KR20230032974A - Method for producing laminate having conductor pattern, transfer film - Google Patents

Abstract

Provided are a method for manufacturing a laminate having a conductor pattern in a desired shape even when a washing treatment with an acid solution is conducted for a resist pattern before plating, and a transfer film. The method for manufacturing a laminate having a conductor pattern comprises: a joining step to join a transfer film and a substrate so that a surface on the opposite side to a temporary supporter side of the transfer film can come in contact with a metal layer of the substrate having a metal layer on a surface; an exposing step to pattern-expose a photosensitive composition layer; a developing step to develop a resist pattern by conducting the developing treatment; a heating step to heat the resist pattern; a washing step to wash the heated resist pattern with an acid solution; a plating step to perform the plating treatment; an exfoliating step to exfoliate the resist pattern; and a removing step to remove the exposed metal layer by the exfoliating step and forming a conductor pattern on the substrate, in that order. The photosensitive composition layer includes a thermal cross-linking agent.

Description

Method for producing a laminate having a conductor pattern, transfer film

The present invention relates to a method for producing a laminate having a conductor pattern, and a transfer film.

Since the number of steps required to obtain a predetermined pattern is small, a method of arranging a photosensitive composition layer on an arbitrary substrate using a transfer film, exposing the photosensitive composition layer through a mask, and then developing it is widely used.

In Patent Document 1, a photosensitive resin layer containing predetermined components is laminated on a support, the photosensitive resin layer is transferred onto a substrate, a resist pattern is formed by exposure treatment and development treatment, and further, plating A method of manufacturing a circuit board by performing a process is disclosed.

Patent Document 1: Japanese Unexamined Patent Publication No. 2016-139154

In recent years, more miniaturization of the shape of the conductor pattern has been demanded, and the demand for the shape control has become higher.

The inventors of the present invention, with reference to the method described in Patent Literature 1, performed a cleaning treatment with an acidic solution to remove contamination of the resist pattern before the plating treatment, and as a result of performing the plating treatment, the shape of the obtained conductor pattern was the desired shape. It was distorted from, and it was found that improvement was necessary.

An object of the present invention is to provide a method for manufacturing a laminate having a conductor pattern capable of producing a conductor pattern having a desired shape even when a resist pattern is washed with an acidic solution prior to plating.

Moreover, this invention also makes it a subject to provide a transfer film.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject was solvable by the following structure, as a result of earnestly examining about the said subject.

(1) Bonding the transfer film and the substrate so that the surface of the transfer film having the temporary support and the negative photosensitive composition layer on the opposite side to the temporary support side is in contact with the metal layer of the substrate having the metal layer on the surface bonding process,

An exposure step of pattern-exposing the photosensitive composition layer;

A developing step of subjecting the exposed photosensitive composition layer to a developing treatment to form a resist pattern;

a heating step of heating the resist pattern;

a cleaning step of cleaning the heated resist pattern with an acidic solution;

a plating step of performing a plating treatment on a metal layer in a region where a resist pattern is not disposed;

A peeling step of peeling the resist pattern;

a removal step of removing the metal layer exposed by the peeling step to form a conductor pattern on the substrate in this order;

Between the pasting step and the exposure step, or between the exposure step and the developing step, further having a temporary support body peeling step of peeling the temporary support body,

A method for producing a laminate having a conductor pattern, wherein the photosensitive composition layer contains a thermal cross-linking agent.

(2) The method for producing a laminate having a conductor pattern according to (1), wherein the surface of the resist pattern heated in the heating step on the opposite side to the substrate side has an elastic modulus of 5.0 GPa or more.

(3) the elastic modulus of the surface of the resist pattern heated by the heating step on the opposite side of the substrate side is the elastic modulus X;

When the elastic modulus in the vicinity of the substrate side of the resist pattern heated by the heating step is the elastic modulus Y,

A method for producing a laminate having the conductor pattern according to (1) or (2), which satisfies X/Y≤1.2.

(4) The manufacturing method of the laminated body which has the conductor pattern in any one of (1)-(3) in which the photosensitive composition layer contains a polymeric compound and a polymerization initiator.

(5) The method for producing a laminate having a conductor pattern as described in (4), wherein the polymerizable compound has an alkylene oxide-modified bisphenol structure.

(6) The manufacturing method of the laminated body which has a conductor pattern in any one of (1)-(5) in which a thermal crosslinking agent contains a block isocyanate compound.

(7) The manufacturing method of the laminated body which has the conductor pattern in any one of (1)-(6) whose haze of a temporary support body is 1.0 % or less.

(8) A method for producing a laminate having a conductor pattern according to any one of (1) to (7), wherein the thickness of the temporary support is 50 µm or less.

(9) The method for producing a laminate having a conductor pattern according to any one of (1) to (8), wherein the transfer film has an intermediate layer between the temporary support and the photosensitive composition layer.

(10) The method for producing a laminate having a conductor pattern according to (9), wherein the intermediate layer is a water-soluble resin layer.

(11) The manufacturing method of the laminated body which has a conductor pattern in any one of (1)-(10) whose exposure process is a process of performing pattern exposure through a photomask.

(12) Lamination having the conductor pattern described in any one of (1) to (10), in which the exposure step is a step of pattern-exposing the photosensitive composition layer through a lens using actinic rays projecting an image of a photomask. How to make a sieve.

(13) Have a temporary support body peeling step between the bonding step and the exposure step,

The method for producing a laminate having a conductor pattern according to any one of (1) to (10), wherein the exposure step is a step of bringing the surface exposed by peeling the temporary support into contact with a photomask to pattern-expose the photosensitive composition layer. .

(14) A transfer film having a temporary support and a negative photosensitive composition layer,

The photosensitive composition layer contains a thermal cross-linking agent,

A transfer film in which the haze of the temporary support is 1.0% or less.

(15) The transfer film according to (14), wherein the temporary support has a thickness of 50 µm or less.

(16) The transfer film according to (14) or (15), wherein the photosensitive composition layer contains a polymerizable compound and a polymerization initiator.

(17) The transfer film according to (16), wherein the polymerizable compound has an alkylene oxide-modified bisphenol structure.

(18) The transfer film according to any one of (14) to (17), which has an intermediate layer between the temporary support and the photosensitive composition layer.

(19) The transfer film according to (18), wherein the intermediate layer is a water-soluble resin layer.

According to the present invention, it is possible to provide a method for manufacturing a laminate having a conductor pattern, capable of manufacturing a conductor pattern having a desired shape even when the resist pattern is washed with an acidic solution before the plating treatment.

Moreover, according to this invention, a transfer film can be provided.

1 is a schematic view showing an example of the layer configuration of a transfer film according to an embodiment.

Hereinafter, the present invention will be described in detail.

The description of the constitutional requirements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

Hereinafter, the meaning of each description in this specification is shown.

In this specification, the numerical range expressed using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In this specification, in the numerical range described stepwise, the upper limit value or lower limit value described as a predetermined numerical range may be replaced with the upper limit value or lower limit value of another numerical range described stepwise. In addition, in the numerical range described in this specification, you may replace the upper limit value or lower limit value described as a predetermined numerical range with the value shown in the Example.

In this specification, the term "process" is included in the term as long as the intended purpose of the process is achieved, not only in an independent process, but also in a case where it cannot be clearly distinguished from other processes.

In this specification, "transparency" means that the average transmittance of visible light of wavelength 400-700nm is 80% or more, and it is preferable that it is 90% or more.

In this specification, the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi Seisakusho Co., Ltd.

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are used as a column, TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation), as an eluent. It is a value converted using THF (tetrahydrofuran), a differential refractometer as a detector, and polystyrene as a standard substance, using polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analyzer.

In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight (Mw).

In this specification, unless otherwise specified, the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectrometer.

In this specification, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.

In this specification, unless otherwise specified, the hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Corporation).

In this specification, “(meth)acryl” is a concept including both acryl and methacryl, and “(meth)acryloxy group” is a concept including both acryloxy and methacryloxy groups. .

In addition, in this specification, "alkali-soluble" means that the solubility with respect to 100 g of 1 mass % aqueous solutions of sodium carbonate at 22 degreeC is 0.1 g or more.

In this specification, “water-soluble” means that the solubility in 100 g of water at pH 7.0 at a liquid temperature of 22° C. is 0.1 g or more. Therefore, for example, a water-soluble resin intends a resin that satisfies the above-mentioned solubility conditions.

In the present specification, the "solid content" of the composition means a component that forms a composition layer formed using the composition, and when the composition includes a solvent (organic solvent, water, etc.), it means all components except the solvent. do. In addition, as long as it is a component forming a composition layer, a liquid component is also regarded as a solid component.

As a feature of the method for producing a laminate having a conductor pattern of the present invention, the photosensitive composition layer contains a thermal cross-linking agent.

As a result of examining the cause of the above problems in the prior art, the inventors of the present invention have found that peeling or decomposition of the resist pattern occurs when the resist pattern is washed with an acidic solution, and as a result, a conductor pattern having a desired shape is obtained. I noticed what was not attainable. Therefore, it was found that resistance to an acidic solution is improved by including a thermal crosslinking agent in the photosensitive composition layer, heat treatment after development, and crosslinking of the resist pattern, resulting in a conductor pattern having a desired shape.

<Method of manufacturing a laminate having a conductor pattern>

The method for manufacturing a laminate having a conductor pattern of the present invention,

A bonding step of bonding the transfer film and the substrate so that the surface of the transfer film having the temporary support and the negative photosensitive composition layer on the opposite side to the temporary support side is in contact with the metal layer of the substrate having a metal layer on the surface,

An exposure step of pattern-exposing the photosensitive composition layer;

A developing step of subjecting the exposed photosensitive composition layer to a developing treatment to form a resist pattern;

a heating step of heating the resist pattern;

a cleaning step of cleaning the heated resist pattern with an acidic solution;

a plating step of performing a plating treatment on a metal layer in a region where a resist pattern is not disposed;

A peeling step of peeling the resist pattern;

a removal step of removing the metal layer exposed by the peeling step to form a conductor pattern on the substrate in this order;

Between the bonding process and the exposure process, or between the exposure process and the image development process, it further has a temporary support body peeling step of peeling the temporary support body.

Hereinafter, each process is demonstrated in detail.

[Bonding process]

The bonding step is a process of bonding the transfer film and the substrate so that the surface of the transfer film having the temporary support and the negative photosensitive composition layer on the opposite side to the temporary support side is in contact with the metal layer of the substrate having a metal layer on the surface. .

By performing this process, the board|substrate with a photosensitive composition layer which has a board|substrate, a metal layer, a photosensitive composition layer, and a temporary support body in this order can be obtained.

The configuration of the transfer film will be described in detail in the latter part.

A substrate having a metal layer on its surface (substrate with a metal layer) has a substrate and a metal layer disposed on the surface of the substrate.

Examples of the substrate include a resin substrate, a glass substrate, a ceramic substrate, and a semiconductor substrate, and the substrate described in paragraph [0140] of International Publication No. 2018/155193 is preferable.

As the material of the resin substrate, polyethylene terephthalate, cycloolefin polymer or polyimide is preferable.

The thickness of the resin substrate is preferably 5 μm to 200 μm, and more preferably 10 μm to 100 μm.

The metal layer is a layer containing a metal, and the metal is not particularly limited, and a known metal can be used. The metal layer is preferably a conductive layer.

As a main component (so-called main metal) of a metal layer, copper, chromium, lead, nickel, gold, silver, tin, and zinc are mentioned, for example. In addition, "main component" means the metal with the largest content among the metals contained in a metal layer.

The method for forming the metal layer is not particularly limited, and examples thereof include known methods such as a method of applying a dispersion liquid in which metal fine particles are dispersed and then sintering a coating film, a sputtering method, and a vapor deposition method.

The thickness of the metal layer is not particularly limited, and is preferably 50 nm or more, and more preferably 100 nm or more. As for an upper limit, 2 micrometers or less are preferable.

On the substrate, one layer or two or more metal layers may be disposed.

When two or more metal layers are arranged, the metal layers arranged in two or more layers may be the same or different, and it is preferable that they are metal layers of different materials.

In the above bonding, it is preferable to bring the photosensitive composition layer side of the transfer film (surface on the opposite side to the temporary support side) into contact with the metal layer on the substrate and pressurize it.

The compression method is not particularly limited, and a known transfer method and a laminating method can be used. Among them, it is preferable that the surface of the photosensitive composition layer is overlaid on a substrate having a metal layer, and pressing and heating with a roll or the like are performed.

For bonding, a known laminator such as a vacuum laminator and an auto-cut laminator can be used.

The lamination temperature is not particularly limited, but is preferably 70 to 130°C, for example.

[Exposure process]

The exposure process is a process of pattern exposure of the photosensitive composition layer.

"Pattern exposure" is a form of exposing in a pattern, and means an exposure of a form in which an exposed portion and an unexposed portion exist.

The positional relationship between the exposed portion (exposed area) and the unexposed portion (unexposed area) in pattern exposure can be appropriately adjusted. It is preferable to perform exposure from the photosensitive composition layer side.

As an exposure method in an exposure process, mask exposure, direct imaging exposure, and projection exposure are mentioned, for example, and mask exposure or projection exposure is preferable.

That is, as an exposure process, the process of performing pattern exposure through a photomask is preferable.

Moreover, it is also preferable that it is a process of carrying out pattern exposure of the photosensitive composition layer through a lens using actinic rays which projected the image of the photomask as an exposure process.

When the temporary support stripping step described later is performed between the bonding step and the exposure step, as the exposure step, an exposure step in which the surface exposed by peeling the temporary support body is brought into contact with a photomask to perform pattern exposure is preferable. In other words, an exposure step in which the exposed surface exposed by peeling of the temporary support of the layered product from which the temporary support is peeled is brought into contact with the photomask to expose the photosensitive composition layer to pattern exposure is preferable. In addition, as said exposed surface, when a transfer film has a 3-layer structure of a temporary support body, an intermediate layer, and a photosensitive composition layer, the surface of an intermediate|middle layer corresponds.

When such an exposure step is adopted, a more highly detailed resist pattern is obtained, and finally, a more highly detailed conductor pattern is obtained.

It is preferable to employ|adopt such an exposure process especially when the temporary support body peeling process mentioned later is performed between a bonding process and an exposure process.

In addition, in the case of performing the temporary support stripping step described later between the exposure step and the developing step, as the exposure step, in the laminate of the substrate and the transfer film obtained by the bonding step, the side of the transfer film opposite to the substrate having the substrate An exposure step in which the surface of the side is brought into contact with a photomask and subjected to pattern exposure is preferred.

In the exposure step of pattern exposure, a curing reaction of components included in the photosensitive composition layer may occur in the exposed region (region corresponding to the opening of the photomask) of the photosensitive composition layer. By carrying out the developing process after exposure, the unexposed area of the photosensitive composition layer is removed and a pattern is formed.

It is also preferable that the method of this invention has a photomask peeling process of peeling the photomask used in the exposure process between an exposure process and a developing process.

As a photomask peeling process, a well-known peeling process is mentioned, for example.

As a light source for pattern exposure, any light source capable of irradiating at least light (for example, 365 nm or 405 nm) in a wavelength range capable of curing the photosensitive composition layer can be appropriately selected and used. Especially, as for the dominant wavelength of the exposure light of pattern exposure, 365 nm is preferable. In addition, a dominant wavelength is a wavelength with the greatest intensity.

As a light source, various lasers, light emitting diodes (LED), ultra-high pressure mercury-vapor lamps, high-pressure mercury-vapor lamps, and metal halide lamps are mentioned, for example.

The exposure amount is preferably 5 to 200 mJ/cm ² and more preferably 10 to 200 mJ/cm ² .

Preferable aspects of the light source used for exposure, the exposure amount, and the exposure method are described, for example, in International Publication No. 2018/155193, paragraphs [0146] to [0147], and these contents are incorporated herein by reference.

[Temporary Support Separation Process]

Between the bonding process and the exposure process, or between the exposure process and the image development process, the temporary support body peeling process is performed.

Especially, it is preferable to have a temporary support body peeling process between the said bonding process and the said exposure process.

A temporary support body peeling process is a process of peeling a temporary support body from the laminated body of a transfer film and a board|substrate with a metal layer.

As a peeling method of a temporary support body, a well-known peeling method is mentioned, for example. Specifically, the cover film peeling mechanism described in Unexamined-Japanese-Patent No. 2010-072589, Paragraph [0161] - [0162] is mentioned.

[Development process]

The developing step is a step of forming a resist pattern by subjecting the exposed photosensitive composition layer to a developing treatment.

The photosensitive composition layer may be developed using a developing solution.

As a developing solution, an alkaline aqueous solution is preferable. Examples of the alkaline compound that may be included in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

The liquid temperature of the developing solution at the time of developing treatment is preferably 10 to 50°C, more preferably 15 to 40°C, and even more preferably 20 to 35°C.

As for the pH of the developing solution at the time of developing treatment, 9 or more are preferable, 10 or more are more preferable, and 11 or more are still more preferable. 14 or less are preferable and, as for an upper limit, less than 13 are more preferable. pH can be measured by a method based on JIS Z8802-1984 using a known pH meter. The measurement temperature of pH is 25 degreeC.

The content of water in the developing solution is preferably 50% by mass or more and less than 100% by mass, and more preferably 90% by mass or more and less than 100% by mass with respect to the total mass of the developing solution.

In the developing solution, the content of the alkaline compound is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the developing solution.

Examples of the developing method include puddle developing, shower developing, spin developing, and dip developing.

Examples of the developing solution suitably used in this specification include the developer described in paragraph [0194] of International Publication No. 2015/093271, and examples of the developing method suitably used include, for example, International Publication The developing method described in paragraph [0195] of No. 2015/093271 can be mentioned.

After image development, it is also preferable to perform a rinse treatment for removing the developing solution remaining on the substrate with a metal layer before proceeding to the next step. For the rinse treatment, water or the like can be used.

After the development and/or rinsing treatment, a drying treatment may be performed in which excess liquid is removed from the substrate with a metal layer.

The position and size of the resist pattern formed on the substrate with a metal layer are not particularly limited, but a thin wire shape is preferable.

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

[Heating process]

The heating step is a step of heating the resist pattern. By carrying out this step, a crosslinked structure is formed in the resist pattern by a thermal crosslinking agent described later, and resistance to washing with an acidic solution performed in a cleaning step described later is imparted to the resist pattern.

The heating temperature is not particularly limited, but is preferably 100 to 200°C, more preferably 120 to 150°C.

The heating time is not particularly limited, but is preferably 10 to 60 minutes, and more preferably 20 to 40 minutes.

The modulus of elasticity of the surface of the resist pattern heated by the heating step opposite to the substrate side is not particularly limited, but is preferably 5.0 GPa or more, more preferably 5.5 GPa or more, from the viewpoint of more excellent effects of the present invention. Although the upper limit is not particularly limited, it is often 7.0 GPa or less.

The measuring method of the said elastic modulus is as follows.

Elastic modulus is measured by an atomic force microscope (AFM). The specific procedure is as follows. Measurement is performed in QNM mode using an atomic force microscope (for example, AFM Dimension Icon manufactured by Bruker). As a probe, for example, RTESPA-150 (150 KHz, 5 N/m) is used. A total of 5 fields of view are measured in a square with a side of 1 μm per field of view, a total of 50 force curves are measured with 10 points per field of view, and the slope of the return force curve (area of 20% to 90% of the maximum load) ), the elastic modulus is calculated using the Hertz contact theory. Further, specific examples of AFM probe calibration are as follows. The warpage sensitivity is calculated from the slope of the force curve by measuring the force curve of the quartz substrate in advance. The spring constant is calculated by measuring the thermal fluctuation of the probe. For example, the spring constant is calculated using the Thermal Tune method included in the software of Bruker's AFM. The curvature of the tip is calculated by measuring the shape of a tip curvature correction sample (RM-12M: Ti Roughness Sample), and using, for example, an image analysis mode (Tip Qualification) attached to Bruker's AFM software.

X/ Y is not particularly limited, but is preferably 1.20 or less, more preferably 1.10 or less, from the viewpoint of more excellent effects of the present invention. The lower limit is not particularly limited, but is preferably 1.05 or more.

As a method for measuring the elastic modulus X, the above-described method using an atomic force microscope (AFM) is exemplified.

The measuring method of the said elasticity modulus Y is as follows.

The resist pattern is cut with a microtome along the thickness direction, and a vertical cross section of the resist pattern is taken, and a vertical cross section is formed at any position between 0 and 20% of the height from the substrate with respect to the total thickness of the resist pattern in the vertical cross section. The elastic modulus is measured in the same way as the elastic modulus X, and is referred to as the elastic modulus Y. That is, the vicinity of the substrate side of the resist pattern means the range of the height position of 0 to 20% from the substrate with respect to the total thickness of the resist pattern in the vertical section of the resist pattern.

[Cleaning process]

The cleaning step is a step of cleaning the resist pattern heated in the heating step with an acidic solution.

The acidic solution is not particularly limited as long as it is a solution containing an acid.

Examples of the acid in the acidic solution include sulfuric acid, nitric acid, hydrogen chloride, phosphoric acid, hydrofluoric acid, sulfamic acid, and oxalic acid.

The concentration of the acid in the acidic solution is not particularly limited, but the concentration of the acid component is preferably 5 to 30% by mass, more preferably 10 to 20% by mass, based on the total mass of the acidic solution.

It is preferable that a solvent is contained in the acidic solution.

As a solvent, water and an organic solvent are mentioned.

Examples of the organic solvent include alcohol solvents, ester solvents, ketone solvents, amide solvents, and hydrocarbon solvents.

The method of cleaning the resist pattern with the acidic solution is not particularly limited, as long as the resist pattern can be brought into contact with the acidic solution. For example, the method of supplying an acidic solution on a resist pattern, and the method of immersing a resist pattern in an acidic solution are mentioned.

The contact time between the resist pattern and the acidic solution is not particularly limited, but is preferably 1 to 20 minutes, and more preferably 3 to 10 minutes.

The liquid temperature of the acidic solution when the resist pattern and the acidic solution are brought into contact is preferably 25 to 50°C, and more preferably 30 to 40°C.

[Plating process]

The plating process is a process of performing a plating process on a metal layer in a region where a resist pattern is not disposed.

By carrying out this process, a plating layer is formed on the metal layer in the region where the resist pattern is not disposed.

As a method of plating treatment, an electrolytic plating method and an electroless plating method are mentioned, for example, and the electrolytic plating method is preferable from a productivity point.

When the plating process is performed, a plating layer having the same pattern shape as the region (opening area of the resist pattern) where the resist pattern is not disposed on the substrate with the metal layer is obtained.

As a metal contained in a plating layer, a well-known metal is mentioned, for example.

Specifically, metals, such as copper, chromium, lead, nickel, gold, silver, tin, and zinc, and alloys of these metals are mentioned.

Among them, it is preferable that the plating layer contains copper or an alloy thereof from the point where the conductivity of the conductor pattern is more excellent. Moreover, it is preferable that the plating layer contains copper as a main component from the point which the conductivity of a conductor pattern is more excellent.

As thickness of a plating layer, 0.1 micrometer or more is preferable and 1 micrometer or more is more preferable. As for an upper limit, 20 micrometers or less are preferable.

[Peel process]

The peeling step is a step of peeling the resist pattern.

The method of removing the remaining resist pattern is not particularly limited, but a method of removing it by chemical treatment is exemplified, and a method of removing it using a stripping solution is preferable.

Moreover, you may remove by a well-known method, such as a spray method, a shower method, and a puddle method, using a peeling liquid.

As the stripping solution, for example, a stripping solution obtained by dissolving an inorganic alkali component or an organic alkali component in water, dimethyl sulfoxide, N-methylpyrrolidone or a mixed solution thereof is exemplified. As an inorganic alkali component, sodium hydroxide and potassium hydroxide are mentioned, for example. Examples of the organic alkali component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. As an alkaline organic compound, tetramethylammonium hydroxide or an alkanolamine compound is preferable. It is also preferable that the peeling solution does not dissolve the metal layer.

As a method for removing the resist pattern, a method in which the substrate having the remaining resist pattern is immersed for 1 to 30 minutes in a stripping solution at a solution temperature of preferably 30 to 80° C., more preferably 50 to 80° C. during stirring is mentioned. can

11 or more are preferable, as for the pH of the peeling liquid at the time of a peeling process, 12 or more are more preferable, and 13 or more are still more preferable. 14 or less are preferable and, as for an upper limit, 13.8 or less are more preferable. pH can be measured by a method based on JIS Z8802-1984 using a known pH meter. The measurement temperature of pH is 25 degreeC.

It is preferable that the liquid temperature of the stripping solution at the time of peeling treatment is higher than the liquid temperature of the developing solution at the time of developing treatment. Specifically, the value obtained by subtracting the liquid temperature of the developing solution from the liquid temperature of the stripping solution (liquid temperature of the stripping solution - liquid temperature of the developing solution) is preferably 10°C or higher, and more preferably 20°C or higher. 100 degrees C or less is preferable, and, as for an upper limit, 80 degrees C or less is more preferable.

It is preferable that the pH of the peeling solution at the time of peeling treatment is higher than the pH of the developing solution at the time of developing treatment. Specifically, the value obtained by subtracting the pH of the developing solution from the pH of the stripping solution (pH of the stripping solution - pH of the developing solution) is preferably 1 or more, and more preferably 1.5 or more. 5 or less are preferable and, as for an upper limit, 4 or less are more preferable.

After stripping the resist pattern with the stripping solution, it is also preferable to perform a rinse treatment to remove the stripping solution remaining on the substrate. For the rinse treatment, water or the like can be used.

After stripping and/or rinsing the resist pattern with the stripping liquid, a drying process may be performed to remove excess liquid from the substrate.

[Removal process]

The removal process is a process of removing the metal layer exposed by the peeling process and forming a conductor pattern on the substrate.

In the removal step, the plating layer formed by the plating step is used as an etching resist, and the metal layer located in the non-pattern formation region (in other words, the region not protected by the plating layer) is etched.

A method for removing part of the metal layer is not particularly limited, but it is preferable to use a known etchant.

As one aspect of a known etching solution, a ferric chloride solution, a cupric chloride solution, an ammonia alkali solution, a sulfuric acid-hydrogen peroxide mixture, a phosphoric acid-hydrogen peroxide mixture, etc. are mentioned, for example.

When the removal step is performed, the metal layer exposed to the surface from the substrate is removed, and a plating layer (conductor pattern) having a pattern shape remains, so that a laminate having a conductor pattern is obtained.

As an upper limit of the line width of the conductor pattern formed, 8 micrometers or less are preferable, and 6 micrometers or less are more preferable. Although it does not specifically limit as a lower limit, it is 1 micrometer or more in many cases.

[Other processes]

The manufacturing method of the laminated body with a conductor pattern may also include arbitrary processes (other processes) other than the process mentioned above.

For example, the step of reducing the visible light reflectance described in paragraph [0172] of International Publication No. 2019/022089, the step of forming a new metal layer on the insulating film described in paragraph [0172] of International Publication No. 2019/022089, etc. but is not limited to these processes.

-Process of lowering visible light reflectance-

The method for manufacturing a laminate having a conductor pattern may include a step of performing a treatment for reducing part or all visible light reflectance of a plurality of metal layers included in the base material.

An oxidation treatment is exemplified as a treatment for lowering the visible light reflectance. When the substrate has a metal layer containing copper, the visible light reflectance of the metal layer can be reduced by oxidizing the copper to obtain copper oxide and blackening the metal layer.

Regarding the treatment for lowering the visible light reflectance, paragraphs [0017] to [0025] of Japanese Unexamined Patent Publication No. 2014-150118, and paragraphs [0041], paragraph [0042], and paragraph [0048] of Japanese Unexamined Patent Publication No. 2013-206315 ] and paragraph [0058], and the content described in these publications is incorporated herein by reference.

-Process of forming an insulating film, process of forming a new metal layer on the surface of an insulating film-

It is also preferable that the method for manufacturing a laminate having a conductor pattern includes a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new metal layer on the surface of the insulating film.

Through the above process, a second electrode pattern insulated from the first electrode pattern may be formed.

The step of forming the insulating film is not particularly limited, and a known permanent film forming method is exemplified. Moreover, you may form the insulating film of a desired pattern by photolithography using the photosensitive material which has insulating property.

In the method for producing a laminate having a conductor pattern, it is also preferable to use a substrate having a plurality of metal layers on both surfaces of the substrate, and sequentially or simultaneously form circuits on the metal layers formed on both surfaces of the substrate. According to such a structure, the circuit wiring for touch panels which formed the 1st conductor pattern on one surface of a base material, and the 2nd conductor pattern on the other surface can be formed. Moreover, it is also preferable to form the circuit wiring for touch panels of such a structure from both surfaces of a base material by roll-to-roll.

<Use of Laminate with Conductor Pattern>

Methods for manufacturing a laminate having a conductor pattern include manufacturing conductive films such as touch panels, transparent heaters, transparent antennas, electromagnetic shielding materials, and light control films; manufacture of printed wiring boards and semiconductor packages; manufacture of pillars and pins for interconnects between semiconductor chips or packages; manufacture of metal masks; It can be applied to the manufacture of tape substrates such as COF (Chip on Film) and TAB (Tape Automated Bonding).

Moreover, as said touchscreen, a capacitance-type touchscreen is mentioned. The manufacturing method of the laminated body which concerns on this invention can be used for formation of the conductive film in a touch panel, and peripheral circuit wiring. The touch panel can be applied to, for example, display devices such as organic EL (electro-luminescence) display devices and liquid crystal display devices.

<Transfer film>

The transfer film used in the manufacturing method of a laminate having a conductor pattern of the present invention has a temporary support and a negative photosensitive composition layer, and the photosensitive composition layer contains a thermal crosslinking agent.

The transfer film may have other layers other than the temporary support and the photosensitive composition layer.

As another layer, the intermediate|middle layer mentioned later is mentioned, for example. Moreover, the transfer film may have other members (for example, a protective film etc.) mentioned later.

As embodiment of a transfer film, the following structure (1) or (2) is mentioned, for example, and structure (2) is preferable.

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

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

The transfer film preferably has an intermediate layer.

From the point of suppression of bubble generation in the bonding process mentioned above, the maximum width of the waviness of the transfer film is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 60 μm or less. Moreover, as a lower limit of the maximum width of a waviness, it is 0 micrometer or more, 0.1 micrometer or more is preferable, and 1 micrometer or more is more preferable.

The maximum width of the waviness of the transfer film is a value measured by the following procedure.

First, a test sample is prepared by cutting a transfer film in a direction perpendicular to the main surface so as to have a size of 20 cm in length x 20 cm in width. Moreover, when a transfer film has a protective film, a protective film is peeled off. Next, the test sample is placed on a stage having a smooth and horizontal surface so that the surface of the temporary support body faces the stage. After stationary, the surface of the test sample is scanned with a laser microscope (for example, VK-9700SP manufactured by Keyence Co., Ltd.) to obtain a three-dimensional surface image, The lowest concave height is subtracted from the maximum convex height observed in the obtained three-dimensional surface image. The above operation is performed for 10 test samples, and the arithmetic average value is taken as "the maximum width of the transfer film's curvature".

In the photosensitive composition layer of the transfer film, when another composition layer is further provided on the surface of the photosensitive composition layer opposite to the temporary support, the total thickness of the other composition layers is 0.1 to 0.1 to the total thickness of the photosensitive composition layer. 30% is preferable and 0.1 to 20% is more preferable.

In terms of more excellent adhesion, the light transmittance of the photosensitive composition layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is preferably 99.9% or less, and more preferably 99.0% or less.

An example of embodiment of the transfer film is described.

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

Although the transfer film 10 shown in FIG. 1 has the intermediate|middle layer 13 and the protective film 19, it is not necessary to have the intermediate|middle layer 13 and the protective film 19.

In FIG. 1, each layer (for example, a photosensitive composition layer and an intermediate layer) excluding the protective film 19 that may be disposed on the temporary support 11 is also referred to as a “composition layer”.

Hereinafter, each member and each component is demonstrated in detail about a transfer film.

[temporary support]

A transfer film has a temporary support body.

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

The temporary support body may have either a single layer structure or a multilayer structure.

As a temporary support body, a film is preferable and a resin film is more preferable. Further, as the temporary support, a film having flexibility and not causing significant deformation, contraction or elongation under pressure or under pressure and heating is also preferable, and a film without deformation such as wrinkles and flaws is also preferable. .

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

The temporary support preferably has high transparency from the viewpoint that pattern exposure can be performed through the temporary support, and the transmittance at 365 nm is preferably 60% or more, more preferably 70% or more.

The smaller the haze of the temporary support from the viewpoint of the pattern formation property at the time of pattern exposure through the temporary support and the transparency of the temporary support. Specifically, the haze value of the temporary support is preferably 2.0% or less, more preferably 1.0% or less, and still more preferably 0.5% or less. Although the lower limit is not particularly limited, 0.1% or more is exemplified.

From the viewpoint of pattern formation during pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign matter, and defects contained in the temporary support is preferably smaller. The number of fine particles, foreign matters, and defects having a diameter of 1 µm or more in the temporary support body is preferably 50/10 mm ² or less, more preferably 10/10 mm ^{2 or} less, and still more preferably 3/10 mm ^{2 or} less. , 0/10 mm ² is particularly preferred.

As for the thickness of a temporary support body, 5 micrometers or more are more preferable. The upper limit is preferably 200 μm or less, more preferably 150 μm or less, more preferably 50 μm or less, particularly preferably 20 μm or less, and most preferably 16 μm or less from the viewpoint of ease of handling and versatility.

The thickness of the temporary support is calculated as an average value of five arbitrary points measured by cross-sectional observation with an SEM (Scanning Electron Microscope).

The temporary support may have a layer (lubricant layer) containing fine particles on one or both surfaces of the temporary support from the viewpoint of handling properties.

As for the diameter of the microparticles|fine-particles contained in a lubricant layer, 0.05-0.8 micrometer is preferable.

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

From the viewpoint of improving the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support in contact with the photosensitive composition layer may be subjected to surface modification treatment.

As a surface modification process, the process using UV irradiation, corona discharge, plasma, etc. is mentioned, for example.

The exposure amount in UV irradiation is preferably 10 to 2000 mJ/cm ² and more preferably 50 to 1000 mJ/cm ² .

If the exposure amount is within the above range, the lamp output and illuminance are not particularly limited.

As a light source for UV irradiation, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and an electrodeless discharge lamp emitting light in a wavelength range of 150 to 450 nm. and light emitting diodes (LEDs).

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

Moreover, as a temporary support body, Paragraph [0017] - [0018] of Unexamined-Japanese-Patent No. 2014-085643, Paragraph [0019] - [0026] of Unexamined-Japanese-Patent No. 2016-027363, and International Publication No. 2012/ Paragraphs [0041] to [0057] of No. 081680 and paragraphs [0029] to [0040] of International Publication No. 2018/179370 are also included, and these contents are incorporated herein by reference.

As a commercial item of a temporary support body, it is registered trademark Lumirror 16KS40 and registered trademark Lumirror 16FB40 (above, Toray Corporation make), for example; Cosmoshine A4100, Cosmoshine A4300, and Cosmoshine A8300 (above, manufactured by Toyobo Co., Ltd.) are mentioned.

[Photosensitive Composition Layer]

The transfer film has a negative photosensitive composition layer.

Below, each component contained in the photosensitive composition layer is demonstrated in order. In addition, below, it demonstrates from the thermal crosslinking agent which is one of the characteristic points of this invention.

(thermal cross-linking agent)

The photosensitive composition layer contains a thermal cross-linking agent.

As a thermal crosslinking agent, a methylol compound and a block isocyanate compound are mentioned. Among them, a block isocyanate compound is preferable from the viewpoint of the strength of the obtained cured film and the tackiness of the obtained uncured film.

Since a block isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and/or a polymerizable compound has at least one of a hydroxyl group and a carboxy group, the hydrophilicity of the formed film This is lowered, and the function in the case of using the film obtained by curing the negative photosensitive composition layer as a protective film tends to be enhanced.

In addition, a block isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected with a blocking agent (so-called mask)".

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

The dissociation temperature of block isocyanate is "the temperature of the endothermic peak accompanying the deprotection reaction of block isocyanate when measured by differential scanning calorimetry (DSC) analysis using a differential scanning calorimeter" it means.

As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Co., Ltd. can be preferably used. However, the differential scanning calorimeter is not limited to this.

As a blocking agent with a dissociation temperature of 100 to 160 ° C., active methylene compounds [diester malonate (dimethyl malonate, diethyl malonate, din-butyl malonate, di2-ethylhexyl malonate, etc.)], oxime and compounds (compounds having a structure represented by -C(=N-OH)- in a molecule such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanoneoxime).

Among these, as a blocking agent whose dissociation temperature is 100-160 degreeC, at least 1 sort(s) chosen from oxime compounds is preferable from the point of storage stability, for example.

The block isocyanate compound preferably has an isocyanurate structure from the viewpoints of, for example, improving the brittleness of the film and improving the adhesion with the body to be transferred.

The block isocyanate compound which has an isocyanurate structure is obtained, for example, by isocyanurate-ized and protected hexamethylene diisocyanate.

Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is more likely to set the dissociation temperature within a preferable range than a compound having no oxime structure, and also reduces development residues. It is preferable in that it is easy to do less.

The block 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 preferable.

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

Especially, as a polymeric group, an ethylenically unsaturated group is preferable, a (meth)acryloxy group is more preferable, and an acryloxy group is still more preferable.

As a block isocyanate compound, a commercial item can be used.

As an example of a commercial item of a block isocyanate compound, Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (above, Showa Denko Co., Ltd. make), Block-type Duranate series (eg, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, Duranate (registered trademark) SBB-70P, etc., manufactured by Asahi Kasei Co., Ltd.). there is.

Moreover, as a block isocyanate compound, the compound of the following structure can also be used.

[Formula 1]

A thermal crosslinking agent may be used individually by 1 type, and may be used 2 or more types.

0.01-10 mass % is preferable with respect to the total mass of the photosensitive composition layer, and, as for content of the thermal crosslinking agent in the photosensitive composition layer, 0.1-5 mass % is more preferable.

(profit)

The photosensitive composition layer may contain resin.

The resin contained in the photosensitive composition layer includes Resin A, which is an alkali-soluble resin.

The acid value of the resin A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, and more preferably less than 190 mgKOH/g, from the viewpoint of more excellent resolution by suppressing swelling of the negative photosensitive composition layer by the developing solution. more preferable

The lower limit of the acid value of Resin A is not particularly limited, but is more preferably 120 mgKOH/g or more, more preferably 150 mgKOH/g or more, and particularly preferably 170 mgKOH/g or more, from the viewpoint of more excellent developability.

The acid value (mgKOH/g) is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample. An acid value is computable from average content of the acidic radical in a compound, for example. What is necessary is just to adjust the acid value of resin A with content of the structural unit containing the kind of structural unit which comprises resin A, and an acidic radical mentioned later.

The weight average molecular weight of Resin A is not particularly limited, and is preferably 5,000 to 500,000. When the weight average molecular weight is 500,000 or less, it is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, and more preferably 60,000 or less. On the other hand, when the weight average molecular weight is 5,000 or more, it is preferable in terms of controlling the properties of the developed aggregate and the properties of the unexposed film such as edge fuse property and cut chip property when used as a negative photosensitive resin laminate. The weight average molecular weight is more preferably 10,000 or more, more preferably 20,000 or more, and particularly preferably 30,000 or more.

Edge fuseability refers to the degree of ease of projecting of the negative photosensitive composition layer from the end surface of the roll when the transfer film is wound in a roll shape as a negative photosensitive resin laminate. Cut chip property refers to the degree of scattering of chips when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the negative photosensitive resin laminate, etc., it is transferred to the mask in a subsequent exposure step or the like, causing a defective product.

The dispersion degree of Resin A 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. In this disclosure,

The degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight). In the present disclosure, the weight average molecular weight and number average molecular weight are values measured using gel permeation chromatography.

As for the glass transition temperature Tg of resin A, 30-135 degreeC is preferable. By using the resin A having a Tg of 135°C or lower, it is possible to suppress a line width increase and deterioration in resolution when the focus position during exposure is shifted. In this regard, the Tg of the alkali-soluble polymer is more preferably 130°C or lower, more preferably 120°C or lower, and particularly preferably 110°C or lower. In addition, it is preferable to use Resin A having a Tg of 30°C or higher in terms of improving edge fuse resistance. In this regard, the Tg of Resin A is more preferably 40°C or higher, more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

-Structural unit derived from a monomer having an aromatic hydrocarbon group-

Moreover, it is preferable that resin A contains the structural unit derived from the monomer which has an aromatic hydrocarbon group from the point which suppresses the deterioration of the line width and resolution when the focal position at the time of exposure shifts. Moreover, as such an aromatic hydrocarbon group, a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group are mentioned, for example.

20 mass % or more is preferable with respect to all the structural units of Resin A, and, as for content of the structural unit derived from the monomer which has an aromatic hydrocarbon group in Resin A, 30 mass % or more is more preferable. Although it does not specifically limit as an upper limit, 95 mass % or less is preferable and 85 mass % or less is more preferable. Moreover, when multiple types of resin A are included, it is preferable that the average value of content of the structural unit derived from the monomer which has an aromatic hydrocarbon group becomes in the said range.

As a monomer having an aromatic hydrocarbon group, for example, a monomer having an aralkyl group, styrene, and polymerizable styrene derivatives (eg, methyl styrene, vinyltoluene, tert-butoxy styrene, acetoxy styrene) , styrene dimers, and styrene trimers, etc.). Among them, a monomer having an aralkyl group or styrene is preferable.

When the monomer having an aromatic hydrocarbon group is styrene, the content of the structural unit derived from styrene is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, based on all the structural units of Resin A. , 20 to 60% by mass is more preferable, and 25 to 55% by mass is particularly preferable. In addition, when a photosensitive composition layer contains several types of alkali-soluble polymer, the content rate of the structural unit derived from the monomer which has an aromatic hydrocarbon group is calculated|required as a weight average value.

As an aralkyl group, the phenylalkyl group which may have a substituent is mentioned, and the benzyl group which may have a substituent is preferable.

Phenylethyl (meth)acrylate etc. are mentioned as a monomer which has a phenylalkyl group which may have a substituent.

Examples of the monomer having a benzyl group which may have a substituent include (meth)acrylates having a benzyl group such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol. A (meth)acrylate having a benzyl group is preferable, and benzyl (meth)acrylate is more preferable.

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 to 90 mass% with respect to all the structural units of Resin A, and 15 ~ 85% by mass is more preferred.

-Constructive unit derived from a monomer having a carboxy group-

Resin A may have a structural unit derived from a monomer having a carboxy group.

Examples of the monomer having a carboxyl group include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid hemiester. Among these, (meth)acrylic acid is preferable.

5-50 mass % is preferable with respect to all the structural units of Resin A, as for content of the structural unit derived from the monomer which has a carboxyl group in Resin A, 10-40 mass % is more preferable, and 15-30 mass % % is more preferred.

Making the said content into 5 mass % or more is preferable at the point of expressing favorable developability, controlling edge fuse property, etc. Setting the content to 50% by mass or less is preferable from the viewpoint of high resolution and footing shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.

-Constitutive unit of non-acidity-

Resin A is non-acidic and may contain a non-acidic structural unit derived from a monomer having at least one polymerizable unsaturated group in its molecule.

Examples of the monomer (non-acidic monomer) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate. Acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and (meth)acrylates such as 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Especially, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or n-butyl (meth)acrylate is preferable, and methyl (meth)acrylate is more preferable.

1-60 mass % is preferable with respect to all the structural units of Resin A, as for content of the structural unit derived from the non-acidic monomer in Resin A, 2-50 mass % is more preferable, and 2-40 mass % is more preferable

Resin A may have any of a linear structure, a branched structure, and an alicyclic structure in a side chain.

In this specification, "main chain" refers to a relatively longest bonded chain among molecules of a polymer compound constituting the resin, and "side chain" refers to an atomic group branching from the main chain.

By using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or alicyclic structure can be introduced into the side chain of the alkali-soluble polymer. The group having an alicyclic structure may be monocyclic or polycyclic.

Specific examples of the monomer containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 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 these, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or tert-butyl methacrylate is preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred.

Specific examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Moreover, the (meth)acrylate which has an alicyclic hydrocarbon group of 5-20 carbon atoms is mentioned. As more specific examples, (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2-adamantyl, (meth)acrylic acid-3- Methyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-1-adamantyl, (meth)acrylate-3-ethyladamantyl, (meth)acrylate-3-methyl-5-ethyl -1-adamantyl, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl, (meth)acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, ( 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4 (meth)acrylate ,7-mentanoinden-5-yl, (meth)acrylic acid octahydro-4,7-mentanoinden-1-ylmethyl, (meth)acrylic acid-1-menthyl, (meth)acrylic acid tricyclodecane, ( Meth)acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4.1 .0]heptyl, (meth)acrylate (no)bornyl, (meth)acrylate isobornyl, (meth)acrylate pentyl, (meth)acrylate-2,2,5-trimethylcyclohexyl, and (meth)acrylate cyclo Hexyl etc. are mentioned. Among these (meth)acrylic acid esters, (meth)acrylic acid cyclohexyl, (meth)acrylic acid (no)bornyl, (meth)acrylic acid isobornyl, (meth)acrylic acid-1-adamantyl, (meth)acrylic acid-2- Adamantyl, (meth)acrylate pentyl, (meth)acrylate-1-menthyl, or (meth)acrylate tricyclodecane are preferred, (meth)acrylate cyclohexyl, (meth)acrylate (no)bornyl, (meth)acrylate ) Isobornyl acrylate, (meth)acrylate-2-adamantyl, or (meth)acrylate tricyclodecane is more preferred.

-Structural unit having a polymerizable group-

The resin A may have a polymerizable group or may have a structural unit having a polymerizable group.

As a polymerizable group, a radical polymerizable group is preferable and an ethylenically unsaturated group is more preferable. Moreover, when resin A has an ethylenically unsaturated group, it is preferable that resin A has a structural unit which has an ethylenically unsaturated group in a side chain.

As an ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferable.

As a structural unit which has a polymeric group, the structural unit represented by Formula (P) is preferable.

[Formula 2]

In Formula (P), R ^P represents a hydrogen atom or a methyl group. L ^P represents a divalent linking group. P represents a polymerizable group.

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

As R ^P , a hydrogen atom is preferable.

L ^P represents a divalent linking group.

Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO ₂ -, -NR ^N -, a divalent hydrocarbon group, and a divalent group obtained by combining them. there is. R ^N represents a substituent.

As said hydrocarbon group, an alkylene group, a cycloalkylene group, and an arylene group are mentioned, for example.

The alkylene group may be linear or branched. 1-10 are preferable, as for carbon number of the said alkylene group, 2-8 are more preferable, and 3-5 are still more preferable. The alkylene group may have a hetero atom, and the methylene group in the alkylene group may be substituted with a hetero atom. As said heteroatom, an oxygen atom, a sulfur atom, or a nitrogen atom is preferable, and an oxygen atom is more preferable.

The cycloalkylene group may be either monocyclic or polycyclic. 3-20 are preferable, as for carbon number of the said cycloalkylene group, 5-10 are more preferable, and 6-8 are still more preferable.

The arylene group may be either monocyclic or polycyclic. 6-20 are preferable, as for carbon number of the said arylene group, 6-15 are more preferable, and 6-10 are more preferable. As said arylene group, a phenylene group is preferable.

The cycloalkylene group and the arylene group may have a hetero atom as a reducing atom. As said heteroatom, an oxygen atom, a sulfur atom, or a nitrogen atom is preferable, and an oxygen atom is more preferable.

The said hydrocarbon group may have a substituent further.

As said substituent, a halogen atom (for example, a fluorine atom etc.), a hydroxyl group, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and an alkenyl group are mentioned, for example, A hydroxyl group A oxy group is preferred.

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

P represents a polymerizable group.

The polymerizable group is as described above.

As an example of the structural unit which has a polymeric group, although what is shown below is mentioned, It is not limited to these.

[Formula 3]

Among the structural units, Rx represents a hydrogen atom or a methyl group. Moreover, among the said structural units, Ry represents a hydrogen atom or a methyl group.

Resin A may contain the structural unit which has a polymeric group individually by 1 type, and may contain it 2 or more types.

When the resin A has a structural unit having a polymerizable group, the content of the structural unit having a polymerizable group is preferably 5 to 70% by mass with respect to all the structural units of the resin A from the viewpoint of more excellent effects of the present invention. , 10 to 50 mass% is more preferable, and 20 to 40 mass% is more preferable.

Moreover, content of the structural unit which has a polymeric group in resin A is 5-70 mol% is preferable with respect to all the structural units of resin A, and 10-60 mol% is more excellent in the effect of this invention. is more preferable, and 20 to 50 mol% is more preferable.

As a means for introducing the polymerizable group into the resin A, functional groups such as a hydroxyl group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, and a sulfo group, an epoxy compound, a block isocyanate compound , a method of reacting compounds such as isocyanate compounds, vinylsulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides.

As a preferred example of a means for introducing a polymerizable group into the resin A, after synthesizing a polymer having a carboxy group by a polymerization reaction, a part of the carboxy group of the obtained polymer is synthesized by a polymer reaction, and an epoxy group such as glycidyl (meth)acrylate A means for introducing a (meth)acryloxy group into a polymer by reacting a (meth)acrylate having As another method, a polymer having a hydroxyl group is synthesized by a polymerization reaction, and then (meth)acrylate having an isocyanate group is reacted with a part of the hydroxyl group of the obtained polymer by the polymerization reaction to form a (meth)acryloxy group in the polymer. A means of introducing it can be mentioned.

By this means, resin A which has a (meth)acryloxy group in a side chain can be obtained.

It is preferable to carry out the said polymerization reaction under temperature conditions of 70-100 degreeC, and it is more preferable to carry out under temperature conditions of 80-90 degreeC. As the polymerization initiator used in the polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. is more preferable. The polymer reaction is preferably carried out under temperature conditions of 80 to 110°C. In the polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

Resin A may be used individually by 1 type, and may be used 2 or more types.

When using 2 or more types, resin A containing the structural unit derived from the monomer which has an aromatic hydrocarbon group is used by mixing 2 types, or resin containing the structural unit derived from the monomer which has an aromatic hydrocarbon group. It is preferable to mix and use A and resin A which does not contain the structural unit derived from the monomer which has an aromatic hydrocarbon group. In the case of the latter, the use ratio of Resin A containing a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, and more preferably 70% by mass or more, with respect to the total mass of Resin A, 80 mass % or more is more preferable, and 90 mass % or more is especially preferable.

Synthesis of resin A is performed by combining the above-mentioned singular or plural monomers with radical polymerization initiators such as peroxide-based polymerization initiators (eg, benzoyl peroxide) and azo-based polymerization initiators (eg, azobisisobutyronitrile). It can be carried out by polymerization using

The content of the resin A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, and 40 to 60% by mass with respect to the total mass of the photosensitive composition layer. particularly preferred. It is preferable from the viewpoint of controlling the development time that the content of the resin A is 90% by mass or less. On the other hand, making the content of the resin A 10% by mass or more is preferable from the point of improving the anti-fuse property.

The photosensitive composition layer may also contain resin other than resin A mentioned above.

Examples of other resins include acrylic resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyester resins, epoxy resins, polyacetal resins, polybenzoxazole resins, polysiloxane resins, and polyethylene. imines, polyallylamines, and polyalkylene glycols.

(polymerizable compound)

The photosensitive composition layer may contain a polymerizable compound having a polymerizable group. As a polymeric compound, an ethylenically unsaturated compound is preferable.

In addition, in this specification, a "polymerizable compound" means a compound that polymerizes under the action of a polymerization initiator described later, and is different from the resin A described above.

The polymerizable group included in the polymerizable compound may be any group involved in the polymerization reaction, and includes, for example, groups having ethylenically unsaturated groups such as vinyl, acryloyl, methacryloyl, styryl and maleimide groups; A group having a cationic polymerizable group such as an epoxy group and an oxetane group is exemplified, and a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.

As an ethylenically unsaturated group which an ethylenically unsaturated compound has, a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, a maleimide group, etc. are mentioned. As an ethylenically unsaturated group, an acryloyl group or a methacryloyl group is preferable.

The polymerizable group of the polymerizable compound other than the ethylenically unsaturated compound is not particularly limited as long as it is a group involved in the polymerization reaction, and examples thereof include a group having a cationic polymerizable group such as an epoxy group and an oxetane group.

Hereinafter, the ethylenically unsaturated compound is demonstrated.

An ethylenically unsaturated compound is preferably a compound (polyfunctional ethylenically unsaturated compound) having two or more ethylenically unsaturated groups in one molecule from the viewpoint of more excellent photosensitivity.

Further, from the viewpoint of more excellent resolution and releasability, the number of ethylenically unsaturated groups of the ethylenically unsaturated compound in one molecule is preferably 6 or less, more preferably 3 or less, and further 2 or less. desirable.

It is preferable to contain a bifunctional or trifunctional ethylenically unsaturated compound having two or three ethylenically unsaturated groups in one molecule, from the viewpoint of better balance of the photosensitivity, resolution, and peelability of the photosensitive composition layer, and in one molecule It is more preferable to include a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups.

The content of the bifunctional ethylenically unsaturated compound relative to the total mass of the polymerizable compound is preferably 20% by mass or more, more preferably more than 40% by mass, and still more preferably 55% by mass or more, from the viewpoint of excellent peelability. . The upper limit is not particularly limited, and may be 100% by mass. That is, all of the polymerizable compounds may be bifunctional ethylenically unsaturated compounds.

Moreover, as an ethylenically unsaturated compound, the (meth)acrylate compound which has a (meth)acryloyl group as a polymeric group is preferable.

-Polymerizable Compound B1-

It is also preferable that the photosensitive composition layer contains, as a polymerizable compound, polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups.

In the photosensitive composition layer, the mass ratio of the content of the polymerizable compound B1 to the total mass of the polymerizable compound is preferably 40% by mass or more, more preferably 50% by mass or more, and 55% by mass, from the viewpoint of better resolution. % or more is more preferable, and 60 mass % or more is particularly preferable. The upper limit is not particularly limited, but from the viewpoint of peelability, it is, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass The following are particularly preferred.

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

Polymeric compound B1 may have only one aromatic ring, and may have two or more aromatic rings.

Polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving resolution by suppressing swelling of the photosensitive composition layer with a developing solution.

Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis (4-hydroxyphenyl) propane), and 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 a compound having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. there is.

Both ends of the bisphenol structure and the two polymerizable groups may be bonded directly, or may be bonded through one or more alkyleneoxy groups, and preferably bonded through one or more alkyleneoxy groups.

As an alkyleneoxy group added to both ends of a bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable. The number of added alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, more preferably 6 to 14.

About polymeric compound B1 which has a bisphenol structure, it describes in Paragraph [0072] - [0080] of Unexamined-Japanese-Patent No. 2016-224162, and the content described in this publication is integrated in this specification.

As the polymerizable compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable.

Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA- 324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2, 2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl) Propane (BPE-200, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethoxylated (10) bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and ethoxylated bisphenol A dimetha and acrylate (BPE-100, manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

Polymeric compound B1 may be used individually by 1 type, and may be used 2 or more types.

10 mass % or more is preferable with respect to the total mass of the photosensitive composition layer, and, as for content of polymeric compound B1, 20 mass % or more is more preferable at the point with more excellent resolution. The upper limit is not particularly limited, but is preferably 70% by mass or less, and more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which the photosensitive resin oozes from the end of the transfer member).

As the polymerizable compound, a polymerizable compound having an alkylene oxide-modified bisphenol structure is preferable, and a compound represented by the following general formula (B1) (also applicable to the polymerizable compound B1) is more preferable.

[Formula 4]

In General Formula (B1), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. A represents C ₂ H ₄ . B represents C ₃ H ₆ . n1 and n3 are each independently an integer of 1 to 39, and n1+n3 is an integer of 2 to 40. n2 and n4 are each independently an integer of 0 to 29, and n2+n4 is an integer of 0 to 30. The arrangement of the constituent units of -(AO)- and -(BO)- may be random or may be a block. And in the case of a block, either -(AO)- and -(BO)- may be on the bisphenyl group side.

1 aspect WHEREIN: 2-20 are preferable, as for n1+n2+n3+n4, 2-16 are more preferable, and 4-12 are still more preferable. Moreover, as for n2+n4, 0-10 are preferable, 0-4 are more preferable, 0-2 are still more preferable, and 0 is especially preferable.

The photosensitive composition layer may also contain other polymeric compounds other than the polymeric compound mentioned above.

Other polymerizable compounds are not particularly limited and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher functional ethylenically unsaturated compound are exemplified.

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

Examples of the bifunctional 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, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecane dimethanol dimethacrylate (DCP , Shin-Nakamura Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD -N, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), polyethylene glycol dimethacrylate (4G, 9G, 14G, and 23G, etc., manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Aronix (registered trademark) M-220 (Doa) Kosei Co., Ltd.), Aronix (registered trademark) M-240 (Toa Kosei Co., Ltd.), Aronix (registered trademark) M-270 (Toa Kosei Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decane die old 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. Lycol di(meth)acrylate is mentioned.

Examples of urethanedi(meth)acrylate include propylene oxide-modified urethanedi(meth)acrylate, and ethylene oxide and propylene oxide-modified urethanedi(meth)acrylate. As a commercial item, 8UX-015A (made by Taisei Fine Chemical Co., Ltd.), UA-32P (made by Shin-Nakamura Chemical Industry Co., Ltd.), and UA-1100H (made by Shin-Nakamura Chemical Industry Co., Ltd.) are mentioned, for example.

Examples of trifunctional or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra) (meth)acrylate, and trimethylolpro Paint rye(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerine tri(meth)acrylate rates, and alkylene oxide modified products thereof.

Here, “(tri/tetra/penta/hexa)(meth)acrylate” refers to tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. It is a concept including, and "(tri/tetra)(meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate.

In one aspect, the photosensitive composition layer preferably contains the above-described polymerizable compound B1 and a trifunctional or higher functional ethylenically unsaturated compound, and contains the above-described polymerizable compound B1 and two or more kinds of trifunctional or higher functional ethylenically unsaturated compounds It is more preferable to In this case, the mass ratio of the polymerizable compound B1 and the trifunctional or higher functional ethylenically unsaturated compound is (total mass of the polymerizable compound B1): (total mass of the trifunctional or higher functional ethylenically unsaturated compound) = 1: 1 to 5: 1 It is preferable, 1.2:1 to 4:1 is more preferable, and 1.5:1 to 3:1 is still more preferable.

Moreover, in one aspect|mode, it is preferable that the photosensitive composition layer contains the above-mentioned polymeric compound B1 and 2 or more types of trifunctional ethylenically unsaturated compounds.

As an alkylene oxide modified product of a trifunctional or higher functional ethylenically unsaturated compound, a caprolactone-modified (meth)acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd., etc. ), ethoxylated trimethylolpropane triacrylate (SR454, SR499, and SR502, etc., manufactured by Tomoe Kogyo Co., Ltd.), alkylene oxide-modified (meth)acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., Shin Nakamura Kaga ATM-35E and A-9300 manufactured by Ku Kogyo Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Allnex Co., etc.), ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin Nakamura Kagaku Kogyo Co., etc.), Aronix ( Registered trademark) TO-2349 (made by Toa Kosei Co., Ltd.), Aronix M-520 (made by Toa Kosei Co., Ltd.), and Aronix M-510 (made by Toa Kosei Co., Ltd.) are mentioned.

Moreover, you may use the polymeric compound which has an acidic radical (a carboxyl group etc.) as a polymeric compound. The acid group may form an acid anhydride group. As the polymerizable compound having an acid group, Aronix (registered trademark) TO-2349 (manufactured by Toa Kosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toa Kosei Co., Ltd.), and Aronix (registered trademark) M-510 (Toa Kosei Co., Ltd.) made by Kosei Co., Ltd.).

As the polymerizable compound having an acid group, for example, a polymerizable compound having an acid group described in paragraphs [0025] to [0030] of Unexamined-Japanese-Patent No. 2004-239942 may be used.

As molecular weight (weight average molecular weight when having molecular weight distribution) of a polymeric compound (including polymeric compound B1), 200-3000 are preferable, 280-2200 are more preferable, and 300-2200 are still more preferable.

A polymeric compound may be used individually by 1 type, and may use 2 or more types simultaneously.

The content of the polymerizable compound is preferably 0 to 70% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, with respect to the total mass of the photosensitive composition layer.

(Polymerization initiator)

The photosensitive composition layer may contain a polymerization initiator.

As a polymerization initiator, a well-known polymerization initiator can be used depending on the format of a polymerization reaction, for example. Specifically, a thermal polymerization initiator and a photopolymerization initiator are mentioned.

Any of a radical polymerization initiator and a cationic polymerization initiator may be sufficient as a polymerization initiator.

The photosensitive composition layer preferably contains a photopolymerization initiator.

The photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound by receiving actinic rays such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

As a photoinitiator, a photoradical polymerization initiator and a photocationic polymerization initiator are mentioned, for example, and a photoradical polymerization initiator is preferable.

Examples of the photoradical 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, and a photopolymerization initiator having an acylphosphine oxide structure. , and a photopolymerization initiator having an N-phenylglycine structure.

Further, the photosensitive composition layer is selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives thereof as a photoradical polymerization initiator in terms of photosensitivity, visibility of exposed and unexposed areas, and resolution. It is preferable to include at least one species that is. Note that the two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and derivatives thereof may be the same or different.

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

As an optical radical polymerization initiator, the polymerization initiator of paragraph [0031] - [0042] of Unexamined-Japanese-Patent No. 2011-095716, and paragraph [0064] - [0081] of Unexamined-Japanese-Patent No. 2015-014783, for example. You can use it.

As an optical radical polymerization initiator, for example, ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ- 110 (trade name: manufactured by Midori Chemical Co., Ltd.), benzophenone, 4,4'-bis(diethylamino)benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF) , Omnirad651 and 369 (trade name: manufactured by IGM Resins B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (Tokyo Kasei High School).

As a commercial item of radical photopolymerization initiator, for example, 1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE -01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02 , BASF), IRGACURE OXE-03 (BASF), IRGACURE OXE-04 (BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name) : Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name) : Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy -2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-di Methoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins B.V.) agent), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins B.V.), oxime ester photopolymerization initiator (trade name: Lunar 6, manufactured by DKSH Japan), 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name : B-CIM, Hampfo rd), 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Kasei Kogyo Co., Ltd.), 1-[4-(phenylthio)phenyl]-3- Cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Trolly New Electronic Materials Co., Ltd.) ), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O- acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl- 9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.); there is.

A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid by receiving actinic light. As the photocationic polymerization initiator, a compound that generates an acid in response to actinic rays with a wavelength of 300 nm or more, preferably with a wavelength of 300 to 450 nm is preferable, but the chemical structure thereof is not limited. In addition, even for a photocationic polymerization initiator that does not directly respond to actinic rays with a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer as long as it is a compound that generates an acid by being sensitive to actinic rays with a wavelength of 300 nm or more by using it in combination with a sensitizer. .

As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid with a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid with a pKa of 3 or less is more preferable, and photocationic polymerization that generates an acid with a pKa of 2 or less Initiators are more preferred. Although the lower limit of pKa is not particularly determined, for example, -10.0 or more is preferable.

As a photocationic polymerization initiator, an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator are mentioned.

As an ionic photocationic polymerization initiator, onium salt compounds, such as diaryliodonium salts and triaryl sulfonium salts, and quaternary ammonium salts are mentioned, for example.

As an ionic photocationic polymerization initiator, you may use the ionic photocationic polymerization initiator of Unexamined-Japanese-Patent No. 2014-085643, Paragraph [0114] - [0133].

Examples of the nonionic photocationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds, you may use the compounds described in Unexamined-Japanese-Patent No. 2011-221494, Paragraph [0083] - [0088]. Moreover, as an oxime sulfonate compound, you may use the compound described in Paragraph [0084] - [0088] of International Publication No. 2018/179640.

The photosensitive composition layer preferably contains a radical photopolymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.

A polymerization initiator may be used individually by 1 type, and may be used 2 or more types.

The content of the polymerization initiator (preferably a photopolymerization initiator) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more with respect to the total mass of the photosensitive composition layer. desirable. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less with respect to the total mass of the photosensitive composition layer.

(sensitizer)

The photosensitive composition layer preferably contains a sensitizer.

The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, and thiazole compounds. , Benzothiazole compounds, triazole compounds (eg, 1,2,4-triazole), stilbene compounds, distyrylbenzene compounds, styrylpyridine compounds, triazine compounds, thiophene compounds, naphthal A mid compound, a triarylamine compound, and an aminoacridine compound are mentioned. In addition, the compounds listed above include derivatives of the above compounds.

Among these, as a sensitizer, a dialkylamino benzophenone compound, an anthracene compound, a distyrylbenzene compound, or a styrylpyridine compound is preferable, and an anthracene compound, a distyrylbenzene compound, or a styrylpyridine compound is more preferable. And, an anthracene derivative, a distyrylbenzene derivative, or a styrylpyridine derivative is more preferable.

A sensitizer may be used individually by 1 type, and may be used 2 or more types.

When the photosensitive composition layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to a light source and improving the curing rate due to the balance between the polymerization rate and chain transfer, 0.01-5 mass % is preferable with respect to the total mass of the photosensitive composition layer, and 0.05-1 mass % is more preferable.

(pigment)

The photosensitive composition layer has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 to 780 nm at the time of color development, from the viewpoint of visibility of the exposed portion and unexposed portion, pattern visibility after development, and resolution, and is also acid, base, or It is also preferable to include a dye (also referred to as "dye N") whose maximum absorption wavelength changes with radicals. When dye N is included, although the detailed mechanism is unknown, the adhesion to the adjacent layer (for example, the water-soluble resin layer) is improved, and the resolution is more excellent.

In the present specification, the term "maximum absorption wavelength of a dye changes by an acid, base, or radical" means that a dye in a color development state is discolored by an acid, base, or radical, or in a discolored state. It may mean either an aspect in which a dye present in color develops by an acid, a base, or a radical, and an aspect in which a dye in a color development state changes to a color development state of a different color.

Specifically, the dye N may be a compound that changes from a color-disappearing state and develops color with exposure, or may be a compound that changes from a color-developing state and disappears with exposure. In this case, it may be a dye whose color development or dissipation state changes when an acid, base, or radical is generated and acts in the photosensitive composition layer upon exposure to light, and the state in the photosensitive composition layer (for example, For example, it may be a dye whose color appearance or color loss state changes as pH) changes. In addition, it may be a dye whose color development or discoloration state changes by directly receiving an acid, base, or radical as a stimulus without exposure to light.

Among them, from the viewpoint of visibility and resolution of the exposed portion and the unexposed portion, the dye N is preferably a dye whose maximum absorption wavelength changes with an acid or a radical, and a dye whose maximum absorption wavelength changes with a radical is more preferable.

In the case where the photosensitive composition layer is a negative photosensitive composition layer, the negative photosensitive composition layer contains a dye whose maximum absorption wavelength changes by radicals as dye N in view of the visibility and resolution of the exposed portion and the unexposed portion, and an optical radical. It is preferable to include both polymerization initiators.

In view of the visibility of the exposed portion and the unexposed portion, the dye N is preferably a dye that develops color with an acid, a base, or a radical.

As an example of the color development mechanism of the dye N, a radical photopolymerization initiator, a photocationic polymerization initiator (photoacid generator), or a photobase generator is added to the photosensitive composition layer, and a photoradical polymerization initiator, a photocationic polymerization initiator, or a photobase generator is added after light exposure. An embodiment in which a radical, an acid, or a base generated from a base generator causes a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (for example, a leuco dye) to develop color.

Dye N has a maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development, preferably 550 nm or more, more preferably 550 to 700 nm, more preferably 550 to 650 nm, from the viewpoint of visibility of the exposed portion and the unexposed portion. it is more preferable

In addition, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 to 780 nm at the time of color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm at the time of color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

The maximum absorption wavelength of the dye N is determined by using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an air atmosphere, and the transmission spectrum of a solution containing the dye N (liquid temperature 25°C) in the wavelength range of 400 to 780 nm. It is obtained by measuring and detecting the wavelength (maximum absorption wavelength) at which the intensity of light becomes minimum.

As a pigment|dye which develops or disappears color by exposure, a leuco compound is mentioned, for example.

Examples of the dye that is discolored by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethane dyes, and anthraquinone dyes. .

As the dye N, a leuco compound is preferable from the viewpoint of the visibility of the exposed portion and the unexposed portion.

As the leuco compound, for example, a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropyran skeleton (spiropyran dye), a leuco compound having a fluoran skeleton (fluoro egg dye), leuco compound having a diarylmethane skeleton (diarylmethane pigment), leuco compound having a rhodaminelactam skeleton (rhodamine lactam pigment), leuco compound having an indolylphthalide skeleton (indolyl phthalide-based pigments), and leuco compounds having a leuco-auramine skeleton (leuco-auramine-based pigments).

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

As a leuco compound, what has a lactone ring, a sultine ring, or a sultone ring is preferable from the point of visibility of an exposed part and an unexposed part. As a result, the lactone ring, sultine ring, or sultone ring of the leuco compound is reacted with a radical generated from the photoradical polymerization initiator or an acid generated from the photocationic polymerization initiator, and the leuco compound is changed to a ring-closed state to make it disappear, or Color can be developed by changing the leuco compound to a ring-opening state. As the leuco compound, a compound having a lactone ring, a sultine ring, or a sultone ring, and having a lactone ring, a sultine ring, or a sultone ring ring-opening with a radical or an acid to develop color is preferable, and has a lactone ring, and has a lactone ring with a radical or an acid. A compound that develops color by ring opening is more preferred.

As dye N, the following dyes and leuco compounds are mentioned, for example.

Specific examples of dyes among dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, methane yellow, thymol sulfophthalein, xylenol blue, and methyl orange. , Paramethyl Red, Congo Red, Benzopurpurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuxin, Victoria Pure Blue-Naphthalenesulfonate, Victoria Pure Blue BOH (walnut Gaya Gagaku High School), Oil Blue #603 (Orient Gagaku High School), Oil Pink #312 (Orient Gagaku High School), Oil Red 5B (Orient Gagaku High School), Oil Scarlet #308 (Orient Gagaku) High school students), Oil red OG (Orient Gagaku high school students), Oil red RR (Orient Gagaku high school students), Oil green #502 (Orient Gagaku high school students), Spiron Red BEH Special (Hodogaya Gagaku high school students) ), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-di Ethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylamino phenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of the leuco compound in the dye N include p,p',p"-hexamethyltriaminotriphenylmethane (Leuco Crystal Violet), Pergascript Blue SRB (manufactured by Chiba Geigy Co., Ltd.), crystal violet lactone, malachite green lactone, benzoyl Leuko Methylene Blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p- Toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-( N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N, N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino) )-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7 -Chlorofluorane, 3-(N,N-diethylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N -Dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluoran, 3-piperidino-6-methyl- 7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3,3- Bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethyl Amino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl- 2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one. there is.

The dye N is preferably a dye whose maximum absorption wavelength changes by radicals, and more preferably a dye that develops color by radicals, from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution.

As the dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalenesulfonate is preferable.

Dye N may be used individually by 1 type, and may be used 2 or more types.

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

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

A solution in which 0.001 g and 0.01 g of the pigment were dissolved in 100 mL of methyl ethyl ketone was prepared. Radical photopolymerization initiator Irgacure OXE01 (trade name, BASF Japan Co., Ltd.) is added to each obtained solution, radicals are generated by irradiation with light having a wavelength of 365 nm, and all dyes are colored. Thereafter, the absorbance of each solution having a liquid temperature of 25°C is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under an air atmosphere, and a calibration curve is prepared.

Next, the absorbance of the solution in which all of the dyes were developed was measured in the same manner as above, except that 3 g of the photosensitive composition layer was dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the solution containing the obtained photosensitive composition layer, the content of the dye contained in the photosensitive composition layer is calculated based on the calibration curve.

In addition, 3 g of the photosensitive composition layer is the same as 3 g of the total solid content in the photosensitive composition.

(Pigment)

The photosensitive composition layer may contain a pigment.

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

In order to protect the liquid crystal display window of recent electronic devices, there is a case where a cover glass having a black frame-shaped light shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is attached to the liquid crystal display window. A colored resin layer may be used to form such a light blocking layer.

What is necessary is just to select suitably as a pigment according to a desired color, For example, a black pigment, a white pigment, and the pigment of a chromatic color other than black and white are mentioned, When forming a black pattern, as a pigment, black Pigments are preferred.

As a black pigment, a well-known black pigment (For example, an organic pigment and an inorganic pigment etc.) is mentioned, for example.

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

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

"Particle diameter" means the diameter of a circle when the area of a pigment particle is obtained from a photographic image of the pigment particle taken with an electron microscope and a circle having the same area as the area of the pigment particle is considered. In addition, the "number average particle diameter" means an average value obtained by obtaining the particle diameter of 100 arbitrary particles and averaging the obtained 100 particle diameters.

As a white pigment, an inorganic pigment and the white pigment of Unexamined-Japanese-Patent No. 2005-007765, Paragraph [0015] and [0114] are mentioned, for example.

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 more preferable, and rutile Particularly preferred is titanium oxide in the form or anatase form, and most preferred is titanium oxide in the rutile form.

Moreover, the surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic matter treatment, or two or more of these treatments may be performed. As a result, the catalytic activity of titanium oxide is suppressed, and heat resistance and photoregression properties can be improved.

From the viewpoint of reducing the thickness of the photosensitive composition layer after heating, as the surface treatment for the surface of the titanium oxide, at least one of an alumina treatment and a zirconia treatment is preferably performed, and it is more preferable to perform both an alumina treatment and a zirconia treatment. desirable.

When the photosensitive composition layer is a colored resin layer, it is also preferable that the photosensitive composition layer contains a pigment of a chromatic color other than a black pigment and a white pigment from a transferable point.

The particle size (number average particle size) of the chromatic pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, from the viewpoint of better dispersibility. As for a lower limit, 10 nm or more is preferable.

As chromatic pigments, for example, Victoria Pure Blue BO (Color Index (hereinafter also referred to as “C.I.”) 42595), Auramine (C.I. 41000), Pat Black HB (C.I. 26150), Monolight Yellow GT (C. I. Pigment Yellow 12), Permanent Yellow GR (C. I. Pigment Yellow 17), Permanent Yellow HR (C. I. Pigment Yellow 83), Permanent Carmine FBB (C. I. Pigment Red 146), No. Stubomb Red ESB (C. I. Pigment Violet 19), Permanent Ruby FBH (C. I. Pigment Red 11), Pastel Pink B Spler (C. I. Pigment Red 81), Monastral First Blue (C. I. Pig) Ment Blue 15), Mono Light First Black B (C. I. Pigment Black 1) and Carbon, C. I. Pigment Red 97, C. I. Pigment Red 122, C. I. Pigment Red 149, C. I. Pigment Red 168, C. I. Pigment Red 177, C. I. Pigment Red 180, C. I. Pigment Red 192, C. I. Pigment Red 215, C. I. Pigment Green 7, C. I. Pigment Blue 15:1, C. I. Pigment Blue 15:4, C. I. Pigment Blue 22, C. I. Pigment Blue 60, C. I. Pigment Blue 64 and C. I. Pigment Violet 23, and C. I. Pigment Red 177 is preferable.

A pigment may be used individually by 1 type, and may be used by 2 or more types.

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 more preferably more than 5% by mass and 35% by mass or less with respect to the total mass of the photosensitive composition layer. and 10 to 35% by mass is particularly preferred.

When the photosensitive composition layer contains pigments other than black pigments (for example, white pigments and chromatic pigments, etc.), the content of pigments other than black pigments is preferably 30% by mass or less with respect to the total mass of black pigments. And, 1 to 20 mass% is more preferable, and 3 to 15 mass% is more preferable.

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

The dispersion liquid may be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (or vehicle) and dispersing the mixture in a dispersing machine. What is necessary is just to select a pigment dispersant according to a pigment and a solvent, For example, a commercially available dispersant can be used.

"Vehicle" means a part of a medium in which a pigment is dispersed in the case of a pigment dispersion. The vehicle is liquid and contains a binder component for maintaining the black pigment in a dispersed state, and a solvent component (organic solvent) for dissolving and diluting the binder component.

As a disperser, well-known dispersers, such as a kneader, a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill, are mentioned, for example.

Further, it may be finely pulverized using frictional force by mechanical grinding. Examples of the disperser and fine pulverization include descriptions in "Dictionary of Pigments" (Written by Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pages 438 and 310).

(other additives)

The photosensitive composition layer may also contain a well-known additive other than the said component as needed.

Examples of additives include radical polymerization inhibitors, antioxidants (eg, phenidone), rust preventives (eg, benzotriazoles and carboxybenzotriazoles), sensitizers, surfactants, and plasticizers. , heterocyclic compounds (eg, triazole, etc.), pyridines (eg, isonicotinamide, etc.), and purine bases (eg, adenine, etc.).

In addition, as other additives, for example, metal oxide particles, chain transfer agent, antioxidant, dispersing agent, acid increasing agent, development accelerator, conductive fiber, ultraviolet absorber, thickener, crosslinking agent, organic or inorganic precipitation inhibitor, and Japanese Laid-open Patent Paragraphs [0165] of Publication No. 2014-085643 - [0184] are mentioned, and these content is integrated in this specification.

Each additive may be used individually by 1 type, and may be used 2 or more types.

The photosensitive composition layer may also contain a radical polymerization inhibitor.

Examples of the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph [0018] of Japanese Patent Publication No. 4502784. Among them, phenothiazine, phenoxazine, or 4-methoxyphenol is preferable. Examples of other radical polymerization inhibitors include naphthylamine, cuprous chloride, N-nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive composition layer, it is preferable to use N-nitrosophenylhydroxylamine aluminum salt as a radical polymerization inhibitor.

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 with respect to the total mass of the polymerizable compound.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2, 3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole An azole etc. are mentioned.

Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2- Ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxy A benzotriazole etc. are mentioned. As carboxybenzotriazoles, commercial items, such as CBT-1 (Chohoku Chemical Industry Co., Ltd., a brand name), can be used, for example.

The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the photosensitive composition layer. When the content is 0.01% by mass or more, the storage stability of the photosensitive composition layer is more excellent. On the other hand, when the content is 3% by mass or less, the maintenance of the sensitivity and suppression of discoloration of the dye are more excellent.

As surfactant, the surfactant of paragraph [0017] of Unexamined-Japanese-Patent No. 4502784, and Paragraph [0060] - [0071] of Unexamined-Japanese-Patent No. 2009-237362 is mentioned, for example.

As surfactant, a nonionic surfactant, a fluorochemical surfactant, or a silicone type surfactant is preferable.

As commercially available products of fluorine-based surfactants, for example, Megafac 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, EXP. MFS-578, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Co., Ltd.), Suffron S-382, SC-101, SC-103, SC-104, SC-105 , SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by AGC Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA), Futergent 710FL , 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (above, manufactured by NEOS Co., Ltd.), U- 120E (made by Unichem Co., Ltd.) etc. are mentioned.

As the fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom and in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heated is also preferably used. As such a fluorine-based surfactant, DIC Co., Ltd.'s Megafac DS series (Gagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shinbun (February 23, 2016)), for example Megafac DS -21 can be heard.

Moreover, it is also preferable to use the polymer of the vinyl ether compound containing a fluorine atom which has a fluorinated alkyl group or a fluorinated alkylene ether group, and a hydrophilic vinyl ether compound as a fluorochemical surfactant.

Moreover, a block polymer can also be used as a fluorochemical surfactant.

Further, as the fluorine-based surfactant, a structural unit derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group and a propyleneoxy group) having two or more (preferably five or more) A fluorine-containing high molecular compound containing a structural unit derived from a (meth)acrylate compound can also be preferably used.

Moreover, as a fluorochemical surfactant, the fluoropolymer which has an ethylenically unsaturated bond containing group in a side chain can also be used. Megafac RS-101, RS-102, RS-718K, RS-72-K (above, manufactured by DIC Corporation), etc. are mentioned.

As a fluorine-based surfactant, from the viewpoint of improving environmental suitability, it is a substitute material for compounds having a straight-chain perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). It is preferable that it is a surfactant derived.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl Ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate , sorbitan fatty acid ester, and the like. Specific examples include Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, HYDROPALAT WE 3323 (above, manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (above, manufactured by BASF), Solsperse 20000 (above, manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (above, manufactured by Fujifilm Wako Junyaku Co., Ltd.), Pionin D-1105, D-6112 , D-6112-W, D-6315 (above, manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (above, manufactured by Nisshin Chemical Co., Ltd.), and the like.

Examples of the silicone surfactant include straight-chain polymers formed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains and terminals.

As a specific example of a silicone type surfactant, EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 (above, manufactured by DIC Corporation), DOWSIL 8032 ADDITIVE, Toray Silicon DC3PA, Toray Silicon SH7PA, Toray Silicon DC11PA, Toray Silicon SH21PA, Toray Silicon SH28PA, Toray Silicon SH29PA, Toray Silicon SH30PA, Toray Silicon SH8400 (above) , Toray Dow Corning Co., Ltd.) and, 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, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP- 327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (above, manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300 , TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK335 , BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 (above, manufactured by Big Chemie Co., Ltd.), and the like.

Surfactant may be used individually by 1 type, and may be used 2 or more types.

When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, and 0.05 to 0.80% by mass with respect to the total mass of the photosensitive composition layer. more preferable

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

The layer thickness (film thickness) of the photosensitive composition layer is generally 0.1 to 300 μm, preferably 0.2 to 100 μm, more preferably 0.5 to 50 μm, still more preferably 0.5 to 15 μm, particularly preferably 0.5 to 10 μm. , most preferably 0.5 to 8 μm. Thereby, the developability of the photosensitive composition layer can be improved, and resolution can be improved.

Moreover, in one aspect, 0.5 to 5 μm is preferable, 0.5 to 4 μm is more preferable, and 0.5 to 3 μm is still more preferable.

(impurities, etc.)

The photosensitive composition layer may contain impurities.

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

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

Among them, sodium ions, potassium ions, and halide ions are easily mixed, so it is preferable to set them as the following content.

The metal impurity is a compound different from the particles (eg, metal oxide particles) that may be included in the transfer film.

The content of the metallic impurities is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and still more preferably 2 ppm by mass or less with respect to the total mass of the photosensitive composition layer. 1 mass ppb or more is preferable and, as for a minimum, 0.1 mass ppm or more is more preferable.

As a method for adjusting the content of impurities, for example, a method of selecting a material having a low content of impurities as a raw material for the photosensitive composition layer, a method of preventing contamination of impurities during formation of the photosensitive composition layer, and washing to remove them way can be

The content of impurities can be quantified by known methods such as ICP emission spectroscopy, atomic absorption spectroscopy, and ion chromatography, for example.

As the residual organic solvent, for example, benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and hexane three people can be heard.

The content of the remaining organic solvent is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and still more preferably 4 ppm by mass or less with respect to the total mass of the photosensitive composition layer. 10 mass ppb or more is preferable with respect to the total mass of the photosensitive composition layer, and, as for a minimum, 100 mass ppb or more is more preferable.

As a method of adjusting the content of the residual organic solvent, a method of adjusting the drying treatment conditions in the manufacturing method of a transfer film described later is exemplified. In addition, the content of the residual organic solvent can be quantified by a known method such as gas chromatography analysis.

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

[middle layer]

The transfer film preferably has an intermediate layer between the temporary support and the photosensitive composition layer.

Examples of the intermediate layer include a water-soluble resin layer and an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in Japanese Unexamined Patent Publication No. Hei 5-072724.

As the intermediate layer, an oxygen barrier layer is preferable, exhibiting low oxygen permeability, and water or an alkaline aqueous solution (1 mass of sodium carbonate at 22 ° C. % aqueous solution) are more preferred.

Hereinafter, each component that can be included in the water-soluble resin layer (intermediate layer) will be described.

The water-soluble resin layer (intermediate layer) contains resin.

It is preferable that the said resin contains water-soluble resin as a part or whole.

As the resin usable as the water-soluble resin, for example, polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and resins such as copolymers thereof.

Moreover, as a water-soluble resin, the copolymer of (meth)acrylic acid/vinyl compound etc. can be used. As the copolymer of (meth)acrylic acid/vinyl compound, a copolymer of (meth)acrylic acid/allyl (meth)acrylate is preferable, and a copolymer of methacrylic acid/allyl methacrylate is more preferable.

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

As a lower limit of the weight average molecular weight of water-soluble resin, 5000 or more are preferable, 7000 or more are more preferable, and 10000 or more are still more preferable. Moreover, as the upper limit, 200000 or less is preferable, 100000 or less is more preferable, and 50000 or less is still more preferable.

The degree of dispersion (Mw/Mn) of the water-soluble resin is preferably 1 to 10, and more preferably 1 to 5.

Water-soluble resin may be used individually by 1 type, and may be used 2 or more types.

The content of the water-soluble resin is not particularly limited, but is preferably 50% by mass or more, and preferably 70% by mass or more, with respect to the total mass of the water-soluble resin layer (intermediate layer), from the viewpoint of further improving the oxygen barrier properties and the ability to inhibit interlayer mixing. More preferably, 80 mass% or more is more preferable, and 90 mass% or more is particularly preferable. Further, the upper limit is not particularly limited, but is preferably 99.9% by mass or less, and more preferably 99.8% by mass or less, for example.

The intermediate layer may contain other components in addition to the water-soluble resin.

As the other component, polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, phenol derivatives or amide compounds are preferable, and polyhydric alcohols, phenol derivatives or amide compounds are more preferable.

Moreover, as another component, a well-known surfactant is also mentioned, for example.

As polyhydric alcohols, glycerol, diglycerol, and diethylene glycol are mentioned, for example.

As the number of hydroxy groups that polyhydric alcohols have, 2 to 10 are preferable.

As an alkylene oxide adduct of polyhydric alcohol, the compound which added the ethyleneoxy group, the propyleneoxy group, etc. to the said polyhydric alcohol is mentioned, for example.

1-100 are preferable, as for the average addition number of alkyleneoxy groups, 2-50 are more preferable, and 2-20 are still more preferable.

As a phenol derivative, bisphenol A and bisphenol S are mentioned, for example.

As an amide compound, N-methylpyrrolidone is mentioned, for example.

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

The molecular weight of the other components is preferably less than 5000, more preferably 4000 or less, still more preferably 3000 or less, particularly preferably 2000 or less, and most preferably 1500 or less. As for a minimum, 60 or more are preferable.

The other components may be used singly or in combination of two or more.

The content of the other components is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more with respect to the total mass of the middle layer. The upper limit is preferably less than 30% by mass, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

The intermediate layer may contain impurities.

As an impurity, the impurity contained in the said photosensitive composition layer is mentioned, for example.

The layer thickness of the water-soluble resin layer (intermediate layer) is not particularly limited, but is preferably 0.1 to 5 μm, and more preferably 0.5 to 3 μm. When the thickness of the water-soluble resin layer (intermediate layer) is within the above range, the oxygen barrier property is not lowered, and the ability to suppress interlayer mixing is excellent. In addition, the increase in the removal time of the water-soluble resin layer (intermediate layer) during development can be further suppressed.

[Protection Film]

The transfer film may have a protective film on the photosensitive composition layer.

As the protective film, a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films. can be heard

Moreover, you may use the resin film comprised from the same material as the above-mentioned temporary support body as a protective film.

Especially, as a protective film, a polyolefin film is preferable, a polypropylene film or a polyethylene film is more preferable, and a polyethylene film is still more preferable.

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

The thickness of the protective film is preferably 1 μm or more in terms of excellent mechanical strength, and preferably 100 μm or less in terms of relatively low cost.

Moreover, in a protective film, it is preferable that the number of fish eyes with a diameter of 80 micrometers or more contained in a protective film is 5 pieces/m ^<2> or less.

In addition, "fish eye" means that foreign substances, undissolved substances, oxidative deterioration products, etc. of materials are formed when materials are thermally melted and a film is produced by methods such as kneading, extrusion, biaxial stretching and casting methods. was introduced during

The number of particles with a diameter of 3 µm or more contained in the protective film is preferably 30/mm ² or less, more preferably 10/mm ² or less, and still more preferably 5/mm ² or less.

In this way, it is possible to suppress defects caused by transfer of irregularities caused by particles included in the protective film to the photosensitive composition layer or the metal layer.

From the point of imparting rollability, the arithmetic average roughness Ra of the surface of the protective film on the opposite side to the surface in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more 0.03 μm or more. desirable. On the other hand, less than 0.50 μm is preferable, 0.40 μm or less is more preferable, and 0.30 μm or less is still more preferable.

The surface roughness Ra of the surface of the protective film in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more, from the viewpoint of suppression of defects during transfer. On the other hand, less than 0.50 μm is preferable, 0.40 μm or less is more preferable, and 0.30 μm or less is still more preferable.

[Method for producing transfer film]

The manufacturing method of the transfer film is not particularly limited, and publicly known methods are exemplified.

As a method for producing the transfer film 10, for example, a step of applying a composition for forming an intermediate layer to the surface of the temporary support 11 to form a coating film, and further drying the coating film to form the intermediate layer 13; , a method including a step of applying a photosensitive composition to the surface of the intermediate layer 13 to form a coating film, and further drying the coating film to form the photosensitive composition layer 15.

When the transfer film 10 has the protective film 19, the protective film 19 may be pressed onto the composition layer 17 of the transfer film 10 manufactured by the above manufacturing method.

As a method for producing the transfer film 10, the temporary support 11, It is preferable to manufacture a transfer film 10 having an intermediate layer 13, a photosensitive composition layer 15 and a protective film 19.

After manufacturing the transfer film 10 by the above manufacturing method, the transfer film 10 may be wound up to produce and store a roll-shaped transfer film. The transfer film 10 in the form of a roll can be provided in a form as it is to a bonding step with a substrate by a roll-to-roll system described later.

Moreover, the manufacturing method of the said transfer film 10 may be the method of forming the composition layer 17 on the protective film 19.

(Water-soluble resin composition and method of forming intermediate layer (water-soluble resin layer))

As the water-soluble resin composition, it is preferable to include various components and solvents that form the above-described intermediate layer (water-soluble resin layer). In addition, in the water-soluble resin composition, the suitable range of the content of each component with respect to the total solids of the composition is the same as the suitable range of the content of each component with respect to the total mass of the water-soluble resin layer described above.

The solvent is not particularly limited as long as it can dissolve or disperse the water-soluble resin, and at least one selected from the group consisting of water and water-miscible organic solvents is preferable, and water or a mixed solvent of water-miscible organic solvents is more preferable. do.

As a water-miscible organic solvent, C1-C3 alcohol, acetone, ethylene glycol, and glycerol are mentioned, for example, C1-C3 alcohol is preferable, and methanol or ethanol is more preferable.

A solvent may be used individually by 1 type, and may be used 2 or more types.

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

The method for forming the water-soluble resin layer is not particularly limited as long as it can form a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, and inkjet coating). can

(Photosensitive composition and method of forming photosensitive composition layer)

A coating method using a photosensitive composition containing components constituting the photosensitive composition layer (for example, Resin A, a polymerizable compound, a polymerization initiator, and a thermal crosslinking agent) and a solvent from the viewpoint of excellent productivity. It is preferable to be formed by.

As a method for producing a transfer film, it is preferable to specifically apply a photosensitive composition on an intermediate layer to form a coating film, and apply a drying treatment to the coating film at a predetermined temperature to form a photosensitive composition layer.

As the photosensitive composition, it is preferable to include various components and solvents that form the photosensitive composition layer described above. In addition, in the photosensitive composition, the suitable range of the content of each component with respect to the total solids of the composition is the same as the suitable range of the content of each component with respect to the total mass of the photosensitive composition layer described above.

The solvent is not particularly limited as long as it can dissolve or disperse each component other than the solvent, and a known solvent can be used. Specifically, for example, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (such as methanol and ethanol), ketone solvents (such as acetone and methyl ethyl ketone), aromatic hydrocarbon solvents ( toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents (n-propyl acetate, etc.), amide solvents, lactone solvents, and their The mixed solvent containing 2 or more types is mentioned.

As the solvent, it is preferable to include at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among them, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, and at least one selected from the group consisting of ketone solvents and cyclic ether solvents More preferred is a mixed solvent containing at least three kinds of an alkylene glycol ether, an alkylene glycol ether acetate solvent, and a ketone solvent.

As the alkylene glycol ether solvent, for example, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether (propylene glycol monomethyl ether acetate, etc. ), propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether.

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

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone.

As the solvent, you may use the solvent described in paragraph [0092] - [0094] of International Publication No. 2018/179640, and the solvent described in paragraph [0014] of Unexamined-Japanese-Patent No. 2018-177889. is used

A solvent may be used individually by 1 type, and may be used 2 or more types.

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

Examples of the coating method of the photosensitive composition include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (namely, a slit coating method).

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

The drying temperature is preferably 90°C or higher, more preferably 100°C or higher, and still more preferably 110°C or higher. Moreover, although it does not specifically limit as its upper limit, 130 degrees C or less is preferable and 120 degrees C or less is more preferable.

Moreover, as drying time, 20 second or more is preferable, 40 second or more is more preferable, and 60 second or more is still more preferable. Further, the upper limit is not particularly limited, but is preferably 450 seconds or less, and more preferably 300 seconds or less. As a drying temperature, 80 degreeC or more is preferable and 90 degreeC or more is more preferable. Moreover, as its upper limit, 130 degrees C or less is preferable and 120 degrees C or less is more preferable. It is also possible to dry by continuously varying the temperature.

Moreover, as drying time, 20 second or more is preferable, 40 second or more is more preferable, and 60 second or more is still more preferable. Moreover, although it does not restrict|limit especially as its upper limit, 600 second or less is preferable and 300 second or less is more preferable.

Moreover, a transfer film can be manufactured by bonding a protective film to the photosensitive composition layer.

The method of bonding the protective film to the photosensitive composition layer is not particularly limited, and a known method may be used.

As an apparatus for bonding the protective film to the photosensitive composition layer, known laminators such as a vacuum laminator and an auto-cut laminator are exemplified.

It is preferable that the laminator is provided with an optional heatable roller such as a rubber roller, and can pressurize and heat.

Example

The features of the present invention will be described in more detail below with reference to Examples and Comparative Examples. Materials, amount of use, ratio, process content, process procedure, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

In the following examples, the weight average molecular weight of the resin is a weight average molecular weight determined in terms of polystyrene by gel permeation chromatography (GPC). In addition, the theoretical acid value was used for the acid value.

<Materials used for production of transfer film>

The materials (photosensitive composition and composition for forming an intermediate layer) used in the production of the transfer film used in Examples are described.

(Components of photosensitive composition)

The photosensitive composition layer included in the transfer film was formed using the photosensitive composition.

The components used for preparation of the photosensitive composition are as follows, and each component shown below was mixed in the formulation shown in Tables 2 and 3 shown in the following paragraphs to obtain each photosensitive composition used in Examples or Comparative Examples. The numerical value of each component in Tables 2-3 is a mass part.

In addition, when preparing the photosensitive composition, a mixed solvent containing methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd., 60 parts by mass) and propylene glycol monomethyl ether acetate (manufactured by Showa Denko Co., Ltd., 40 parts by mass) is prepared, , In the mixed solvent, each component was added in the formulation shown in the table below. In addition, the solid content concentration of each photosensitive composition was 13 mass %.

[profit]

・Compounds 1 to 4: Resins (compounds) each having characteristics as shown below

In addition, compounds 1-4 correspond to alkali-soluble resin.

[Table 1]

In the table above, in the "composition" column, for each resin (compound), the type of constituent unit the resin has is shown, and the mass ratio of the content of each constituent unit is shown in parentheses.

As the kind of each structural unit, the name of the monomer derived from each structural unit is shown.

For example, Compound 1 is a resin having a structural unit based on styrene, a structural unit based on methacrylic acid, and a structural unit based on methyl methacrylate at a mass ratio of 32:28:40, respectively. am.

[Polymerizable compound]

・BPE-500: ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.

・BPE-200: ethoxylated bisphenol A dimethacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.

・BPE-100: ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.

Polymerizable compound 1: Dimethacrylate of polyethylene glycol obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A, respectively.

M-270: Aronix M-270, polypropylene glycol diacrylate (n≒12), manufactured by Toagosei Co., Ltd.

A-TMPT: trimethylolpropane triacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.

SR454: ethoxylated (3) trimethylolpropane triacrylate, manufactured by Akema Co., Ltd.

SR502: ethoxylated (9) trimethylolpropane triacrylate, manufactured by Akema Co., Ltd.

A-9300-CL1: caprolactone-modified tris-(2-acryloxyethyl) isocyanurate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.

[thermal cross-linking agent]

・SBB-70P: Duranate, manufactured by Asahi Kasei Co., Ltd.

・TPA-B80E: Duranate, manufactured by Asahi Kasei Co., Ltd.

[Polymerization initiator]

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

[additive]

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

・Ryuko Crystal Violet: Made by Tokyo Kasei High School

・N-phenylglycine: manufactured by Tokyo Kasei Kogyo Co., Ltd.

・Brilliant Green: Made by Tokyo Kasei High School

・CBT-1: Carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.

Mixture 1: 1:1 of 1-(2-di-n-butylaminomethyl)-5-carboxylbenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxylbenzotriazole mass ratio) mixture

・Phenothiazine: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

・Irganox245: manufactured by BASF

N-Nitrosophenylhydroxylamine aluminum salt: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

・Penidone: Tokyo Kasei High School Festival

・F-552: fluorine-based surfactant, manufactured by DIC

(Components of composition for forming intermediate layer)

The following components were mixed to prepare a composition for forming an intermediate layer. In addition, the unit of the quantity of each component is a mass part.

Ion-exchanged water: 38.12 parts by mass

Methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.): 57.17 parts by mass

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

Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.): 1.49 parts by mass

Megafac F-444 (fluorine-based surfactant, manufactured by DIC Co., Ltd.): 0.0035 parts by mass

<Production of transfer film>

Regarding Examples 1, 5 to 7 and Comparative Example 1, transfer films were produced in the following procedure.

First, on a temporary support (polyethylene terephthalate film (Lumirror 16KS40, manufactured by Toray Co., Ltd.), haze: 0.6% with a thickness of 16 μm), the photosensitive composition of each Example and Comparative Example was dried using a bar coater, the thickness of which is shown in Table 2 It was applied so as to have a thickness shown in -3, and dried at 80°C using an oven to form a photosensitive composition layer (negative photosensitive composition layer).

On the obtained photosensitive composition layer, as a protective film, polyethylene terephthalate (16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm was crimped to prepare a transfer film.

In Examples 2 to 4 and 8 to 10, transfer films were produced in the following procedure.

First, on a temporary support (polyethylene terephthalate film (Lumiror 16KS40, manufactured by Toray Co., Ltd.), haze: 0.6% with a thickness of 16 μm), a composition for forming an intermediate layer was applied using a bar coater, and the thickness after drying is shown in Tables 2 and 3. It was applied to a thickness and dried at 90°C using an oven to form an intermediate layer.

Further, on the intermediate layer, a photosensitive composition was applied using a bar coater so that the thickness after drying became the thickness shown in Tables 2 and 3, and dried at 80°C using an oven to form a photosensitive composition layer (negative photosensitive composition layer). has formed

On the obtained photosensitive composition layer, as a protective film, polyethylene terephthalate (16KS40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm was crimped to prepare a transfer film.

<Manufacture of laminated body>

A PET substrate with a copper layer in which a copper layer having a thickness of 500 nm was prepared by a sputtering method on a PET film (polyethylene terephthalate film) having a thickness of 200 μm was used.

The prepared transfer film was cut into a square having a side of 10 cm, the protective film was peeled off, and the photosensitive composition layer was in contact with the copper layer on the surface of the PET substrate at a roll temperature of 90 ° C., a linear pressure of 0.8 MPa, and a linear speed of 3.0 m/min. It laminated to the PET board|substrate with a copper layer under the lamination conditions of, and obtained the laminated body.

At this point, the laminate has a configuration of "PET film-copper layer-photosensitive composition-temporary support" when the transfer film does not include an intermediate layer, and "PET film-copper" when the transfer film includes an intermediate layer. layer-photosensitive composition-intermediate layer-temporary support".

Next, the temporary support was peeled off from the obtained laminate, and a photomask having a pattern of 5/5 lines (μm)/space (μm) was brought into close contact with the exposed surface of the laminate. Light was irradiated at an exposure amount of 50 mJ/cm ² using a high-pressure mercury-vapor lamp exposure machine (MAP-1200L, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm). The exposure amount was such that the resist pattern obtained after development reproduced the line-and-space shape of the photomask.

Then, development was performed using a 1.0% sodium carbonate aqueous solution at 30°C as a developing solution. As for development, specifically, a shower treatment was performed for 40 seconds, an AirKnife (air knife) treatment was performed to cut off the developing solution, a shower treatment was performed with pure water for 30 seconds, and an AirKnife treatment was further performed.

Thus, a laminate having a line-and-space resist pattern was obtained.

Next, the laminate having the resist pattern was heated under the heating conditions ("heating temperature and heating time") described in Tables 2 and 3 described later.

Then, the obtained laminate was immersed in a 10% by mass sulfuric acid aqueous solution (liquid temperature: 40°C) for 3 minutes.

Next, the obtained laminate was put into a copper sulfate plating solution (copper sulfate 75 g/L, sulfuric acid 190 g/L, chlorine ion 50 mass ppm, manufactured by Meltex Co., Ltd., “Copper Grim PCM”, 5 mL/L), and 1 A/dm The copper plating process was performed on condition of ² .

After washing and drying the laminated body after the copper plating process, the resist pattern was peeled off by immersing in a 50°C 1% by mass aqueous solution of potassium hydroxide (pH = 13.5).

The copper layer (seed layer) of the laminate after the resist pattern peeling step was removed with an aqueous solution containing 0.1% by mass sulfuric acid and 0.1% by mass hydrogen peroxide to obtain a copper wiring pattern. The copper wiring pattern was observed with an optical microscope, and the shape of the conductor pattern was evaluated according to the following criteria.

1: No conductor pattern is formed, or the shape of the formed conductor pattern is greatly distorted.

2: Although the shape of the formed conductor pattern is approximately the desired shape, distortion is seen in part.

3: The shape of the formed conductor pattern is a desired shape, and there is no distortion.

In Tables 2 and 3, the "heating temperature and heating time" column describes the temperature and time for heating the laminate having a resist pattern. It is described, and it means heating at 120 ° C. for 20 minutes.

In Tables 2 and 3, the "elastic modulus X (GPa)" column represents the above-described elastic modulus X (GPa), and the "elastic modulus X/elastic modulus Y" column represents the above-described X/Y.

[Table 2]

[Table 3]

As shown in the table, according to the method of the present invention, it was confirmed that desired effects were obtained.

10 transfer film
11 support
13 middle layer
15 photosensitive composition layer
17 composition layer
19 protective film

Claims (19)

A bonding step of bonding the transfer film and the substrate so that the surface of the transfer film having the temporary support and the negative photosensitive composition layer on the opposite side to the temporary support is in contact with the metal layer of the substrate having a metal layer on the surface. class,
An exposure step of pattern-exposing the photosensitive composition layer;
a developing step of subjecting the exposed photosensitive composition layer to a developing treatment to form a resist pattern;
a heating step of heating the resist pattern;
a cleaning step of cleaning the heated resist pattern with an acidic solution;
a plating step of performing plating treatment on the metal layer in a region where the resist pattern is not disposed;
a peeling step of peeling off the resist pattern;
a removal step of removing the metal layer exposed by the peeling step and forming a conductor pattern on the substrate in this order;
Between the bonding step and the exposure step, or between the exposure step and the development step, further comprising a temporary support member peeling step of peeling the temporary support member,
A method for producing a laminate having a conductor pattern, wherein the photosensitive composition layer contains a thermal cross-linking agent. The method of claim 1,
The method of manufacturing a laminate having a conductor pattern, wherein an elastic modulus of a surface of a resist pattern heated in the heating step on a side opposite to the substrate side is 5.0 GPa or more. According to claim 1 or claim 2,
The elastic modulus of the surface of the resist pattern heated by the heating step on the opposite side to the substrate side is the elastic modulus X,
When the elastic modulus near the substrate side of the resist pattern heated in the heating step is the elastic modulus Y,
A method for producing a laminate having a conductor pattern that satisfies X/Y≤1.2. According to claim 1 or claim 2,
The method for producing a laminate having a conductor pattern, wherein the photosensitive composition layer contains a polymerizable compound and a polymerization initiator. The method of claim 4,
The method for producing a laminate having a conductor pattern, wherein the polymerizable compound has an alkylene oxide-modified bisphenol structure. According to claim 1 or claim 2,
The method for producing a laminate having a conductor pattern, wherein the thermal crosslinking agent contains a block isocyanate compound. According to claim 1 or claim 2,
A method for producing a laminate having a conductor pattern in which the haze of the temporary support is 1.0% or less. According to claim 1 or claim 2,
A method for producing a laminate having a conductor pattern, wherein the thickness of the temporary support is 50 μm or less. According to claim 1 or claim 2,
The method of manufacturing a laminate having a conductor pattern, wherein the transfer film has an intermediate layer between the temporary support and the photosensitive composition layer. The method of claim 9,
A method for producing a laminate having a conductor pattern, wherein the intermediate layer is a water-soluble resin layer. According to claim 1 or claim 2,
The method for manufacturing a laminate having a conductor pattern, wherein the exposure step is a step of performing pattern exposure through a photomask. According to claim 1 or claim 2,
The method of manufacturing a laminate having a conductor pattern, wherein the exposure step is a step of pattern-exposing the photosensitive composition layer through a lens using actinic light on which an image of a photomask is projected. According to claim 1 or claim 2,
Between the bonding step and the exposure step, the temporary support member peeling step is provided;
The method for producing a laminate having a conductor pattern, wherein the exposure step is a step of pattern-exposing the photosensitive composition layer by bringing the surface exposed by peeling the temporary support member into contact with a photomask. A transfer film having a temporary support and a negative photosensitive composition layer,
The photosensitive composition layer contains a thermal cross-linking agent,
A transfer film in which the haze of the temporary support is 1.0% or less. The method of claim 14,
A transfer film in which the thickness of the temporary support is 50 μm or less. According to claim 14 or claim 15,
The transfer film in which the photosensitive composition layer contains a polymerizable compound and a polymerization initiator. The method of claim 16
The transfer film in which the said polymeric compound has an alkylene oxide modified bisphenol structure. According to claim 14 or claim 15,
A transfer film having an intermediate layer between the temporary support and the photosensitive composition layer. The method of claim 18
The transfer film wherein the intermediate layer is a water-soluble resin layer.

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