JP7030828B2 - Photosensitive transfer material, circuit wiring manufacturing method, and touch panel manufacturing method - Google Patents

Description

The present disclosure relates to a photosensitive transfer material, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel.

For example, in a display device having a touch panel such as a capacitance type input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), the electrode pattern corresponding to the sensor of the visual recognition part, the peripheral wiring part, and the extraction Circuit wiring such as wiring of the wiring portion is provided inside the touch panel.
For the formation of such a patterned circuit wiring, the use of a dry film resist as a photosensitive transfer material has been studied because the number of steps for obtaining a required pattern shape is small.

For example, Patent Document 1 has a support, a thermoplastic resin layer, and a photosensitive resin layer in this order, and the photosensitive resin layer (A) has an acid group protected by an acid-degradable group. Described is a photosensitive transfer material comprising a polymer component containing a polymer having a structural unit (a1) having a group and (B) a photoacid generator.
Patent Document 2 describes a positive type dry film resist having a resist layer on a temporary support, and a dry film resist having a total light haze of 0.3% or less of the temporary support.

Patent Document 1: Japanese Patent Application Laid-Open No. 2014-085643 Patent Document 2: Japanese Patent Application Laid-Open No. 2017-078852

Patent Document 1 and Patent Document 2 describe that the transferability is improved by forming a thermoplastic resin layer between the temporary support of the photosensitive transfer material and the photosensitive resin layer.
However, the present inventors have described the methods described in Patent Document 1 and Patent Document 2 in that the temporary support has adhesiveness (hereinafter, also simply referred to as “adhesion”) and the photosensitive resin layer has transferability (hereinafter, also referred to as “adhesiveness”). , Simply referred to as "transferability") was found to have room for further improvement.

An object to be solved by the embodiment of the present invention is to provide a photosensitive transfer material having excellent adhesion and transferability.
Another object to be solved by another embodiment of the present invention is to provide a method for manufacturing a circuit wiring using the photosensitive transfer material and a method for manufacturing a touch panel.

The means for solving the above problems include the following aspects.
<1> Temporary support and
It has a polymer containing a structural unit having a group in which the acid group is protected by an acid-degradable group, and a photosensitive resin layer containing a photoacid generator.
A photosensitive transfer material having at least one layer containing a urethane compound or a modified polyolefin between the temporary support and the photosensitive resin layer.
<2> The photosensitive transfer material according to <1>, wherein the film thickness of the layer containing the urethane compound or the modified polyolefin is 10 nm or more and 500 nm or less.
<3> When the layer containing the urethane compound or the modified polyolefin is a layer containing the urethane compound, the isocyanate group content with respect to the total volume of the layer containing the urethane compound is 0.01 mol / m ³ to 0. The photosensitive transfer material according to <1> or <2>, which is 40 mol / m ³ .
<4> The temporary support is in contact with the layer containing the urethane compound or the modified polyolefin, and the adhesion between the layer containing the urethane compound or the modified polyolefin and the temporary support is 0.22 N / cm or more. The photosensitive transfer material according to any one of <1> to <3>.
<5> When the layer containing the urethane compound or the modified polyolefin is a layer containing the urethane compound, the urethane compound contained in the layer containing the urethane compound causes at least the reaction between the alkylene diisocyanate compound and the diol compound. The photosensitive transfer material according to any one of <1> to <4>, which comprises a reaction product.
<6> The layer according to <1>, <2> or <4>, wherein the modified polyolefin is an acid-modified polyolefin when the layer containing the urethane compound or the modified polyolefin is a layer containing the modified polyolefin. Photosensitive transfer material.
<7> The photosensitive unit according to any one of <1> to <6>, wherein the structural unit having a group in which the acid group is protected by an acid-degradable group is a structural unit represented by the following formula A1. Sex transfer material.

In formula A1, R ³¹ and R ³² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group or an aryl group. An aryl group may be represented, and R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, where R ³⁴ represents a hydrogen atom or a methyl group and X ⁰ represents a single bond or an arylene group.

<8> A step of contacting and bonding the outermost layer of the photosensitive transfer material according to any one of <1> to <7> on the photosensitive resin layer side of the temporary support to the substrate. When,
A step of pattern-exposing the photosensitive resin layer of the photosensitive transfer material after the bonding step, and a step of pattern exposure.
The step of developing the photosensitive resin layer after the above-mentioned exposure step to form a pattern, and
Including a step of etching a substrate in a region where the above pattern is not arranged.
How to manufacture circuit wiring.
<9> With respect to the substrate, the outermost layer of the photosensitive transfer material of the photosensitive transfer material according to any one of <1> to <7> on the photosensitive resin layer side of the temporary support is in contact with the substrate. The process of letting and pasting together,
A step of pattern-exposing the photosensitive resin layer of the photosensitive transfer material after the bonding step, and a step of pattern exposure.
The step of developing the photosensitive resin layer after the above-mentioned exposure step to form a pattern, and
Including a step of etching a substrate in a region where the above pattern is not arranged.
How to manufacture a touch panel.

According to the embodiment of the present invention, it is possible to provide a photosensitive transfer material having excellent adhesion and transferability.
Further, according to another embodiment of the present invention, it is possible to provide a method for manufacturing a circuit wiring using the above-mentioned photosensitive transfer material and a method for manufacturing a touch panel.

It is a schematic diagram which shows an example of the layer structure of the photosensitive transfer material which concerns on this disclosure. It is a schematic diagram which shows an example of the manufacturing method of the circuit wiring for a touch panel using the photosensitive transfer material which concerns on this disclosure.

Hereinafter, the contents of the present disclosure will be described. Although the description will be given with reference to the attached drawings, the reference numerals may be omitted.
Further, the numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, "(meth) acrylic" represents both acrylic and methacrylic, or either, and "(meth) acrylate" represents both acrylate and methacrylate, or either.
Further, in the present specification, the amount of each component in the composition is the sum of the plurality of applicable substances present in the composition when a plurality of the substances corresponding to each component are present in the composition, unless otherwise specified. Means quantity.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
As used herein, the term "total solid content" refers to the total mass of the components excluding the solvent from the total composition of the composition. Further, the "solid content" is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Further, the chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
Further, for the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure, unless otherwise specified, columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.) are used. The molecular weight is detected by the solvent THF (tetrahydrofuran) and the differential refractometer by the gel permeation chromatography (GPC) analyzer and converted using polystyrene as a standard substance.

(Photosensitive transfer material)
The photosensitive transfer material according to the present disclosure includes a temporary support, a polymer containing a structural unit having a group in which an acid group is protected by an acid-degradable group, and a photosensitive resin layer containing a photoacid generator. Have,
At least one layer containing a urethane compound or a modified polyolefin (hereinafter, also referred to as a “specific layer”) is provided between the temporary support and the photosensitive resin layer.

For example, in a photosensitive transfer material, the structure may be cut after transferring to a substrate to produce a structure including a photosensitive resin layer, a temporary support, and the substrate.
When the adhesive force of the temporary support in the photosensitive transfer material is low, the present inventors may partially peel off the temporary support due to the above cutting, and the temporary support may float or the like. I found that. In the present disclosure, suppressing the occurrence of floating of the temporary support at the time of cutting or the like is referred to as "excellent in adhesion of the temporary support". Exposure or the like may be difficult at the portion where the above-mentioned floating or the like occurs.
Further, if the adhesion is too high, the photosensitive resin layer is lifted when the temporary support is peeled off, and the photosensitive resin layer and the base material cannot be adhered to each other. It has been found that the transfer area of the resin layer may become small. In the present disclosure, a large transfer area at the time of transfer is referred to as "excellent in transferability of the photosensitive resin layer".
As described above, it is considered that the photosensitive transfer material is required to have both adhesiveness and transferability, which are contradictory performances.
Therefore, as a result of diligent studies, the present inventors have obtained at least one layer containing a urethane compound or a modified polyolefin between the temporary support and the photosensitive resin layer to improve adhesion and transferability. It has been found that an excellent photosensitive transfer material can be obtained.
Although the detailed mechanism by which the above effect is obtained is unknown, in the layer containing the urethane compound or the modified polyolefin, the urethane compound and the modified polyolefin in the layer are bonded or modified with a hydrophobic portion such as a hydrocarbon group or a polyolefin. It is presumed that the interaction with the photosensitive resin layer and the intermediate layer described later is appropriately maintained because it has both the non-hydrophobic part such as the acid group formed therein, and the adhesion and transferability are excellent. In particular, when the specific layer has a urethane compound, the adhesion of the temporary support becomes an appropriate value due to the interaction between the isocyanate group which may remain and the photosensitive resin layer, and the adhesion and transferability become appropriate. It is presumed to be excellent.

Hereinafter, the photosensitive transfer material according to the present disclosure will be described in detail.
FIG. 1 schematically shows an example of the layer structure of the photosensitive transfer material according to the present disclosure. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 10, a specific layer 14, a photosensitive resin layer 12, and a cover film 16 are laminated in this order.
The photosensitive resin layer 12 contains a polymer having a structural unit having an acid group protected by an acid-degradable group and a photoacid generator.
The specific layer 14 is a layer containing a urethane compound or a modified polyolefin described later.
Hereinafter, the constituent materials and the like of the photosensitive transfer material according to the present disclosure will be described. The above configuration in the present disclosure may be referred to as follows in the present specification.
A polymer having a structural unit having an acid group protected by an acid-degradable group may be referred to as "polymer A1".
The photosensitive resin layer is a positive photosensitive resin layer, and may be referred to as a “positive photosensitive resin layer”.

<Temporary support>
The temporary support is a support that supports the photosensitive resin layer and the specific layer and can be peeled off from the specific layer or another layer existing between the specific layer and the temporary support.
The temporary support used in the present disclosure is preferably light-transmitting from the viewpoint that the photosensitive resin layer can be exposed via the temporary support when the photosensitive resin layer is exposed to a pattern.
Having light transmittance means that the transmittance of the main wavelength of the light used for the pattern exposure is 50% or more, and the transmittance of the main wavelength of the light used for the pattern exposure is from the viewpoint of improving the exposure sensitivity. Therefore, 60% or more is preferable, and 70% or more is more preferable. Examples of the method for measuring the transmittance include a method for measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film, polyethylene naphthalate film and the like.

The temporary support may be an unstretched film, but is preferably a stretched film.
The stretched film may be a uniaxially stretched film, a biaxially stretched film, or a multiaxially stretched film such as triaxially stretched, but a biaxially stretched film is preferable.
Among them, a biaxially stretched polyester film is preferable, and a biaxially stretched polyethylene terephthalate film is more preferable.

The thickness of the temporary support is not particularly limited, and is preferably in the range of 5 μm to 200 μm, more preferably in the range of 10 μm to 150 μm, in terms of ease of handling and versatility.
The thickness of the temporary support is selected according to the material from the viewpoints of strength as a support, flexibility required for bonding to a circuit wiring forming substrate, and light transmission required in the first exposure process. do it.

Preferred embodiments of the provisional support are described in, for example, paragraphs 0017 to 0018 of Japanese Patent Application Laid-Open No. 2014-85643, and the contents of this publication are incorporated in the present specification.

<Photosensitive resin layer>
The photosensitive transfer material according to the present disclosure has a photosensitive resin layer on a temporary support, and the photosensitive resin layer has a structural unit having an acid group protected by an acid-degradable group. And a photoacid generator.
Further, the photosensitive resin layer in the present disclosure is a positive type photosensitive resin layer, and is preferably a chemically amplified positive type photosensitive resin layer.
In the photoacid generators such as onium salts and oxime sulfonate compounds described later, the acid generated in response to active radiation (active light) catalyzes the deprotection of the protected acid group in the polymer A1. The acid generated by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, which is a large value such as the power of 10, so-called chemical amplification. As a result, high sensitivity is obtained.
On the other hand, when a quinonediazide compound is used as a photoacid generator that is sensitive to active radiation, a carboxy group is generated by a sequential photochemical reaction, but the quantum yield is always 1 or less, and it does not correspond to the chemically amplified type.

[Polymer A1 containing a polymer having a structural unit having an acid group protected by an acid-degradable group]
The photosensitive resin layer contains a polymer A1 (also simply referred to as “polymer A1”) having a structural unit (also referred to as “constituent unit A”) having an acid group protected by an acid-degradable group.
Further, the photosensitive resin layer may contain another polymer in addition to the polymer A1 having the structural unit A. In the present disclosure, the polymer A1 having the structural unit A and other polymers are collectively referred to as a "polymer component".
In the polymer A1, the structural unit A having an acid group protected by an acid-degradable group in the polymer A1 undergoes a deprotection reaction to become an acid group due to the action of a catalytic amount of an acidic substance generated by exposure. This acid group enables dissolution in a developing solution.
A preferred embodiment of the structural unit A will be described below.

The photosensitive resin layer may further contain a polymer other than the polymer A1 having a structural unit having an acid group protected by an acid-degradable group.
Further, it is preferable that all the polymers contained in the polymer components are polymers having at least a structural unit having an acid group described later.
Further, the photosensitive resin layer may further contain a polymer other than these. Unless otherwise specified, the above-mentioned polymer component in the present disclosure is meant to include other polymers added as needed. The compound corresponding to the cross-linking agent and the dispersant described later is not included in the polymer component even if it is a polymer compound.

The polymer A1 is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof. In addition, it may have a structural unit other than the structural unit derived from (meth) acrylic acid or an ester thereof, for example, a structural unit derived from styrene, a structural unit derived from a vinyl compound, or the like.

The photosensitive resin layer contains a polymer having a structural unit represented by the following formula A1 as the structural unit A as a polymer component from the viewpoint of suppressing deformation of the pattern shape, solubility in a developing solution, and transferability. As the polymer component, it is more preferable to include the structural unit represented by the following formula A1 as the structural unit A and the polymer A1 having the structural unit B having an acid group described later.
The polymer A1 contained in the photosensitive resin layer may be only one kind or two or more kinds.

-Constituent unit A-
The polymer component includes a polymer A1 having at least a structural unit A having an acid group protected by an acid-degradable group. By including the polymer having the constituent unit A in the polymer component, an extremely sensitive chemically amplified positive type photosensitive resin layer can be obtained.
As the "acid group protected by an acid-degradable group" in the present disclosure, known acid groups and acid-degradable groups can be used, and the present invention is not particularly limited. Specific examples of the acid group include a carboxyl group and a phenolic hydroxyl group. Further, as the acid group protected by the acid-degradable group, a group relatively easily decomposed by an acid (for example, an ester group protected by a group represented by the formula A1, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester). Use an acetal-based functional group such as a group) or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group). Can be done.
Among these, the acid-degradable group is preferably a group having a protected structure in the form of acetal.

<< Structural unit A1 >>
The structural unit A having an acid group protected by the acid-degradable group is preferably a structural unit represented by the following formula A1 from the viewpoint of sensitivity and resolution.

In formula A1, R ³¹ and R ³² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group or an aryl group. An aryl group may be represented, and R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, where R ³⁴ represents a hydrogen atom or a methyl group and X ⁰ represents a single bond or an arylene group.

In the formula A1, when R ³¹ or R ³² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ³¹ or R ³² is an aryl group, a phenyl group is preferable. R ³¹ and R ³² are preferably hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively.
In the formula A1, R ³³ represents an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
Further, the alkyl group and the aryl group in R ³¹ to R ³³ may have a substituent.
In the formula A1, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, and it is preferable that R ³¹ or R ³² and R ³³ are linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In the formula A1, X ⁰ represents a single bond or an arylene group, and a single bond is preferable. The arylene group may have a substituent.
The structural unit represented by the above formula A1 is a structural unit having a carboxy group protected by an acid-degradable group. By including the structural unit represented by the formula A1 in the polymer A1, the sensitivity at the time of pattern formation is excellent, and the resolution is superior to the resolution.

In the formula A1, R ³⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the polymer A1 can be lowered.
More specifically, the structural unit in which R ³⁴ is a hydrogen atom in the formula A is preferably 20% by mass or more with respect to the total amount of the structural units represented by the formula A1 contained in the polymer A1.
The content (content ratio: mass ratio) of the structural unit in which R ³⁴ is a hydrogen atom in the structural unit represented by the formula A1 is always determined from the ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity calculated by the method.

<< Structural unit A2 >>
Among the structural units represented by the formula A1, the structural unit represented by the following formula A2 is more preferable from the viewpoint of further increasing the sensitivity at the time of pattern formation.

In the formula A2, R ³⁴ represents a hydrogen atom or a methyl group, and R ³⁵ to R ⁴¹ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula A2, R ³⁴ is preferably a hydrogen atom.
In the formula A2, hydrogen atoms are preferable for R ³⁵ to R ⁴¹ .

The following structural units can be exemplified as a preferable specific example of the structural unit having a carboxy group protected by an acid-degradable group represented by the formula A1. In addition, R ³⁴ represents a hydrogen atom or a methyl group.

<< Structural unit A3 >>
Further, as the structural unit A, the structural unit represented by the following formula A3 is preferable from the viewpoint of suppressing deformation of the pattern shape.

In formula A3, ^RB1 and ^RB2 independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of ^RB1 and ^RB2 is an alkyl group or an aryl group, and ^RB3 is an alkyl group or an aryl group. Representing an aryl group, RB1 or ^RB2 and ^RB3 may be linked to form a cyclic ether, ^RB4 represents a hydrogen atom or a methyl ^{group, and X B is} a single-bonded or divalent linking group. , R ^B12 represents a substituent, and n represents an integer of 0 to 4.

In the formula A3, when ^RB1 or ^RB2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When ^RB1 or ^RB2 is an aryl group, a phenyl group is preferable. ^RB1 and ^RB2 are preferably hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, respectively.
In the formula A3, ^RB3 represents an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
Further, the alkyl group and the aryl group in ^RB1 to ^RB3 may have a substituent.
In the formula A3, ^RB1 or ^RB2 and ^RB3 may be linked to form a cyclic ether, and it is preferable that ^RB1 or ^RB2 and ^RB3 are linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In formula A3, ^XB represents a single bond or a divalent linking group, a single bond or an alkylene group, -C (= O) O-, -C (= O) NR ^N- , -O- or a combination thereof. Is preferable, and a single bond is more preferable. The alkylene group may be linear, has a branch, may have a cyclic structure, or may have a substituent. The alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. When X ^B contains -C (= O) O-, it is preferable that the carbon atom contained in -C (= O) O- and the carbon atom to which RB ⁴ is bonded are directly bonded. When X ^B contains -C (= O) NR ^N- , it is preferable that the carbon atom contained in -C (= O) NR ^N- and the carbon atom to which ^RB4 is bonded are directly bonded. ^RN represents an alkyl group or a hydrogen atom, and an alkyl group or a hydrogen atom having 1 to 4 carbon atoms is preferable, and a hydrogen atom is more preferable.
In the formula A3, it is preferable that the group containing ^RB1 to ^RB3 and ^XB are bonded to each other at the para position.
In the formula A3, ^RB12 represents a substituent, and an alkyl group or a halogen atom is preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 4.
In the formula A3, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the formula A3, ^RB4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the polymer A1 can be lowered.
More specifically, the structural unit in which ^RB4 is a hydrogen atom in the formula A3 is preferably 20% by mass or more with respect to the total content of the structural unit A contained in the polymer A1.
The content (content ratio: mass ratio) of the structural unit in which ^RB4 in the formula A3 is a hydrogen atom in the structural unit A is calculated by a conventional method from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity.

<< Structural unit A4 >>
Among the structural units represented by the formula A3, the structural unit represented by the following formula A4 is more preferable from the viewpoint of suppressing deformation of the pattern shape.

In formula A4, ^{RB4 represents a hydrogen atom or a methyl group, RB5 to RB11} independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^RB12 represents a substituent, and n is 0. Represents an integer of ~ 4.
In the formula A4, ^RB4 is preferably a hydrogen atom.
In the formula A4, ^RB5 to ^RB11 are preferably hydrogen atoms.
In the formula A4, ^RB12 represents a substituent, and an alkyl group or a halogen atom is preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 4.
In the formula A4, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

As a preferable specific example of the structural unit A4 represented by the formula A4, the following structural unit can be exemplified. In addition, ^RB4 represents a hydrogen atom or a methyl group.

The structural unit A contained in the polymer A1 may be one kind or two or more kinds.
The content of the structural unit A in the polymer A1 is preferably 20% by mass or more, more preferably 20% by mass to 90% by mass, and more preferably 30% by mass or more, based on the total mass of the polymer A1. It is more preferably 70% by mass.
The content (content ratio: mass ratio) of the structural unit A in the polymer A1 can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR measurement.
Further, after decomposing all the polymer components into constituent units (monomer units), the ratio of the constituent unit A is preferably 5% by mass to 80% by mass with respect to the total mass of the polymer components. It is more preferably 10% by mass to 80% by mass, and particularly preferably 30% by mass to 70% by mass.

-Constituent unit B-
The polymer A1 preferably contains a structural unit B having an acid group.
The structural unit B is a structural unit having an acid group that is not protected by a protecting group, for example, an acid-degradable group, that is, an acid group that does not have a protecting group. When the polymer A1 contains the structural unit B, the sensitivity at the time of pattern formation becomes good, it becomes easy to dissolve in an alkaline developer in the developing process after pattern exposure, and the developing time can be shortened.
The acid group in the present specification means a proton dissociative group having a pKa of 12 or less. The acid group is usually incorporated into the polymer as a structural unit having an acid group (constituent unit B) using a monomer capable of forming an acid group. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, more preferably 6 or less. Further, the pKa of the acid group is preferably −5 or more.

Examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonylimide group and the like. Among them, at least one acid group selected from the group consisting of a carboxylic acid group and a phenolic hydroxyl group is preferable.
The introduction of the structural unit having an acid group into the polymer A1 can be carried out by copolymerizing a monomer having an acid group or by copolymerizing a monomer having an acid anhydride structure and hydrolyzing the acid anhydride. ..
The structural unit having an acid group, which is the structural unit B, is derived from a structural unit derived from a styrene compound, a structural unit derived from a vinyl compound in which an acid group is substituted, or a (meth) acrylic acid. It is more preferable that it is a structural unit. Specifically, examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene and the like, and examples of the monomer having a phenolic hydroxyl group include p-. Examples thereof include hydroxystyrene and 4-hydroxyphenylmethacrylate, and examples of the monomer having an acid anhydride include maleic anhydride and the like.

As the structural unit B, a structural unit having a carboxylic acid group or a structural unit having a phenolic hydroxyl group is preferable from the viewpoint of improving the sensitivity at the time of pattern formation.
The monomer having an acid group capable of forming the structural unit B is not limited to the above-mentioned example.

The structural unit B contained in the polymer A1 may be only one kind or two or more kinds.
The polymer A1 preferably contains 0.1% by mass to 20% by mass, and 0.5% by mass to 15% by mass of a structural unit having an acid group (constituent unit B) with respect to the total mass of the polymer A1. It is more preferable, and it is more preferable to contain 1% by mass to 10% by mass. Within the above range, the pattern forming property becomes better.
The content (content ratio: mass ratio) of the structural unit B in the polymer A1 can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR measurement.

-Other building blocks-
The polymer A1 does not impair the effect of the photosensitive transfer material according to the present disclosure with respect to other structural units (hereinafter, may be referred to as structural unit C) other than the above-mentioned structural unit A and structural unit B. It may be included in the range.
The monomer forming the structural unit C is not particularly limited, and is, for example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester. , Bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, groups with an aliphatic cyclic skeleton, and other unsaturated compounds. Saturated compounds can be mentioned.
Various properties of the polymer A1 can be adjusted by adjusting at least one of the type and the content using the structural unit C. In particular, the Tg of the polymer A1 can be easily adjusted by appropriately using the structural unit C.
By setting the glass transition temperature to 120 ° C. or lower, the positive photosensitive resin layer containing the polymer A1 maintains a good level of transferability and peelability from the temporary support, and has a resolution at the time of pattern formation. And the sensitivity becomes better.
The polymer A1 may contain only one type of structural unit C, or may contain two or more types of the constituent unit C.

Specifically, the constituent unit C is styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meth). Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) Examples thereof include structural units formed by polymerizing benzyl acrylate, isobornyl (meth) acrylate, acrylonitrile, or ethylene glycol monoacetate acetate mono (meth) acrylate. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A-2004-246623 can be mentioned.

Further, as the structural unit C, a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical properties of the obtained transfer material. Specific examples of the monomers forming these constituent units include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate. And benzyl (meth) acrylate and the like. Among them, as the structural unit C, a structural unit derived from cyclohexyl (meth) acrylate is preferably mentioned.

Further, as the monomer forming the structural unit C, for example, a (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Of these, a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The content of the structural unit C is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, based on the total mass of the polymer A1. The lower limit may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more. Within the above range, the resolution and adhesion are further improved.

The fact that the polymer A1 contains the structural unit having the ester of the acid group in the structural unit B as the structural unit C is also from the viewpoint of optimizing the solubility in the developing solution and the physical properties of the photosensitive resin layer. preferable.
Among them, the polymer A1 preferably contains a structural unit having a carboxylic acid group as the structural unit B, and further preferably contains a structural unit C containing a carboxylic acid ester group as a copolymerization component, for example, (meth) acrylic acid. A polymer containing the derived structural unit B and the structural unit (c) derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate is more preferable.
Hereinafter, preferred examples of the polymer A1 in the present disclosure will be given, but the present disclosure is not limited to the following examples. The ratio of the structural units and the weight average molecular weight in the following exemplified compounds are appropriately selected in order to obtain preferable physical properties.

-Glass transition temperature of polymer A1: Tg-
The glass transition temperature (Tg) of the polymer A1 in the present disclosure is preferably 120 ° C. or lower, and more preferably 20 ° C. or higher and 90 ° C. or lower, from the viewpoint of transferability.

The glass transition temperature of the polymer in the present disclosure can be measured using differential scanning calorimetry (DSC).
The specific measuring method was carried out according to the method described in JIS K 7121 (1987) or JIS K 6240 (2011). As the glass transition temperature in the present specification, the extrapolated glass transition start temperature (hereinafter, may be referred to as Tig) is used.
The method for measuring the glass transition temperature will be described more specifically.
When determining the glass transition temperature, after holding the device at a temperature about 50 ° C. lower than the expected polymer Tg until the apparatus stabilizes, the heating rate is 20 ° C./min, which is about 30 ° C. than the temperature at which the glass transition is completed. Heat to a higher temperature and have a differential thermal analysis (DTA) curve or DSC curve drawn.
The extra glass transition start temperature (Tig), that is, the glass transition temperature Tg in the present specification is a straight line extending the baseline on the low temperature side of the DTA curve or the DSC curve to the high temperature side, and the stepwise change portion of the glass transition. It is calculated as the temperature at the intersection with the tangent line drawn at the point where the slope of the curve becomes maximum.

As a method for adjusting the Tg of the polymer to the above-mentioned preferable range, for example, the FOX formula is used as a guideline from the Tg of the homopolymer of each structural unit of the target polymer and the mass ratio of each structural unit. It is possible to control the Tg of the target polymer A1.
Regarding the FOX formula, the Tg of the homopolymer of the first constituent unit contained in the polymer is Tg1, the mass fraction of the copolymer of the first constituent unit is W1, and the Tg of the homopolymer of the second constituent unit is Tg1. Is Tg2, and when the mass fraction in the copolymer of the second constituent unit is W2, the Tg0 (K) of the copolymer containing the first constituent unit and the second constituent unit is as follows. It is possible to estimate according to the equation.
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)
Using the FOX formula described above, the type and mass fraction of each structural unit contained in the copolymer can be adjusted to obtain a copolymer having a desired Tg.
It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.

-Acid value of polymer A1-
From the viewpoint of developability and transferability, the acid value of the polymer A1 is preferably 0 mgKOH / g or more and 200 mgKOH / g or less, and more preferably 5 mgKOH / g or more and 100 mgKOH / g or less.

The acid value of the polymer in the present disclosure represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of the polymer. Specifically, the measurement sample was dissolved in a mixed solvent of tetrahydrofuran / water = 9/1, and the obtained solution was prepared using a potential difference titrator (trade name: AT-510, manufactured by Kyoto Electronics Manufacturing Co., Ltd.). At ° C, neutralize titration with 0.1 mol / L aqueous sodium hydroxide solution. The acid value is calculated by the following equation with the inflection point of the titration pH curve as the titration end point.
A = 56.11 × Vs × 0.1 × f / w
A: Acid value (mgKOH / g)
Vs: Amount of 0.1 mol / l sodium hydroxide aqueous solution required for titration (mL)
f: Potency of 0.1 mol / l sodium hydroxide aqueous solution w: Mass (g) of measurement sample (in terms of solid content)

-Molecular weight of polymer A1: Mw-
The molecular weight of the polymer A1 is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. When the weight average molecular weight of the polymer A1 is 60,000 or less, the melt viscosity of the photosensitive resin layer can be kept low, and the bonding at a low temperature (for example, 130 ° C. or less) can be realized when the polymer A1 is bonded to the substrate. Can be done.
The weight average molecular weight of the polymer A1 is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.
The weight average molecular weight of the polymer can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device. It is known to those skilled in the art.
For the measurement of the weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) is used as a measuring device, and TSKgel (registered trademark) Super HZM-M (4) is used as a column. .6 mm ID x 15 cm, manufactured by Tosoh Corporation, Super HZ4000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ2000 (4.6 mm ID) × 15 cm, one each manufactured by Tosoh Corporation, connected in series, and THF (tetratetra) can be used as the eluent.
The measurement conditions are a sample concentration of 0.2% by mass, a flow velocity of 0.35 ml / min, a sample injection amount of 10 μL, and a measurement temperature of 40 ° C., using a differential refractive index (RI) detector. be able to.
The calibration curve is "Standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", " It can be prepared using any of 7 samples of "A-2500" and "A-1000".

The ratio (dispersity) of the number average molecular weight and the weight average molecular weight of the polymer A1 is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

-Method for producing polymer A1-
The method for producing the polymer A1 (synthesis method) is not particularly limited, but to give an example, a polymerizable monomer for forming the structural unit A represented by the formula A and a structural unit B having an acid group are formed. It can be synthesized by polymerizing with a polymerization initiator in an organic solvent containing a polymerizable monomer for forming a polymerizable monomer and, if necessary, a polymerizable monomer for forming another structural unit C. can. It can also be synthesized by a so-called polymer reaction.

The photosensitive resin layer in the present disclosure contains 50% by mass to 99.9% by mass of the polymer component with respect to the total solid content of the photosensitive resin layer from the viewpoint of exhibiting good adhesion to the substrate. It is preferable to contain it in a ratio of 70% by mass to 98% by mass, and it is more preferable to contain it in a ratio of 70% by mass to 98% by mass.
Further, from the viewpoint of exhibiting good adhesion to the substrate, the photosensitive resin layer contains 50% by mass to 99.9% by mass of the polymer A1 with respect to the total solid content of the photosensitive resin layer. It is preferably contained in a proportion, and more preferably contained in a proportion of 70% by mass to 98% by mass.

[Other polymers]
The photosensitive resin layer does not contain the polymer A1 as a polymer component and does not contain the structural unit (a) represented by the formula A as long as the effect of the photosensitive transfer material according to the present disclosure is not impaired. It may be referred to as "another polymer"). When the photosensitive resin layer contains another polymer, the blending amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total polymer components. It is more preferably 20% by mass or less.

The photosensitive resin layer may contain only one type of other polymer in addition to the polymer A1, or may contain two or more types.
As another polymer, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (all manufactured by Sartmer). , ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (all manufactured by Toagosei Co., Ltd.), and Joncryl 690, Jonc. , Joncryl 67, Joncryl 586 (above, manufactured by BASF) and the like can also be used.

[Photoacid generator]
The photosensitive resin layer contains a photoacid generator.
The photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiating with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
As the photoacid generator used in the present disclosure, a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm and generates an acid is preferable, but its chemical structure is not limited. In addition, a photoacid generator that is not directly sensitive to active light with a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
As the photoacid generator used in the present disclosure, a photoacid generator that generates an acid having a pKa of 4 or less is preferable, a photoacid generator that generates an acid having a pKa of 3 or less is more preferable, and a photoacid generator having a pKa of 2 or less is more preferable. A photoacid generator that generates the acid of the above is particularly preferable. The lower limit of pKa is not particularly determined, but is preferably -10.0 or more, for example.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
Further, the photoacid generator preferably contains at least one compound selected from the group consisting of the onium salt compound described later and the oxime sulfonate compound described later from the viewpoint of sensitivity and resolution, and the oxime sulfonate compound. It is more preferable to include.

Examples of the nonionic photoacid generator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds and the like. Among these, from the viewpoint of sensitivity, resolution, and adhesion, the photoacid generator is preferably an oxime sulfonate compound. These photoacid generators can be used alone or in combination of two or more. Specific examples of the trichloromethyl-s-triazines and the diazomethane derivative include the compounds described in paragraphs 0083 to 0088 of JP-A-2011-22149.

As the oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, a compound having an oxime sulfonate structure represented by the following formula (B1) is preferable.

In formula (B1), R ²¹ represents an alkyl group or an aryl group, and * represents a binding site with another atom or another group.

The compound having an oxime sulfonate structure represented by the formula (B1) may be substituted with any group, and the alkyl group in R ²¹ may be linear or have a branched structure. It may have a ring structure. Acceptable substituents are described below.
As the alkyl group of R ²¹ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ²¹ is an abridged alicyclic group such as an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group). , Preferably a bicycloalkyl group, etc.), or may be substituted with a halogen atom.
As the aryl group of R ²¹ , an aryl group having 6 to 18 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group and a halogen atom.

The compound having an oxime sulfonate structure represented by the formula (B1) is also preferably the oxime sulfonate compound described in paragraphs 0078 to 0111 of JP-A-2014-85643.

Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Of these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.

As the ionic photoacid generator, the ionic photoacid generator described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.

The photoacid generator may be used alone or in combination of two or more.
The content of the photoacid generator in the photosensitive resin layer is preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of sensitivity and resolution, and is 0. It is more preferably 5.5% by mass to 5% by mass.

〔solvent〕
The photosensitive resin layer may contain a solvent.
Further, in the photosensitive resin composition forming the photosensitive resin layer, in order to easily form the photosensitive resin layer, the photosensitive resin composition is once contained with a solvent to adjust the viscosity of the photosensitive resin composition, and the photosensitive resin composition contains the solvent. The photosensitive resin layer can be suitably formed by applying and drying the sex resin composition.
As the solvent used in the present disclosure, a known solvent can be used. Examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, and diethylene glycol dialkyl ethers. , Diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones and the like can be exemplified. Further, specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP-A-2011-22149, and the contents thereof are incorporated in the present specification.

Further, in addition to the above-mentioned solvent, if necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, capric acid, 1-octanol, 1 -Solvents such as nonar, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, or propylene carbonate can also be added.
Only one type of solvent may be used, or two or more types may be used.
The solvent that can be used in the present disclosure may be used alone or in combination of two. When two or more kinds of solvents are used, for example, propylene glycol monoalkyl ether acetates and dialkyl ethers are used in combination, diacetates and diethylene glycol dialkyl ethers are used in combination, or esters and butylene glycol alkyl ether acetates are used in combination. It is preferable to use it in combination with the like.

The solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents with a boiling point of 130 ° C or higher and lower than 160 ° C include propylene glycol monomethyl ether acetate (boiling point 146 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), propylene glycol methyl-n-butyl ether (boiling point 155 ° C), and Propylene glycol methyl-n-propyl ether (boiling point 131 ° C.) can be exemplified.
Examples of the solvent having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), and dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethiel ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C.), dipropylene glycol dimethyl ether (boiling point 175 ° C.), and 1,3-butylene glycol diacetate (boiling point 232 ° C.) can be exemplified.

The content of the solvent when the photosensitive resin composition is applied is preferably 50 parts by mass to 1,900 parts by mass, preferably 100 parts by mass to 100 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, it is 900 parts by mass.
The content of the solvent in the photosensitive resin layer is preferably 2% by mass or less, more preferably 1% by mass or less, and 0.5% by mass, based on the total mass of the photosensitive resin layer. % Or less is more preferable.

[Other additives]
The photosensitive resin layer in the present disclosure may contain a known additive, if necessary, in addition to the polymer A1 and the photoacid generator.

-Plasticizer-
The photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity.
The plasticizer preferably has a smaller weight average molecular weight than the polymer A1.
The weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and further preferably 800 or more and less than 4,000 from the viewpoint of imparting plasticity.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the polymer A1 and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

In the above formula, R is an alkyl group having 2 to 8 carbon atoms, n represents an integer of 1 to 50, and * represents a binding site with another atom.

For example, even a compound having an alkyleneoxy group having the above structure (referred to as “Compound X”) is chemically amplified positive photosensitive obtained by mixing Compound X, the polymer A1 and a photoacid generator. If the resin composition does not have improved plasticity as compared with the chemically amplified positive photosensitive resin composition formed without containing compound X, it does not fall under the plastic agent in the present disclosure. For example, the arbitrarily added surfactant is not generally used in an amount that causes plasticity in the photosensitive resin composition, and therefore does not fall under the plasticizer in the present specification.

Examples of the plasticizer include, but are not limited to, compounds having the following structures.

From the viewpoint of adhesion, the content of the plasticizer is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 20% by mass, based on the total mass of the photosensitive resin layer. preferable.
The photosensitive resin layer may contain only one type of plasticizer, or may contain two or more types of plasticizer.

-Sensitizer-
The photosensitive resin layer may further contain a sensitizer.
The sensitizer absorbs the active light beam and becomes an electronically excited state. The sensitizer in the electron-excited state comes into contact with the photoacid generator, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the photoacid generator undergoes a chemical change and decomposes to produce an acid.
By containing a sensitizer, the exposure sensitivity can be improved.

As the sensitizer, a compound selected from the group consisting of anthracene derivative, aclidene derivative, thioxanthone derivative, coumarin derivative, base styryl derivative, and distyrylbenzene derivative is preferable, and anthracene derivative is more preferable.
Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 , 10-Dibromoanthracene, 2-ethylanthracene, or 9,10-dimethoxyanthracene is preferred.

Examples of the sensitizer include the compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/093271.

The content of the sensitizer is preferably 0% by mass to 10% by mass, more preferably 0.1% by mass to 10% by mass, based on the total mass of the photosensitive resin layer.

-Basic compound-
The photosensitive resin layer preferably further contains a basic compound.
As the basic compound, it can be arbitrarily selected and used from the basic compounds used in the chemically amplified resist. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include the compounds described in paragraphs 0204 to 0207 of JP-A-2011-22149, the contents of which are incorporated in the present specification.

Specifically, examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine and tri. Examples thereof include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, and the like. 4-Dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinolin, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholin, 4-methylmorpholin, 1,5-diazabicyclo [4.3.0] -5-nonen, and 1,8-diazabicyclo [5.3.0] -7-Undesen and the like.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of the carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

The above basic compounds may be used alone or in combination of two or more.
The content of the basic compound is preferably 0.001% by mass to 5% by mass, more preferably 0.005% by mass to 3% by mass, based on the total mass of the photosensitive resin layer. ..

-Heterocyclic compound-
The photosensitive resin layer in the present disclosure may contain a heterocyclic compound.
The heterocyclic compound in the present disclosure is not particularly limited. For example, compounds having an epoxy group or oxetanyl group in the molecules described below, heterocyclic compounds containing an alkoxymethyl group, various cyclic ethers, oxygen-containing monomers such as cyclic esters (lactones), and nitrogen-containing monomers such as cyclic amines and oxazolines. Further, a heterocyclic monomer having d-electrons such as silicon, sulfur and phosphorus can be added.

When the heterocyclic compound is added, the amount of the heterocyclic compound added in the photosensitive resin layer is preferably 0.01% by mass to 50% by mass with respect to the total mass of the photosensitive resin layer. It is more preferably 0.1% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. The above range is preferable from the viewpoint of adhesion and etching resistance. Only one kind of heterocyclic compound may be used, or two or more kinds may be used in combination.

Specific examples of the compound having an epoxy group in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.

Compounds having an epoxy group in the molecule are available as commercial products. For example, commercial products described in paragraph 0189 of JP-A-2011-22149, such as JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings, Inc.), and the like can be mentioned.
Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-. 1000, EPPN-501, EPPN-502 (all manufactured by ADEKA CORPORATION), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX- 411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC- 203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (above Nagase Chemtech), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) Serokiside 2021P, 2081, 2000, 3000, EHPE3150, Eporide GT400, Serviners B0134, B0177 (manufactured by Daicel Corporation) and the like can be mentioned.
The compound having an epoxy group in the molecule may be used alone or in combination of two or more.

Among the compounds having an epoxy group in the molecule, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.

Specific examples of the compound having an oxetanyl group in the molecule include Aron Oxetane OXT-201, OXT-221, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, and PNOX (above, Toagosei). (Manufactured by Co., Ltd.) can be used.

Further, the compound containing an oxetanyl group is preferably used alone or in combination with a compound containing an epoxy group.

In the photosensitive resin layer in the present disclosure, it is preferable that the heterocyclic compound is a compound having an epoxy group from the viewpoint of etching resistance and line width stability.

-Alkoxysilane compound-
The photosensitive resin layer may contain an alkoxysilane compound. As the alkoxysilane compound, a trialkoxysilane compound is preferably mentioned.
Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferred, γ-glycidoxypropyltrialkoxysilane is even more preferred, and 3-glycidoxypropyltrimethoxysilane is particularly preferred. preferable. These can be used alone or in combination of two or more.

-Surfactant-
The photosensitive resin layer preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic (nonionic) or amphoteric surfactants can be used, but the preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, polyoxyethylene glycol higher fatty acid diesters, silicone-based and fluorine-based surfactants. .. In addition, under the following product names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ftop (manufactured by JEMCO), Megafuck (manufactured by DIC Co., Ltd.), Florard (manufactured by Sumitomo 3M) Series such as Asahi Guard (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (manufactured by Toray Dow Corning Co., Ltd.) can be mentioned.
Further, as the surfactant, the constituent unit A and the constituent unit B represented by the following formula I-1 are contained, and the polystyrene-equivalent weight average measured by gel permeation chromatography when tetrahydrofuran (THF) is used as a solvent. A copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.

In formula (I-1), R ⁴⁰¹ and R ⁴⁰³ independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or carbon. An alkyl group having a number of 1 to 4 is represented, L is an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is a numerical value of 10% by mass or more and 80% by mass or less. , Q represents a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 or more and 18 or less, s represents an integer of 1 or more and 10 or less, and * represents a bonding site with another structure. show.

L is preferably a branched alkylene group represented by the following formula (I-2). ^R405 in the formula (I-2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and an alkyl group having 1 or more and 3 or less carbon atoms is preferable in terms of compatibility and wettability to the surface to be coated. 2 or 3 alkyl groups are more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

In addition, the surfactants described in paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362 can also be used.

The surfactant may be used alone or in combination of two or more.
The amount of the surfactant added is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and 0.01% by mass with respect to the total mass of the photosensitive resin layer. It is more preferably% to 3% by mass.

-Other ingredients-
The photosensitive resin layer in the present disclosure includes metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, and ultraviolet absorption. Further known additives such as agents, thickeners, crosslinkers, and organic or inorganic antiprecipitants can be added.
Preferred embodiments of other components are described in paragraphs 0165 to 0184 of JP-A-2014-85643, respectively, and the contents of this publication are incorporated in the present specification.

-Method of forming the photosensitive resin layer-
A photosensitive resin composition for forming a photosensitive resin layer can be prepared by mixing each component and a solvent in an arbitrary ratio and by an arbitrary method and stirring and dissolving them. For example, it is also possible to prepare a composition by preparing a solution in which each component is previously dissolved in a solvent and then mixing the obtained solution at a predetermined ratio. The composition prepared as described above can also be used after being filtered using a filter having a pore size of 0.2 μm or the like.

A photosensitive resin layer can be formed by, for example, applying the photosensitive resin composition on a specific layer and drying it.
The coating method is not particularly limited, and coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.

<Layer containing urethane compound or modified polyolefin (specific layer)>
The photosensitive transfer material according to the present disclosure includes a layer (specific layer) containing a urethane compound or a modified polyolefin.
In the photosensitive transfer material according to the present disclosure, another layer may be provided between the temporary support and the specific layer, and between the specific layer and the photosensitive resin layer, but the adhesiveness and transferability are high. From the viewpoint, it is preferable that the temporary support and the specific layer are in contact with each other.
The specific layer may be a layer containing a urethane compound or a modified polyolefin. In the present disclosure, the urethane compound refers to a compound having a urethane bond in its structure, and may be a polymer, an oligomer, or a small molecule compound. Further, the modified polyolefin means a compound that can be dispersed in water by modifying a part of the polyolefin with an acid group, an amino group, and a hydroxyl group, and may be a polymer or an oligomer.

[Layer containing urethane compound]
For the layer containing a urethane compound (hereinafter, also simply referred to as “urethane compound-containing layer”), for example, a coating liquid containing a polyvalent isocyanate compound and a polyhydric alcohol compound is applied onto a temporary support and reacted. It is formed by.
At this time, by adjusting the total molar amount of the isocyanate groups contained in the coating liquid and the total molar amount of the hydroxy groups contained in the coating liquid, the isocyanate group content with respect to the total volume of the urethane compound-containing layer described later will be adjusted. Can be adjusted.
Further, the layer containing a urethane compound may be formed by applying a coating liquid containing a compound such as a urethane polymer on a temporary support and drying the layer.
In this case, the isocyanate group content with respect to the total volume of the urethane compound-containing layer described later is adjusted by further adding a polyhydric isocyanate compound (preferably a polyvalent isocyanate compound protected by a blocking agent) to the coating liquid. Is possible.
That is, the urethane compound contained in the layer containing the urethane compound is a reaction product of the polyhydric isocyanate compound and the polyhydric alcohol compound, or a reaction product of the polyhydric isocyanate compound and the urethane compound. Is preferable.
Further, the urethane compound preferably contains a reactant obtained by at least reacting the alkylene diisocyanate compound with the diol compound. Preferred embodiments of the alkylene diisocyanate compound and the diol compound will be described later.
Hereinafter, the polyhydric isocyanate compound, the polyhydric alcohol compound, the polyvalent carboxylic acid compound optionally contained, and the urethane polymer will be described. These compounds may be contained alone or in combination of two or more.

-Multivalent isocyanate compound-
The polyvalent isocyanate compound may be an aliphatic polyhydric isocyanate compound or an aromatic polyvalent isocyanate compound.
Examples of the polyvalent isocyanate compound include m-phenylenedi isocyanate, p-phenylenedi isocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, and diphenylmethane-4,4'-. Diisocyanate, 3,3'-dimethoxy-biphenyldiisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, 4-chloroxylylene-1 , 3-Diisocyanate, 2-Methylxylylene-1,3-Diisocyanate, 4,4'-diphenylpropane diisocyanate, 4,4'-Diphenylhexafluoropropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2 -Diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1, Examples thereof include 4-bis (isocyanate methyl) cyclohexane, 1,3-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate, and lysine diisocyanate.
Among these, it is preferable to use an alkylene diisocyanate compound. Further, the alkylene group in the alkylene diisocyanate compound may be linear, may have a branched chain or a ring structure, or may be a cycloalkylene group, but shall be linear. Is preferable.
Although the bifunctional diisocyanate compound has been exemplified above, it may be a trifunctional trifunctional triisocyanate compound or a tetrafunctional tetraisocyanate compound inferred from these.

Examples of the trifunctional or higher functional polyvalent isocyanate compound include a trifunctional or higher functional aromatic isocyanate compound and a trifunctional or higher functional aliphatic isocyanate compound. Examples of trifunctional or higher functional isocyanate compounds include bifunctional isocyanate compounds (compounds having two isocyanate groups in the molecule) and compounds having three or more active hydrogen groups in the molecule (eg trifunctional or higher). As an adduct compound (additive) with a polyol, polyamine, polythiol, etc.), an isocyanate compound having trifunctionality or higher (adduct type) and a trimer of a bifunctional isocyanate compound (biuret type or isocyanurate type) are also preferable.
Specific examples of the trifunctional or higher functional isocyanate compound may be xylylene-1,4-diisocyanate, an adduct of xylylene-1,3-diisocyanate and trimethylolpropane, a biuret form, an isocyanurate form, or the like. ..

As the adduct-type trifunctional or higher functional isocyanate compound, a commercially available product on the market may be used, and examples of the commercially available product include Takenate (registered trademark) D-102, D-103, D-103H, and D-103M2. , P49-75S, D-110N, D-120N (isocyanate value = 3.5 mmol / g), D-140N, D-160N (above, Mitsui Chemicals, Inc.), Death Module (registered trademark) L75, UL57SP (Sumika Bayer Urethane Co., Ltd.), Coronate (registered trademark) HL, HX, L (Nippon Polyurethane Co., Ltd.), P301-75E (Asahi Kasei Co., Ltd.) and the like can be mentioned.

Among them, at least one selected from Mitsui Chemicals, Inc.'s Takenate (registered trademark) D-110N, D-120N, D-140N, and D-160N is more preferable as the adduct-type trifunctional or higher functional isocyanate compound.
As the isocyanurate-type trifunctional or higher functional isocyanate compound, a commercially available product on the market may be used. For example, Takenate (registered trademark) D-127N, D-170N, D-170HN, D-172N, D-177N. (Mitsui Chemicals Co., Ltd.), Sumijour N3300, Death Module (registered trademark) N3600, N3900, Z4470BA (Sumitomo Bayer Urethane), Coronate (registered trademark) HX, HK (manufactured by Nippon Polyurethane Industry Co., Ltd.), Duranate (registered trademark) ) TPA-100, TKA-100, TSA-100, TSS-100, TLA-100, TSE-100 (manufactured by Asahi Kasei Corporation) and the like.
As the biuret-type trifunctional or higher functional isocyanate compound, commercially available products on the market may be used, for example, Takenate (registered trademark) D-165N, NP1100 (manufactured by Mitsui Chemicals, Inc.), Death Module (registered trademark) N3200. (Sumika Bayer Urethane), Duranate (registered trademark) 24A-100 (manufactured by Asahi Kasei Corporation) and the like can be mentioned.

The isocyanate groups in these polyvalent isocyanate compounds may be protected by known blocking agents.
Since the isocyanate group is protected by the blocking agent, the above-mentioned coating liquid can be applied onto the temporary support and then heated to react the polyhydric isocyanate compound with the polyhydric alcohol compound. ..

Examples of the blocking agent include lactam compounds [eg, ε-caprolactum, δ-valerolactam, γ-butyrolactam, etc.], oxime compounds [eg, acetoxime, methylethylketooxime (MEK oxime), methylisobutylketooxime (MIBK oxime), cyclohexanone oxime). Etc.], amine compounds [for example, aliphatic amines (dimethylamine, diisopyramine, di-n-propylamine, diisobutylamine, etc.), alicyclic amines (methylhexylamine, dicyclohexylamine, etc.), aromatic amines (aniline, diphenylamine, etc.) )], Aliper alcohol compounds [eg methanol, ethanol, 2-propanol, n-butanol, etc.], phenol and alkylphenol compounds [eg phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, octylphenol, etc. Nonylphenol, xylenol, diisopropylphenol, di-t-butylphenol, etc.], imidazole compounds [eg, imidazole, 2-methylimidazole, etc.], pyrazole compounds [eg, pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, etc.], imine compounds. [For example, ethyleneimine, polyethyleneimine, etc.], active methylene compounds [for example, dimethyl malonate, diethyl malonate, diisopropyl malate, acetylacetone, methyl acetoacetate, ethyl acetoacetate, etc.], JP-A-2002-309217 and JP-A-2008. The blocking agents described in 239890, as well as mixtures of two or more of these are mentioned. Among them, as the blocking agent, an oxime compound, a lactam compound, a pyrazole compound, an active methylene compound, or an amine compound is preferable.

As the blocked isocyanate compound, a commercially available product on the market may be used, and for example, Duranate WM44-L70G (Asahi Kasei Corporation) is preferably used.

-Multivalent alcohol compounds-
Examples of the polyhydric alcohol compound include aliphatic diol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol and neopentylglycol, and alicyclic diol compounds such as cyclohexanediol and hydrogenated bisphenol A. Examples thereof include diol compounds such as ethylene oxide adducts of bisphenol A and aromatic diol compounds such as propylene oxide adducts of bisphenol A.
In the above, bifunctional diol compounds have been exemplified, but trifunctional alcohol compounds (glycerin, trimethylolpropane, etc.) and tetrafunctional alcohol compounds (pentaerythritol), which are inferred from these, may be used.

-Multivalent carboxylic acid compound-
The coating liquid may contain a polyvalent carboxylic acid compound in addition to the polyhydric isocyanate compound and the polyhydric alcohol compound from the viewpoint of further improving the adhesion of the temporary support. It is considered that polyester polyurethane can be obtained after the reaction by further containing the polyvalent carboxylic acid compound in the coating liquid.
The polyvalent carboxylic acid compound may be an aliphatic polyvalent carboxylic acid or an aromatic polyvalent carboxylic acid, but an aliphatic polyvalent carboxylic acid is preferable.
Further, it may be a saturated carboxylic acid or an unsaturated carboxylic acid, but an unsaturated carboxylic acid is preferable.
Examples of the polyvalent carboxylic acid compound include citric acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, malic acid and the like. Can be mentioned.

-Urethane polymer-
Examples of the urethane polymer include a polymer obtained by reacting an isocyanate compound such as the above-mentioned polyhydric isocyanate compound with an alcohol compound such as the above-mentioned polyhydric alcohol compound, and an excessive amount of the polyhydric alcohol compound and a polyhydric compound. A terminal hydroxy group-containing urethane polymer obtained by reacting with an isocyanate compound is preferable.

[Modified polyolefin]
The layer containing the modified polyolefin is formed by applying a coating liquid containing the modified polyolefin on the temporary support and drying it.
The modified polyolefin in the present disclosure refers to a polyolefin in which a polyolefin is modified and a water-dispersible group is introduced so that the polyolefin can be dispersed in water.
Specific examples of the group that can be dispersed in water include an acid group, an amino group, and a hydroxyl group.
As the modified polyolefin, an acid-modified polyolefin, a base-modified polyolefin, or a hydroxyl group-modified polyolefin is preferable.
Of these, acid-modified polyolefins are preferable from the viewpoint of adhesion and transferability.
Examples of the acid group include a carboxy group, a sulfo group and a phosphoric acid group, and a carboxy group is preferable. The acid group may form an acid anhydride and is neutralized with at least one compound selected from the group consisting of alkali metal salts, organic ammonium compounds, organic amine compounds, and ammonia. May be. The amino group as a water dispersible group may also be neutralized with at least one acid selected from the group consisting of hydrochloric acid, sulfuric acid, and acetic acid.
Preferred examples of the polyolefin structure in the modified polyolefin include polyethylene, polypropylene, and polyhexene.
Specific examples of the modified polyolefin include Chemipearl S100, S120, S200, S300, S650, SA100 (manufactured by Mitsui Kagaku Co., Ltd.), Hardlen AP-2, NZ-1004, and NZ-1005 (manufactured by Toyobo Co., Ltd.). , Arrow Base SE-1013, SE-1010, SB-1200, SD-1200, SD-1200, DA-1010, DB-4010 (manufactured by Unitika Co., Ltd.), Zyxen AC, A, L, NC, N (Sumitomo) Examples include Seporjon G315, VA407 (Sumitomo Seika Co., Ltd.), Hi-Tech S3121, S3148K (Toyo Kagaku Kogyo Co., Ltd.) and the like.

-Content-
The specific layer may contain one type of urethane compound or modified polyolefin alone, or may contain two or more types.
When the specific layer contains a urethane compound, it may further have a modified polyolefin.
Further, when the specific layer contains a modified polyolefin, it may further have a urethane compound.
The specific layer preferably contains 25% by mass or more and 100% by mass or less of the urethane compound or the modified polyolefin, and more preferably 50% by mass or more and 95% by mass or less, based on the total mass of the layer.

[Other compounds]
The specific layer may contain a urethane compound and other compounds other than the modified polyolefin.
Examples of other compounds include surfactants, pH adjusters, waxes, catalysts and the like.

-Surfactant-
The specific layer preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic (nonionic) or amphoteric surfactants can be used, but the preferred surfactant is an anionic surfactant.
Examples of anionic surfactants include Lapizol® A-90, A-80, BW-30, B-90, C-70 (all manufactured by NOF CORPORATION), NIKKOL®. OTP-100 (above, manufactured by Nikko Chemical Co., Ltd.), Kohakul (registered trademark) ON, L-40, Phosphanol (registered trademark) 702 (above, manufactured by Toho Chemical Industries, Ltd.), Viewlite (registered trademark) ) A-5000, SSS (all manufactured by Sanyo Chemical Industries, Ltd.) and the like.

The surfactant may be used alone or in combination of two or more.
The content of the surfactant is not particularly limited, but is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and 0, based on the total mass of the specific layer. It is more preferably 0.01% by mass to 3% by mass.

-PH regulator-
The specific layer may contain a pH regulator.
Examples of the pH adjuster include ammonium chloride, sodium hydrogencarbonate, hydrochloric acid, sodium hydroxide and the like.

The pH adjuster may be used alone or in combination of two or more.
The content of the pH adjuster is not particularly limited, but is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and 0, based on the total mass of the specific layer. It is more preferably 0.01% by mass to 3% by mass.

-wax-
The specific layer may contain wax from the viewpoint of the coatability of the coating liquid when the specific layer is formed by coating the coating liquid.
Specific examples of the wax include carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin-modified wax, auricury wax, sugar cane wax, espart wax, bark wax and other vegetable waxes; , Lanorin, Whale wax, Ibotaro, Celac wax and other animal waxes; Montan wax, Ozokerite, Celesin wax and other mineral waxes; Paraffin wax, Microcrystallin wax, Petrolactam and other petroleum waxes; Fishertro push wax, Polyethylene Examples thereof include synthetic hydrocarbon waxes such as wax, polyethylene oxide wax, polypropylene wax, and polypropylene oxide wax.

One type of wax may be used alone, or two or more types may be used in combination.
The content of the wax is not particularly limited, but is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and 0.01 by mass, based on the total mass of the specific layer. It is more preferably mass% to 3% by mass.

-catalyst-
The layer containing the urethane compound may contain a catalyst from the viewpoint of accelerating the reaction between the polyhydric isocyanate compound and the polyhydric alcohol compound.
Examples of the catalyst include known urethanization catalysts.
Examples of the urethanization catalyst include tin-based catalysts (for example, tin octylate), lead-based catalysts (for example, lead octylate, etc.), bismuth-based catalysts, titanium-based catalysts, zirconium-based catalysts, organic metal-based catalysts, and amines. Examples include system catalysts.

The urethanization catalyst may be contained alone or in combination of two or more.
The content of the urethanization catalyst is preferably 0.0001 part by mass to 2.0 part by mass, and 0.0005 part by mass to 1.0 part by mass with respect to the total mass of the layer containing the urethane compound. Is more preferable.

-Other ingredients-
The specific layer according to the present disclosure may further contain other components.
Examples of other components include binder polymers other than urethane polymers, resin particles, particles such as silica particles, and the like.

[Film thickness]
The film thickness of the specific layer is preferably 1000 nm or less, more preferably 500 nm or less, further preferably 300 nm or less, and particularly preferably 200 nm or less.
The lower limit of the film thickness is preferably 10 nm or more, and more preferably 30 nm or more.

[Isocyanate group content]
When the specific layer is a layer containing a urethane compound, the isocyanate group content with respect to the total volume of the specific layer is 0.01 mol / m ³ or more and 0.40 mol / m from the viewpoint of improving adhesion and transferability. It is preferably ³ or less, more preferably 0.01 mol / m ³ or more and 0.35 mol / m ³ or less, and further preferably 0.01 mol / m ³ or more and 0.30 mol / m ³ or less.
The isocyanate group content with respect to the total volume of the layer containing the urethane compound is measured by the following method.
A photosensitive transfer material is heat-laminated on a glass substrate, and the temporary support is peeled off to obtain a temporary support having a layer containing a urethane compound from the photosensitive transfer material.
The obtained temporary support is collected in an area of 20 cm × 20 cm, and the temporary support is extracted with 1 mL of dry toluene to extract a coating layer. If a layer is further formed on the surface of the temporary support opposite to the photosensitive resin layer, the corresponding layer is scraped off with a razor or the like as necessary to perform extraction. According to JIS K7301 (1995), excess dibutylamine is added to a dry toluene solution and reacted to generate the corresponding urea, and then back titration is performed by an indicator titration method using a hydrochloric acid standard solution, and the above dry solidification is performed. Measure the isocyanate group content in the product. Then, the isocyanate group content per unit volume of the layer containing the urethane compound is calculated together with the film thickness obtained from the cross-sectional TEM image.

[Adhesion of specific layer]
In the photosensitive transfer material according to the present disclosure, the temporary support and the specific layer are in contact with each other, and the adhesion between the specific layer and the temporary support is 0.098 N / cm (10.0 gf / cm). It is preferably 0.22 N / cm (22 gf / cm) or more, and more preferably 0.22 N / cm (22 gf / cm) or more.
Further, from the viewpoint of productivity, it is preferable that the temporary support is a stretched film and 0.098 N / cm (10.0 gf / cm) or more, and the temporary support is a stretched film and 0. It is more preferably .22 N / cm (22 gf / cm) or more.
When the adhesive force of the specific layer is within the above range, when the temporary support is peeled off, the specific layer is likely to be peeled off at the interface between the specific layer and the photosensitive resin layer while remaining in close contact with the temporary support side.
Therefore, when the temporary support is peeled off after the photosensitive transfer material is laminated on the substrate, it is peeled off at the interface between the specific layer and the photosensitive resin layer, so that the substrate is photosensitive. It is considered that the resin layer remains and the specific layer is unlikely to remain on the photosensitive resin layer.
As described above, since the specific layer is unlikely to remain on the photosensitive resin layer, it is easy to suppress the generation of development residue derived from the specific layer during development, and when the photosensitive transfer material according to the present disclosure is used, the developability is high. It is thought that it is easy to excel.
When another layer described later is further included between the specific layer and the photosensitive resin layer, the "interface between the specific layer and the photosensitive resin layer" is the "interface between the specific layer and the other layer". It shall be read as.
The adhesion of the specific layer is measured by the following method.
A temporary support having a specific layer is obtained from the photosensitive transfer material by thermally laminating the photosensitive transfer material on a glass substrate and peeling off the temporary support.
A tape (Printac C, manufactured by Nitto Denko Corporation) is attached to the surface of the obtained temporary support having the specific layer on the specific layer side, and cut out to 4.5 cm x 9 cm so that the width of the tape and the support match. .. This is peeled by 180 ° at a peeling speed of 500 mm / min using a Tencilon universal tester manufactured by A & D Co., Ltd., and the adhesion is measured.
The upper limit of the adhesion is not particularly limited, and may exceed the measurement limit by the above measurement method.

[Manufacturing method of specific layer]
Each component and a solvent can be mixed at an arbitrary ratio and by an arbitrary method and dissolved by stirring to prepare a composition for forming a specific layer.
For example, it is also possible to prepare a composition by preparing a solution in which each component is previously dissolved in a solvent and then mixing the obtained solution at a predetermined ratio. The composition prepared as described above can also be used after being filtered using a filter having a pore size of 0.2 μm or the like.

As the solvent, a known solvent can be used. As the solvent, those described above can be preferably used in the photosensitive resin layer.
The solvent used to form the specific layer may be used alone or in combination of two. When two or more kinds of solvents are used, for example, propylene glycol monoalkyl ether acetates and dialkyl ethers, diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates should be used in combination. Is preferable.
Further, in order to suppress mixing with the photosensitive resin layer, it is preferable to use water as a solvent with each component contained in the specific layer as a water-soluble or water-dispersible component.

The content of the solvent in the composition for forming the specific layer is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content in the composition. Is more preferable.

A specific layer can be formed by applying the above composition, for example, on a temporary support, heating and drying.
The coating method is not particularly limited, and coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.

Further, from the viewpoint of improving the adhesion of the specific layer, when the temporary support is a stretched film, it is preferable to apply the above composition before stretching the temporary support.
When the temporary support is a biaxially stretched film, for example, after longitudinal stretching (stretching in the film transport direction), the above composition is applied, and then transverse stretching (stretching in the film transport direction on the surface of the film). By performing stretching in the vertical direction), a specific layer having excellent adhesion is formed.
When the specific layer is a layer containing a urethane compound, the polyhydric isocyanate compound, the polyhydric alcohol compound, the polyvalent carboxylic acid compound, the urethane polymer and the like in the composition are reacted by heating in the stretching. Therefore, it is preferable to use a urethane compound.
Specifically, by using a polyvalent isocyanate compound in which the isocyanate group is blocked by the above-mentioned blocking agent as the polyhydric isocyanate compound, the isocyanate group is regenerated by the above heating, and the above-mentioned isocyanate group reacts with the hydroxy group. It is preferable that the isocyanate group is contained in the urethane compound-containing layer as it is.
When the temporary support is a stretched film, the stretching method is not particularly limited, and a known method is used.

<Other layers>
The photosensitive transfer material according to the present disclosure may have a layer other than the above-mentioned photosensitive resin layer and the specific layer (hereinafter, may be referred to as “other layer”). Examples of other layers include a contrast enhancement layer, an intermediate layer, a cover film, a thermoplastic resin layer, a back layer, and the like.

[Contrast enhancement layer]
The photosensitive transfer material according to the present disclosure may have a contrast enhancement layer in addition to the above-mentioned photosensitive resin layer.
The contrast enhancement layer (CEL) absorbs a large amount of light with respect to the exposure wavelength before exposure, but the absorption gradually decreases with exposure, that is, a material having high light transmittance (light extinction). It is a layer containing) (referred to as a sex pigment component). Diazonium salts, stillvazolium salts, arylnitroso salts and the like are known as photochromic dye components. As the film-forming component, a phenol-based resin or the like is used.
In addition, as the contrast enhancement layer, paragraphs 0004 to 0051 of JP-A-6-97065, paragraphs 0012 to paragraph 0055 of JP-A-6-332167, Photopolymer Handbook, Photopolymer Social gathering edition, Industrial Research Council ( 1989), Photopolymer Technology, Yamaoka, Nagamatsu ed., Nikkan Kogyo Shimbun Co., Ltd. (1988) can be used.

[Middle layer]
An intermediate layer can be provided on the photosensitive resin layer for the purpose of applying the plurality of layers and for the purpose of preventing mixing of the components during storage after application.
As the intermediate layer, the intermediate layer described in paragraphs 0084 to 0087 of JP-A-2005-259138 can be used. The intermediate layer is preferably one that is dispersed or dissolved in water or an alkaline aqueous solution.
Examples of the material used for the intermediate layer include 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 copolymers thereof. Resin is mentioned. Of these, a combination of polyvinyl alcohol and polyvinylpyrrolidone is particularly preferable.

[Thermoplastic resin layer, cover film, etc.]
From the viewpoint of transferability, the photosensitive transfer material according to the present disclosure may have a thermoplastic resin layer between the temporary support and the photosensitive resin layer.
Further, the photosensitive transfer material according to the present disclosure may have a cover film for the purpose of protecting the photosensitive resin layer.
Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP-A-2014-85643, and preferred embodiments of other layers are described in paragraphs 0194 to 0196 of JP-A-2014-85643. The contents of this publication are incorporated herein.
Above all, from the viewpoint of transferability, it is preferable that the thermoplastic resin layer contains at least one thermoplastic resin selected from the group consisting of an acrylic resin and a styrene / acrylic copolymer.

When the photosensitive transfer material according to the present disclosure has another layer such as a thermoplastic resin layer, it is produced according to the method for producing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138. can do.
For example, in the case of producing the photosensitive transfer material according to the present disclosure having a thermoplastic resin layer and an intermediate layer, a specific layer is provided on a temporary support by the above method, and then a thermoplastic organic polymer is used. A solution in which an additive is dissolved (a coating solution for a thermoplastic resin layer) is applied and dried to prepare a thermoplastic resin layer, and a solvent that does not dissolve the thermoplastic resin layer is used on the obtained thermoplastic resin layer. A preparation solution (coating solution for an intermediate layer) prepared by adding a resin and an additive is applied, dried, and the intermediate layer is laminated. The photosensitive transfer material according to the present disclosure is obtained by further applying a photosensitive resin composition prepared by using a solvent that does not dissolve the intermediate layer on the formed intermediate layer, drying the mixture, and laminating the photosensitive resin layer. Can be suitably produced.

[Back layer]
The photosensitive transfer material according to the present disclosure may have a back layer on the opposite side of the temporary support from the photosensitive resin layer.
Various additives such as surfactants, slip agents such as wax, and matting agents, and resin particles can be added to the back layer.
Examples of the resin particles used for forming the back layer include homopolymers and copolymers of acrylic acid-based monomers such as acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester, nitrocellulose, methylcellulose, and ethylcellulose. Co-polymers of cellulose-based polymers such as cellulose acetate, polyethylene, polypropylene, polystyrene, vinyl chloride-based copolymers, vinyl chloride-vinyl acetate copolymers, polyvinyl-based polymers such as polyvinylpyrrolidone, polyvinylbutyral, polyvinyl alcohol and vinyl compounds. Polymers, condensed polymers such as polyester, polyurethane and polyamide, rubber-based thermoplastic polymers such as butadiene-styrene copolymers, and polymers obtained by polymerizing and cross-linking photopolymerizable or thermopolymerizable compounds such as epoxy compounds. , Polymer compounds and the like.
The back layer is formed, for example, by applying a composition in which the components contained in the back layer are dispersed or dissolved in a known solvent such as water on the surface opposite to the photosensitive resin layer of the temporary support.
When the temporary support is produced by stretching, the composition may be applied and then stretched. For example, the temporary support may be applied at the same timing as the application of the composition for forming a specific layer and then stretched. good.

(Manufacturing method of circuit wiring)
A first embodiment of a method for manufacturing a circuit wiring using a photosensitive transfer material according to the present disclosure will be described.
The first embodiment of the method for manufacturing a circuit wiring is
A step of contacting and bonding the outermost layer of the photosensitive transfer material according to the present disclosure on the photosensitive resin layer side of the temporary support to the substrate (bonding step).
A step (exposure step) of pattern-exposing the photosensitive resin layer of the photosensitive transfer material after the bonding step, and
The step of developing the exposed portion after the above-mentioned exposure step to form a pattern (development step) and
It includes a step (etching step) of etching a substrate in a region where the pattern is not arranged.
The substrate in the first embodiment of the method for manufacturing a circuit wiring may be a substrate itself such as glass, silicon, or film, and may be a conductive layer or the like on the substrate such as glass, silicon, or film, if necessary. It may be a substrate provided with any layer of.
According to the first embodiment of the method for manufacturing a circuit wiring, a fine pattern can be formed on the surface of a substrate.

The second embodiment of the method of manufacturing a circuit wiring is
It has a base material and a plurality of conductive layers including a first conductive layer and a second conductive layer having different constituent materials from each other, and the outermost surface layer is placed on the surface of the base material in the order of distance from the surface of the base material. On the substrate on which the first conductive layer and the second conductive layer are laminated, the outermost layer of the photosensitive transfer material according to the present disclosure on the photosensitive resin layer side of the temporary support is the first conductive layer. The bonding process of contacting and bonding to
The first exposure step of pattern-exposing the photosensitive resin layer via the temporary support of the photosensitive transfer material after the bonding step, and
A first developing step of peeling the temporary support from the photosensitive resin layer after the first exposure step and then developing the exposed portion after the first exposure step to form a first pattern.
A first etching step of etching at least the first conductive layer and the second conductive layer among the plurality of conductive layers in the region where the first pattern is not arranged.
A second exposure step of pattern-exposing the first pattern after the first etching step with a pattern different from the first pattern,
A second developing step of developing the first pattern after the second exposure step to form a second pattern, and a second developing step.
The second etching step of etching at least the first conductive layer among the plurality of conductive layers in the region where the second pattern is not arranged is included in this order. As the second embodiment, International Publication No. 2006/190405 can be referred to, the contents of which are incorporated herein.

The circuit wiring manufacturing method according to the present disclosure can be used as a circuit wiring manufacturing method for a touch panel or a touch panel display device.
Hereinafter, details of each step will be described based on the second embodiment.

<Lasting process>
An example of the bonding process is schematically shown in FIG. 2 (a).
First, in the bonding step, the base material 22 has a base material 22 and a plurality of conductive layers including a first conductive layer 24 and a second conductive layer 26 having different constituent materials from each other, and the base material 22 is placed on the surface of the base material 22. The photosensitive transfer material according to the present disclosure is described above with respect to the substrate (circuit wiring forming substrate) 20 in which the first conductive layer 24 and the second conductive layer 26, which are the outermost surface layers, are laminated in the order of distance from the surface of the above. The photosensitive resin layer 12, which is the outermost layer of the temporary support on the photosensitive resin layer side, is brought into contact with the first conductive layer 24 and bonded to each other. It should be noted that such bonding of the circuit wiring forming substrate and the photosensitive transfer material may be referred to as "transfer" or "laminate".
In FIG. 2A, the outermost layer of the photosensitive transfer material 100 on the photosensitive resin layer side of the temporary support is a photosensitive resin layer, but another layer is formed on the photosensitive resin layer, and the outermost layer is formed. May be another layer.

As shown in FIG. 1, when the cover film 16 is provided on the photosensitive resin layer 12 of the photosensitive transfer material 100, the cover film 16 is removed from the photosensitive transfer material 100 (photosensitive resin layer 12) and then photosensitive. The photosensitive resin layer 12 of the sex transfer material 100 is brought into contact with the first conductive layer 24 and bonded.
The bonding (transfer) of the photosensitive transfer material on the first conductive layer is carried out by superimposing the photosensitive resin layer side of the photosensitive transfer material on the first conductive layer, and pressurizing and heating with a roll or the like. It is preferable to be For bonding, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.
When the base material of the circuit wiring forming substrate is a resin film, it can also be bonded by roll-to-roll.

〔Base material〕
In the substrate in which a plurality of conductive layers are laminated on the substrate, the substrate is preferably a glass substrate or a film substrate, and more preferably a film substrate. In the circuit wiring manufacturing method according to the present disclosure, when the circuit wiring is for a touch panel, it is particularly preferable that the base material is a sheet-like resin composition.
Moreover, it is preferable that the base material is transparent.
The refractive index of the substrate is preferably 1.50 to 1.52.
The base material may be composed of a translucent base material such as a glass base material, and tempered glass typified by Corning's gorilla glass or the like can be used. Further, as the above-mentioned transparent base material, the materials used in JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be preferably used.
When a film base material is used as the base material, it is more preferable to use a base material that is not optically distorted and a base material having high transparency, and specific materials include polyethylene terephthalate (PET). Examples thereof include polyethylene terephthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[Conductive layer]
Examples of the plurality of conductive layers formed on the base material include any conductive layer used for general circuit wiring or touch panel wiring.
Examples of the material of the conductive layer include metals and metal oxides.
Examples of the metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), SiO ₂ and the like. Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo and the like.

In the method for manufacturing a circuit wiring according to the present disclosure, it is preferable that at least one of the plurality of conductive layers contains a metal oxide.
As the conductive layer, it is preferable that the electrode pattern corresponds to the sensor of the visual recognition portion used in the capacitive touch panel or the wiring of the peripheral extraction portion.

[Circuit wiring forming board]
It is a substrate having a conductive layer on the surface of the base material. The conductive layer is patterned to form circuit wiring. In this example, it is preferable that a film base material such as PET is provided with a plurality of conductive layers such as metal oxides and metals.

<Exposure process (first exposure process)>
In the first embodiment, the exposure step is performed, and in the second embodiment, the first exposure step is performed. An example of the exposure step (first exposure step) is schematically shown in FIG. 2 (b).
In the exposure step (first exposure step), the photosensitive resin layer 12 is pattern-exposed via the temporary support 10 and the specific layer 14 of the photosensitive transfer material after the bonding step.

As an example of the exposure step, the developing step, and other steps in the present embodiment, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be preferably used in the present embodiment as well.

For example, a mask 30 having a predetermined pattern is placed above the photosensitive transfer material 100 placed on the first conductive layer 24 (the side opposite to the side in contact with the first conductive layer 24), and then the mask 30 is placed. A method of exposing with ultraviolet rays from above the mask via the mask can be mentioned.
In the present embodiment, the detailed arrangement and specific size of the pattern are not particularly limited. Since it is desired to improve the display quality of a display device (for example, a touch panel) including an input device having circuit wiring manufactured by the present embodiment and to make the area occupied by the take-out wiring as small as possible, at least a part of the pattern (particularly a touch panel). The electrode pattern and the portion of the take-out wiring) are preferably thin wires of 100 μm or less, and more preferably 70 μm or less.
Here, the light source used for exposure can be appropriately selected and used as long as the exposed portion of the photosensitive transfer material can irradiate light in a wavelength range that can be dissolved in the developing solution (for example, 365 nm, 405 nm, etc.). .. Specific examples thereof include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps and the like.
The exposure amount is preferably 5 mJ / cm ² to 200 mJ / cm ² , more preferably 10 mJ / cm ² to 100 mJ / cm ² .
Further, it is also preferable to perform heat treatment before development for the purpose of improving the rectangularness and linearity of the pattern after exposure. By the so-called PEB (Post Exposure Bake) process, it is possible to reduce the roughness of the pattern edge due to the standing wave generated in the photosensitive resin layer during exposure.

Even if the pattern exposure is performed after the temporary support is peeled off from the photosensitive resin layer, the temporary support is exposed through the temporary support before the temporary support is peeled off, and then the temporary support is peeled off. May be good. In order to prevent mask contamination due to contact between the photosensitive resin layer and the mask and to avoid the influence of foreign matter adhering to the mask on the exposure, it is preferable to expose the temporary support without peeling it off. The pattern exposure may be an exposure through a mask or a digital exposure using a laser or the like.

<Development process (first development process)>
In the first embodiment, the developing step is performed, and in the second embodiment, the first developing step is performed. An example of the developing step (first developing step) is schematically shown in FIG. 2 (c).
In the developing step (first developing step), after the temporary support 10 (and the specific layer 14) is peeled off from the photosensitive resin layer 12 after the exposure step (first exposure step), after the exposure step (first exposure step). The photosensitive resin layer 12 of the above is developed to form the first pattern 12A.

The developing step (first developing step) is a step of forming a pattern (first pattern) by developing the photosensitive resin layer exposed to the pattern.
The pattern-exposed photosensitive resin layer can be developed using a developing solution.
The developing solution is not particularly limited as long as the exposed portion of the photosensitive resin layer can be removed, and a known developing solution such as the developing solution described in JP-A-5-72724 can be used. The developer is preferably a developer in which the exposed portion of the photosensitive resin layer has a dissolution-type development behavior. For example, an alkaline aqueous solution-based developer containing a compound having pKa = 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is preferable. The developer may further contain an organic solvent miscible with water, a surfactant and the like. Examples of the developer preferably used in the present embodiment include the developer described in paragraph 0194 of International Publication No. 2015/093271.

The development method is not particularly limited and may be any of paddle development, shower development, shower and spin development, dip development and the like. Here, the shower development will be described. By spraying the developer on the photosensitive resin layer after exposure with a shower, the exposed portion can be removed. Further, after the development, it is preferable to spray a cleaning agent or the like with a shower and rub it with a brush or the like to remove the development residue. The liquid temperature of the developing solution is preferably 20 ° C to 40 ° C.

Further, it may have a post-baking step of heat-treating a pattern including a photosensitive resin layer obtained by development.
The post-bake heating is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably performed in an environment of 506.6 kPa or more. On the other hand, it is more preferably performed in an environment of 111.4 kPa or less, and particularly preferably performed in an environment of 101.3 kPa or less.
The temperature of the post bake is preferably 80 ° C to 250 ° C, more preferably 110 ° C to 170 ° C, and particularly preferably 130 ° C to 150 ° C.
The post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
Post-baking may be performed in an air environment or a nitrogen substitution environment.

It may have other steps such as a post-exposure step.

<Etching process (first etching process)>
In the first embodiment, the etching step is performed, and in the second embodiment, the first etching step is performed. An example of the etching process (first etching process) is schematically shown in FIG. 2 (d).
In the etching step (first etching step), at least the first conductive layer 24 and the second conductive layer 26 among the plurality of conductive layers in the region where the first pattern 12A is not arranged are etched. By etching, the first conductive layer 24A and the second conductive layer 26A having the same pattern are formed.

Etching of the conductive layer can be applied by a known method such as the method described in paragraphs 0048 to 0054 of JP-A-2010-152155, and the method by dry etching such as known plasma etching.

For example, as an etching method, a commonly used wet etching method of immersing in an etching solution can be mentioned. As the etching solution used for wet etching, an acidic type or alkaline type etching solution may be appropriately selected according to the etching target.
Examples of the acidic type etching solution include an aqueous solution of an acidic component alone such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and a mixed aqueous solution of an acidic component and a salt such as ferric chloride, ammonium fluoride, and potassium permanganate. Will be done. As the acidic component, a component in which a plurality of acidic components are combined may be used.
Examples of the alkaline type etching solution include an aqueous solution of an alkaline component alone such as a salt of an organic amine such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a tetramethylammonium hydroxide, and an alkaline component and potassium permanganate. Examples include a mixed aqueous solution of salt. As the alkaline component, a component in which a plurality of alkaline components are combined may be used.

The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower. The first pattern used as an etching mask (etching pattern) in the present embodiment preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, the photosensitive resin layer is prevented from peeling off during the etching step, and the portion where the photosensitive resin layer does not exist is selectively etched.

After the etching step, a cleaning step and a drying step may be performed as necessary to prevent contamination of the process line. The washing step is performed by washing the substrate with pure water for 10 seconds to 300 seconds at room temperature, for example, and the drying step is performed by using, for example, an air blow, and the air blow pressure (preferably 0.1 kg / cm ² to 5 kg / cm ² ). Degree) may be adjusted as appropriate to perform drying.

<Second exposure process>
In the second embodiment, the second exposure step is performed. An example of the second exposure step is schematically shown in FIG. 2 (e).
After the first etching step, the first pattern 12A after the first etching step is exposed to a pattern different from the first pattern.

In the second exposure step, the first pattern remaining on the first conductive layer is exposed to a portion corresponding to at least a portion to be removed of the first conductive layer in the second developing step described later.
For the pattern exposure in the second exposure step, the same method as the pattern exposure in the first exposure step can be applied except that the mask 40 having a pattern different from that of the mask 30 used in the first exposure step is used.

<Second development process>
In the second embodiment described above, the second developing step is performed. An example of the second developing step is schematically shown in FIG. 2 (f).
In the second developing step, the first pattern 12A after the second exposure step is developed to form the second pattern 12B.
By the development, the portion of the first pattern exposed in the second exposure step is removed.
In the second development step, the same method as the development in the first development step can be applied.

<Second etching process>
In the second embodiment, the second exposure step is performed. An example of the second etching step is schematically shown in FIG. 2 (g).
In the second etching step, at least the first conductive layer 24A among the plurality of conductive layers in the region where the second pattern 12B is not arranged is etched.

For the etching in the second etching step, the same method as the etching in the first etching step can be applied except that the etching solution corresponding to the conductive layer to be removed by etching is selected.
In the second etching step, it is preferable to selectively etch less conductive layers than in the first etching step, depending on the desired pattern. For example, as shown in FIG. 2, the first conductive layer is obtained by performing etching with an etching solution that selectively etches only the first conductive layer 24B in a region where the photosensitive resin layer is not arranged. The pattern can be different from the pattern of the conductive layer.
After the end of the second etching step, a circuit wiring including at least two patterns of conductive layers 24B and 26A is formed.

<Photosensitive resin layer removal process>
An example of the photosensitive resin layer removing step is schematically shown in FIG. 2 (h).
After the completion of the second etching step, the second patterns 12B and 14B remain in a part of the first conductive layer 24B. If the photosensitive resin layer is unnecessary, the second pattern 12B of all the remaining photosensitive resin layers may be removed.

The method for removing the remaining photosensitive resin layer is not particularly limited, and examples thereof include a method for removing by chemical treatment.
As a method for removing the photosensitive resin layer, a substrate having a photosensitive resin layer or the like is immersed in a stripping solution being stirred at preferably at 30 ° C to 80 ° C, more preferably 50 ° C to 80 ° C for 1 to 30 minutes. There is a way to do it.

As the stripping solution, for example, an inorganic alkaline component such as sodium hydroxide or potassium hydroxide, or an organic alkaline component such as a primary amine, a secondary amine, a tertiary amine, or a quaternary ammonium salt is used as water. , Dimethylsulfoxide, N-methylpyrrolidone or a stripping solution dissolved in a mixed solution thereof. A peeling liquid may be used and peeled by a spray method, a shower method, a paddle method or the like.

The circuit wiring manufacturing method according to the present disclosure may include any other steps. For example, the following steps can be mentioned, but the steps are not limited to these steps.

<Process of attaching protective film>
In the second embodiment, after the first etching step and before the second exposure step, there may be further a step of attaching a light-transmitting protective film (not shown) on the first pattern. good.
In this case, in the second exposure step, it is preferable to perform pattern exposure of the first pattern through the protective film, and after the second exposure step, peel off the protective film from the first pattern, and then perform the second development step.

<Step to reduce visible light reflectance>
The method for manufacturing a circuit wiring according to the present disclosure can include a step of reducing the visible light reflectance of a part or all of a plurality of conductive layers on a base material.
Examples of the treatment for reducing the visible light reflectance include an oxidation treatment. For example, by oxidizing copper to copper oxide, it is possible to reduce the visible light reflectance by blackening the copper.
Preferable embodiments of the treatment for reducing the visible light reflectance are described in paragraphs 0017 to 0025 of Japanese Patent Application Laid-Open No. 2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of Japanese Patent Application Laid-Open No. 2013-206315. There is a description and the contents of this publication are incorporated herein by reference.

<Step of forming a new conductive layer on the insulating film>
It is also preferable that the method for manufacturing a circuit wiring according to the present disclosure includes a step of forming an insulating film on the formed circuit wiring and a step of forming a new conductive layer on the insulating film.
With such a configuration, the above-mentioned second electrode pattern can be formed while being insulated from the first electrode pattern.
The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be mentioned. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
The process of forming a new conductive layer on the insulating film is not particularly limited. A photosensitive material having conductivity may be used to form a new conductive layer with a desired pattern by photolithography.

Further, in the description with reference to FIG. 2, a case where a circuit wiring having two different patterns is formed on a circuit wiring forming substrate provided with two conductive layers has been described, but the circuit wiring according to the present disclosure. The number of conductive layers of the substrate to which the manufacturing method is applied is not limited to two, and a circuit wiring forming substrate in which three or more conductive layers are laminated is used, and the combination of the above-mentioned exposure step, development step, and etching step is used. By performing this three times or more, it is possible to form three or more conductive layers in different circuit wiring patterns.

Further, although not shown in FIG. 2, in the method for manufacturing a circuit wiring according to the present disclosure, the base material has a plurality of conductive layers on both surfaces, and the conductive layers formed on both surfaces of the base material. It is also preferable to form a circuit sequentially or simultaneously with respect to the above. With such a configuration, it is possible to form a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of a base material and a second conductive pattern is formed on the other surface. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the base material by roll-to-roll.

(Circuit wiring and circuit board)
The circuit wiring according to the present disclosure is a circuit wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure.
The circuit board according to the present disclosure is a substrate having a circuit wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure.
The application of the circuit board according to the present disclosure is not limited, but for example, it is preferably a circuit board for a touch panel.

(Input device and display device)
An input device is mentioned as a device provided with the circuit wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure.
The input device in this embodiment is preferably a capacitive touch panel.
The display device according to the present embodiment preferably includes the input device according to the present embodiment. The display device in the present embodiment is preferably an organic EL display device and an image display device such as a liquid crystal display device.

(Touch panel, touch panel display device, and manufacturing method thereof)
The touch panel according to the present disclosure is a touch panel having at least the circuit wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure. Further, the touch panel according to the present disclosure preferably has at least a transparent substrate, electrodes, and an insulating layer or a protective layer.
The touch panel display device according to the present disclosure is a touch panel display device having at least the circuit wiring manufactured by the method for manufacturing the circuit wiring according to the present disclosure, and is preferably a touch panel display device having the touch panel according to the present disclosure.
The manufacturing method of the touch panel or the touch panel display device according to the present disclosure preferably includes the manufacturing method of the circuit wiring according to the present disclosure.
In the method for manufacturing a touch panel or a touch panel display device according to the present disclosure, the outermost layer of the photosensitive transfer material obtained by the method for manufacturing a photosensitive transfer material on the photosensitive resin layer side of the temporary support is brought into contact with the substrate. A step of pattern-exposing the photosensitive layer of the photosensitive transfer material after the bonding step, a step of developing the photosensitive layer after the exposure step to form a pattern, and a pattern of the bonding. It is preferable to include the step of etching the substrate in the region where is not arranged in this order. The details of each step are synonymous with the details of each step in the above-described circuit wiring manufacturing method, and the preferred embodiments are also the same.
As the detection method in the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, any known method such as a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Above all, the capacitance method is preferable.
The touch panel type includes a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7, and 8 of JP-A-2012-51751), and a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2013-168125). The one described in FIG. 19 of the publication, the one described in FIGS. 1 and 5 of Japanese Patent Application Laid-Open No. 2012-89102), OGS (One Glass Solution) type, TOR (Touch-on-Lens) type (for example, Japanese Patent Application Laid-Open No. 2012). (The one described in FIG. 2 of Japanese Patent Application Laid-Open No. 2013-5472), other configurations (for example, the one shown in FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871), various out-cell types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.) can be mentioned.
As the touch panel of this embodiment and the touch panel display device of this embodiment, "Latest Touch Panel Technology" (July 6, 2009, published by Techno Times Co., Ltd.), supervised by Yuji Mitani, "Touch Panel Technology and Development", The configurations disclosed in CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. can be applied.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. The materials, amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the embodiment of the present invention. Therefore, the scope of the embodiment of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Manufacturing example 1>
The temporary support having a specific layer is used as a base material by the following method. The following coating liquid for front surface is applied to one surface of the polyester film, and the coating liquid for back surface is applied to the other surface. It was produced by stretching according to the conditions.
The front surface refers to the surface of the temporary support on the side of the photosensitive resin layer, and the surface on the opposite side of the back surface.

[Coating liquid for forming a coating layer]
Each component was mixed with the composition shown below to obtain a coating liquid for the front surface and a coating liquid for the back surface, respectively. After adjusting the coating liquid, filtration with a 6 μm filter (F20, manufactured by Mare Filter Systems Co., Ltd.) and membrane deaeration (2x6 Radial Flow Superphobic, manufactured by Polypore Co., Ltd.) were carried out before coating.

-Coating liquid for front surface-
-Urethane polymer (Elastron H3DF, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., solid content 28% by mass) 164.9 parts-Block isocyanate (Duranate WM44-L70G, manufactured by Asahi Kasei Co., Ltd., solid content 70% by mass) 15.4 Part ・ Anionic surfactant (Rapisol A-90, manufactured by Nichiyu Co., Ltd., solid content 1% by mass water diluted) 41.7 parts ・ Sodium hydrogen carbonate (manufactured by Asahi Glass Co., Ltd., solid content 5% by mass water diluted) ) 3.2 parts ・ Carnauba wax dispersion (Cerozol 524, manufactured by Chukyo Yushi Co., Ltd., solid content 30% by mass) 4.9 parts ・ Organic tin water dispersion (Elastron Cat21, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Solid content 1% by mass water diluted) 32.5 parts, water 737.3 parts

-Coating liquid for back surface-
-Acrylic polymer (AS-563A, manufactured by Daicel FineChem Co., Ltd., solid content 27.5% by mass) 167 parts-Nonion-based surfactant (Naroacty CL95, manufactured by Sanyo Kasei Kogyo Co., Ltd., solid content 100% by mass) 0.7 parts ・ Anionic surfactant (Lapisol A-90, manufactured by Nichiyu Co., Ltd., solid content 1% by mass diluted with water) 114.4 parts ・ Carnauba wax dispersion (Cerozol 524, manufactured by Chukyo Yushi Co., Ltd.) , Solid content 30% by mass) 7 parts ・ Carbodiimide compound (Carbodilite V-02-L2, manufactured by Nisshinbo Co., Ltd., solid content 10% by mass water diluted) 20.9 parts ・ Matting agent (Snowtex XL, Nissan Chemical Co., Ltd.) ) Made, solid content 40% by mass) 2.8 parts, water 690.2 parts

[Extrusion molding]
Pellets of polyethylene terephthalate using the citric acid chelated organic titanium complex described in Japanese Patent No. 5575671 as a polymerization catalyst are dried to a water content of 50 ppm or less, and then charged into a hopper of a uniaxial kneading extruder having a diameter of 30 mm and 280. Melted at ° C and extruded. This melt was passed through a filter (pore diameter 3 μm) and then extruded from a die onto a cooling roll at 25 ° C. to obtain an unstretched film. The extruded melt was brought into close contact with the cooling roll by using an electrostatic application method.

[Stretching, coating]
The unstretched film extruded onto a cooling roll by the above method and solidified is sequentially biaxially stretched by the following method to obtain a temporary support having a base material (polyester film) having a thickness of 25 μm and a coating layer having a thickness of 80 nm. rice field.

(A) Vertical stretching An unstretched film was passed between two pairs of nip rolls having different peripheral speeds and stretched in the vertical direction (conveying direction). The preheating temperature was 75 ° C., the stretching temperature was 90 ° C., the stretching ratio was 3.4 times, and the stretching speed was 1300% / sec.

(B) Coating The front surface or back surface of the vertically stretched film was coated with the front surface coating solution or the back surface coating solution with a bar coater so as to have a thickness of 80 nm after film formation.

(C) Transverse stretching The film subjected to the above longitudinal stretching and coating was laterally stretched under the following conditions using a tenter.
<< Conditions >>
Preheating temperature: 110 ° C
Stretching temperature: 120 ° C
Stretching ratio: 4.2 times Stretching speed: 50% / sec

[Heat fixation, heat relaxation]
Subsequently, the stretched film after the longitudinal stretching and the transverse stretching were completed was heat-fixed under the following conditions. Further, after heat fixing, the tenter width was shortened and the heat was relaxed under the following conditions.
-Heat fixing conditions-
Heat fixing temperature: 227 ° C
Heat fixing time: 6 seconds-heat relaxation conditions-
Heat relaxation temperature: 190 ° C
Heat relaxation rate: 4%

〔Winding〕
After heat fixing and heat relaxation, both ends were trimmed, and the ends were extruded (knurled) with a width of 10 mm and then wound at a tension of 40 kg / m. The width was 1.5 m and the winding length was 6300 m. The obtained film roll was used as a temporary support for Production Example 1.
The base material of the obtained temporary support had a haze of 0.2, 150 ° C., a heat shrinkage rate by heating for 30 minutes, MD (Machine Direction): 1.0%, and TD (on the surface of the film). The direction orthogonal to the transport direction, Transverse Direction): 0.2%. The film thickness was 80 nm as measured from a cross-sectional TEM photograph. The haze was measured as an all-light haze using a haze meter (NDH2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.).

<Manufacturing Examples 2 to 10>
The composition of the coating liquid for the front surface was changed to the composition shown in Table 2, and the film thickness after film formation was changed to the value shown in Table 2 by adjusting the bar at the time of coating, in the same manner as in Production Example 1. A temporary support having a specific layer of Production Examples 2 to 10 was obtained.

<Manufacturing example 11>
Only the coating liquid for the front surface was applied to the front surface of the laterally stretched film after lateral stretching and before heat fixing so as to have a film thickness of 80 nm, except that the coating liquid for the back surface was not applied. A temporary support having a specific layer of Production Example 11 was obtained in the same manner as in Production Example 1.

<Manufacturing example 12>
A temporary support having no specific layer of Production Example 12 was obtained in the same manner as in Production Example 1 except that the coating liquid for the front surface was not applied.

In Table 1, the numerical values described in the column of the composition of the coating liquid for the front surface indicate the content (parts by mass) of each component, and the description of "-" indicates that the corresponding component is not contained. There is.
The details of the abbreviations in Table 1 are as follows.

-Urethane a: Elastron H3DF (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
-Urethane b: Superflex 150HS (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
-Urethane c: Takelac WS-5100 (manufactured by Mitsui Chemicals, Inc.)
-Na hydrogen carbonate: sodium hydrogen carbonate

<Manufacturing example 13>
The composition of the coating liquid for the front surface was changed as follows, and the bar at the time of coating was adjusted so that the film thickness after film formation was 80 nm. A temporary support having a specific layer was obtained.

(Coating liquid for front surface)
-Zyxen NC (manufactured by Sumitomo Seika Co., Ltd., solid content 28%, acid-modified polyolefin): 16.7 parts-Anionic surfactant (rapizol A-90, manufactured by NOF Corporation, solid content 1% by mass) Dilution with water): 5.6 parts, water: 77.7 parts

<Manufacturing example 14>
A temporary support having a specific layer of Production Example 14 was obtained in the same manner as in Production Example 13 except that the bar at the time of coating was adjusted so that the film thickness after film formation was 180 nm.

<Manufacturing example 15>
A temporary support having a specific layer of Production Example 15 was obtained in the same manner as in Production Example 13 except that Zyxen NC was changed to Chemipearl S120 (manufactured by Mitsui Chemicals, Inc., solid content 27%, acid-modified polyolefin). ..

(Example 1)
<Synthesis of MATTH copolymer>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C. and camphorsulfonic acid (4.6 g, 0.02 mol) was added. 2,3-Dihydrofuran (71 g, 1 mol, 1.0 eq) was added dropwise to the solution. After stirring for 1 hour, saturated sodium hydrogen carbonate (500 mL) is added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, filtered, and the insoluble material is concentrated under reduced pressure at 40 ° C. or lower to remove the residual yellow oil. Distillation under reduced pressure gave 125 g of tetrahydro-2H-furan-2-yl (MATTH) methacrylate having a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg as a colorless oil (yield 80 mol%).
Using this, the following MATTH copolymer was synthesized by the method described in 0248 to 0249 of JP2013-61616A. The weight average molecular weight of the obtained MATTH copolymer measured by gel permeation chromatography (GPC) was 14,000. The structure of the MATTH copolymer was as shown below (numerical values in the structural formula are molar ratios).

<Preparation of Photosensitive Resin Composition 1>
The photosensitive resin composition 1 was prepared by mixing each component so as to have the following composition.

-composition-
-MATTH copolymer: 93.9 parts-Photoacid generator (PAG-1): 5.0 parts-Surfactant (surfactant 1): 0.1 parts-Additive (additive 1): 1. .0 parts ・ Propylene glycol monomethyl ether acetate (PGMEA): 900 parts

PAG-1: Compound A-1 having the following structure
Surfactant 1: F-554, nonionic surfactant containing perfluoroalkyl group (manufactured by DIC)
Additive 1: (N-cyclohexyl-N'-[2- (4-morpholinyl) ethyl] thiourea abbreviation CHMETU)

The photosensitive resin composition 1 was applied onto the front surface of the temporary support produced in Production Example 1 using a slit-shaped nozzle so that the dry film thickness was 3.0 μm. Then, it was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (OSM-N manufactured by Tredegar) was pressure-bonded as a protective film to prepare a dry film resist. The obtained dry film resist was used as the photosensitive transfer material of Example 1.

(Examples 2 to 11 and 15 to 17)
Examples 2 to 11 and Examples 2 to 11 and the same as in Example 1 except that the temporary support produced in Production Examples 2 to 11 or 15 to 17 was used instead of the temporary support produced in Production Example 1. , 15 to 17 photosensitive transfer materials were obtained, respectively.

(Example 12)
The photosensitive transfer material of Example 12 was obtained in the same manner as in Example 1 except that the following photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.

<Preparation of Photosensitive Resin Composition 2>
The photosensitive resin composition 2 was prepared by mixing each component so as to have the following composition.

-composition-
-Novolak resin (meta-cresol: para-cresol = 30: 70 (mass ratio), molecular weight 5,500): 79.9 parts-Photosensitizer: naphthoquinone diazide described on page 4 of JP-A No. 4-2955. ,
Compound (1): 20 parts ・ Surfactant (hereinafter referred to as surfactant 1): 0.1 part ・ PGMEA: 900 parts Surfactant 1: F-554, perfluoroalkyl group-containing nonionic surfactant Agent (made by DIC)

(Example 13)
<Preparation of Composition 1 for Intermediate Layer>
Each component was mixed so as to have the following composition to prepare a composition 1 for an intermediate layer.

-composition-
-Distilled water: 39.0 parts-Methanol: 58.0 parts-Hypromellose methylcellulose (trade name: TC-5, manufactured by Shin-Etsu Chemical Co., Ltd.):
3.0 copies

The composition 1 for the intermediate layer was slit-coated on the temporary support produced in Production Example 1 so as to have a dry film thickness of 0.8 μm, and dried in a convection oven at 100 ° C. for 2 minutes. Next, the photosensitive resin composition 1 was applied onto the intermediate layer using a slit-shaped nozzle so that the dry film thickness was 3.0 μm. Then, it was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (OSM-N manufactured by Tredegar) was pressure-bonded as a protective film to prepare a dry film resist. The obtained dry film resist was used as the photosensitive transfer material of Example 13.

(Example 14)
<Preparation of Composition 2 for Intermediate Layer>
Each component was mixed so as to have the following composition to prepare a composition 2 for an intermediate layer.

-composition-
-Distilled water: 38.0 parts-Methanol: 57.0 parts-Polyvinyl alcohol (trade name: Kuraray Poval PVA-205, manufactured by Kuraray Co., Ltd.): 3.0 parts-Polyvinylpyrrolidone (trade name: Polyvinylpyrrolidone K-) 30, manufactured by Nippon Shokubai Co., Ltd.): 2.0 copies

The composition 2 for the intermediate layer was slit-coated on the temporary support produced in Production Example 1 so as to have a dry film thickness of 0.8 μm, and dried in a convection oven at 100 ° C. for 2 minutes. Next, the photosensitive resin composition 1 was applied onto the intermediate layer using a slit-shaped nozzle so that the dry film thickness was 3.0 μm. Then, it was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (OSM-N manufactured by Tredegar) was pressure-bonded as a protective film to prepare a dry film resist. The obtained dry film resist was used as the photosensitive transfer material of Example 14.

(Comparative Example 1)
The photosensitive transfer material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the temporary support prepared in Production Example 12 having no specific layer was used instead of the temporary support prepared in Production Example 1.

(Comparative Example 2)
<Preparation of Photosensitive Resin Composition 3>
A negative photosensitive composition 3 was prepared with the following formulation.
-Acrylic acid-methyl methacrylate copolymer (Mw20000, acid value 130 mgKOH / g): 30 parts-Propylene glycol monomethyl ether: 100 parts-Irgacure 907 (manufactured by BASF Corporation): 4.0 parts-trimethylolpropane triacrylate: 15.0 copies

The photosensitive transfer material of Comparative Example 2 was obtained in the same manner as in Example 1 except that the photosensitive resin composition 3 was used instead of the photosensitive resin composition 1.

(evaluation)
<Measurement of adhesion between specific layer and temporary support>
The photosensitive transfer material of each Example or Comparative Example was heat-laminated (100 ° C.) on a glass substrate, and the temporary support was peeled off to obtain a temporary support having a specific layer from the photosensitive transfer material.
A tape (Printac C, manufactured by Nitto Denko Co., Ltd.) is attached to the surface of the obtained temporary support having the specific layer on the specific layer side, and the width of the tape and the support is adjusted to 4.5 cm x 9 cm. cut out. This was peeled by 180 ° at a peeling speed of 500 mm / min using a Tencilon universal testing machine manufactured by A & D Co., Ltd., and the adhesion was measured.
After that, evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 2 or Table 3.
〔Evaluation criteria〕
5: Larger than the upper limit of measurement (22 gf / cm (0.22 N / cm)) 4: 10.0 gf / cm (0.098 N / cm) or more and less than 22.0 gf / cm 3: 5.0 gf / cm (0.049 N) / Cm) or more and less than 10.0 gf / cm 2: 1.0 gf / cm (0.0098 N / cm) or more and less than 5.0 gf / cm 1: 1.0 gf / cm or less

<Method for measuring isocyanate group content when the specific layer is a layer containing a urethane compound>
The photosensitive transfer material of each Example or Comparative Example was heat-laminated (100 ° C.) on a glass substrate, and the temporary support was peeled off to obtain a temporary support having a layer containing a urethane compound from the photosensitive transfer material. ..
The obtained temporary support was collected in an area of 20 cm × 20 cm, and the temporary support was extracted with 1 mL of dry toluene to extract a coating layer. When a layer was further formed on the surface of the temporary support opposite to the photosensitive resin layer, the corresponding layer was scraped off with a razor or the like as necessary for extraction. According to JIS K7301 (1995), excess dibutylamine is added to a dry toluene solution and reacted to generate the corresponding urea, and then back titration is performed by an indicator titration method using a hydrochloric acid standard solution, and the above dry solidification is performed. The isocyanate group content in the product was measured. Then, the isocyanate group content per unit volume of the layer containing the urethane compound was calculated together with the film thickness obtained from the cross-sectional TEM image.
The evaluation results are shown in Table 2 or Table 3.

<Cut float evaluation>
Next, copper was formed as a conductive layer on a PET substrate having a film thickness of 100 μm to a film thickness of 200 nm by a vacuum vapor deposition method to form a circuit forming substrate.
The protective film was peeled off from the photosensitive transfer material of each Example or Comparative Example, and the photosensitive transfer material from which the protective film was peeled off was placed on the copper layer at 100 ° C. at 4 m / m so that the photosensitive resin layer and the copper layer were in contact with each other. Laminating was performed under the conditions of a speed of min and a linear pressure of 0.6 MPa to prepare a laminated body in which a temporary support, a specific layer, and a photosensitive resin layer were laminated on a copper layer.
The laminate laminated on the copper layer was cut together with the copper layer using a utility knife. At that time, the distance from the cut end where air entered was measured, and the cut float was evaluated according to the following evaluation criteria. An NT cutter (manufactured by NT) was used for the cutter knife, and BA-160 was used for the blade. It can be said that the smaller the distance that air enters, the better the adhesion of the temporary support in the photosensitive transfer material. From a practical point of view, the evaluation result is preferably 3 to 5, more preferably 4 or 5, and even more preferably 5. The evaluation results are shown in Table 2 or Table 3.
〔Evaluation criteria〕
5: Less than 250 μm 4: 250 μm or more and less than 500 μm 3: 500 μm or more and less than 750 μm 2: 750 μm or more and less than 1000 μm 1: 1000 μm or more

<Evaluation of transferability>
The transferability was evaluated according to the following evaluation criteria for the transfer area when the temporary support was peeled off from the laminate laminated on the circuit-forming substrate under the conditions of 100 ° C., 2 m / min, and linear pressure of 0.6 MPa. The transfer area refers to the area of the portion where the photosensitive resin layer and the substrate are in close contact with each other, and the area value was calculated by taking a photograph of the transferred substrate and binarizing the image. It can be said that the larger the transfer area, the better the transferability of the photosensitive resin layer in the photosensitive low transfer material. From a practical point of view, the evaluation result is preferably 3 to 5, more preferably 4 or 5, and even more preferably 5. The evaluation results are shown in Table 2 or Table 3.
〔Evaluation criteria〕
5: 100%
4: 98% or more and less than 100% 3: 96% or more and less than 98% 2: 90% or more and less than 96% 1: 90% or less

<Edge roughness evaluation>
[Manufacturing of circuit wiring]
The protective film was peeled off from the photosensitive transfer material of each Example or Comparative Example, and the photosensitive transfer material from which the protective film was peeled off was placed on the circuit forming substrate at 100 ° C. so that the photosensitive resin layer and the copper layer were in contact with each other. Laminated under the conditions of a speed of 2 m / min and a linear pressure of 0.6 MPa, and a temporary support, a specific layer (intermediate layer if an intermediate layer), and a photosensitive resin layer are laminated on a copper layer. Was produced.
Contact pattern exposure was performed on this laminated body using a photomask provided with a line-and-space wiring pattern (opening: width ratio of light-shielding portion 1: 1) with a line width of 4 μm without peeling off the temporary support. went. For the exposure, a high-pressure mercury lamp having an i-line (365 nm) as the exposure main wavelength was used.
After peeling the temporary support from the exposed laminate, it was developed by shower development for 40 seconds using a 1.0 mass% sodium carbonate aqueous solution at 28 ° C., and washed with water. Next, the copper layer was etched with a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.) to obtain a copper wiring board. The obtained circuit wiring was used as the circuit wiring of each Example or Comparative Example.

[Pattern linearity (LWR)]
The pattern width of the portion randomly selected from the line and space pattern of the circuit wiring board having the circuit wiring of each of the obtained Examples or Comparative Examples was measured at 20 locations. The standard deviation σ was calculated from the obtained line width data, and the value obtained by multiplying the standard deviation σ by 3 was defined as LWR (Line Wide Noise) and used as an index of pattern linearity.
By definition, the smaller the LWR, the smaller the line width fluctuation, which is preferable. For a pattern with a line width of 4 μm, it is evaluated as follows according to the value of LWR. It can be said that the smaller the LWR value, the better the pattern linearity. Further, it can be said that the better the pattern linearity, the better the roughness of the line width (edge roughness). From a practical point of view, the evaluation result is preferably 3 to 5, more preferably 4 or 5, and even more preferably 5. The evaluation results are shown in Table 2 or Table 3.
-Evaluation criteria-
5: LWR <300 nm: Very preferable as a circuit wiring board.
4: 300 nm ≤ LWR <500 nm: Preferable as a circuit wiring board.
3: 500 nm ≤ LWR <700 nm: Can be used as a circuit wiring board.
2: 700 nm ≤ LWR <1000 nm: There is a possibility that defects may occur, which is not preferable.
1: 1000 nm ≦ LWR: The line width fluctuation is large and leads to a circuit failure, which is not preferable.

From Tables 2 and 3, it can be seen that the photosensitive transfer material according to the examples is excellent in adhesion and transferability, and is also excellent in pattern linearity.
The photosensitive transfer material without a specific layer described in Comparative Example 1 has a low evaluation of "cut float" and is considered to be inferior in adhesion.
Further, the photosensitive transfer material having a negative photosensitive resin layer described in Comparative Example 2 has a low evaluation of "transferability" and "pattern linearity (LWR)", and is inferior in transferability and edge roughness. rice field.

The disclosure of Japanese Patent Application No. 2017-190833 filed on September 29, 2017 and the disclosure of Japanese Patent Application No. 2018-168471 filed on September 10, 2018 are as a whole. Incorporated herein by reference.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Is incorporated herein by reference.

10 Temporary support, 12 Photosensitive resin layer, 12A 1st pattern, 12B 2nd pattern, 14 Specific layer, 16 Cover film, 20 Circuit forming substrate, 22 Base material, 24 1st conductive layer, 24A 1st conductive layer (After the first etching step), 24B 1st conductive layer (after the 2nd etching step), 26 2nd conductive layer, 26A 2nd conductive layer (after the 1st etching step and the 2nd etching step), 30 masks, 40 masks , 100 Photosensitive transfer material, SL solid line part, G gray part, DL dotted line part

Claims (8)

Temporary support and
It has a polymer containing a structural unit having a group in which the acid group is protected by an acid-degradable group, and a photosensitive resin layer containing a photoacid generator.
At least one layer containing a urethane compound or a modified polyolefin is provided between the temporary support and the photosensitive resin layer.
A photosensitive transfer material in which the modified polyolefin is an acid-modified polyolefin when the layer containing the urethane compound or the modified polyolefin is a layer containing the modified polyolefin. The photosensitive transfer material according to claim 1, wherein the film thickness of the layer containing the urethane compound or the modified polyolefin is 10 nm or more and 500 nm or less. When the layer containing the urethane compound or the modified polyolefin is a layer containing the urethane compound, the isocyanate group content with respect to the total volume of the layer containing the urethane compound is 0.01 mol / m ³ to 0.40 mol / m. ^3. The photosensitive transfer material according to claim 1 or 2. The temporary support is in contact with the layer containing the urethane compound or the modified polyolefin, and the adhesion between the layer containing the urethane compound or the modified polyolefin and the temporary support is 0.22 N / cm or more. The photosensitive transfer material according to any one of claims 1 to 3. When the layer containing the urethane compound or the modified polyolefin is a layer containing the urethane compound, the urethane compound contained in the layer containing the urethane compound is a reaction product obtained by at least reacting the alkylene diisocyanate compound with the diol compound. The photosensitive transfer material according to any one of claims 1 to 4, which comprises. The photosensitive transfer material according to any one of claims 1 to 5, wherein the structural unit having a group in which the acid group is protected by an acid-degradable group is a structural unit represented by the following formula A1. ..

In formula A1, R ³¹ and R ³² independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group or an aryl group. An aryl group may be represented, and R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, where R ³⁴ represents a hydrogen atom or a methyl group and X ⁰ represents a single bond or an arylene group. A step of contacting and bonding the outermost layer of the photosensitive transfer material according to any one of claims 1 to 6 on the photosensitive resin layer side of the temporary support to the substrate.
A step of pattern-exposing the photosensitive resin layer of the photosensitive transfer material after the bonding step, and a step of pattern exposure.
The step of developing the photosensitive resin layer after the exposure step to form a pattern, and the step of forming a pattern.
A step of etching a substrate in a region where the pattern is not arranged is included.
How to manufacture circuit wiring. The outermost layer of the photosensitive transfer material of the photosensitive transfer material according to any one of claims 1 to 6 on the photosensitive resin layer side of the temporary support is brought into contact with the substrate and attached to the substrate. The process of matching and
A step of pattern-exposing the photosensitive resin layer of the photosensitive transfer material after the bonding step,
The step of developing the photosensitive resin layer after the exposure step to form a pattern, and the step of forming a pattern.
A step of etching a substrate in a region where the pattern is not arranged is included.
How to manufacture a touch panel.

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