layer is more excellent in balance between the photosensitivity and the resolution and the peelability, 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 40.0% by mass or more, and further preferably 55.0% 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 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 further preferably 50.0% by mass or less. That is, all of the polymerizable compounds contained in the photosensitive 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 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, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a 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 the resolution by suppressing swelling of the photosensitive 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), with the bisphenol a structure being 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 polyalkoxy) phenyl) propane include ethoxylated bisphenol a dimethacrylate (BPE series, SHIN-NAKAMURA CHEMICAL Co., ltd. System), such as 2, 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (FA-324m, showa Denko Materials Co., ltd. System), 2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane and 2, 2-bis (4- (methacryloyloxypentaethoxy) phenyl) propane (fan-NAKAMURA CHEMICAL Co., ltd. System), 2-bis (4- (methacryloyloxydodecaethoxytetrapropoxy) phenyl) propane (FA-3200my, showa Denko Materials Co., ltd. System), and ethoxylated (10) bisphenol a diacrylate (esnk ter a-BPE-10, SHIN-nakai, nakai Co., ltd. System).

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

[ chemical formula 1]

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- (A-O) -and- (B-O) -may be either random or block 1. In the case of a block, any 1 of- (A-O) -and- (B-O) -may be on the bisphenyl side.

The number 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 mass% or more, more preferably 20.0 mass% or more, and further preferably 25.0 mass% or more with respect to the total mass of the 1 st photosensitive layer or the 2 nd photosensitive layer, from the viewpoint of further improving the 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).

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

Other polymerizable compounds

The photosensitive 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.), ethylene glycol dimethacrylate, 1, 10-decanediol diacrylate and neopentyl glycol di (meth) acrylate.

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, glycerol 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., manufactured by Ltd., kayarad (registered trademark) DPCA-20 and SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd., A-9300-1CL, etc.), alkylene oxide-modified (meth) acrylate compounds (e.g., nippon Kayaku Co., manufactured by Ltd., karad (registered trademark) RP-1040, SHIN-NAKAMURA CHEMICAL Co., ATM-35E and A-9300, DAICEL-ALLNEX LTD, manufactured by EBECRYL (registered trademark) 135, etc.), ethoxylated glycerol esters (e.g., SHIN-NAKAMURA CHEMICAL Co., ltd., A-GLY-9E, etc.), ARONIX (registered trademark) TO-2349 (TOAGOSCO., manufactured by TOAGOSCO., ARIN-520, AROX-NAKAMURA CHEMICAL Co., manufactured by Ltd., LTEI).

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) (e.g., TO-2349, M-520, and M-510, manufactured by LTD., TOAGOSEI CO., 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 3000, more preferably 280 to 2200, and still more preferably 300 to 2200.

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.

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

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 30.0 to 70.0% by mass, based on the total mass of the 1 st photosensitive layer or the 2 nd photosensitive layer.

(polymerization initiator)

The photosensitive 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.

In the present specification, a compound having a polymerization initiating function is classified as a polymerization initiator. That is, the polymerization initiator is a compound different from the light absorber.

The photosensitive 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 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-triaryl imidazole dimers and derivatives thereof, 2,4, 5-triaryl imidazole dimers may have the same or different structures.

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) ] phenyl-1, 2-octanedione-2- (O-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-morpholino) phenyl ] -1-butanone (Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Omnirad 907, IGM Resins B.V), 2-hydroxy-1- [4- (2-hydroxypropionyl) benzyl } -2-oxopropionyl) -2- (2-methyl-acetyl oxime (IRGACURE, IRGACURE-02, manufactured by BASF), and methylpropan-1-one (Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (Omnirad 369, manufactured by IGM Resins 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, IGM Resins B.V., inc.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (Omnirad 819, IGM Resins B.V.), oxime ester-based photopolymerization initiator (Lunar 6, DKSH Management Ltd.), 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (B-CIM, manufactured by Hampford Inc.), 2- (O-chlorophenyl) -4, 5-diphenylimidazole dimer (BCTB, tokyo Chemical Industry Co., ltd.), 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropan-1, 2-dione-2- (O-benzoyl oxime) (TR-PBG-305, 2-dione, changzhou 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-acetyloxime) (TR-PBG-326, changzhou Tronly New Electronic Materials Co., ltd., ltd.)) and 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (O-benzoyloxime) (TR-PBG-391, changzhou Tronly New Electronic Materials Co., ltd.).

The photo cation polymerization initiator (photoacid generator) is a compound that receives active light to generate an acid.

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 cation 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 the ionic photo-cationic polymerization initiators described in paragraphs [0114] to [0133] of Japanese patent application laid-open Nos. 2014-085643.

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

Examples of the diazomethane compound and the imide sulfonate compound include compounds described in paragraphs [0083] to [0088] of Japanese patent application laid-open No. 2011-221494.

Examples of the oxime sulfonate compound include compounds described in paragraphs [0084] to [0088] of International publication No. 2018/179640.

The polymerization initiator may be used singly in 1 kind or 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 1 st photosensitive layer or the 2 nd photosensitive layer. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less, based on the total mass of the 1 st photosensitive layer or the 2 nd photosensitive layer.

(pigments)

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

Although the detailed mechanism is not clear, when the dye N is contained, the adhesion with an adjacent layer (for example, an intermediate layer or the like) is improved and the resolution is more excellent.

The "dye changes its maximum absorption wavelength by an acid, an alkali, or a radical" may indicate any of a method in which a dye in a developed state is decolorized by an acid, an alkali, or a radical, a method in which a dye in a decolorized state is developed by an acid, an alkali, or a radical, and a method in which a dye in a developed state is changed to a developed 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 color development or decoloration by generating an acid, a base, or a radical in the photosensitive layer by exposure and acting, or may be one that changes the state of color development or decoloration by changing the state (for example, pH or the like) in the photosensitive layer by an acid, a base, or a 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 dye N 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 a radical, from the viewpoints of visibility and resolution of an exposed portion and a non-exposed portion.

In view of the visibility and resolution of the exposed portion and the unexposed portion, the photosensitive 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 a photosensitive 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 exceed 450 nm.

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 (maximum absorption wavelength) at which the light intensity is extremely small.

Examples of the coloring matter which develops color or discolors by exposure include colorless compounds.

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

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 these, 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 a radical generated from the photo radical polymerization initiator or an acid generated from the photo cation polymerization initiator to change the colorless compound into a closed ring state and decolor it, or the colorless compound can be changed into an open ring state and develop color. 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 magenta, 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 magenta, victoria pure BLUE-naphthalene sulfonate, victoria pure BLUE BOH (manufactured by Hodogaya Chemical co., LTD.), OIL BLUE #603 (manufactured by orlent Chemical INDUSTRIES co., LTD.), OIL PINK #312 (ORIENT Chemical INDUSTRIES, inc., LTD, manufactured by LTD), OIL RED 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 special (Hodgaya Chemical Co., manufactured by Ltd), m-cresol purple, cresol RED, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenylimido-naphthoquinone, 2-carboxyanilino-4-p-diethylaminophenylnaphthoquinone, 2-carboxy-p-stearylamido-4-p-stearylaminophenylnaphthoquinone, 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-xylidine, 3- (N, N-diethylamino) -6-methyl-7-chloroanilide, 3- (N, N-diethylamino) -6-methyl-7-fluoroanilide, 3- (N, N-diethylamino) -6-chloro-7-fluoroanilide, 3- (N, N-diethylamino) -7-fluoroanilide, 4- (3, N-diethylamino) -7-fluoroanilide, 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-piperidin-6-methyl-7-anilinofluorane, 3-pyrrolidin-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-yl) -4-phthalide, 3- (4-diethylamino) -3- (1-ethyl-2-methylindol-3-yl) -4-phthalide, and 3- (1 ' -diethylamino) -6-methyl-anilinofluor-3 ' -1-3-bis (1-ethyl-2-methylindol-3 ' -anilinofluoride), 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 excellent 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 or 2 or more.

The content of the dye N is preferably 0.1% by mass or more, more preferably 0.1 to 10% by mass, and further preferably 0.1 to 5% by mass, based on the total mass of the 1 st photosensitive layer or the 2 nd photosensitive 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 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 1 st photosensitive layer or the 2 nd photosensitive layer (3 g) was dissolved in methyl ethyl ketone instead of the dye N. From the obtained absorbance of the solution containing the photosensitive layer, the content of the pigment N contained in the photosensitive layer was calculated from the calibration curve.

(thermally crosslinkable Compound)

The photosensitive layer may contain a thermally crosslinkable compound in view 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 is regarded as a thermally crosslinkable compound, and is not regarded 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 of the film obtained by curing the photosensitive layer when used as a protective film tends to be enhanced.

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 DSC (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 them, an oxime compound is preferable as the capping agent having a dissociation temperature of 100 to 160 ℃ in view of storage stability.

The blocked isocyanate compound preferably has an isocyanurate structure in terms of improving the brittleness of the film and improving the adhesion to the transferred object.

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 2]

The thermally crosslinkable compound may be used alone in 1 kind or in 2 kinds or more.

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 1 st photosensitive layer or the 2 nd photosensitive layer.

(pigment)

The photosensitive layer may contain a pigment.

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

A liquid crystal display window of a recent electronic device is sometimes provided with a cover glass in which a black frame-shaped light shielding layer is formed on a peripheral edge portion of a back surface of a transparent glass base material or the like 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 pigment)

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 white pigment include inorganic pigments and the 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 the heat resistance and the light fading property.

In view of reducing the thickness of the photosensitive 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 layer is a colored resin layer, the photosensitive 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 0.01 μm or more.

<xnotran> , , BO ( : color Index (, "C.I.".) 42595), (C.I.41000), HB (C.I.26150), MONOLITE 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 PINK B 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 or 2 or more.

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, and further preferably more than 5% by mass and 35% by mass or less, based on the total mass of the 1 st photosensitive layer or the 2 nd photosensitive layer.

When the photosensitive 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 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 "vehicle" refers to a part 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, binghui bookstore, 2000, pages 438 and 310).

(heterocyclic compound)

The photosensitive layer may include a heterocyclic compound.

The heterocyclic compound is preferably a compound different from each of the above components.

As the heterocyclic compound, carboxybenzotriazoles are preferable.

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 heterocyclic compound may be used alone in 1 or 2 or more.

The heterocyclic compound 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 1 st photosensitive layer or the 2 nd photosensitive layer.

(other additives)

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

Examples of the other additives include radical polymerization inhibitors, sensitizers, surfactants, plasticizers, heterocyclic compounds, 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-proliferating agent, a development accelerator, conductive fibers, 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.

Other additives may be used singly in 1 or 2 or more.

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 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 1 st photosensitive layer or the 2 nd photosensitive 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.

Sensitizers

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, 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 1 st photosensitive layer or the 2 nd photosensitive 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 those 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-01, R-40-LM, RS-43, TF-1956, RS-90, R-94 and DS-21 (manufactured by Corporation); fluorad FC430, FC431 and FC171 (above, 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 can also be preferably used: 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-containing surfactants include MEGAFACE DS series (The Chemical Daily Co., ltd. (2016: 2/22 days) and NIKKEI BUSINESS DAILY (2016: 2/23 days))

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 (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF corporation); TETRONIC 304, 701, 704, 901, 904 and 150R1 (BASF, supra); solsperse 20000 (manufactured by The Lubrizol Corporation); NCW-101, NCW-1001, and NCW-1002 (both of which are 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, surfynol 104, 400 and 440 (above, made by Nissin Chemical Industry co., ltd.).

Examples of the silicone surfactant include linear polymers composed of siloxane bonds, and modified siloxane polymers having organic groups introduced into side chains and/or terminals thereof.

Examples of the silicone surfactant include DOWNSIL 8032ADDITIVE, TORAY SI LICON DC3PA, TORAY SILICON SH7PA, TORAY SILICON DC11PA, TORAY SILICO N SH21PA, TORAY SILICON SH28PA, TORAY SILICON SH29PA, TORAY SILICON SH30PA, and TORAY SILICON SH8400 (described above, manufactured by Dow Corning Toray Co., ltd.); 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 1 st photosensitive layer or the 2 nd photosensitive 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 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 impurity 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 1 st photosensitive layer or the 2 nd photosensitive layer. The lower limit is preferably 1 mass ppb or more, and more preferably 0.1 mass ppm or more, with respect to the total mass of the photosensitive layer.

Examples of the method of 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 layer; a method of preventing impurities from being mixed in when forming a photosensitive layer; and a method of cleaning and removing.

For example, the content of impurities can be quantified 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 still more preferably 4 mass ppm or less, based on the total mass of the 1 st photosensitive layer or the 2 nd photosensitive 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 1 st photosensitive layer or the 2 nd photosensitive 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 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, with respect to the total mass of the resin, from the viewpoints 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.

In view 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 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 1 st photosensitive layer or the 2 nd photosensitive 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 within 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 content of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.

The water content in the 1 st photosensitive layer or the 2 nd photosensitive layer is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%, from the viewpoint of improving reliability and laminatability.

(characteristics of photosensitive layer)

The average thickness of the photosensitive layer is usually 0.1 to 300. Mu.m, preferably 0.2 to 100. Mu.m, more preferably 0.5 to 50 μm, and still more preferably 1 to 20 μm. This can improve the developability of the photosensitive layer and also improve the resolution.

The method of measuring the average thickness includes a method of measuring the average thickness of the base material.

< 1 st intermediate layer and 2 nd intermediate layer >

The 1 st composition layer may have a 1 st intermediate layer between the 1 st thermoplastic resin layer and the 1 st photosensitive layer. Also, the 2 nd composition layer may have a 2 nd intermediate layer between the 2 nd thermoplastic resin layer and the 2 nd photosensitive layer. The 1 st intermediate layer and the 2 nd intermediate layer may have 1 of the same structure or different structures, and preferably have the same structure. For example, the 1 st intermediate layer and the 2 nd intermediate layer have the same structure means that the 1 st intermediate layer and the 2 nd intermediate layer contain the same components and the contents thereof are also the same. The 1 st intermediate layer and the 2 nd intermediate layer are also collectively referred to as "intermediate layers".

The 1 st intermediate layer is preferably disposed on the side of the 1 st photosensitive layer opposite to the substrate when the 1 st thermoplastic resin layer is not present, or disposed between the 1 st thermoplastic resin layer and the 1 st photosensitive layer when the 1 st thermoplastic resin layer is present. The 2 nd intermediate layer is preferably disposed on the side of the 2 nd photosensitive layer opposite to the substrate when the 2 nd thermoplastic resin layer is not present, or disposed between the 2 nd thermoplastic resin layer and the 2 nd photosensitive layer when the 2 nd thermoplastic resin layer is present.

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 having low oxygen permeability and 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 improving the productivity by reducing the time load of the exposure machine.

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, and alkylene oxide (alkylene oxide) adducts thereof, and a vinyl ether resin.

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 dispersity (Mw/Mn) 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 or 2 or more.

The content of the water-soluble resin is preferably 50% by mass or more, and more preferably 70% by mass or more, relative to the total mass of the 1 st intermediate layer or the 2 nd intermediate layer. The upper limit is preferably 100% by mass or less, more preferably 99.9% by mass or less, further preferably 99.8% by mass or less, and particularly preferably 99% by mass or less, based on the total mass of the 1 st intermediate layer or the 2 nd intermediate layer.

(other Components)

The intermediate layer may contain other components in addition to the above-mentioned 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 an ethyleneoxy group, a propyleneoxy group, and the like to the above polyol.

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, oxide adducts of polyols, 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, and most preferably 1,500 or less. The lower limit is preferably 60 or more.

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

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 1 st intermediate layer or the 2 nd intermediate layer. The upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, and further preferably 5% by mass or less, with respect to the total mass of the 1 st intermediate layer or the 2 nd intermediate layer.

(impurities)

The intermediate layer may contain impurities.

Examples of the impurities include impurities contained in the photosensitive 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.

< 1 st and 2 nd thermoplastic resin layers >

The 1 st composition layer may have a 1 st thermoplastic resin layer. Also, the 2 nd composition layer may have a 2 nd thermoplastic resin layer. The 1 st thermoplastic resin layer and the 2 nd thermoplastic resin layer may have 1 of the same structure or different structures, and preferably have the same structure. For example, the 1 st thermoplastic resin layer and the 2 nd thermoplastic resin layer have the same structure means that the 1 st thermoplastic resin layer and the 2 nd thermoplastic resin layer contain the same components and the contents thereof are also the same. Hereinafter, the 1 st thermoplastic resin layer and the 2 nd thermoplastic resin layer are collectively referred to as "thermoplastic resin layers".

The 1 st thermoplastic resin layer is preferably disposed on the side of the 1 st photosensitive layer opposite to the substrate when the 1 st intermediate layer is not present, and on the side of the 1 st intermediate layer opposite to the 1 st photosensitive layer when the 1 st intermediate layer is present. The 2 nd thermoplastic resin layer is preferably disposed on the side of the 2 nd photosensitive layer opposite to the substrate when the 2 nd intermediate layer is not present, and on the side of the 2 nd intermediate layer opposite to the 2 nd photosensitive layer when the 2 nd intermediate layer is present.

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 layer)

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 layer described above may also be used.

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

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 phosphate 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 from the viewpoint of developability. The upper limit is preferably 300mgKOH/g or less, more preferably 250mgKOH/g or less, and still more preferably 200mgKOH/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.

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 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 or 2 or more.

The content of the thermoplastic resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, and still more preferably 40 to 80% by mass, based on the total mass of the 1 st thermoplastic resin layer or the 2 nd thermoplastic resin layer, from the viewpoints of developability and adhesion to an adjacent layer.

(pigments)

The thermoplastic resin layer may contain a coloring matter (hereinafter, also simply referred to as "coloring matter B") having a maximum absorption wavelength exceeding 450nm in a wavelength range of 400 to 780nm during color development and changing the maximum absorption wavelength 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.

The thermoplastic resin layer preferably contains both a dye whose maximum absorption wavelength as the dye B is changed by an acid and a compound which generates an acid by light, which will be described later, from the viewpoints of visibility and resolution of an exposed portion and a non-exposed portion.

The pigment B may be used alone in 1 or 2 or more.

The content of the coloring matter B is preferably 0.2 mass% or more, more preferably 0.2 to 6.0 mass%, and further preferably 0.2 to 5.0 mass% with respect to the total mass of the 1 st thermoplastic resin layer or the 2 nd 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 determining 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.

(Compounds generating acids, bases or radicals 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 photoacid generator include a photo cation polymerization initiator that can be contained in the photosensitive 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 3]

Photo radical polymerization initiator

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

Examples of the photo radical polymerization initiator include photo radical polymerization initiators that can be included in the photosensitive 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 or 2 or more.

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 1 st thermoplastic resin layer or the 2 nd thermoplastic resin layer, from the viewpoints of visibility and resolution of the exposed portion and the unexposed 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 plasticization.

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 layer.

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 viewpoints of resolution of the thermoplastic resin layer, adhesion to adjacent layers, 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 2 or more kinds.

The content of the plasticizer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and further preferably 20 to 50% by mass, based on the total mass of the 1 st thermoplastic resin layer or the 2 nd thermoplastic resin layer, from the viewpoints of resolution of the thermoplastic resin layer, adhesion to adjacent layers, and developability.

(sensitizer)

The thermoplastic resin layer may contain a sensitizer.

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

The number of the sensitizer used may be 1 or 2 or more.

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 1 st thermoplastic resin layer or the 2 nd thermoplastic resin layer, from the viewpoints of improvement of sensitivity to a light source and visibility of exposed portions and unexposed portions.

(heterocyclic compound)

The thermoplastic resin layer may contain a heterocyclic compound.

The heterocyclic compound is the same as the heterocyclic compound that can be contained in the photosensitive layer, and the same preferred embodiment is also applied.

(other additives)

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

Examples of the other additive include other additives that can be contained in the photosensitive layer.

(impurities)

The thermoplastic resin layer may contain impurities.

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

The average thickness (layer thickness) of the thermoplastic resin layer is preferably 1 μm or more, and 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.

The method of measuring the average thickness includes a method of measuring the average thickness of the base material.

[ transparent conductive layer ]

The laminate has a 1 st transparent conductive layer and a 2 nd transparent conductive layer.

The 1 st transparent conductive layer and the 2 nd transparent conductive layer may have the same structure or 1 of different structures, and preferably have the same structure. For example, the 1 st composition layer and the 2 nd composition layer have the same structure, which means that the 1 st transparent conductive layer and the 2 nd transparent conductive layer contain the same kind of metal and the content thereof is also the same.

The volume resistivity of the transparent conductive layer is preferably less than 1 × 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 toThe above is more preferable to be 1X 10 ^-3 As described above. The volume resistivity can be measured by using a known resistivity meter (e.g., resistance tester EC-80p, napson CORPORATION, etc.).

The transparent conductive layer preferably contains a metal in terms of more excellent conductivity.

Examples of the metal include copper, silver, tin, palladium, gold, nickel, chromium, platinum, iron, gallium, and indium. The metal may be any 1 of single metals and alloys. Examples of the alloy include a copper alloy and a silver alloy.

From the viewpoint of more excellent conductivity, the transparent conductive layer preferably contains at least 1 selected from copper, silver, tin, and indium, and more preferably contains silver.

Examples of the transparent conductive layer include a layer containing a metal oxide, a layer containing a metal nanowire, and a layer containing a metal nanoparticle, preferably at least one of the 1 st transparent conductive layer and the 2 nd transparent conductive layer contains at least 1 selected from the group consisting of a metal nanowire and a metal nanoparticle, and more preferably the 1 st transparent conductive layer and the 2 nd transparent conductive layer contain at least 1 selected from the group consisting of a metal nanowire and a metal nanoparticle.

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.

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

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

The average thickness of the transparent conductive layer is preferably 0.001 to 1000 μm, more preferably 0.005 to 15 μm, and still more preferably 0.01 to 10 μm, from the viewpoint of further excellent conductivity and film formability. The average thickness of the transparent conductive layer can be measured by a method conforming to the method for measuring the average thickness of the base material described above.

The 1 st transparent conductive layer and the 2 nd transparent conductive layer may be disposed on the entire substrate or may be disposed on a part of the substrate.

[ other layers ]

The laminate may have other layers in addition to the above-described components.

Examples of the other layer include a temporary support and a protective film.

The temporary support and the protective film are the same as those of a transfer film described later, and the same preferable embodiment is also applied. When the other layer is a temporary support or a protective film, the laminate preferably has the other layer on one side of the 1 st composition layer opposite to the substrate or on one side of the 2 nd composition layer opposite to the substrate.

Examples of the other layer include a layer containing an organic substance, a layer containing an inorganic substance, a layer in which an inorganic substance is dispersed in an organic substance, and a layer in which an organic substance is dispersed in an inorganic substance. When the other layer is a layer containing an organic substance, a layer containing an inorganic substance, a layer in which an inorganic substance is dispersed in an organic substance, or a layer in which an organic substance is dispersed in an inorganic substance, the laminate preferably has another layer between the 1 st transparent conductive layer and the 1 st photosensitive layer and/or between the 2 nd transparent conductive layer and the 2 nd photosensitive layer, from the viewpoints of protecting the transparent conductive layer, controlling electrical characteristics, controlling adhesion between the 1 st transparent conductive layer and the 1 st photosensitive layer, and controlling adhesion between the 2 nd transparent conductive layer and the 2 nd photosensitive layer.

< 2 nd embodiment >)

< photosensitive layer >

The composition layer of embodiment 2 has a photosensitive layer.

By transferring the photosensitive layer onto a transfer object and then performing exposure and development, a pattern can be formed on the transfer object.

The photosensitive layer is preferably a negative photosensitive layer. The negative photosensitive layer is a photosensitive layer in which the solubility of an exposed portion in a developer is lowered by exposure. When the photosensitive layer is a negative photosensitive layer, the pattern formed corresponds to the cured layer.

Hereinafter, components that can be contained in the photosensitive layer will be described.

(adhesive Polymer)

The photosensitive layer may include a binder polymer.

Examples of the binder polymer include (meth) acrylic resins, styrene resins, epoxy resins, polyamide epoxy resins, alkyd resins, phenol resins, polyester resins, urethane resins, epoxy acrylate resins obtained by reaction of an epoxy resin with (meth) acrylic acid, and acid-modified epoxy acrylate resins obtained by reaction of an epoxy acrylate resin with an acid anhydride.

As one preferred embodiment of the binder polymer, a (meth) acrylic resin is mentioned from the viewpoint of excellent alkali developability and film-forming properties.

In the present specification, a (meth) acrylic resin refers to a resin having a structural unit derived from a (meth) acrylic compound. The content of the structural unit derived from the (meth) acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more, relative to all the structural units of the (meth) acrylic resin.

The (meth) acrylic resin may be composed of only a structural unit derived from a (meth) acrylic compound, or may have a structural unit derived from a polymerizable monomer other than a (meth) acrylic compound. That is, the upper limit of the content of the structural unit derived from the (meth) acrylic compound is 100 mass% or less with respect to all the structural units of the (meth) acrylic resin.

Examples of the (meth) acrylic compound include (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides, and (meth) acrylonitriles.

Examples of the (meth) acrylic acid ester include alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-trifluoroethyl (meth) acrylate, and 2, 3-tetrafluoropropyl (meth) acrylate, and alkyl (meth) acrylate is preferable.

Examples of the (meth) acrylamide include acrylamides such as diacetone acrylamide.

The alkyl group of the alkyl (meth) acrylate may be linear or branched. Specific examples thereof include alkyl (meth) acrylates having an alkyl group having 1 to 12 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylate.

The (meth) acrylate is preferably an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, and more preferably methyl (meth) acrylate or ethyl (meth) acrylate.

The (meth) acrylic resin may have a structural unit other than the structural unit derived from the (meth) acrylic compound.

The polymerizable monomer forming the structural unit is not particularly limited as long as it is a compound other than the (meth) acrylic acid compound copolymerizable with the (meth) acrylic acid compound, and examples thereof include styrene compounds which may have a substituent at the α -position or at the aromatic ring, such as styrene, vinyltoluene and α -methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α -cyanocinnamic acid, itaconic acid and crotonic acid.

These polymerizable monomers may be used alone in 1 or 2 or more.

Also, from the viewpoint of further improving the alkali developability, the (meth) acrylic resin preferably contains a structural unit having an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group, and a phosphonic acid group.

Among them, the (meth) acrylic resin more preferably contains a structural unit having a carboxyl group, and further preferably has a structural unit derived from the above (meth) acrylic acid.

The content of the structural unit having an acid group (preferably, a structural unit derived from (meth) acrylic acid) in the (meth) acrylic resin is preferably 10% by mass or more with respect to the total mass of the (meth) acrylic resin from the viewpoint of excellent developability. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, from the viewpoint of excellent alkali resistance.

The (meth) acrylic resin more preferably has a structural unit derived from the above-mentioned alkyl (meth) acrylate.

The content of the structural unit derived from the alkyl (meth) acrylate in the (meth) acrylic resin is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and still more preferably 65 to 90% by mass, based on all the structural units of the (meth) acrylic resin.

The (meth) acrylic resin is preferably a resin having both a structural unit derived from (meth) acrylic acid and a structural unit derived from an alkyl (meth) acrylate, and more preferably a resin composed of only a structural unit derived from (meth) acrylic acid and a structural unit derived from an alkyl (meth) acrylate.

Further, as the (meth) acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.

The (meth) acrylic resin preferably has at least 1 kind selected from a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate, and more preferably has both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate.

The total content of the methacrylic acid-derived structural unit and the alkyl methacrylate-derived structural unit in the (meth) acrylic resin is preferably 40% by mass or more, and more preferably 60% by mass or more, based on all the structural units of the (meth) acrylic resin. The upper limit is not particularly limited, and may be 100 mass% or less, preferably 80 mass% or less.

The (meth) acrylic resin preferably further contains at least 1 kind selected from a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate and at least 1 kind selected from a structural unit derived from acrylic acid and a structural unit derived from an alkyl acrylate.

The total content of the structural unit derived from methacrylic acid and the structural unit derived from alkyl methacrylate is preferably 60/40 to 80/20 in terms of a mass ratio to the total content of the structural unit derived from acrylic acid and the structural unit derived from alkyl acrylate.

The (meth) acrylic resin preferably has an ester group at a terminal thereof in view of excellent developability of the photosensitive layer after transfer.

In addition, the terminal portion of the (meth) acrylic resin is composed of a site derived from a polymerization initiator used for synthesis. The (meth) acrylic resin having an ester group at the terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

In addition, another preferable embodiment of the binder polymer is an alkali-soluble resin.

For example, the binder polymer is preferably a binder polymer having an acid value of 60mgKOH/g or more from the viewpoint of developability.

Further, for example, from the viewpoint of facilitating the formation of a strong film by thermal crosslinking with the crosslinking component by heating, the binder polymer is more preferably a resin having a carboxyl group having an acid value of 60mgKOH/g or more (so-called carboxyl group-containing resin), and still more preferably a (meth) acrylic resin having a carboxyl group having an acid value of 60mgKOH/g or more (so-called carboxyl group-containing (meth) acrylic resin).

When the binder polymer is a resin having a carboxyl group, for example, a thermally crosslinkable compound such as a blocked isocyanate compound is added to thermally crosslink the resin, whereby the three-dimensional crosslinking density can be increased. In addition, the moisture and heat resistance can be improved by dehydrating and hydrophobizing the carboxyl group of the resin having a carboxyl group.

The carboxyl group-containing (meth) acrylic resin having an acid value of 60mgKOH/g or more is not particularly limited as long as the above-mentioned acid value condition is satisfied, and can be appropriately selected from known (meth) acrylic resins.

For example, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraph [0025] of Japanese patent application laid-open No. 2011-095716, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more in the polymer described in paragraphs [0033] to [0052] of Japanese patent application laid-open No. 2010-237589, or the like can be preferably used.

Another preferable embodiment of the binder polymer is a styrene-acrylic acid copolymer.

In the present specification, the styrene-acrylic acid copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic acid compound, and the total content of the structural unit derived from the styrene compound and the structural unit derived from the (meth) acrylic acid compound is preferably 30% by mass or more, and more preferably 50% by mass or more, based on all the structural units of the copolymer. The upper limit is often 100 mass% or less.

The content of the structural unit derived from a styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 5 to 80% by mass, based on all the structural units of the copolymer.

The content of the structural unit derived from the (meth) acrylic acid compound is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20 to 95% by mass, based on all the structural units of the copolymer.

The binder polymer preferably has an aromatic ring structure, and more preferably contains a structural unit having an aromatic ring structure.

Examples of the monomer forming the structural unit having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, and the like). Among them, monomers having an aralkyl group or styrene are preferable.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding benzyl group) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group 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; vinyl monomers having a benzyl group such as vinylbenzyl chloride, vinylbenzyl alcohol and the like. Among them, benzyl (meth) acrylate is preferable.

Further, the binder polymer more preferably has a structural unit (structural unit derived from styrene) represented by the following formula (S).

[ chemical formula 4]

When the binder polymer contains a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass, based on all the structural units of the binder polymer.

The content of the structural unit having an aromatic ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 60 mol% based on all the structural units of the binder polymer.

The content of the structural unit represented by the formula (S) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, further preferably 20 to 60 mol%, and particularly preferably 20 to 50 mol%, based on all the structural units of the binder polymer.

In the present specification, when the content of the "structural unit" is defined by a molar ratio, the meaning of the "structural unit" is the same as that of the "monomer unit". In the present specification, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

The binder polymer preferably has an aliphatic hydrocarbon ring structure. That is, the binder polymer preferably contains a structural unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be a single ring or a plurality of rings. Among them, the binder polymer more preferably has a ring structure in which 2 or more aliphatic hydrocarbon rings are condensed.

Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring and an isophorone ring.

Among these, preferred are rings obtained by fusing 2 or more aliphatic hydrocarbon rings, and more preferred is a tetrahydrodicyclopentadiene ring (tricyclo [5.2.1.0 ] ^2,6 ]Decane ring).

Examples of the monomer forming a structural unit having an aliphatic hydrocarbon ring structure include dicyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.

The binder polymer more preferably has a structural unit represented by the following formula (Cy), and more preferably has a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[ chemical formula 5]

In the formula (Cy), R ^M Represents a hydrogen atom or a methyl group, R ^Cy Represents a 1-valent group having an aliphatic hydrocarbon ring structure.

R in the formula (Cy) ^M Preferably methyl.

R in the formula (Cy) ^Cy Preferably a 1-valent group having an aliphatic hydrocarbon ring structure of 5 to 20 carbon atoms, more preferably a 1-valent group having an aliphatic hydrocarbon ring structure of 6 to 16 carbon atoms, and still more preferably 8 to 1 carbon atom4 having an aliphatic hydrocarbon ring structure.

And R of the formula (Cy) ^Cy The aliphatic hydrocarbon ring structure in (2) is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure or an isophorone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and still more preferably a tetrahydrodicyclopentadiene ring structure.

And R of the formula (Cy) ^Cy The aliphatic hydrocarbon ring structure in (2) is preferably a ring structure obtained by fusing 2 or more aliphatic hydrocarbon rings, and more preferably a ring structure obtained by fusing 2 to 4 aliphatic hydrocarbon rings.

And R in the formula (Cy) ^Cy Preferred is a group in which an oxygen atom of-C (= O) O-in the formula (Cy) is directly bonded to an aliphatic hydrocarbon ring structure, that is, an aliphatic hydrocarbon ring group, more preferred is cyclohexyl or dicyclopentyl, and further preferred is dicyclopentyl.

The binder polymer may have 1 kind of structural unit having an aliphatic hydrocarbon ring structure alone or 2 or more kinds.

When the binder polymer contains a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 70% by mass, based on all the structural units of the binder polymer.

The content of the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer.

The content of the structural unit represented by the formula (Cy) in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer.

When the binder polymer contains a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, the total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 40 to 75% by mass, based on all the structural units of the binder polymer.

The total content of the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon ring structure in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol% based on all the structural units of the binder polymer.

The total content of the structural unit represented by the formula (S) and the structural unit represented by the formula (Cy) in the binder polymer is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and still more preferably 40 to 60 mol% based on all the structural units in the binder polymer.

The binder polymer preferably comprises structural units having acid groups.

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

The structural unit having an acid group is preferably a structural unit derived from (meth) acrylic acid shown below, and more preferably a structural unit derived from methacrylic acid.

[ chemical formula 6]

The binder polymer may contain 1 kind of structural unit having an acid group alone, or may contain 2 or more kinds.

When the binder polymer contains a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass, based on all the structural units of the binder polymer.

The content of the structural unit having an acid group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% based on all the structural units of the binder polymer.

The content of the structural unit derived from (meth) acrylic acid in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol% based on all the structural units of the binder polymer.

The binder polymer preferably has a reactive group, and more preferably contains a structural unit having a reactive group.

The reactive group is preferably a radical polymerizable group, and more preferably an ethylenically unsaturated group. When the binder polymer has an ethylenically unsaturated group, the binder polymer preferably contains a structural unit having an ethylenically unsaturated group in a side chain.

In the present specification, "main chain" means a relatively longest bonding chain in a molecule of a polymer compound constituting a resin, and "side chain" means a group of atoms branched from the main chain.

As the ethylenically unsaturated group, allyl or (meth) acryloyloxy is more preferable.

Examples of the structural unit having a reactive group include the following, but are not limited thereto.

[ chemical formula 7]

The binder polymer may contain 1 kind of structural unit having a reactive group alone, or may contain 2 or more kinds.

When the binder polymer contains a structural unit having a reactive group, the content of the structural unit having a reactive group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 40% by mass, based on all the structural units of the binder polymer.

The content of the structural unit having a reactive group in the binder polymer is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol% based on all the structural units of the binder polymer.

Examples of a method for introducing a reactive group into the binder polymer include a method in which a compound such as an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, or a carboxylic anhydride is reacted with a functional group such as a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, or a sulfo group.

Preferred examples of the method for introducing a reactive group into a binder polymer include the following methods: after a polymer having a carboxyl group is synthesized by polymerization, a glycidyl (meth) acrylate is reacted with a part of the carboxyl group of the obtained polymer by a high molecular reaction, thereby introducing a (meth) acryloyloxy group into the polymer. By this method, a binder polymer having a (meth) acryloyloxy group in a side chain can be obtained.

The polymerization reaction is preferably carried out at a temperature of 70 to 100 ℃ and more preferably at a temperature of 80 to 90 ℃. As the polymerization initiator used in the above polymerization reaction, an azo-based initiator is preferred, and for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferred. The polymerization reaction is preferably carried out at a temperature of 80 to 110 ℃. In the above-mentioned polymer reaction, a catalyst such as an ammonium salt is preferably used.

As the binder polymer, polymers X1 to X4 shown below are preferable. The content ratios (a to d) of the respective constituent units shown below, the weight average molecular weight Mw, and the like can be appropriately changed according to the purpose, and among them, the following configuration is preferable from the viewpoint of further improving the effects of the present invention.

(Polymer X1) a:20 to 60 mass%, b:10 to 50 mass%, c:5.0 to 25 mass%, d:10 to 50 mass%.

(Polymer X2) a:20 to 60 mass%, b:10 to 50 mass%, c:5.0 to 25 mass%, d:10 to 50 mass%.

(Polymer X3) a:30 to 65 mass%, b:1.0 to 20 mass%, c:5.0 to 25 mass%, d:10 to 50 mass%.

(Polymer X4) a:1.0 to 20 mass%, b:20 to 60 mass%, c:5.0 to 25 mass%, d:10 to 50 mass%.

[ chemical formula 8]

[ chemical formula 9]

Also, the binder polymer may contain a polymer (hereinafter, also referred to as "polymer X") containing a structural unit having a carboxylic anhydride structure.

The carboxylic anhydride structure may be 1 of a chain carboxylic anhydride structure and a cyclic carboxylic anhydride structure, and is preferably a cyclic carboxylic anhydride structure.

The ring of the cyclic carboxylic acid anhydride structure is preferably a 5-to 7-membered ring, more preferably a 5-or 6-membered ring, and still more preferably a 5-membered ring.

The structural unit having a carboxylic anhydride structure is preferably a structural unit containing in the main chain a 2-valent group obtained by removing 2 hydrogen atoms from a compound represented by the following formula P-1 or a structural unit in which a 1-valent group obtained by removing 1 hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a 2-valent linking group.

[ chemical formula 10]

In the formula P-1, R ^A1a Represents a substituent, n ^1a R is ^A1a May be the same or different, Z ^1a Represents a 2-valent group, n, forming a ring containing-C (= O) -O-C (= O) - ^1a Represents an integer of 0 or more.

As a group R ^A1a Examples of the substituent include an alkyl group.

As Z ^1a The alkylene group having 2 to 4 carbon atoms is preferable, the alkylene group having 2 or 3 carbon atoms is more preferable, and the alkylene group having 2 carbon atoms is further preferable.

n ^1a Represents an integer of 0 or more. At Z ^1a When it represents an alkylene group having 2 to 4 carbon atoms, n ^1a Preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0.

n ^1a When an integer of 2 or more is represented, a plurality of R ^A1a May be the same or different. And a plurality of R ^A1a The ring may be bonded to each other to form a ring, but preferably is not bonded to each other to form a ring.

The structural unit having a carboxylic anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, still more preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride, particularly preferably a structural unit derived from maleic anhydride or itaconic anhydride, and most preferably a structural unit derived from maleic anhydride.

Specific examples of the structural unit having a carboxylic anhydride structure are given below, but the structural unit having a carboxylic anhydride structure is not limited to these specific examples. In the following structural units, rx represents a hydrogen atom, a methyl group, or CH ₂ OH group or CF ₃ Me represents a methyl group.

[ chemical formula 11]

[ chemical formula 12]

The number of the structural units having a carboxylic anhydride structure in the polymer X may be 1 or 2 or more.

The total content of the structural units having a carboxylic anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and still more preferably 10 to 35 mol% based on all the structural units of the polymer X.

The photosensitive layer may contain only 1 kind of polymer X, or may contain 2 or more kinds.

When the photosensitive layer contains the polymer X, the content of the polymer X is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, even more preferably 0.5 to 20% by mass, and even more preferably 1 to 20% by mass, based on the total mass of the photosensitive layer.

The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 50,000, and particularly preferably 20,000 to 30,000.

The acid value of the binder polymer is preferably 10 to 200mgKOH/g, more preferably 60 to 200mgKOH/g, still more preferably 60 to 150mgKOH/g, and particularly preferably 70 to 125mgKOH/g.

The acid value of the binder polymer was set to a value in accordance with JIS K0070:1992, the method described in the section of the text.

From the viewpoint of developability, the dispersion degree of the binder polymer 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 layer may contain only 1 binder polymer, or may contain 2 or more kinds.

The content of the binder polymer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass, based on the total mass of the photosensitive layer.

(polymerizable Compound)

The photosensitive layer may contain a polymerizable compound.

The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cation polymerizable group, and a radical polymerizable group is preferable.

The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter, may be simply referred to as "ethylenically unsaturated compound").

As the ethylenically unsaturated group, (meth) acryloyloxy group is preferable.

The ethylenically unsaturated compound in the present specification is a compound other than the above binder polymer, and the molecular weight is preferably less than 5,000.

As one of preferable embodiments of the polymerizable compound, a compound represented by the following formula (M) (also simply referred to as "compound M") can be mentioned.

Q ² -R ¹ -Q ¹ Formula (M)

In the formula (M), Q ¹ And Q ² Each independently represents a (meth) acryloyloxy group, R ¹ Represents a 2-valent linking group having a chain structure.

With respect to Q in the formula (M) ¹ And Q ² From the viewpoint of ease of synthesis, Q is preferably Q ¹ And Q ² Are the same group.

And, from the reactivity viewpoint, Q in the formula (M) ¹ And Q ² Preference is given to acryloyloxy.

As R in formula (M) ¹ Preferably an alkylene group, alkyleneoxyalkylene group (-L) ¹ -O-L ¹ -) or polyalkyleneoxyalkylene (- (L) ¹ -O) _p -L ¹ -) more preferably a hydrocarbon group or a polyalkyleneoxyalkylene group having 2 to 20 carbon atoms, still more preferably an alkylene group having 4 to 20 carbon atoms, and particularly preferably a linear alkylene group having 6 to 18 carbon atoms.

The hydrocarbon group may have a chain structure in at least a part thereof, and the part other than the chain structure is not particularly limited, and may be, for example, a branched, cyclic or linear alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond, or any 1 of combinations thereof, preferably an alkylene group or a combination of 1 or more arylene groups and 2 or more alkylene groups, more preferably an alkylene group, and still more preferably a linear alkylene group.

Further, L is as defined above ¹ Each independently represents an alkylene group, preferably an ethylene group, a propylene group or a butylene group, more preferably an ethylene group or a 1, 2-propylene group. p represents an integer of 2 or more, preferably an integer of 2 to 10 And (4) counting.

And Q in the compound M ¹ And Q ² The number of atoms of the shortest connecting chain connecting between them is preferably 3 to 50, more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.

In this specification, "connection Q ¹ And Q ² The number of atoms of the shortest connecting chain therebetween "means the number of atoms to be bonded to Q ¹ Attached R ¹ Is connected to Q ² Attached R ¹ The shortest atom number of (a).

Specific examples of the compound M include 1, 3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 7-heptanediol di (meth) acrylate, 1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, di (meth) acrylate of hydrogenated bisphenol A, di (meth) acrylate of hydrogenated bisphenol F, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol/propylene glycol) di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate. The above ester monomers can also be used as mixtures.

Of the above compounds, at least 1 compound selected from 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate is preferable, at least 1 compound selected from 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate is more preferable, and at least 1 compound selected from 1, 9-nonanediol di (meth) acrylate and 1, 10-decanediol di (meth) acrylate is further preferable.

Further, as one of preferable embodiments of the polymerizable compound, an ethylenically unsaturated compound having 2 or more functions is exemplified.

In the present specification, "an ethylenically unsaturated compound having 2 or more functions" means a compound having 2 or more ethylenically unsaturated groups in one molecule.

As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth) acryloyl group is preferable.

As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

The 2-functional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.

Examples of the 2-functional ethylenically unsaturated compound other than the compound M include tricyclodecanedimethanol di (meth) acrylate and 1, 4-cyclohexanediol di (meth) acrylate.

Examples of commercially available products of 2-functional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK ESTETTR A-DCP, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK ESTTR DCP, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.), 1, 9-nonanediol diacrylate (trade name: NK ESTTR A-NOD-N, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd.), and 1, 6-hexanediol diacrylate (trade name: NK ESTTR A-HD-N, SHIN-NAKARA CHEMICAL Co., manufactured by Ltd.).

The ethylenically unsaturated compound having 3 or more functions is not particularly limited, and can be appropriately selected from known compounds.

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, isocyanuric acid (meth) acrylate, and a (meth) acrylate compound having a glycerin tri (meth) acrylate skeleton.

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

Examples of the polymerizable compound include caprolactone-modified compounds of (meth) acrylate compounds (e.g., nippon Kayaku Co., ltd., KAYARAD (registered trademark) DPCA-20, SHIN-NAKAMURA CHEMICAL Co., ltd., A-9300-1CL Co., ltd.), (e.g., alkylene oxide-modified compounds of (meth) acrylate compounds (e.g., nippon Kayaku Co., ltd., KAYARAD (registered trademark) RP-1040, SHIN-NAKAMURA CHEMICAL Co., ltd., EBECRYL ATM-35E, A-9300, DAICEL-ALLNEX LTD. EBECRYL (registered trademark) 135), and ethoxylated glycerol triacrylate (SHIN-NAKAMURA CHEMICAL Co., ltd., NK ESTER A-GLY-9E).

The polymerizable compound may also be a urethane (meth) acrylate compound.

Examples of the urethane (meth) acrylate include urethane di (meth) acrylates, and examples thereof include propylene oxide-modified urethane di (meth) acrylates, and ethylene oxide-and propylene oxide-modified urethane di (meth) acrylates.

Further, as the urethane (meth) acrylate, there may be mentioned a 3-or more-functional urethane (meth) acrylate. The lower limit of the number of functional groups is preferably 6 or more functional groups, and more preferably 8 or more functional groups. The upper limit of the number of functional groups is more preferably 20 or less. Examples of the 3-or more-functional urethane (meth) acrylate include 8UX-015A (manufactured by Taisei Fine Chemical Co., ltd.), UA-32P (manufactured by SHIN-NAKAMURA CHEMICAL Co., ltd.), U-15HA (manufactured by Ltd.), UA-1100H (manufactured by SHIN-NAKAMURA CHEMICAL Co., ltd.), KYOEISHA CHEMICAL CO., LTD AH-600 (product name) manufactured by LTD, UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (both manufactured by Nippon Kayaku Co., ltd.).

As a preferable embodiment of the polymerizable compound, an ethylenically unsaturated compound having an acid group can be mentioned.

Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group.

Among them, as the acid group, a carboxyl group is preferable.

Examples of the ethylenically unsaturated compound having an acid group include a 3 to 4-functional ethylenically unsaturated compound having an acid group [ a compound having an acid group (acid value: 80 to 120 mgKOH/g) obtained by introducing a carboxyl group into a pentaerythritol tri-and tetraacrylate (PETA) skeleton ], a 5 to 6-functional ethylenically unsaturated compound having an acid group [ a compound having an acid group (acid value: 25 to 70 mgKOH/g) obtained by introducing a carboxyl group into a dipentaerythritol penta-and hexaacrylate (DPHA) skeleton ], and the like.

These ethylenically unsaturated compounds having 3 or more functions of an acid group may be used together with the ethylenically unsaturated compounds having 2 functions of an acid group, if necessary.

The ethylenically unsaturated compound having an acid group is preferably at least 1 selected from the group consisting of ethylenically unsaturated compounds having 2 or more functions of a carboxyl group and carboxylic anhydrides thereof.

When the ethylenically unsaturated compound having an acid group is at least 1 selected from the group consisting of ethylenically unsaturated compounds having 2 or more functions of a carboxyl group and carboxylic anhydrides thereof, the developability and the film strength are further improved.

The ethylenically unsaturated compound having a carboxyl group and a 2-or more-functional group is not particularly limited, and can be appropriately selected from known compounds.

Examples of the ethylenically unsaturated compound having 2 or more functional groups containing a carboxyl group include aroneix (registered trademark) TO-2349 (manufactured by TOAGOSEI co., ltd.), aroneix (registered trademark) M-520 (manufactured by TOAGOSEI co., ltd.), and aroneix (registered trademark) M-510 (manufactured by TOAGOSEI co., ltd.).

As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs [0025] to [0030] of Japanese patent application laid-open No. 2004-239942 is preferable, and the contents described in this publication are incorporated in the present specification.

Examples of the polymerizable compound include a compound obtained by reacting a polyhydric alcohol with an α, β -unsaturated carboxylic acid, a compound obtained by reacting a glycidyl group-containing compound with an α, β -unsaturated carboxylic acid, a urethane monomer such as a (meth) acrylate compound having a urethane bond, an phthalic acid compound such as γ -chloro- β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxyethyl- β ' - (meth) acryloyloxyethyl-phthalate, and β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, and an alkyl (meth) acrylate.

These may be used alone or in combination of 2 or more.

Examples of the compound obtained by reacting a polyhydric alcohol with an α, β -unsaturated carboxylic acid include bisphenol a-based (meth) acrylate compounds such as 2, 2-bis (4- ((meth) acryloyloxypolyethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxypolypropoxy) phenyl) propane and 2, 2-bis (4- ((meth) acryloyloxypolyethoxy polypropoxy) phenyl) propane, polyethylene glycol di (meth) acrylates having an ethylene oxide number of 2 to 14, polypropylene glycol di (meth) acrylates having an propylene oxide number of 2 to 14, polyethylene glycol polypropylene glycol di (meth) acrylates having an ethylene oxide number of 2 to 14 and a propylene oxide number of 2 to 14, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxy tri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxy tri (meth) acrylate, trimethylolpropane tetra (meth) acrylate, tetramethylolpropane di (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Among them, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or ditrimethylolpropane tetraacrylate is more preferable.

Examples of the polymerizable compound include caprolactone-modified compounds of ethylenically unsaturated compounds (e.g., nippon Kayaku Co., ltd., DPCA-20 manufactured by Kayarad (registered trademark) manufactured by Ltd., SHIN-NAKAMURA CHEMICAL Co., ltd., A-9300-1CL manufactured by Ltd.), alkylene oxide-modified compounds of ethylenically unsaturated compounds (e.g., nippon Kayaku Co., ltd., KAYARADR-1040 manufactured by Ltd., SHIN-NAKAMURA CHEMICAL Co., ltd., ATM-35E manufactured by Ltd., A-9300, DAICEL-ALLNEX LTD, EBECRYL (registered trademark) 135 manufactured by Ltd.), ethoxylated glycerol esters (SHIN-NAKARA CHEMICAL Co., ltd., A-GLY-9E manufactured by Ltd.), and the like.

Among them, the polymerizable compound (particularly, ethylenically unsaturated compound) preferably further contains an ester bond in view of excellent developability of the photosensitive layer after transfer.

The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, and from the viewpoint of the excellent effect of the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferable, and tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, or ditrimethylolpropane tetraacrylate is more preferable.

From the viewpoint of providing reliability, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and an ethylenically unsaturated compound having the above-described tetramethylolmethane structure or trimethylolpropane structure.

Examples of the ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms include 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate.

One of preferred embodiments of the polymerizable compound is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably, a 2-functional ethylenically unsaturated compound).

The polymerizable compound is preferably a polymerizable compound having a ring structure in which 2 or more aliphatic hydrocarbon rings are condensed (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure), more preferably a 2-functional ethylenically unsaturated compound having a ring structure in which 2 or more aliphatic hydrocarbon rings are condensed, and still more preferably tricyclodecanedimethanol di (meth) acrylate.

The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isophorone structure.

The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

The proportion of the content of the polymerizable compound having a molecular weight of 300 or less in the polymerizable compound contained in the photosensitive layer is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, relative to the content of all the polymerizable compounds contained in the photosensitive layer.

As one of preferable embodiments of the photosensitive layer, the photosensitive layer preferably contains an ethylenically unsaturated compound having 2 or more functions, more preferably contains an ethylenically unsaturated compound having 3 or more functions, and further preferably contains an ethylenically unsaturated compound having 3 or 4 functions.

In a preferred embodiment of the photosensitive layer, the photosensitive layer preferably contains a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and a binder polymer containing a structural unit having an aliphatic hydrocarbon ring.

Further, as one of preferable embodiments of the photosensitive layer, the photosensitive layer preferably contains a compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group, more preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, and further preferably contains a succinic acid-modified product of 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and dipentaerythritol pentaacrylate.

In addition, as one of preferable embodiments of the photosensitive layer, the photosensitive layer preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described later, and more preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

In addition, as one of preferable embodiments of the photosensitive layer, the photosensitive layer preferably contains a 2-functional ethylenically unsaturated compound (preferably a 2-functional (meth) acrylate compound) and a 3-functional or higher ethylenically unsaturated compound (preferably a 3-functional or higher (meth) acrylate compound) from the viewpoint of development residue inhibition and rust prevention.

The mass ratio of the content of the 2-functional ethylenically unsaturated compound to the content of the 3-or more-functional ethylenically unsaturated compound is preferably 10 to 90, more preferably 30.

The content of the 2-functional ethylenically unsaturated compound relative to the total amount of all ethylenically unsaturated compounds is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.

The 2-functional ethylenically unsaturated compound in the photosensitive layer is preferably 10 to 60% by mass, more preferably 15 to 40% by mass.

In addition, as one of preferable embodiments of the photosensitive layer, the photosensitive layer preferably contains the compound M and a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention.

In addition, as one of preferable embodiments of the photosensitive layer, from the viewpoint of substrate adhesion, development residue suppression property, and rust prevention property, the photosensitive layer preferably contains the compound M and an ethylenically unsaturated compound having an acid group, more preferably contains the compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group, further preferably contains the compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having 3 or more functions, and an ethylenically unsaturated compound having an acid group, and particularly preferably contains the compound M, a 2-functional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, an ethylenically unsaturated compound having 3 or more functions, an ethylenically unsaturated compound having an acid group, and a urethane (meth) acrylate compound.

In addition, as one of preferable embodiments of the photosensitive layer, from the viewpoint of substrate adhesion, development residue suppression property, and rust prevention property, the photosensitive layer preferably contains 1, 9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, still more preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably contains 1, 9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

The photosensitive layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.

The content of the ethylenically unsaturated compound having 2 or more functions in the ethylenically unsaturated compound is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass, based on the total content of all ethylenically unsaturated compounds contained in the photosensitive layer.

The polymerizable compound (particularly, the ethylenically unsaturated compound) may be used alone in 1 kind or in combination of 2 or more kinds.

The content of the polymerizable compound (particularly, an ethylenically unsaturated compound) in the photosensitive layer is preferably 1 to 70% by mass, more preferably 5 to 70% by mass, still more preferably 5 to 60% by mass, and particularly preferably 5 to 50% by mass, based on the total mass of the photosensitive layer.

(polymerization initiator)

The photosensitive layer may contain a polymerization initiator.

As the polymerization initiator, a photopolymerization initiator is preferable.

The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α -aminoalkylphenone structure (hereinafter, also referred to as an "α -aminoalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an α -hydroxyalkylphenone structure (hereinafter, also referred to as an "α -hydroxyalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, also referred to as an "N-phenylglycine-based photopolymerization initiator").

The photopolymerization initiator preferably contains at least 1 selected from the group consisting of oxime-based photopolymerization initiators, α -aminoalkylphenyl ketone-based photopolymerization initiators, α -hydroxyalkylphenyl ketone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators, and more preferably contains at least 1 selected from the group consisting of oxime-based photopolymerization initiators, α -aminoalkylphenyl ketone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators.

Further, as the photopolymerization initiator, for example, the photopolymerization initiators described in paragraphs [0031] to [0042] of Japanese patent application laid-open No. 2011-95716 and paragraphs [0064] to [0081] of Japanese patent application laid-open No. 2015-014783 can be used.

Examples of commercially available photopolymerization initiators include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (O-benzoyloxime) [ product name: IRGACURE (registered trademark) OXE-01, manufactured by basf corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetoxime) [ product name: IRGACURE (registered trademark) OXE-02 manufactured by BASF, IRGACURE (registered trademark) OXE03 manufactured by BASF, IRGACURE (registered trademark) OXE04 manufactured by BASF, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone [ trade name: omnirad (registered trade Mark) 379EG, IGM Resins B.V., manufactured, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [ trade name: omnirad (registered trademark) 907, manufactured by IGM Resins B.V., 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one [ trade name: omnirad (registered trademark) 127, manufactured by IGM Resins b.v., 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 [ trade name: omnirad (registered trademark) 369, igm Resins b.v., manufactured, 2-hydroxy-2-methyl-1-phenylpropan-1-one [ trade name: omnirad (registered trademark) 1173, igm Resins b.v., manufactured ], 1-hydroxycyclohexyl phenyl ketone [ trade name: omnirad (registered trademark) 184, manufactured by igm Resins b.v., 2-dimethoxy-1, 2-diphenylethan-1-one [ trade name: omnirad (registered trademark) 651, IGM Resins B.V., and the like, and oxime ester photopolymerization initiators [ trade names: lunar (registered trademark) 6, DKKH Management Ltd. ], 1- [4- (phenylthio) phenyl ] -3-cyclopentylpropane-1, 2-dione-2- (O-benzoyloxime) (trade name: TR-PBG-305, changzhou 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-acetyloxime) (trade name: TR-PBG-326, changzhou Tronly New Electronic Materials Co., manufactured by LTD), 3-cyclohexyl-1- (6- (2- (benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazol-3-yl) -propane-1, 2-dione-2- (O-benzoyl) (trade name: 391-dimethyl-3-yl) -propane-1, 2-dione-2- (O-benzoyl) biphenyl, UV-2- (morpholine-1- (4-methyl-ethyl-1, TM-phenyl) -propane-1, 2-dione-2- (O-benzoyl-3-ethyl-carbazole Co., manufactured by LTD., LTD, etc.

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

When 2 or more kinds are used simultaneously, at least 1 kind selected from the oxime type photopolymerization initiator, the α -aminoalkylbenzophenone type photopolymerization initiator, and the α -hydroxyalkylphenone type photopolymerization initiator is preferably used.

When the photosensitive layer contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more, based on the total mass of the photosensitive layer. The upper limit is preferably 10 mass% or less, and more preferably 5 mass% or less, based on the total mass of the photosensitive composition layer.

(heterocyclic compound)

The photosensitive layer may include a heterocyclic compound.

The heterocyclic ring of the heterocyclic compound may be any of monocyclic and polycyclic.

Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom and a sulfur atom. The heterocyclic compound preferably has at least 1 atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably has a nitrogen atom.

Examples of the heterocyclic compound include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, and a pyrimidine compound.

Among the above, the heterocyclic compound is preferably at least 1 compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzimidazole compound and a benzoxazole compound, and more preferably at least 1 compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound and a benzoxazole compound.

Preferred specific examples of the heterocyclic compound are shown below. Examples of the triazole compound and benzotriazole compound include the following compounds.

[ chemical formula 13]

[ chemical formula 14]

Examples of the tetrazole compound include the following compounds.

[ chemical formula 15]

[ chemical formula 16]

Examples of the thiadiazole compound include the following compounds.

[ chemical formula 17]

Examples of the triazine compound include the following compounds.

[ chemical formula 18]

Examples of the rhodanine compound include the following compounds.

[ chemical formula 19]

Examples of the thiazole compound include the following compounds.

[ chemical formula 20]

Examples of the benzothiazole compound include the following compounds.

[ chemical formula 21]

Examples of the benzimidazole compound include the following compounds.

[ chemical formula 22]

[ chemical formula 23]

As the benzoxazole compound, the following compounds can be exemplified.

[ chemical formula 24]

The heterocyclic compounds can be used alone in 1 kind, also can be used simultaneously in more than 2 kinds.

When the photosensitive layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20.0% by mass, more preferably 0.10 to 10.0% by mass, even more preferably 0.30 to 8.0% by mass, and particularly preferably 0.50 to 5.0% by mass, based on the total mass of the photosensitive layer.

(aliphatic thiol Compound)

The photosensitive layer may contain an aliphatic thiol compound.

The photosensitive layer contains an aliphatic thiol compound, and thus curing shrinkage and stress relaxation of a film formed by an ene-thiol reaction between the aliphatic thiol compound and a radical polymerizable compound having an ethylenically unsaturated group are suppressed.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., an aliphatic thiol compound having 2 or more functions) is preferable.

Among the above, the aliphatic thiol compound is preferably a polyfunctional aliphatic thiol compound in view of the adhesion of the formed pattern (particularly, the adhesion after exposure).

In the present specification, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having 2 or more thiol groups (also referred to as "mercapto groups") in the molecule.

The polyfunctional aliphatic thiol compound is preferably a low-molecular-weight compound having a molecular weight of 100 or more. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and still more preferably 150 to 1,000.

The number of functional groups of the polyfunctional aliphatic thiol compound is, for example, preferably 2 to 10 functional groups, more preferably 2 to 8 functional groups, and still more preferably 2 to 6 functional groups, from the viewpoint of adhesion of a formed pattern.

Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolethane tris (3-mercaptobutyrate), tris [ (3-mercaptopropionyloxy) ethyl ] isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), ethylene glycol bisthiopropionate, 1, 2-ethanedithiol, 1, 3-propane dithiol, 1, 6-hexamethylene dithiol, 2' - (ethylenedithio) diethylthiol, meso-2, 3-dimercapto, and bis (mercaptoethyl) succinate.

Among the above, as the polyfunctional aliphatic thiol compound, at least 1 compound selected from trimethylolpropane tris (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane and 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6 (1h, 3h, 5h) -trione is preferable.

Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

The photosensitive layer may contain 1 kind of aliphatic thiol compound alone, or may contain 2 or more kinds of aliphatic thiol compounds.

When the photosensitive layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, further preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass, based on the total mass of the photosensitive layer.

(thermally crosslinkable Compound)

The photosensitive layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group is regarded as a thermally crosslinkable compound, and is not regarded as an ethylenically unsaturated compound.

Examples of the thermally crosslinkable compound include an epoxy compound, an oxetane compound, a methylol compound and a blocked isocyanate compound. Among them, blocked isocyanate compounds are preferable from the viewpoint 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 at least one of the binder polymer and the radical polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film tends to decrease and the function as a protective film tends to be enhanced.

The blocked isocyanate compound is a "compound having a structure in which an isocyanate group of an isocyanate is protected (so-called masked) by a blocking agent".

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100 to 160 ℃ and more preferably 130 to 150 ℃.

The dissociation temperature of the blocked isocyanate means "a temperature of an endothermic peak accompanying deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a Differential scanning calorimeter".

As the differential scanning calorimeter, for example, a differential scanning calorimeter made by Seiko Instruments Inc. (model: DSC 6200) can be preferably used. However, the differential scanning calorimeter is not limited thereto.

Examples of the blocking agent having a dissociation temperature of 100 to 160 ℃ include an active methylene compound [ malonic diester (dimethyl malonate, diethyl malonate, di-N-butyl malonate, di-2-ethylhexyl malonate, etc.) ], an oxime compound (a compound having a structure represented by-C (= N-OH) -in a molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime).

Among them, the blocking agent having a dissociation temperature of 100 to 160 ℃ is preferably at least 1 selected from oxime compounds, for example, from the viewpoint of storage stability.

For example, the blocked isocyanate compound preferably has an isocyanurate structure in terms of improving the brittleness of the film, increasing the adhesion force with the transfer target, and the like.

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

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

The blocked isocyanate compound may have a polymerizable group.

The polymerizable group is not particularly limited, and a known polymerizable group can be used, and a radical polymerizable group is preferred.

Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloyloxy group, a (meth) acrylamide group, and a styryl group, and a group having an epoxy group such as a glycidyl group.

Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloyloxy group, and still more preferably an acryloyloxy group.

As the blocked isocyanate compound, commercially available products can be used.

Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BP, and the like (hereinafter, made by SHOWA DENKO K.), and blocked Duranate series (for example, duranate (registered trademark) TPA-B80E, duranate (registered trademark) WT32-B75P, and the like, made by Asahi Kasei Corporation).

The thermally crosslinkable compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When the photosensitive layer contains a thermally crosslinkable compound, 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.

(Hydrogen donor Compound)

The photosensitive layer may contain a hydrogen donor compound.

The hydrogen donor compound has the effects of further improving the sensitivity of the photopolymerization initiator to active light, suppressing inhibition of polymerization of the polymerizable compound by oxygen, and the like.

Examples of the hydrogen donor compound include amines and amino acid compounds.

Examples of the amines include compounds described in M.R. Sander et al, "Journal of Polymer Society" at volume 10, 3173 (1972), japanese patent publication No. 44-020189, japanese patent publication No. 51-082102, japanese patent publication No. 52-134692, japanese patent publication No. 59-138205, japanese patent publication No. 60-084305, japanese patent publication No. 62-018537, japanese patent publication No. 64-033104, and Research Disclosure No. 33825. More specifically, 4' -bis (diethylamino) benzophenone, tris (4-dimethylaminophenyl) methane (otherwise known as leuco crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline and p-methylthiodimethylaniline are mentioned.

Among them, in view of further excellent effects of the present invention, the amine is preferably at least 1 selected from the group consisting of 4,4' -bis (diethylamino) benzophenone and tris (4-dimethylaminophenyl) methane.

Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

Among them, N-phenylglycine is preferable as the amino acid compound in view of further improving the effect of the present invention.

Further, examples of the hydrogen donor compound include an organometallic compound (tributyltin acetate, etc.) described in Japanese patent publication No. 48-042965, a hydrogen donor described in Japanese patent publication No. 55-034414, and a sulfur compound (trithiane, etc.) described in Japanese patent publication No. 6-308727.

The hydrogen donor compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When the photosensitive layer contains a hydrogen donor compound, the content of the hydrogen donor compound is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 8.0% by mass, and further preferably 0.03 to 5.0% by mass, based on the total mass of the photosensitive layer, from the viewpoint of improvement of the curing rate based on the balance between the polymerization growth rate and the chain transfer.

(other additives)

The photosensitive layer may contain other additives than the above components.

The other additives are the same as those contained in the photosensitive layer in the composition layer of embodiment 1, and the preferred embodiment is also the same.

(impurities)

The photosensitive layer may contain impurities.

The impurities are the same as those contained in the photosensitive layer in the composition layer of embodiment 1, and the preferable embodiment is also the same.

(other Components)

The photosensitive layer may contain a component other than the above-described components (hereinafter, also referred to as "other component"). Examples of the other components include a colorant, an antioxidant, and particles (for example, metal oxide particles). Further, as other components, there may be mentioned other additives described in paragraphs [0058] to [0071] of Japanese patent laid-open No. 2000-310706.

Particles-

As the particles, metal oxide particles are preferable.

The metal in the metal oxide particles also includes semimetals such As B, si, ge, as, sb and Te.

For example, the average primary particle diameter of the particles is preferably 1 to 200nm, more preferably 3 to 80nm, from the viewpoint of transparency of the cured film.

The average primary particle size of the particles is calculated by measuring the particle sizes of arbitrary 200 particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particles is not spherical, the longest side is defined as the particle diameter.

Colorants-

The photosensitive layer may contain a small amount of a colorant (pigment, dye, etc.), but preferably contains substantially no colorant from the viewpoint of transparency, for example.

When the photosensitive layer contains a colorant, the content of the colorant is preferably less than 1% by mass, and more preferably less than 0.1% by mass, based on the total mass of the photosensitive layer.

Antioxidants-

Examples of the antioxidant include 3-pyrazolones such as 1-phenyl-3-pyrazolone (also referred to as phenanthrinone), 1-phenyl-4, 4-dimethyl-3-pyrazolone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; p-methyl aminophenol, p-hydroxyphenylglycine and p-phenylenediamine.

Among them, from the viewpoint of further improving the effect of the present invention, 3-pyrazolones are preferable, and 1-phenyl-3-pyrazolones are more preferable as the antioxidant.

[ method for producing laminate ]

Examples of the method for producing the laminate of the present invention include known production methods.

Specifically, there is a method for producing the composition, in which the 1 st composition layer, the 1 st transparent conductive layer, the substrate, the 2 nd transparent conductive layer, and the 2 nd composition are formed in this order simultaneously or sequentially.

[ method for Forming transparent conductive layer ]

As a method for forming the 1 st transparent conductive layer and the 2 nd transparent conductive layer, for example, a known method can be given.

Specific examples thereof include a coating method, a vacuum deposition method, a sputtering method, and a plating method. Examples of the coating method include 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).

Further, a method of mixing components, a solvent, and a resin that can be contained in the transparent conductive layer and coating with the composition for forming a transparent conductive layer is preferable.

[ method of Forming composition layer ]

Examples of the method for forming the 1 st composition layer and the 2 nd composition layer include a coating method and a method using a transfer film described later.

The method for forming the 1 st composition layer and the 2 nd composition layer may be the same or different.

As the method for forming the 1 st composition layer and the 2 nd composition layer, a method for forming a transfer film is preferably used for each of the 1 st photosensitive layer and the 2 nd photosensitive layer.

As a method for forming a transfer film, for example, a method of bonding a substrate on which a 1 st transparent conductive layer and a 2 nd transparent conductive layer are formed (hereinafter, also referred to as a "substrate with a transparent conductive layer") to a transfer film is given.

The substrate with a transparent conductive layer is not particularly limited as long as it has the substrate, the 1 st transparent conductive layer, and the 2 nd transparent conductive layer. Preferred embodiments of the substrate and the transparent conductive layer are as described above.

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. In the method of bonding the substrate with the transparent conductive layer and the transfer film, roll-to-roll may be performed according to the material of the substrate with the transparent conductive layer.

The transfer of the 1 st composition layer to the substrate with the transparent conductive layer and the transfer of the 2 nd photosensitive layer to the substrate with the transparent conductive layer may be performed simultaneously or separately.

[ method for Forming light-absorbing layer ]

Examples of the method for forming the light absorbing layer include a coating method and a method using a transfer film described later.

In the case of the method using a transfer film having a composition layer on which a light-absorbing layer is further formed, the transfer film having the composition layer and the light-absorbing layer is preferably used.

Further, the following method may be used: after the transfer film having the composition layer but not having the light absorbing layer was transferred to the substrate with the transparent conductive layer, the light absorbing layer was further formed on the composition layer.

[ formation method of other layer ]

Examples of the method for forming the other layer include known methods such as coating, vacuum deposition, sputtering, and lamination.

[ use of laminate ]

The laminate of the present invention can be applied to various apparatuses. Examples of the device having 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 the production of conductive films 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).

[ Pattern Forming method ]

The pattern forming method comprises exposing the 1 st photosensitive layer and the 2 nd photosensitive layer of the laminate to light and developing to form a pattern,

the pattern forming method includes:

Exposing the 1 st photosensitive layer;

exposing the 2 nd photosensitive layer; and

and a developing step of developing the exposed 1 st photosensitive layer and the exposed 2 nd photosensitive layer to form a 1 st pattern and a 2 nd pattern.

[ Exposure procedure ]

The pattern forming method includes a step of exposing the 1 st photosensitive layer and a step of exposing the 2 nd photosensitive layer as an exposure step. That is, the pattern forming method includes a step of performing exposure from both sides of one side of the 1 st photosensitive layer opposite to the substrate and one side of the 2 nd photosensitive layer opposite to the substrate. The step of exposing the 1 st photosensitive layer and the step of exposing the 2 nd photosensitive layer may be performed sequentially or simultaneously. In other words, the 1 st photosensitive layer may be exposed from the side of the 1 st photosensitive layer opposite to the substrate, and then the 2 nd photosensitive layer may be exposed from the side of the 2 nd photosensitive layer opposite to the substrate, or the 1 st photosensitive layer may be exposed from the side of the 1 st photosensitive layer opposite to the substrate, and then the 2 nd photosensitive layer may be exposed from the side of the 2 nd photosensitive layer opposite to the substrate.

Further, the exposure from the side of the 1 st photosensitive layer opposite to the substrate to the 1 st photosensitive layer and the exposure from the side of the 2 nd photosensitive layer opposite to the substrate to the 2 nd photosensitive layer may be performed simultaneously.

The photosensitive layer exposed in the exposure step has a change in solubility in a developer between the exposed portion and the unexposed portion. For example, when the photosensitive layer is a positive photosensitive layer, the exposed portion of the photosensitive layer has higher solubility in a developer than the unexposed portion. On the other hand, for example, when the photosensitive layer is a negative photosensitive layer, the exposed portion of the photosensitive layer has 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 layer and the exposure light source, the 1 st photosensitive layer can be pattern-exposed through the photomask. By pattern-exposing the 1 st photosensitive layer, exposed portions and unexposed portions can be formed on the 1 st photosensitive layer.

In the exposure step, exposure is preferably performed by bringing the composition layer or the temporary support into contact with a photomask in view of further improving the resolution (hereinafter, also referred to as "contact exposure").

In the exposure step, in addition to the contact exposure, a proximity exposure, a lens-based or mirror-based projection exposure system, or a direct exposure system 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 a suitable lens in accordance with the resolution and the depth of focus. The direct exposure method may be a method of directly drawing on the photosensitive layer or a method of performing reduction projection exposure on the photosensitive layer through a lens. The exposure may be performed under the atmosphere, under reduced pressure or under vacuum, or may be performed by adding a liquid such as water between the exposure light source and the photosensitive layer.

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

The temporary support used when the photosensitive layer is exposed through the temporary support is preferably a film that can transmit light irradiated during exposure. Further, as the temporary support, a temporary support provided in the transfer film is also preferable.

In the exposure step, the main wavelength λ of the exposure wavelength is directed to one side of the 1 st photosensitive layer opposite to the substrate ₁ A main wavelength lambda of an exposure wavelength for a side of the 2 nd photosensitive layer opposite to the substrate ₂ May be the same or different.

Dominant wavelength lambda ₁ And dominant wavelength lambda ₂ Is usually 10 to 450nm, preferably 300 to 450nm, more preferably 350 to 450nm, and still more preferably365nm or 436nm is selected.

The exposure amount is preferably 5 to 1000mJ/cm ² More preferably 10 to 500mJ/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 exposure light source include an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a Light Emitting Diode (LED).

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

In the case where the photosensitive layer is exposed without using a photomask (hereinafter, also referred to as "maskless exposure"), the photosensitive 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 (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 irradiating light having a wavelength of 350 to 410 nm. Dominant wavelength λ of exposure wavelength in maskless exposure ₁ And the main wavelength lambda of the exposure wavelength in the 2 nd photosensitive layer exposure step ₂ May be the same or different.

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 computer controlled.

[ development step 1 and development step 2 ]

The 1 st developing step is a step of developing the exposed 1 st photosensitive layer to form a 1 st pattern, and the 2 nd developing step is a step of developing the exposed 2 nd photosensitive layer to form a 2 nd pattern. The 1 st developing step and the 2 nd developing step may be performed sequentially or simultaneously. In other words, the 2 nd developing step may be performed after the 1 st developing step, or the 1 st developing step may be performed after the 2 nd developing step. Further, the 1 st developing step and the 2 nd developing step may be performed simultaneously.

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 ].

The developer is preferably an aqueous alkaline developer containing a compound having a pKa of 7 to 13. In the above aqueous alkali developer, the concentration of the compound having a pKa of 7 to 13 is preferably 0.05 to 5mol/L.

The developer may contain, for example, an organic solvent (water-soluble organic solvent) which can be mixed with water and a surfactant in addition to the above components.

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 development, spin development, and dip development.

A preferred embodiment of the pattern forming method includes simultaneously performing the step of exposing the 1 st photosensitive layer and the step of exposing the 2 nd photosensitive layer, and simultaneously performing the 1 st developing step and the 2 nd developing step. According to the above embodiment, since the time and environment from the exposure to the development start can be set to be the same, the product quality can be easily stabilized, and the process length can be shortened and the process cost can be reduced.

In another preferred embodiment of the pattern forming method, the step of exposing the 1 st photosensitive layer and the step of exposing the 2 nd photosensitive layer are preferably performed separately, or the 1 st developing step and the 2 nd developing step are preferably performed separately. For example, in the case where the reaction rate after exposure is significantly different between the 1 st photosensitive layer and the 2 nd photosensitive layer or in the case where different exposure light sources need to be arranged apart from the photosensitive layers, it is preferable to separately perform the step of exposing the 1 st photosensitive layer and the step of exposing the 2 nd photosensitive layer. For example, when the developer used for developing the 1 st photosensitive layer is different from the developer used for developing the 2 nd photosensitive layer, the 1 st developing step and the 2 nd developing step are preferably performed separately.

[ etching Process ]

The pattern forming method preferably further includes an etching step after the 1 st and 2 nd developing steps.

The etching step is a step of performing at least 1 of the following steps: and etching the 1 st transparent conductive layer using the 1 st pattern as a mask, and etching the 2 nd transparent conductive layer using the 2 nd pattern as a mask.

By performing the etching step, the pattern of the 1 st transparent conductive layer and/or the pattern of the 2 nd transparent conductive layer can be formed on the substrate.

Examples of the etching include dry etching and wet etching. Wet etching is preferable in terms of no need for a vacuum process and simplicity of the process. Examples of the etching include methods described in paragraphs [0048] to [0054] of Japanese patent application laid-open No. 2010-152155.

Examples of the etching solution used for wet etching include an acidic etching solution and an alkaline etching solution.

Examples of the acidic etching solution include an aqueous solution containing an acidic component (e.g., hydrochloric acid, sulfuric acid, nitric acid, fluoric acid, and phosphoric acid) and an aqueous solution containing an acidic component and a salt (e.g., ferric chloride, ammonium fluoride, ferric nitrate, and potassium permanganate).

The acidic etching solution may contain 1 kind of acidic component alone, or may contain 2 or more kinds. The acidic etching solution may contain 1 kind of salt alone, or may contain 2 or more kinds.

Examples of the alkaline etching solution include an aqueous solution containing an alkaline component [ e.g., sodium hydroxide, potassium hydroxide, ammonium, organic amine, and a salt of an organic amine (e.g., tetramethylammonium hydroxide) ], and an aqueous solution containing an alkaline component and a salt (e.g., potassium permanganate).

The alkaline etching solution may contain 1 alkali component alone, or may contain 2 or more alkali components. The alkaline etching solution may contain 1 kind of salt alone, or may contain 2 or more kinds.

The etching solution may contain a rust inhibitor in view of control of the etching rate. Examples of the rust inhibitor include nitrogen-containing compounds (e.g., triazole-based compounds, imidazole-based compounds, and tetrazole-based compounds).

The temperature of the etching solution is preferably 60 ℃ or lower, more preferably 45 ℃ or lower. The lower limit is usually 0 ℃ or higher.

In the pattern forming method of the present invention, it is preferable that the 1 st pattern used as a mask and the 2 nd pattern used as a mask have excellent resistance in an etching solution at 60 ℃.

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 productivity, it is preferable to simultaneously perform the etching treatment of the 1 st transparent conductive layer and the 2 nd transparent conductive layer.

[ cleaning step and drying step ]

The pattern forming method of the present invention may include a cleaning step and a drying step after the etching step, as necessary, in order to prevent contamination of the production line.

As the cleaning step, for example, a method of cleaning the laminate with pure water at normal temperature (e.g., 25 ℃) is exemplified. The washing time is usually 10 to 300 seconds.

As the drying step, a method of drying the laminate using a blower may be mentioned. The pressure of the blower is preferably 0.1-5 kg/cm ² 。

[ Whole surface Exposure Process ]

The pattern forming method of the present invention may include a step of performing full-surface exposure on at least one of the 1 st pattern and the 2 nd pattern (hereinafter, also referred to as a "full-surface exposure step").

The entire surface exposure step is preferably performed before the removal step described later. The pattern forming method of the present invention includes a full-surface exposure step, and thus has an effect of further improving the reactivity of a pattern remaining after development and/or improving the pattern removability in a removal step described later.

For example, a pattern formed of a positive photosensitive layer is subjected to a full-surface exposure step, thereby further improving the removability in a removal step to be described later. On the other hand, the resin pattern formed of the negative photosensitive layer is further cured in the entire surface exposure step, whereby the process resistance of the resin pattern is improved.

The term "full-surface exposure" refers to exposure of a region on the substrate where the 1 st pattern and the 2 nd pattern are arranged. The region of the substrate where the 1 st pattern is not disposed and the region of the substrate where the 2 nd pattern is not disposed may be exposed or not exposed. From the viewpoint of further excellent simplicity, the entire surface of the substrate is preferably exposed.

The exposure light source for the entire surface exposure is not particularly limited, and a known light source can be used. Examples of the exposure light source include an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and a Light Emitting Diode (LED).

The exposure wavelength in the entire exposure is the same as that in the double-side exposure step described above, and the preferred embodiment is the same.

The exposure dose in the whole exposure is preferably 5 to 1000mJ/cm from the viewpoint of removability ² More preferably 10 to 800mJ/cm ² More preferably 100 to 500mJ/cm ² 。

In view of removability, the exposure amount in the whole-surface exposure is preferably equal to or more than the exposure amount in the double-surface exposure step.

The exposure illuminance in the whole exposure is preferably 5 to 25000mW/cm ² More preferably 20 to 20000mW/cm ² More preferably 30 to 15000mW/cm ² . By increasing the illuminance, the time required for the entire exposure is shortened.

[ heating procedure ]

The pattern forming method of the present invention may include a step of heating at least one of the 1 st pattern and the 2 nd pattern (hereinafter, also referred to as a "heating step") at least one of during the entire exposure step, before the entire exposure step is performed, and before the removal step described later is performed.

The pattern forming method of the present invention includes a heating step, and thus the 1 st pattern and the 2 nd pattern can be easily removed. For example, in a pattern formed of a positive photosensitive layer, since the reaction rate of a photoacid generator and the reaction rate of a generated acid with a positive photosensitive composition can be increased, the removal performance can be improved.

The heating device is not particularly limited, and a known heating device can be used. Examples of the heating device include an infrared heater, a hot air blower, and a convection oven.

The heating temperature is preferably 30 to 100 ℃, more preferably 30 to 80 ℃, and still more preferably 30 to 60 ℃ from the viewpoint of removability.

The heating time is preferably 1 to 600 seconds, more preferably 1 to 120 seconds, and further preferably 5 to 60 seconds from the viewpoint of removability. The "heating time" herein means a time from the time when the surface of the substrate reaches a set temperature, and does not include a time during the temperature rise.

The heating environment is preferably air (relative humidity: 10 to 90% RH). The heating environment may be an inert gas (e.g., nitrogen and argon). The gas pressure is preferably normal pressure.

When a large amount of water adheres to the substrate, a step of blowing off excess water with an air knife or the like may be combined before and during at least one of the heating steps, from the viewpoint of improving the heating efficiency.

[ removal Process ]

The pattern forming method of the present invention may include a step of removing at least one of the 1 st pattern and the 2 nd pattern (hereinafter, also referred to as a "removal step").

As a method for removing the 1 st pattern and the 2 nd pattern, for example, a method using a chemical such as a removing solution is given, and as one specific example, a method of immersing the laminate in a removing solution is given.

The removing liquid is preferably a removing liquid capable of dissolving or dispersing the 1 st pattern and the 2 nd pattern.

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

The immersion time in the removing solution is preferably 1 to 30 minutes.

From the viewpoint of further improving the removability, the removing liquid is preferably aqueous.

The content of water in the removal liquid is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more.

The removing solution preferably contains an inorganic base component or an organic base component.

Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include primary to tertiary amine compounds and quaternary ammonium salt compounds.

The removal liquid preferably contains an organic alkali component in order to further improve the removal property. The content of the organic base component in the removal solution is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the removal solution, from the viewpoint of more excellent removal performance.

From the viewpoint of removability, the removing solution preferably contains a surfactant. The surfactant is not particularly limited, and a known surfactant can be used.

From the viewpoint of removability, the content of the surfactant is preferably 0.1 to 10% by mass based on the total mass of the removal liquid.

The removal solution also preferably contains a water-soluble organic solvent. Examples of the water-soluble organic solvent include dimethyl sulfoxide, a lower alcohol, a glycol ether, and N-methylpyrrolidone.

Examples of the method of bringing the removal liquid into contact with the resin pattern in the removal step include a spray method, a shower method, and a spin-coating immersion method.

As the removing liquid, the removing liquids described in Japanese patent application laid-open Nos. 11-021483, 2002-129067, 07-028254, 2001-188363, 04-048633 and 5318773 can be applied.

The removal of the 1 st resin pattern and the removal of the 2 nd resin pattern may be performed simultaneously or separately. From the viewpoint of productivity, the removal of the 1 st resin pattern and the removal of the 2 nd resin pattern are preferably performed simultaneously.

[ volume-to-volume approach ]

The pattern forming method of the present invention is preferably carried out by a roll-to-roll method.

The roll-to-roll method is not particularly limited, and a known roll-to-roll method can be used. For example, in the pattern forming method of the present invention, the step of winding out at least the laminate and the step of winding up at least the laminate are provided before and after at least 1 step, respectively, whereby the laminate can be processed while being carried.

[ other procedures ]

The pattern forming method of the present invention may include steps other than those described above.

Examples of the other steps include the following steps.

< Process for reducing reflectance of visible ray >

The pattern forming method of the present invention may include the steps of: the first transparent conductive layer 1 and the second transparent conductive layer 2 are partially or entirely reduced in visible light reflectance.

As the treatment for reducing the visible light reflectance, for example, oxidation treatment is given. For example, when the 1 st transparent conductive layer and the 2 nd transparent conductive layer contain copper, the visible light reflectance of the 1 st transparent conductive layer and the 2 nd transparent conductive layer can be reduced by oxidizing copper to form copper oxide.

Examples of the treatment for reducing the visible light reflectance include the descriptions in paragraphs [0017] to [0025] of Japanese patent application laid-open No. 2014-150118 and paragraphs [0041], [0042], [0048] and [0058] of Japanese patent application laid-open No. 2013-206315, which are incorporated herein by reference.

[ transfer film ]

The composition layer in the laminate is preferably formed using a transfer film.

The transfer film has a temporary support and a composition layer. The transfer film may further include another member (e.g., a protective film) or may include a light absorbing layer.

The composition layer is the same as the composition layer 1 and the composition layer 2, and the preferred embodiment is the same. The light absorbing layer is the same as the light absorbing layer described above, and the preferred embodiment is the same.

[ temporary support body ]

The transfer film has a temporary support.

The temporary support is a member that supports the photosensitive layer and is finally removed by a peeling process.

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 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 any 5 points measured by cross-sectional observation based on SEM (Scanning Electron Microscope).

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.

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

Examples of commercially available temporary supports include registered trademarks of Lumirror16KS40 and Lumirror16FB40 (both of which are incorporated herein by reference); COSMOSHINE a4100, COSMOSHINE a4300 and COSMOSHINE a8300 (made by TOYOBO co.

[ other details ]

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. The transfer film preferably has a protective film on the side of the composition layer opposite to the temporary support.

Examples of the protective film include a resin film having heat resistance and solvent resistance. Specifically, polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films are exemplified. 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 average 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 method of measuring the average thickness includes a method of measuring the average thickness of the base material.

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.

In the following examples, the weight average molecular weight of the resin was determined as a weight average molecular weight (Mw) in terms of polystyrene based on the Gel Permeation Chromatography (GPC).

[ transfer film ]

The following compositions were prepared, and using the obtained compositions, transfer films were produced in the following order.

[ photosensitive composition ]

Photosensitive compositions were prepared according to the components and ratios shown in table 1 below.

In table 1, the numerical values shown in the columns of the respective components indicate the contents (parts by mass) of the respective components.

< resin >

Resin A1: styrene/methacrylic acid/methyl methacrylate =32/28/40 (mass%) copolymer (Mw =40,000)

Resin A2: styrene/methacrylic acid/methyl methacrylate =50/28/22 (mass%) copolymer (Mw =60,000)

Resin A3: copolymer of benzyl methacrylate/methacrylic acid =81/19 (mass%) (Mw =40,000)

Resin A4: copolymer of benzyl methacrylate/methacrylic acid =80/20 (mass%) (Mw =30,000)

< polymerizable Compound >

BPE-500: ethoxylated bisphenol A dimethacrylate, SHIN-NAKAMURA CHEMICAL Co., ltd

BPE-200: ethoxylated bisphenol A dimethacrylate, SHIN-NAKAMURA CHEMICAL Co., ltd

Dimethacrylate of polyethylene glycol obtained by adding ethylene oxide and propylene oxide in an amount of 15mol and 2mol, respectively, 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., ltd

SR-454: ethoxylated (3) trimethylolpropane triacrylate, manufactured by Arkema s.a

SR-502: ethoxylated (9) trimethylolpropane triacrylate, manufactured by Arkema s.a

A-9300-1CL: caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd

A-HD-N:1, 6-hexanediol diacrylate, SHIN-NAKAMURA CHEMICAL Co., manufactured by Ltd

8UX-015A: multifunctional urethane acrylate compound (manufactured by Taisei Fine Chemical Co., ltd.)

< polymerization initiator >

B-CIM:2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (Kurogane Kasei Co., manufactured by Ltd.)

1, 2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (o-benzoyloxime) ]

< light absorbers >

TINUVIN391: benzotriazole Compound (maximum absorption wavelength 355nm, manufactured by BASF Co., ltd.)

< additive >

SB-PI 701:4,4' -bis (diethylamino) benzophenone (Sanyo Trading Co., ltd., manufactured by Ltd.)

3-acetyl-7- (diethylamino) coumarin (manufactured by FUJIFILM Wako Pure Chemical Corporation)

Colorless crystal violet (Tokyo Chemical Industry Co., ltd.)

N-phenylglycine (Tokyo Chemical Industry Co., ltd.)

Bright green (Tokyo Chemical Industry Co., ltd.)

CBT-1: carboxybenzotriazole (JOHOKU CHEMICAL CO., LTD products)

1

TDP-G: phenothiazine (Kawaguchi Chemical Industry Co., LTD. Product.)

Irganox 245 (manufactured by BASF corporation)

N-nitrosophenylhydroxylamine aluminum salt (manufactured by FUJIFILM Wako Pure Chemical Corporation)

Phenothiazine (manufactured by FUJIFILM Wako Pure Chemical Corporation)

Phenidone (Tokyo Chemical Industry Co., ltd.)

MEGAFACE F-552: fluorine type surfactant (DIC Corporation)

< 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 obtained mixed solvent was used so that the solid content concentration of each photosensitive composition became 13 mass%.

[ Table 1]

[ composition for Forming intermediate layer ]

The following components were mixed to prepare an intermediate layer-forming composition 1.

Ion exchange water: 38.12 parts by mass

Methanol (MITSUBISHI GAS CHEMICAL COMPANY, inc.): 57.17 parts by mass

Kuraray Poval 4-88LA (polyvinyl alcohol, manufactured by Kuraray Co., ltd.): 3.22 parts by mass

Polyvinylpyrrolidone K-30 (NIPPON shokubali co., ltd.): 1.49 parts by mass

MEGAFACE F-444 (fluorine-based surfactant, manufactured by DIC Corporation): 0.0035 parts by mass

[ composition for Forming thermoplastic resin layer ]

Composition 1 for forming a thermoplastic resin layer was prepared by mixing the components shown in the following table.

< resin >

Resin A5: benzyl methacrylate/methacrylic acid/acrylic acid copolymer =75/10/15 (mass%), weight average molecular weight: 30,000, glass transition temperature: 75 ℃, acid value: 186mgKOH/g

< pigments >

B-1: the following compounds

[ chemical formula 25]

< photoacid generators >

C-1: the following compounds (the compounds described in paragraph [0227] of Japanese patent laid-open No. 2013-047765)

[ chemical formula 26]

< polymeric Compound >

NK ESTER A-DCP: dicidol diacrylate (SHIN-NAKAMURA CHEMICAL Co., ltd.)

8UX-015A: multifunctional urethane acrylate compound (manufactured by Taisei Fine Chemical Co., ltd.)

Aronex TO-2349: polyfunctional acrylate compound having carboxyl group (TOAGOSEI CO., LTD. Manufactured)

< additive >

MEGAFACE F-552: fluorine-based surfactant (manufactured by DIC Corporation)

Phenothiazine (manufactured by FUJIFILM Wako Pure Chemical Corporation)

CBT-1: carboxybenzotriazole (JOHOKU CHEMICAL CO., LTD products)

< solvent >

MEK: methyl ethyl ketone

PGME: propylene glycol monomethyl ether

PGMEA: propylene glycol monomethyl ether acetate

The numerical values of the contents of the respective components in the tables are parts by mass.

[ Table 2]

[ temporary support body ]

The temporary support 1 is produced by the following method.

< composition for forming particle-containing layer >

The respective components were mixed in the following compounding ratio to obtain a composition 1 for forming a particle-containing layer. After the preparation of the composition 1 for forming a particle-containing layer, the mixture was filtered through a 6 μm filter (F20, manufactured by MAHLE Japan ltd.), and then the membrane was degassed with 2 × 6RADIAL FLOW supprboic (manufactured by Polypore International, inc.).

Acrylic polymer (AS-56TA, manufactured by Daicel Mirazu Ltd., solid content 27.5 mass%): 167 parts by mass of

Nonionic surfactant (NAROACTY CL95, manufactured by Sanyo Chemical Industries, ltd., solid content 100 mass%): 0.7 part by mass

An anionic surfactant (RAPISOL A-90, manufactured by NOF CORPORATION, diluted with water to a solid content of 1% by mass): 114.4 parts by mass

Carnauba wax dispersion (Cellosol 524, chukyo YUSHI CO., ltd., 30 mass% solid content): 7 parts by mass

Carbodiimide compound (CARBODILITE V-02-L2, nisshinbo co., ltd., made by diluting with water to a solid content of 10 mass%): 20.9 parts by mass

Matting agent (SNOWTEX XL, manufactured by Nissan Chemical Corporation, solid content 40 mass%, average particle diameter 50 nm): 2.8 parts by mass

Water: 690.2 parts by mass

< production of temporary support >

The temporary support 1 was produced in the following order.

(extrusion Molding)

The polyethylene terephthalate pellets obtained were dried to a water content of 50ppm or less using a citric acid chelate organic titanium complex (Japanese patent No. 5575671) as a polymerization catalyst, and then placed in a hopper of a single-shaft kneading extruder having a diameter of 30mm, melted at 280 ℃ and extruded. 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 coating)

The cured unstretched film was successively subjected to biaxial stretching by the following method to obtain a temporary support comprising a polyester film having a thickness of 16 μm and a particle-containing layer having a thickness of 40 nm.

(a) Longitudinal stretching

The unstretched film was stretched in the longitudinal direction (carrying direction) by passing between 2 pairs of nip rolls having different peripheral speeds. Further, stretching was performed with 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

The particle-containing layer-forming composition 1 was applied to one surface of the longitudinally stretched film by a bar coater until the thickness became 40nm after film formation.

(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.

Preheating temperature: 110 deg.C

Stretching temperature: 120 deg.C

Stretching ratio: 4.2 times of

Stretching speed: 50%/second

(d) Heat setting and heat relaxation

The biaxially stretched film after the end of the longitudinal stretching and the transverse stretching was heat-set under the following conditions.

Heat setting temperature: 227 deg.C

Heat setting time: 6 seconds

After heat setting, the width of the tenter was reduced, and heat relaxation was performed under the following conditions.

Thermal relaxation temperature: 190 deg.C

Thermal relaxation rate: 4 percent of

(e) Coiling

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 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 measured from the cross-sectional TEM photograph and was 40nm. The average particle diameter of the particles contained in the particle-containing layer was measured by the above method using a transmission electron microscope (TEM, manufactured by Hitachi High-Technologies Corporation) of model HT-7700, and found to be 50nm.

[ transfer printing film production ]

The obtained temporary support 1 was coated with the thermoplastic resin layer-forming composition 1 using a slit nozzle until the coating width became 25cm and the thickness of the thermoplastic resin layer 1 became 3.0 μm. The obtained coating film was dried at 80 ℃ for 40 seconds, whereby the thermoplastic resin layer 1 was formed on the temporary support 1.

The intermediate layer-forming composition 1 was applied to the surface of the thermoplastic resin layer 1 opposite to the temporary support using a slit nozzle until the application width became 25cm and the film thickness of the intermediate layer 1 became 1.0 μm. The obtained coating film was dried at 80 ℃ for 40 seconds, whereby the intermediate layer 1 was formed on the thermoplastic resin layer 1.

Then, the photosensitive composition 1 was applied to the surface of the formed intermediate layer 1 opposite to the thermoplastic resin layer 1 by using a slit nozzle until the application width became 25cm and the film thickness of the photosensitive composition layer 1 became 4.0 μm, and the photosensitive composition layer 1 was dried at 100 ℃ for 2 minutes, thereby forming the photosensitive composition layer 1. A protective film (polypropylene film, thickness: 12 μm) was bonded to the surface of the obtained photosensitive resin layer 1 opposite to the intermediate layer 1 to prepare a transfer film 1 (transfer film used in example 1).

< light absorbing layer >

When the laminate has a light absorbing layer, the light absorbing layer 1 is formed in the following order.

First, a composition 1 for forming a light-absorbing layer was prepared in accordance with the following table.

The protective film of the transfer film obtained above was peeled off, and the light absorbing layer forming composition 1 was applied to the surface of the exposed photosensitive composition layer using a slit nozzle until the application width became 25cm and the film thickness of the light absorbing layer 1 became 2 μm. The obtained coating film was dried at 80 ℃ for 40 seconds, whereby the light absorbing layer 1 was formed on the photosensitive composition layer 1. A protective film (polypropylene film, thickness: 12 μm) was attached to the surface of the obtained light-absorbing layer 1 opposite to the photosensitive composition layer 1 to prepare a transfer film 2 (transfer film used in example 9).

(resin)

Resin A5: benzyl methacrylate/methacrylic acid/acrylic acid copolymer =75/10/15 (mass%), weight average molecular weight: 30,000, glass transition temperature: 75 ℃, acid value: 186mgKOH/g

(polymerizable Compound)

NK ESTER A-DCP: dicidol diacrylate (SHIN-NAKAMURA CHEMICAL Co., ltd.)

8UX-015A: multifunctional urethane acrylate compound (manufactured by Taisei Fine Chemical Co., ltd.)

Aronium TO-2349: polyfunctional acrylate compound having carboxyl group (TOAGOSEI CO., LTD. Manufactured by Ltd.)

< light absorbers >

TINUVIN391: benzotriazole Compound (maximum absorption wavelength 355nm, manufactured by BASF Co., ltd.)

TINUVIN1577ED: triazine Compound (maximum absorption wavelength 274nm and 341nm, manufactured by BASF corporation)

TINUVIN400: triazine Compound (maximum absorption wavelength 336nm, manufactured by BASF Co., ltd.)

TINUVIN384-2: benzotriazole Compound (maximum absorption wavelength 345nm, manufactured by BASF corporation)

UVINEL 3049: benzophenone Compound (maximum absorption wavelength 280nm and 348nm, manufactured by BASF Co., ltd.)

Uvinell 3039: cyanoacrylate Compound (absorption maximum wavelength 305nm, manufactured by BASF Co., ltd.)

2-ethylhexyl salicylate: salicylate compound (maximum absorption wavelength 307 nm)

KEMISORB 500: benzoxazine compound (maximum absorption wavelengths 315nm, 338nm and 348nm, chemipro Kasei Kaisha, ltd.)

< additive >

MEGAFACE F-552: fluorine-based surfactant (manufactured by DIC Corporation)

Phenothiazine (manufactured by FUJIFILM Wako Pure Chemical Corporation)

CBT-1: carboxybenzotriazole (JOHOKU CHEMICAL CO., LTD products)

< solvent >

MEK: methyl ethyl ketone

PGME: propylene glycol monomethyl ether

PGMEA: propylene glycol monomethyl ether acetate

The numerical values of the contents of the respective components in the tables are parts by mass.

[ Table 3]

Referring to the order of production of the transfer films 1 and 2, transfer films were produced using the compositions for forming various layers to produce laminates shown in table 4 below. For example, in example 28, a laminate was formed using a transfer film obtained by using composition 2 for forming a light-absorbing layer instead of composition 1 for forming a light-absorbing layer.

In examples 26, 27, 38, and 39, a laminate was formed using a transfer film in which various photosensitive composition layers were provided on the temporary support 1 without providing a thermoplastic resin layer and an intermediate layer.

[ base Material with transparent conductive layer 1]

An ink (DNS-0163i, manufactured by daicel Corporation) containing silver nanoparticles and a resin was applied to a substrate 1 (polyester film, lumirror (registered trademark) #100-U34, manufactured by TORAY INDUSTRIES, inc.) by an ink jet method until the applied width became 25cm and the dried film thickness became 1.0 μm, and the substrate 1 with the transparent conductive layer was formed by firing at 120 ℃ for 30 minutes. As shown in table 5, the substrate 1 with a transparent conductive layer corresponds to a mode in which the transparent conductive layer 1, the substrate 1, and the transparent conductive layer 1 are provided in this order.

[ base Material 2 with transparent conductive layer ]

The light-absorbing layer-forming composition 2 was coated on one surface of a substrate 1 (polyester film, lumiror (registered trademark) #100-U34, manufactured by TORAY INDUSTRIES, inc.) until the film thickness of the light-absorbing layer 2 became 2 μm. The obtained coating film was dried at 80 ℃ for 40 seconds, and the light absorbing layer 2 was formed on the substrate 1. Next, an ink containing silver nanoparticles and a resin (DNS-0163i, manufactured by daicel Corporation) was applied to the surface of the light absorbing layer 2 by an ink jet method until the application width became 25cm and the film thickness after drying became 1.0 μm, and the transparent conductive layer 1 was formed on the surface of the light absorbing layer 2 by firing at 120 ℃ for 30 minutes. Further, the transparent conductive layer 1 was also formed in the same order on the other surface of the substrate 1, thereby obtaining a substrate 2 with a transparent conductive layer having the transparent conductive layer 1 on both surfaces of the substrate 1.

[ light-absorbing base with transparent conductive layer ]

A base material 1 (polyester film, lumirror (registered trademark) #100-U34, TORAY INDUSTRIES, inc. Manufactured) was dissolved in toluene to prepare a resin-containing solution. To the obtained solution, the following compound (TINUVIN 1577 ED) was added as a light absorber in an amount of 1 mass% based on the total mass of the resin, and a film having a thickness of 100 μm was formed to obtain a substrate 2.

[ chemical formula 27]

Next, an ink containing silver nanoparticles and a resin (DNS-0163i, manufactured by daicel Corporation) was applied by an ink jet method until the application width became 25cm and the film thickness after drying became 1.0 μm, and the light-absorbing substrate 2 with a transparent conductive layer was formed by firing at 120 ℃ for 30 minutes. As shown in table 4, the light-absorbing substrate 2 with a transparent conductive layer corresponds to a mode in which the transparent conductive layer 1, the substrate 2 (or any one of the substrates 2-1 to 2-8), and the transparent conductive layer 1 are provided in this order.

A light-absorbing substrate with a transparent conductive layer having the transparent conductive layer 1 on both surfaces of each of the substrates 2-1 to 2-8 was obtained in the same order as the above-described light-absorbing substrate with a transparent conductive layer, except that the kind of the light absorber and the content of the resin shown below were changed.

Base material 2-1: TINUVIN1577ED: triazine Compound (maximum absorption wavelength of 274nm and 341nm, manufactured by BASF corporation), 2% by mass

Base material 2-2: TINUVIN1577ED: triazine Compound (maximum absorption wavelength 274nm and 341nm, manufactured by BASF Co., ltd.), 0.4% by mass

2-3 of base material: TINUVIN400: triazine Compound (maximum absorption wavelength 336nm, manufactured by BASF Corp.), 1% by mass

2-4 of base material: TINUVIN384-2: benzotriazole Compound (maximum absorption wavelength 345nm, manufactured by BASF corporation), 1% by mass

2-5 parts of base material: UVINEL 3049: benzophenone Compound (maximum absorption wavelength of 280nm and 348nm, manufactured by BASF Co., ltd.), 1% by mass

Base material 2-6: uvinell 3039: cyanoacrylate compound (maximum absorption wavelength 305nm, manufactured by BASF corporation), 1% by mass

Base materials 2 to 7: 2-ethylhexyl salicylate: salicylate compound (maximum absorption wavelength 307 nm), 1% by mass

Base material 2-8: KEMISORB 500: benzoxazine compound (maximum absorption wavelength 315nm, 338nm and 348nm, chemipro Kasei Kaisha, ltd.), 1% by mass

[ laminate ]

As shown in the table below, after the protective film was peeled off from each transfer film with respect to each substrate having a transparent conductive layer, each transfer film was laminated on both surfaces of each substrate having a transparent conductive layer under lamination conditions of a roll temperature of 100 ℃, a line pressure of 0.8MPa, and a line speed of 3.0 m/min, thereby producing each laminate.

In comparative examples 1 to 2 and examples 1 to 8 and 17 to 27, a transfer film having no light absorbing layer was laminated to various light absorbing substrates with transparent conductive layers including a light absorbing layer of the type shown in table 4 described below to prepare a laminate.

In examples 9 to 16 and examples 28 to 39, a transfer film including a light absorbing layer of the type shown in table 5 described below was bonded to the substrate 1 with a transparent conductive layer to prepare a laminate.

In example 40, a laminate was produced by bonding a transfer film including a light absorbing layer shown in table 5 described later to the substrate 2 with a transparent conductive layer.

[ measurement and evaluation ]

[ Exposure atomization ]

In each laminate obtained above, the 1 st composition layer and the 2 nd composition layer were subjected to double-sided exposure using an ultrahigh pressure mercury lamp with a dominant wavelength and an incident exposure amount shown in the following table, through a photomask having a line and space (L/S = 1/1) with a line width of 20 μm, without peeling the temporary support. When double-sided exposure is performed, the line and the pattern of the photomask in space are arranged so as not to overlap each other. That is, light passing through the space of one photomask passes through the 1 st composition layer and the 2 nd composition layer and is shielded from light by the other photomask. The other side is also set to be exposed by light of only one side, similarly. After exposure and after leaving for 1 hour, the temporary support was peeled off and both sides were developed simultaneously.

For development, a 1.0% sodium carbonate aqueous solution at 28 ℃ was used, and shower development was performed for 30 seconds.

When exposure is performed at a main wavelength of 436nm, the 1 st composition layer or the 2 nd composition layer is exposed through a bandpass filter (HB 0436, asahi Spectra co., ltd.) by disposing the bandpass filter between an exposure light source and a photomask.

When the transfer film has only the 1 st photosensitive layer of the 1 st composition layer and only the 2 nd photosensitive layer of the 2 nd composition layer, the 1 st photosensitive layer and the 2 nd photosensitive layer are exposed.

The patterns of the obtained both sides were observed, and exposure fogging was evaluated as follows.

A: no residue was observed by observation with an optical microscope at a magnification of 50 times or by naked eye.

B: a small amount of residue was observed with an optical microscope at a magnification of 50 times, and no residue was observed with the naked eye.

C: the residue was observed with an optical microscope at a magnification of 50 times or with the naked eye.

[ resolution ]

A photomask was prepared in which the line width was changed by 1 μm for each of 3 to 10 μm, and the space (L/S = 1/1).

After subjecting the 1 st composition layer or the 2 nd composition layer to double-sided exposure using the photomask with the dominant wavelength and the incident exposure amount shown in the following table, the temporary support was left for 1 hour, and both sides were developed while peeling off the temporary support. For development, a 1.0% sodium carbonate aqueous solution at 28 ℃ was used, and 30 seconds of shower development was performed, whereby a pattern was obtained. The obtained two-sided pattern was observed, and the minimum line width of the pattern having no residue between patterns under an optical microscope was obtained, and the resolution was evaluated according to the following criteria.

When the transfer film has only the 1 st photosensitive layer of the 1 st composition layer and only the 2 nd photosensitive layer of the 2 nd composition layer, the 1 st photosensitive layer and the 2 nd photosensitive layer are exposed.

A: the minimum line width is 3-6 μm

B: the minimum line width is 7-10 μm

C: residue was confirmed at a line width of 10 μm (minimum line width exceeding 10 μm).

The evaluation results are shown in tables 4 and 5.

Tables 4 and 5 show the following contents.

The column "structure of laminate" shows the layer structure of each laminate.

The case where the column "structure of the laminate" is "1": the laminate comprises a 1 st thermoplastic resin layer, a 1 st intermediate layer and a 1 st photosensitive layer (1 st composition layer)/a 1 st transparent conductive layer/a substrate/a 2 nd transparent conductive layer/a 2 nd photosensitive layer, a 2 nd intermediate layer and a 2 nd thermoplastic resin layer (2 nd composition layer) in this order.

The case where the column "structure of laminate" is "1-1": the laminated body sequentially comprises a 1 st photosensitive layer, a 1 st transparent conductive layer, a substrate, a 2 nd transparent conductive layer and a 2 nd photosensitive layer.

The case where the column "structure of the laminate" is "2": the laminated body sequentially comprises a 1 st thermoplastic resin layer, a 1 st intermediate layer and a 1 st photosensitive layer (1 st composition layer) light absorption layer/a 1 st transparent conductive layer/a substrate/a 2 nd transparent conductive layer/a 2 nd photosensitive layer, a 2 nd intermediate layer and a 2 nd thermoplastic resin layer (2 nd composition layer).

The case where the column "structure of laminate" is "2-1": the laminated body sequentially comprises a 1 st photosensitive layer, a light absorption layer, a 1 st transparent conductive layer, a substrate, a 2 nd transparent conductive layer and a 2 nd photosensitive layer.

The case where the column "structure of the laminate" is "3": the laminate comprises a 1 st thermoplastic resin layer, a 1 st intermediate layer and a 1 st photosensitive layer (1 st composition layer)/a 1 st transparent conductive layer/a light-absorbing layer/a substrate/a 2 nd transparent conductive layer/a 2 nd photosensitive layer, a 2 nd intermediate layer and a 2 nd thermoplastic resin layer (2 nd composition layer) in this order.

The case where the column "specific wavelength transmittance" is "A": the transmittance of the substrate at least 1 position of 365nm, 405nm and 436nm is less than or equal to 20%.

The case where the column "specific wavelength transmittance" is "B": indicating that the transmittance of the substrate at 365nm, 405nm and 436nm was more than 20%.

The case where the column "specific substrate" is "A": the minimum transmittance of the substrate at a wavelength of 350 to 450nm is 70% or more.

The case where the column "specific substrate" is "B": representing a minimum transmission of less than 70% of the substrate at a wavelength of 350 to 450 nm.

The numerical values in the column of each layer indicate the kind of each composition used for forming each layer. Specifically, when the column of the "1 st thermoplastic resin layer" is "1", it means that the composition 1 for forming a thermoplastic resin layer is used, and when the column of the "1 st photosensitive composition layer" is "3", it means that the photosensitive composition 3 is used, and when the column of the "light absorbing layer" is "1", it means that the composition 1 for forming a light absorbing layer is used.

[ Table 4]

[ Table 5]

From the results in tables 4 and 5, it was confirmed that the laminate of the present invention can obtain the desired effects of the present invention.

It was confirmed that the effect of the present invention is more excellent when the content of the light absorbing agent is 0.5 to 5.0 mass% with respect to the total mass of the light absorbing substrate (examples 1, 17 and 18).

It was confirmed that the effect of the present invention is more excellent when the content of the light absorbing agent is 1.0 to 5.0 mass% with respect to the total mass of the light absorbing layer (examples 28 to 30).

It was confirmed that the effect of the present invention is more excellent when the light absorber contains at least 1 selected from the benzotriazole compound and the triazine compound (examples 1, 17, and 19 to 24, and 9, 28, 29, and 31 to 36).

Claims (15)

1. A laminate comprising a 1 st composition layer, a 1 st transparent conductive layer, a substrate, a 2 nd transparent conductive layer and a 2 nd composition layer in this order,

the 1 st composition layer has a 1 st photosensitive layer,

the 2 nd composition layer has a 2 nd photosensitive layer,

the laminate satisfies at least one of requirements 1 to 3,

requirement 1: the substrate is a light-absorbing substrate comprising a light absorber having an absorption maximum wavelength in the wavelength range of 200nm to 450nm,

Requirement 2: the substrate is a transparent substrate, the laminate further has a layer containing the light absorbing agent between the 1 st photosensitive layer and the 2 nd photosensitive layer,

requirement 3: the lowest transmittance of the substrate at a wavelength of 350nm to 450nm is 70% or more, and the laminate further has a layer containing the light absorbing agent between the 1 st photosensitive layer and the 2 nd photosensitive layer.

2. The laminate according to claim 1, 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.

3. The laminate according to claim 1 or 2, which satisfies at least one of requirement 2 and requirement 3,

disposing a layer containing the light absorbing agent between the 1 st photosensitive layer and the 1 st transparent conductive layer or between the 2 nd photosensitive layer and the 2 nd transparent conductive layer.

4. The laminate according to claim 1 or 2, which satisfies at least one of requirement 2 and requirement 3,

disposing a layer including the light absorber between the 1 st transparent conductive layer and the transparent substrate or between the 2 nd transparent conductive layer and the transparent substrate.

5. The laminate according to claim 1 or 2, which satisfies the requirement 1.

6. The laminate according to claim 1 or 2,

at least one of the 1 st composition layer and the 2 nd composition layer has at least 1 selected from an intermediate layer and a thermoplastic resin layer.

7. The laminate according to claim 1 or 2,

the 1 st photosensitive layer and the 2 nd photosensitive layer each contain an alkali-soluble resin, a polymerizable compound, and a polymerization initiator.

8. The laminate according to claim 1 or 2,

the 1 st photosensitive layer and the 2 nd photosensitive layer contain a heterocyclic compound.

9. The laminate according to claim 1 or 2,

the molecular weight of the light absorber is 20000 or less.

10. A substrate with a transparent conductive layer comprises a 1 st transparent conductive layer, a substrate and a 2 nd transparent conductive layer in this order,

the transmittance of the base material at a wavelength of 550nm is 70% or more,

the transmittance of the base material at least 1 point in the wavelength 365nm, the wavelength 405nm and the wavelength 436nm is 20% or less.

11. The substrate with a transparent conductive layer according to claim 10,

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.

12. The substrate with a transparent conductive layer according to claim 10 or 11,

the substrate is a light-absorbing substrate comprising a light absorber having an absorption maximum wavelength in the wavelength range of 200nm to 450 nm.

13. The substrate with a transparent conductive layer according to claim 12,

the molecular weight of the light absorber is 20000 or less.

14. A pattern forming method comprising subjecting the 1 st photosensitive layer and the 2 nd photosensitive layer in the laminate according to any one of claims 1 to 9 to exposure treatment and development treatment,

the pattern forming method includes:

exposing the 1 st photosensitive layer;

exposing the 2 nd photosensitive layer; and

and a developing step of developing the exposed 1 st photosensitive layer and the exposed 2 nd photosensitive layer to form a pattern.

15. The pattern forming method according to claim 14, wherein,

the step of exposing the 1 st photosensitive layer and the step of exposing the 2 nd photosensitive layer are performed simultaneously or sequentially.