WO2020054660A1

WO2020054660A1 - Photosensitive transfer material, method for producing circuit wiring line, method for producing touch panel, method for producing resin pattern, and film

Info

Publication number: WO2020054660A1
Application number: PCT/JP2019/035363
Authority: WO
Inventors: 一真両角; 悠樹豊嶋; 漢那　慎一
Original assignee: 富士フイルム株式会社
Priority date: 2018-09-12
Filing date: 2019-09-09
Publication date: 2020-03-19
Also published as: JPWO2020054660A1; JP7065991B2; CN112470074A; TW202017748A

Abstract

A photosensitive transfer material which sequentially comprises a temporary support, a positive photosensitive resin layer and a protective film in this order, and wherein a surface of the protective film satisfies the requirements (A) and (B) described below, said surface being in contact with the positive photosensitive resin layer; and an application of this photosensitive transfer material. (A) The water contact angle is 75° or more. (B) The surface roughness Ra is 45 nm or less.

Description

Photosensitive transfer material, method for manufacturing circuit wiring, method for manufacturing touch panel, method for manufacturing resin pattern, and film

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

For example, in a display device having a touch panel such as a capacitance type input device (for example, an organic electroluminescence (EL) display device, a liquid crystal display device, etc.), an electrode pattern corresponding to a sensor of a viewing portion, a peripheral wiring portion In addition, circuit wiring such as a wiring of a take-out wiring part is provided inside the touch panel.
For forming such a patterned circuit wiring, use of a photosensitive transfer material also called a dry film resist is being studied because the number of steps for obtaining a required pattern shape is small. . Then, in order to protect the photosensitive resin layer contained in the photosensitive transfer material, a protective film is usually provided on the photosensitive resin layer.

For example, WO 2014/175274 has a support film, a polypropylene film, and a photosensitive layer disposed between the support film and the polypropylene film, wherein the polypropylene film is provided on the photosensitive layer side. A photosensitive element is disclosed that has a first surface and a second surface opposite the first surface, wherein the first surface and the second surface are smooth.

Japanese Patent Application Laid-Open No. 2007-293006 discloses a photosensitive resin transfer material having, in this order, a photosensitive resin layer containing a colorant and a photosensitive resin and a cover film on a support. A photosensitive resin transfer material having an intermediate layer between the film and the photosensitive resin layer and a cover film having an adhesive strength in the range of 1.5 to 8.0 g / 10 cm is disclosed.

JP-A-2018-2947 discloses a protective film characterized in that at least one surface has a surface average roughness (Sa) of a resin having a thickness of 15 nm or less.

However, as described below, a technique that can achieve both improvement of the peelability of the protective film and reduction of the pattern failure has not yet been established.
The peelability of the protective film can be improved, for example, by providing irregularities on the surface of the protective film. On the other hand, if irregularities are provided on the surface of the protective film, the irregularities of the protective film are transferred to the surface of the photosensitive resin layer in contact with the protective film, and irregularities may be formed on the surface of the photosensitive resin layer. When a photosensitive resin layer having irregularities is attached to a substrate, bubbles remain between the photosensitive resin layer and the substrate, and thus a pattern failure such as a defect in a formed pattern or a defective shape occurs.
Further, since the positive photosensitive resin layer usually has a high resin content, it has poor flexibility compared to the negative photosensitive resin layer. The positive photosensitive resin layer, which has less flexibility than the negative photosensitive resin layer, is difficult to deform following the shape of the substrate surface, so the positive photosensitive resin layer with irregularities formed on the surface is attached to the substrate. When combined, air bubbles are likely to remain between the positive photosensitive resin layer and the substrate. For this reason, the frequency of occurrence of the pattern failure becomes remarkable when a photosensitive transfer material having a positive photosensitive resin layer is applied.

The present disclosure has been made in view of the above circumstances.
An object of one embodiment of the present disclosure is to provide a photosensitive transfer material that is excellent in peelability of a protective film and that can reduce pattern failure.
Another embodiment of the present disclosure aims to provide a method for manufacturing a circuit wiring with reduced pattern failure.
Another embodiment of the present disclosure aims to provide a method for manufacturing a touch panel with reduced pattern failure.
Another embodiment of the present disclosure aims to provide a method for manufacturing a resin pattern with reduced pattern failure.
Another embodiment of the present disclosure aims to provide a film that is excellent in releasability and that can reduce the transfer of unevenness to the surface of an adherend.

Means for solving the above problems include the following aspects.
<1> A temporary support, a positive photosensitive resin layer, and a protective film are provided in this order, and the surface of the protective film on the side in contact with the positive photosensitive resin layer has the following (A) And a photosensitive transfer material satisfying (B).
(A) The water contact angle is 75 ° or more.
(B) The surface roughness Ra is 45 nm or less.
<2> The photosensitive transfer material according to <1>, wherein the surface roughness Ra is 25 nm or less.
<3> The protective film has a base material and an undercoat layer, and the outermost layer of the protective film on the side in contact with the positive photosensitive resin layer is the undercoat layer <1> or <2> The photosensitive transfer material described in any one of the above.
<4> a biaxially stretched film in which the protective film is a uniaxially stretched film that is a stretched product in the first stretching direction and is stretched along a film surface in a second stretching direction orthogonal to the first stretching direction; An undercoat layer that is a stretched product in the second stretching direction of the coating layer formed on one surface of the stretched film, and the protective film, the outermost layer on the side in contact with the positive photosensitive resin layer, The photosensitive transfer material according to <1> or <2>, which is the undercoat layer.
<5> The photosensitive transfer material according to <3> or <4>, wherein the undercoat layer contains an acid-modified polyolefin.
<6> The photosensitive transfer material according to <5>, wherein the acid-modified polyolefin has an acid group, and at least one of the acid groups is an alkali metal salt.
<7> The photosensitive transfer material according to any one of <3> to <6>, wherein the undercoat layer has a thickness of 10 nm to 550 nm.
<8> The photosensitive transfer material according to any one of <1> to <7>, having a water-soluble resin layer between the temporary support and the positive photosensitive resin layer.
<9> The photosensitive transfer material according to any one of <1> to <8>, wherein the positive photosensitive resin layer contains an acid-decomposable resin.
<10> Any of <1> to <9>, wherein the positive photosensitive resin layer contains a polymer component at a ratio of 80% by mass to 98% by mass based on the total solid content of the positive photosensitive resin layer. The photosensitive transfer material according to any one of the above.
<11> a step of peeling off the protective film of the photosensitive transfer material according to any one of <1> to <10>, and the positive photosensitive layer of the photosensitive transfer material with respect to the temporary support; Bonding the outermost layer on the side having the resin layer to the substrate having the conductive layer; pattern-exposing the positive-type photosensitive resin layer of the photosensitive transfer material after the bonding step; and A method for manufacturing circuit wiring, comprising: a step of developing the positive photosensitive resin layer after the step of forming a resin pattern to form a resin pattern; and a step of etching a substrate in a region where the resin pattern is not arranged.
<12> The step of removing the protective film of the photosensitive transfer material according to any one of <1> to <10>, and a positive photosensitive resin of the photosensitive transfer material with respect to the temporary support. Bonding the outermost layer on the side having the layer to the substrate having the conductive layer, pattern-exposing the positive-type photosensitive resin layer of the photosensitive transfer material after the bonding step, and performing the pattern exposure A method for manufacturing a touch panel, comprising: a step of developing the positive photosensitive resin layer after the step to form a resin pattern; and a step of etching a substrate in a region where the resin pattern is not arranged.
<13> a step of removing the protective film of the photosensitive transfer material according to any one of <1> to <10>, and a positive photosensitive resin of the photosensitive transfer material with respect to the temporary support Bonding the outermost layer on the side having the layer to the substrate, pattern-exposing the positive-type photosensitive resin layer of the photosensitive transfer material after the bonding step, and performing the pattern-exposing step. Developing the positive photosensitive resin layer to form a resin pattern.
<14> a biaxially stretched polyethylene terephthalate film in which a uniaxially stretched polyethylene terephthalate film, which is a stretched product in the first stretching direction, is stretched along a film surface in a second stretching direction orthogonal to the first stretching direction; A film formed on one surface of the polyethylene terephthalate film, the undercoat layer being a stretched product in the second stretching direction, wherein the undercoat layer satisfies the following (A) and (B).
(A) The water contact angle is 75 ° or more.
(B) The surface roughness Ra is 45 nm or less.
<15> The film according to <14>, wherein the undercoat layer contains an acid-modified polyolefin.
<16> having a first resin layer and a second resin layer provided on the first resin layer, wherein the first resin layer contains polyester, and the surface of the second resin layer is A film satisfying the following (A) and (B).
(A) The water contact angle is 75 ° or more.
(B) The surface roughness Ra is 45 nm or less.
<17> The film according to <16>, wherein the thickness of the first resin layer is 5 μm to 200 μm, and the thickness of the second resin layer is 10 nm to 550 nm.
<18> The film according to any one of <14> to <17>, which is a protective film.

According to an embodiment of the present disclosure, it is possible to provide a photosensitive transfer material that is excellent in peelability of a protective film and that can reduce pattern failure.
According to another embodiment of the present disclosure, it is possible to provide a method of manufacturing a circuit wiring with reduced pattern failure.
According to another embodiment of the present disclosure, it is possible to provide a method of manufacturing a touch panel with reduced pattern failure.
According to another embodiment of the present disclosure, it is possible to provide a method for manufacturing a resin pattern with reduced pattern failure.
According to another embodiment of the present disclosure, it is possible to provide a film that is excellent in releasability and that can reduce the transfer of unevenness to the surface of an adherend.

FIG. 1 is a schematic diagram illustrating an example of a layer configuration of the photosensitive transfer material according to the present disclosure. FIG. 2 is a schematic diagram illustrating an example of a method for manufacturing a circuit wiring according to the present disclosure. FIG. 3 is a schematic diagram showing the pattern A. FIG. 4 is a schematic diagram showing the pattern B.

Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the present disclosure.

In the present disclosure, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit. In the numerical ranges described stepwise in the present disclosure, an upper limit or a lower limit described in a certain numerical range may be replaced with an upper limit or a lower limit of another numerical range described in a stepwise manner. Further, in the numerical ranges described in the present disclosure, the upper limit or the lower limit described in a certain numerical range may be replaced with the value shown in the embodiment.
In the present disclosure, “(meth) acryl” represents both acryl and methacryl, or either one, and “(meth) acrylate” means both acrylate and methacrylate, or either one. .
In the present disclosure, the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, means the total amount of the plurality of substances present in the composition .
In the present disclosure, the term “step” includes not only an independent step but also the term as long as the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps. .
In the notation of a group (atomic group) in the present disclosure, the notation of not indicating substituted or unsubstituted includes not only a group having no substituent but also a group 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).
In the present disclosure, “% by mass” and “% by weight” have the same meaning, and “parts by mass” and “parts by weight” have the same meaning.
In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In the present disclosure, a chemical structural formula may be described as a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, the total solid content refers to the total mass of components excluding volatile components such as solvents.

<Photosensitive transfer material>
The photosensitive transfer material according to the present disclosure has a temporary support, a positive photosensitive resin layer, and a protective film in this order, and the surface of the protective film on the side in contact with the positive photosensitive resin layer. Satisfies the following (A) and (B).
(A) The water contact angle is 75 ° or more.
(B) The surface roughness Ra is 45 nm or less.

ADVANTAGE OF THE INVENTION According to the photosensitive transfer material which concerns on this indication, it is excellent in the peelability of a protective film, and can reduce a pattern failure. The reason why the photosensitive transfer material according to the present disclosure exhibits such an effect is not clear, but is presumed as follows.
In order to satisfy the above (A) and (B), the protective film applied to the photosensitive transfer material according to the present disclosure lowers the surface energy of the surface in contact with the positive photosensitive resin layer and reduces unevenness. Can be reduced. And since the unevenness of the surface of the protective film can be reduced, the transfer of the unevenness of the protective film to the surface of the positive photosensitive resin layer can be suppressed. For this reason, it is considered that the photosensitive transfer material according to the present disclosure can achieve both improvement of the releasability of the protective film and reduction of the pattern failure.
On the other hand, for example, in the protective film applied to the photosensitive transfer material described in the above-mentioned WO 2014/175274 and JP-A-2007-293006, the above (A) and (B) are satisfied. It is considered impossible. In the above-mentioned WO 2014/175274, JP-A-2007-293006, and JP-A-2018-2947, the photosensitive resin layer to which the protective film is applied is not a positive photosensitive resin layer. No studies have been made on the case where a protective film is applied to a photosensitive transfer material having a positive photosensitive resin layer. In the case of a conventionally proposed protective film, when applied to a photosensitive transfer material having a positive photosensitive resin layer that is less flexible than a negative photosensitive resin layer, the peelability of the protective film is improved and the pattern is improved. It is considered that the reduction of failure cannot be achieved at the same time.

FIG. 1 schematically illustrates an example of a layer configuration of the photosensitive transfer material according to the present disclosure. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 12, a positive photosensitive resin layer 14, and a protective film 16 are laminated in this order.

[Temporary support]
The photosensitive transfer material according to the present disclosure has a temporary support.
The temporary support is a support that supports the positive photosensitive resin layer and can be separated from the positive photosensitive resin layer.
The temporary support used in the present disclosure preferably has light transmittance from the viewpoint that the positive photosensitive resin layer can be exposed through the temporary support when the positive photosensitive resin layer is subjected to pattern exposure.
Having the light transmittance means that the transmittance of the main wavelength of the light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of the light used for pattern exposure is determined from the viewpoint of improving the exposure sensitivity. Therefore, it is preferably at least 60%, more preferably at least 70%. As a method of measuring the transmittance, a method of measuring by using MCPD Series manufactured by Otsuka Electronics Co., Ltd. may be mentioned.
Examples of the temporary support include a glass substrate, a resin film, and paper, and a resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include a cycloolefin polymer film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a polyethylene terephthalate film is preferred from the viewpoint of solvent resistance and optical characteristics.

The thickness of the temporary support is not particularly limited, but is preferably in the range of 5 μm to 200 μm, and 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 may be selected according to the material in view of the strength as the support, the flexibility required for bonding to the substrate, the light transmittance required in the first exposure step, and the like.

好ましい Preferred embodiments of the temporary support are described in, for example, paragraphs 0017 to 0018 of JP-A-2014-85643, the contents of which are incorporated herein.

[Positive photosensitive resin layer]
The photosensitive transfer material according to the present disclosure has a positive photosensitive resin layer.
The positive photosensitive resin layer used in the present disclosure is not particularly limited, and a known positive photosensitive resin layer can be used. The positive photosensitive resin layer is preferably a positive photosensitive resin layer containing an acid-decomposable resin from the viewpoint of sensitivity, resolution and removability, and is preferably an acid group protected by an acid-decomposable group. More preferably, it is a chemically amplified positive photosensitive resin layer containing a polymer having a structural unit having the formula: and a photoacid generator. The acid-decomposable resin is not limited as long as it is a resin that can be decomposed by the action of an acid, and examples thereof include a polymer having a structural unit having an acid group protected by an acid-decomposable group described below.
Photoacid generators such as onium salts and oxime sulfonate compounds described below generate an acid in response to actinic radiation (actinic rays). The generated acid acts as a catalyst for the deprotection of the protected acid groups in the polymer. For this reason, the acid generated by the action of one photon contributes to a large number of deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as a power of ten. As a result, high sensitivity can be obtained.
On the other hand, when a quinonediazide compound is used as a photoacid generator sensitive to actinic radiation, a carboxy group is generated by a sequential photochemical reaction, but the quantum yield is always 1 or less, and does not correspond to a chemically amplified type.

(Polymer having a structural unit having an acid group protected by an acid-decomposable group)
The positive photosensitive resin layer is a polymer having a structural unit having an acid group protected by an acid-decomposable group (hereinafter, also referred to as “structural unit A”) (hereinafter, also simply referred to as “polymer A1”). ) Is preferable.
Further, the positive photosensitive resin layer may contain another polymer in addition to the polymer A1. The other polymer is a polymer that does not contain a structural unit having an acid group protected by an acid-decomposable group, as described later. Details of other polymers will be described later. In the present disclosure, a polymer (including an acid-decomposable resin) contained in the positive photosensitive resin layer is collectively referred to as a “polymer component”. For example, when the positive photosensitive resin layer contains the polymer A1, the "polymer component" refers to the polymer A1. When the positive photosensitive resin layer contains the polymer A1 and another polymer, the “polymer component” refers to both the polymer A1 and the other polymer. However, a compound corresponding to a surfactant, a cross-linking agent, or a dispersant described below is not included in the “polymer component”.
In the polymer A1, an acid group protected by an acid-decomposable group in the polymer A1 undergoes a deprotection reaction to become an acid group by the action of a catalytic amount of an acidic substance generated by exposure. This acid group enables dissolution in a developer.
Further, the polymer A1 preferably further has a structural unit having an acid group (hereinafter, also referred to as “structural unit B”).
Further, the polymer A1 is preferably a non-particle-shaped polymer (also referred to as a “binder polymer”) from the viewpoints of pattern shape, solubility in a developer, and transferability.
Further, it is preferable that all of the polymers contained in the above-mentioned polymer component are each a polymer having at least a constituent unit having an acid group described below.

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 (meth) acrylate. In addition, you may have the structural unit other than the structural unit derived from (meth) acrylic acid or (meth) acrylic acid ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.

The positive photosensitive resin layer is represented by a structural unit represented by the following formula A1 or a structural unit represented by the following formula A2 as a polymer component from the viewpoints of suppressing deformation of a pattern shape, solubility in a developing solution, and transferability. It is preferable to include a polymer having a structural unit and at least one structural unit selected from the group consisting of structural units represented by the following formula A3. Further, from the same viewpoint, as the polymer component, at least one selected from the group consisting of a structural unit represented by the following formula A1, a structural unit represented by the following formula A2, and a structural unit represented by the following formula A3 It is more preferable to include one kind of constituent unit and a polymer having a constituent unit having an acid group.
The polymer A1 contained in the positive photosensitive resin layer may be only one kind or two or more kinds.
Hereinafter, preferred embodiments of the structural unit A will be described.

(Structural unit A)
The polymer component preferably includes a polymer A1 having at least a structural unit (structural unit A) having an acid group protected by an acid-decomposable group. When the polymer component contains a polymer having the structural unit A, a highly sensitive chemically amplified positive photosensitive resin layer can be obtained.
As the “acid group protected by an acid-decomposable group” in the present disclosure, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited. Specific examples of the acid group include a carboxy group and a phenolic hydroxyl group. The acid group protected by an acid-decomposable group includes a group that is relatively easily decomposed by an acid (for example, an acetal-based functional group such as a tetrahydropyranyl ester group and a tetrahydrofuranyl ester group), and is relatively hard to be decomposed by an acid. Groups (eg, a tertiary alkyl group such as a tert-butyl ester group, a tertiary alkyl carbonate group such as a tert-butyl carbonate group) and the like can be used.
Among these, the acid-decomposable group is preferably a group having a structure protected in the form of an acetal.
Further, the acid-decomposable group is preferably an acid-decomposable group having a molecular weight of 300 or less from the viewpoint of suppressing variation in line width in the obtained circuit wiring.

The structural unit having the acid group protected by the acid-decomposable group (structural unit A) is represented by a structural unit represented by the following formula A1, a structural unit represented by the following formula A2, and a structural unit represented by the following formula A3 It is preferably at least one type of structural unit selected from the group consisting of structural units, and from the viewpoint of sensitivity and resolution, more preferably a structural unit represented by the formula A3 described below, and more preferably a formula A3- The structural unit represented by 3 is particularly preferred.

In Formula A1, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group, and R ¹³ is an alkyl group or Represents an aryl group, R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, R ¹⁴ represents a hydrogen atom or a methyl group, and X ¹ represents a single bond or a divalent linking group R ¹⁵ represents a substituent, and n represents an integer of 0 to 4.
In Formula A2, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ²¹ and R ²² is an alkyl group or an aryl group, and R ²³ is an alkyl group or Represents an aryl group, R ²¹ or R ²² and R ²³ may be linked to form a cyclic ether, and R ²⁴ is each independently a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, Represents an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.
In Formula A3, R ³¹ and R ³² each 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 Represents an aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, X ⁰ represents a single bond or an arylene group, Y represents -S- or -O-.

-Preferred embodiment of the structural unit represented by Formula A1-
In the formula A1, when R ¹¹ or R ¹² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹¹ or R ¹² is an aryl group, a phenyl group is preferred. Each of R ¹¹ and R ¹² is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula A1, R ¹³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Further, the alkyl group and the aryl group in R ¹¹ to R ¹³ may have a substituent.
In Formula A1, R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, and it is preferable that R ¹¹ or R ¹² and R ¹³ be 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 ¹ 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 have a linear structure, a branched structure or a cyclic structure, and may have a substituent. The carbon number of the alkylene group is preferably 1 to 10, more preferably 1 to 4. When X ¹ contains —C (＝ O) O—, a mode in which the carbon atom contained in —C (＝ O) O— and the carbon atom to which R ¹⁴ is bonded is directly bonded is preferable. When ^{containing, -C (= O) NR N} - - X 1 is -C (= O) NR ^N and carbon atoms contained in ^a mode in which the carbon atom ^{to which R 14} is bonded is directly bonded is preferable. R ^N represents an alkyl group or a hydrogen atom, preferably an alkyl group or a hydrogen atom having 1 to 4 carbon atoms, more preferably a hydrogen atom.
In the formula A1, the group containing R ¹¹ to R ¹³ and X ¹ are preferably bonded to each other at the para position.
In the formula A1, R ¹⁵ represents a substituent, and is preferably an alkyl group or a halogen atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4.
In the formula A1, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the formula A1, R ¹⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the polymer A1 can be further reduced.
More specifically, the content of the structural unit in which R ¹⁴ in the formula A1 is a hydrogen atom is preferably 20% by mass or more based on the total content of the structural units A contained in the polymer A1.
The content (content ratio: mass ratio) of the structural unit in the structural unit A in which R ¹⁴ in the formula A1 is a hydrogen atom is calculated from a ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement by an ordinary method. It can be confirmed from the peak intensity ratio.

中でも Among the structural units represented by the formula A1, a structural unit represented by the following formula A1-2 is more preferable from the viewpoint of suppressing deformation of the pattern shape.

In Formula A1-2, R ^B4 represents a hydrogen atom or a methyl group, R ^B5 to R ^B11 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^B12 represents a substituent, and n Represents an integer of 0 to 4.
In the formula ^{A1-2, R B4} is preferably a hydrogen atom.
In formula A1-2, R ^B5 to R ^B11 are preferably hydrogen atoms.
In the formula ^{A1-2, R B12} represents a substituent, an alkyl group or a halogen atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4.
In the formula A1-2, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

Preferred specific examples of the structural unit represented by Formula A1 include the following structural units. Incidentally, R ^B4 in the structural unit of the following represents a hydrogen atom or a methyl group.

-Preferred embodiment of the structural unit represented by Formula A2-
In the formula A2, when R ²¹ and R ²² are an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ²¹ and R ²² are an aryl group, a phenyl group is preferred. Each of R ²¹ and R ²² is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably one is a hydrogen atom and the other is an alkyl group having 1 to 4 carbon atoms.
In the general formula A2, R ²³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
R ²¹ or R ²² and R ²³ may be linked to form a cyclic ether.
In the formula A2, R ²⁴ is preferably each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. R ²⁴ may be further substituted by the same group as R ²⁴ .
In the formula A2, m is preferably 1 or 2, and more preferably 1.

好ましい Preferable specific examples of the structural unit represented by Formula A2 include the following structural units.

-Preferred embodiment of the structural unit represented by Formula A3-
In the formula A3, 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 preferred. Each of R ³¹ and R ³² is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In Formula A3, R ³³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Further, the alkyl group and the aryl group in R ³¹ to R ³³ may have a substituent.
In Formula A3, 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 be 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, X ⁰ represents a single bond or an arylene group, and a single bond is preferable. The arylene group may have a substituent.
In Formula A3, Y represents —S— or —O—, and is preferably —O— from the viewpoint of exposure sensitivity.

The structural unit represented by the formula A3 is a structural unit having a carboxy group protected by an acid-decomposable group. When the polymer A1 contains the structural unit represented by the formula A3, the sensitivity during pattern formation is excellent, and the resolution is more excellent.
In the formula A3, 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 further reduced.
More specifically, the amount of the structural unit in which R ³⁴ in the formula A3 is a hydrogen atom is preferably 20% by mass or more based on the total amount of the structural unit represented by the formula A3 contained in the polymer A1.
Incidentally, in the structural unit represented by the formula A3, the content of the structural unit ^{R 34} is a hydrogen atom in the formula A1 (content: weight ^ratio), 13 C-nuclear magnetic resonance spectrum (NMR) normal from the measurement It can be confirmed by the intensity ratio of the peak intensity calculated by the method.

Among the structural units represented by the formula A3, as a structural unit having an acid group protected by an acid-decomposable group, the structural unit represented by the following formula A is more preferred from the viewpoint of further increasing the exposure sensitivity during pattern formation. preferable.

In Formula A, R ³¹ , R ³² , R ³³ , R ³⁴ and X ⁰ have the same meanings as R ³¹ , R ³² , R ³³ , R ³⁴ and X ⁰ in Formula A3, respectively, and the preferred embodiments are also the same. .

構成 Among the structural units represented by the formula A3, the structural unit represented by the following formula A3-3 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.

In Formula A3-3, R ³⁴ represents a hydrogen atom or a methyl group, and R ³⁵ to R ⁴¹ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula ^{A3-3, R 34} is preferably a hydrogen atom.
In Formula A3-3, R ³⁵ to R ⁴¹ are preferably a hydrogen atom.

Preferred specific examples of the structural unit having a carboxy group protected by an acid-decomposable group represented by the formula A3 include the following structural units. Incidentally, R ³⁴ in the structural unit of the following represents a hydrogen atom or a methyl group.

The structural unit A contained in the polymer A1 may be one type or two or more types.
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 to the total mass of the polymer A1. More preferably, it is 70% by mass.
The content (content ratio: mass ratio) of the structural unit A in the polymer A1 can be confirmed by an intensity ratio of peak intensities calculated by a conventional method from ¹³ C-NMR measurement.
Further, after all the polymer components are decomposed 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 from 10% by mass to 80% by mass, particularly preferably from 30% by mass to 70% by mass.

(Structural unit B)
The polymer A1 preferably contains a structural unit having an acid group (structural unit B).
The structural unit B is a structural unit having an acid group not protected by a protecting group, for example, an acid group not protected by an acid-decomposable group, that is, an acid group having no protecting group. When the polymer A1 contains the structural unit B, the sensitivity at the time of pattern formation is improved, and the polymer A1 is easily dissolved in an alkaline developing solution in a developing step after pattern exposure, so that the development time can be reduced.
The acid group in the present specification means a proton dissociable 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 (structural unit B) using a monomer capable of forming an acid group. In light of improvement in sensitivity, the pKa of the acid group is preferably equal to or less than 10 and more preferably equal to or less than 6. 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 phosphono group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group. Among them, at least one acid group selected from the group consisting of a carboxy group and a phenolic hydroxyl group is preferable.
The introduction of the structural unit having an acid group into the polymer A1 can be performed by copolymerizing a monomer having an acid group or 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 a structural unit derived from a styrene compound or a structural unit derived from a vinyl compound in which an acid group is substituted, or derived from (meth) acrylic acid. More preferably, 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, and 4-carboxystyrene. Examples of the monomer having a phenolic hydroxyl group include p- Examples include hydroxystyrene and 4-hydroxyphenyl methacrylate, and examples of the monomer having an acid anhydride structure include maleic anhydride.

As the structural unit B, a structural unit having a carboxy group or a structural unit having a phenolic hydroxyl group is preferable from the viewpoint that sensitivity during pattern formation becomes better.
The monomer having an acid group capable of forming the structural unit B is not limited to the examples described above.

The structural unit B contained in the polymer A1 may be only one type or two or more types.
The polymer A1 preferably contains 0.1% to 20% by mass, and preferably 0.5% to 15% by mass of a structural unit having an acid group (structural unit B) based on the total mass of the polymer A1. More preferably, the content is 1% by mass to 10% by mass. When it is in the above range, the pattern formability will be better.
The content (content ratio: mass ratio) of the structural unit B in the polymer A1 can be confirmed by an intensity ratio of peak intensities calculated by a conventional method from ¹³ C-NMR measurement.

(Other constituent units)
The polymer A1 does not impair the effect of the photosensitive transfer material according to the present disclosure on other structural units (hereinafter, sometimes referred to as structural units C) other than the structural units A and B described above. It may be included in the range.
The monomer forming the structural unit C is not particularly limited, and examples thereof include styrenes, alkyl (meth) acrylate, cyclic alkyl (meth) acrylate, aryl (meth) acrylate, and unsaturated dicarboxylic diester. , Bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, groups having an aliphatic cyclic skeleton, other Saturated compounds can be mentioned.
Various characteristics 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, by appropriately using the structural unit C, the glass transition temperature of the polymer A1 can be easily adjusted.
By setting the glass transition temperature to 120 ° C. or lower, the positive photosensitive resin layer containing the polymer A1 can maintain good transferability and removability from the temporary support at a favorable level, while maintaining good transferability. Better resolution and sensitivity.
The polymer A1 may include only one type of the structural unit C, or may include two or more types of the structural unit C.

The structural unit C is, specifically, styrene, tert-butoxystyrene, 4-methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, ( Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ( Structural units formed by polymerizing benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, or ethylene glycol monoacetoacetate mono (meth) acrylate can be given. Other examples include compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623.

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 characteristics of the obtained transfer material. Specific examples of monomers forming these structural units include styrene, tert-butoxystyrene, 4-methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) ) Isobornyl acrylate and benzyl (meth) acrylate. Among them, as the structural unit C, a structural unit derived from cyclohexyl (meth) acrylate is preferably exemplified.

モノマー As the monomer forming the structural unit C, for example, an alkyl (meth) acrylate is preferable from the viewpoint of adhesion. Among them, alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion. Specific examples 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, and still more preferably 50% by mass or less, based on the total mass of the polymer A1. The lower limit of the content may be 0% by mass, but the content is preferably 1% by mass or more, more preferably 5% by mass or more. When the content is in the above range, the resolution and the adhesion are further improved.

The fact that the polymer A1 contains, as the structural unit C, a structural unit having an ester of the acid group in the structural unit B also optimizes solubility in a developer and physical properties of the positive photosensitive resin layer. Preferred from a viewpoint.
Above all, the polymer A1 preferably includes, as the structural unit B, a structural unit having a carboxy group, and further includes, as a copolymerization component, a structural unit C having a carboxylate ester group. And a structural unit (c) derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate.
Hereinafter, preferable examples of the polymer A1 in the present disclosure will be described, 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 90 ° C. or less, and more preferably 20 ° C. or more and 60 ° C. or less from the viewpoint of transferability and adjusting the heating temperature in the above-described heating step. Is more preferable, and it is still more preferable that it is 30 to 50 degreeC.

As a method for adjusting the Tg of the polymer A1 to the above-described preferable range, for example, the FOX formula is used as a guideline based on the Tg of the homopolymer of each structural unit of the target polymer A1 and the mass ratio of each structural unit. Then, a method of controlling the Tg of the desired polymer A1 can be mentioned.
For example, the Tg of the homopolymer of the first structural unit contained in the copolymer is Tg1, the mass fraction in the copolymer of the first structural unit is W1, and the Tg of the homopolymer of the second structural unit is Tg1. And Tg2 (K: Kelvin) of the copolymer containing the first structural unit and the second structural unit, where Tg2 is the mass fraction of the second structural unit in the copolymer and W2 is It can be estimated according to the following equation:
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)
By using the above-described FOX formula, the type and mass fraction of each structural unit contained in the copolymer can be adjusted to obtain a copolymer having a desired Tg.
Further, it is also possible to adjust the Tg of the polymer A1 by adjusting the weight average molecular weight of the polymer A1.

(Acid value of polymer A1)
The acid value of the polymer A1 is preferably from 0 mgKOH / g to 200 mgKOH / g, more preferably from 0 mgKOH / g to 100 mgKOH / g, and more preferably from 0 mgKOH / g, from the viewpoint of developability and transferability. It is more preferably 50 mgKOH / g or less, particularly preferably 0 mgKOH / g or more and 20 mgKOH / g or less, most preferably 0 mgKOH / g or more and 10 mgKOH / g or less.

The acid value of the polymer in the present disclosure indicates the mass of potassium hydroxide required to neutralize the acidic component per 1 g of the polymer. Specifically, the measurement sample is dissolved in a mixed solvent of tetrahydrofuran / water = 9/1 (volume ratio) and obtained using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.). The resulting solution is neutralized and titrated with a 0.1 M aqueous sodium hydroxide solution at 25 ° C. The acid value is calculated by the following equation using the inflection point of the titration pH curve as the end point of the titration.
A = 56.11 × Vs × 0.1 × f / w
A: Acid value (mgKOH / g)
Vs: amount of 0.1 mol / L aqueous sodium hydroxide solution required for titration (mL)
f: titer of 0.1 mol / L aqueous solution of sodium hydroxide w: mass (g) of a 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 positive-type photosensitive resin layer is suppressed to be low, and bonding at a low temperature (for example, 130 ° C. or less) is realized when bonding with the substrate. be able to.
The weight average molecular weight of the polymer A1 is preferably from 2,000 to 60,000, and more preferably from 10,000 to 60,000.
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. The contents of the device and the measuring technique are as follows. It is known to those skilled in the art.
The weight average molecular weight was measured by gel permeation chromatography (GPC) using HLC (registered trademark) -8220 GPC (manufactured by Tosoh Corporation) as a measuring device and TSKgel (registered trademark) Super HZM-M (4) as a column. 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, manufactured by Tosoh Corporation) connected in series, and THF (tetrahydrofuran) can be used as an eluent.
The measurement was performed using a differential refractive index (RI) detector with a sample concentration of 0.2% by mass, a flow rate of 0.35 mL / min, a sample injection amount of 10 μL, and a measurement temperature of 40 ° C. 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", " A-2500 "and" A-1000 "can be produced using any of the seven samples.

(4) The ratio (dispersion degree) between 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 production method (synthesis method) of the polymer A1 is not particularly limited, but examples thereof include a polymerizable monomer for forming the structural unit A and a polymerizable monomer for forming the structural unit B having an acid group. It can be synthesized by polymerizing a monomer and, if necessary, an organic solvent containing a polymerizable monomer for forming the other structural unit C using a polymerization initiator. Further, it can be synthesized by a so-called polymer reaction.

The positive photosensitive resin layer in the present disclosure, from the viewpoint of developing good adhesion to the substrate and from the viewpoint of forming a high-resolution pattern, with respect to the total solid content of the positive photosensitive resin layer, The polymer component is preferably contained in a proportion of 50% by mass to 99.9% by mass, more preferably in a proportion of 70% by mass to 98% by mass, and more preferably in a proportion of 80% by mass to 98% by mass. More preferably, it is particularly preferably contained in a proportion of 90% by mass to 98% by mass.
The positive photosensitive resin layer preferably contains the acid-decomposable resin in a proportion of 50% by mass to 99.9% by mass, and preferably 70% by mass to 9% by mass, based on the total solid content of the positive type photosensitive resin layer. It is more preferably contained in a proportion of 98% by mass, further preferably contained in a proportion of 80% by mass to 98% by mass, and particularly preferably contained in a proportion of 90% by mass to 98% by mass.
Further, from the viewpoint of developing good adhesion to the substrate, the positive photosensitive resin layer contains the polymer A1 in an amount of 50% by mass to 99.99% based on the total solid content of the positive photosensitive resin layer. The content is preferably 9% by mass, more preferably 70% to 98% by mass, even more preferably 80% to 98% by mass, and 90% to 98% by mass. It is particularly preferable to include them in the ratio of

(Other polymers)
The positive photosensitive resin layer has, as a polymer component, a structural unit having, in addition to the polymer A1, an acid group protected with an acid-decomposable group as long as the effect of the photosensitive transfer material according to the present disclosure is not impaired. (Hereinafter, may be referred to as “another polymer”). When the positive photosensitive resin layer contains another polymer, the amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, based on all polymer components. It is more preferably at most 20% by mass.

The positive photosensitive resin layer may include only one type of other polymer in addition to the polymer A1, or may include two or more types of other polymers.
As another polymer, for example, polyhydroxystyrene can be used, and SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (all manufactured by Sartomer Co.) are commercially available. ARUFON UC-3000, ARUFON UC-3510, ARUFOON UC-3900, ARUFOON UC-3910, ARUFOON UC-3920, and ARUFON UC-3080 (all manufactured by Toagosei Co., Ltd.), and Joncryl 690, Joncryl 78 , Joncryl 67 and Joncryl 586 (all manufactured by BASF) can also be used.

(Photoacid generator)
The positive photosensitive resin layer preferably contains a photoacid generator.
The photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiation with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
The photoacid generator used in the present disclosure is preferably a compound that generates an acid in response to actinic rays having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but the chemical structure is not limited. Also, a photoacid generator that is not directly sensitive to actinic light having a wavelength of 300 nm or more, if it is a compound that responds to actinic light having a wavelength of 300 nm or more by using it in combination with a sensitizer and generates an acid, is used as 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 pKa is 2 or less. Particularly preferred are photoacid generators that generate an acid. The lower limit of pKa is not particularly defined. The pKa is preferably, for example, -10.0 or more.

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

例 Examples of the nonionic photoacid generator include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds. Among these, the photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion. These photoacid generators can be used alone or in combination of two or more. As specific examples of trichloromethyl-s-triazines and diazomethane derivatives, the compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 can be exemplified.

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 the formula (B1), R ²¹ represents an alkyl group or an aryl group, and * represents a bonding site to another atom or another group.

In the compound having an oxime sulfonate structure represented by the formula (B1), any group may be substituted, 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 for R ^21, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group represented by R ²¹ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group) , Preferably a bicycloalkyl group or the like) or a halogen atom.
The aryl group for R ²¹ is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group for 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.

化合物 The compound having an oxime sulfonate structure represented by the formula (B1) is also preferably an 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 preferred, and triarylsulfonium salts and diaryliodonium salts are particularly preferred.

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

One photoacid generator may be used alone, or two or more photoacid generators may be used in combination.
The content of the photoacid generator in the positive photosensitive resin layer is 0.1% by mass to 10% by mass based on the total mass of the positive photosensitive resin layer from the viewpoint of sensitivity and resolution. Is more preferable, and more preferably 0.5% by mass to 5% by mass.

〔solvent〕
The positive photosensitive resin layer may contain a solvent.
Further, the photosensitive resin composition for forming the positive photosensitive resin layer, in order to easily form the positive photosensitive resin layer, once containing a solvent to adjust the viscosity of the photosensitive resin composition, The positive photosensitive resin layer can be suitably formed by drying after applying the photosensitive resin composition containing a solvent.
Known solvents can be used as the solvent used in the present disclosure. Solvents 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, 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, and lactones. Further, specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP-A-2011-221494, the contents of which are incorporated herein.

Further, if necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, -Solvents such as nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate can also be added.
As the solvent to be added, only one kind may be used, or two or more kinds may be used.
The solvents that can be used in the present disclosure may be used alone or in combination of two or more. When using two or more solvents, for example, a combination of propylene glycol monoalkyl ether acetates and dialkyl ethers, a combination of diacetates and diethylene glycol dialkyl ethers, or an ester and butylene glycol alkyl ether acetate It is preferable to use the compound in combination with a compound.

The solvent is preferably a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., a solvent having a boiling point of 160 ° C. or more, or a mixture thereof.
Examples of the solvent having a boiling point of 130 ° C. or more and less 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.
Solvents 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.), dipropylene glycol methyl ether acetate (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl 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 190 ° C) (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), and 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be exemplified.

Preferred examples of the solvent include esters, ethers, and ketones described below.
Examples of the esters include ethyl acetate, propyl acetate, isobutyl acetate, sec-butyl acetate, isopropyl acetate, and butyl acetate.
Examples of ethers include diisopropyl ether, 1,4-dioxane, 1,2-dimethoxyethane, 1,3-dioxolan, propylene glycol dimethyl ether, propylene glycol monoethyl ether, and the like.
Examples of ketones include methyl n-butyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, and the like.
Other solvents include toluene, acetonitrile, isopropanol, 2-butanol, isobutyl alcohol and the like.

The content of the solvent when applying the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and more preferably 100 parts by mass, per 100 parts by mass of the total solids in the photosensitive resin composition. More preferably, it is 900 parts by mass.
Further, the content of the solvent in the positive photosensitive resin layer is preferably 2% by mass or less, more preferably 1% by mass or less, based on the total mass of the positive photosensitive resin layer. More preferably, it is 0.5% by mass or less.

[Other additives]
The positive photosensitive resin layer in the present disclosure may include a known additive as needed.

(Plasticizer)
The positive 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 even more 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.

中 In the above formula, R represents an alkylene group having 2 to 8 carbon atoms, n represents an integer of 1 to 50, and * represents a bonding site to another atom.

In addition, for example, even with a compound having an alkyleneoxy group having the above structure (hereinafter, referred to as “compound X”), a positive photosensitive resin layer obtained by mixing the compound X, the polymer A1, and the photoacid generator. However, when the plasticity is not improved as compared with the positive photosensitive resin layer formed without containing the compound X, it does not correspond to the plasticizer in the present disclosure. For example, an optionally added surfactant is not generally used in an amount that brings plasticity to the positive photosensitive resin layer, and thus does not fall under the plasticizer in the present specification.

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

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 positive photosensitive resin layer. Is more preferred.
The positive photosensitive resin layer may include only one type of plasticizer, or may include two or more types of plasticizers.

(Sensitizer)
The positive photosensitive resin layer may further include a sensitizer.
The sensitizer absorbs actinic rays and enters an electronically excited state. The sensitizer in the electronically excited state comes into contact with the photoacid generator, and causes actions such as electron transfer, energy transfer, and heat generation. As a result, the photoacid generator undergoes a chemical change and is decomposed to generate an acid.
Exposure sensitivity can be improved by including a sensitizer.

As the sensitizer, a compound selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a basestyryl derivative, and a distyrylbenzene derivative is preferable, and an anthracene derivative is more preferable.
Examples of the anthracene derivative 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.

として Examples of the sensitizer include the compounds described in paragraphs 0139 to 0141 of WO 2015/093271.

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

(Basic compound)
The positive photosensitive resin layer preferably further contains a basic compound.
The basic compound can be arbitrarily selected 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-2011-221494, the contents of which are incorporated herein.

Specifically, examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, and triethanolamine. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] -7-undecene.
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 a 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, and more preferably 0.005% by mass to 3% by mass based on the total mass of the positive photosensitive resin layer. More preferred.

(Heterocyclic compound)
The positive photosensitive resin layer in the present disclosure can include a heterocyclic compound.
The heterocyclic compound in the present disclosure is not particularly limited. The positive photosensitive resin layer includes, for example, compounds having an epoxy group or an oxetanyl group in the molecule described below, heterocyclic compounds containing an alkoxymethyl group, various cyclic ethers, oxygen-containing monomers such as cyclic esters (lactones); cyclic amines And nitrogen-containing monomers such as oxazoline; and heterocyclic monomers having d electrons such as silicon, sulfur and phosphorus.

When the heterocyclic compound is contained in the positive photosensitive resin layer, the content of the heterocyclic compound is 0.01% by mass to 50% by mass based on the total mass of the positive photosensitive resin layer. Is preferably 0.1% by mass to 10% by mass, and more preferably 1% by mass to 5% by mass. The above range is preferable from the viewpoint of adhesion and etching resistance. One heterocyclic compound may be used alone, or two or more heterocyclic compounds may be used in combination.

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

Compounds having an epoxy group in the molecule are commercially available. Examples thereof include JER828, JER1007, JER157S70, JER157S65 (manufactured by Mitsubishi Chemical Corporation), and commercially available products described in paragraph 0189 of JP-A-2011-221494.
Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, and XD- 1000, EPPN-501, EPPN-502 (all made 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-212 , 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 (all manufactured by Nagase Chemtech), YH-300, YH-301, YH-302, YH-315 , YH-324, YH-325 (all manufactured by Nippon Steel & Sumitomo Metal Corporation) Celloxide 2021P, 2081, 2000, 3000, EHPE3150, Eporide GT400, Cellbinars B0134, B0177 (manufactured by Daicel Corporation). .
The compound having an epoxy group in the molecule may be used alone or in combination of two or more.

の Among the compounds having an epoxy group in the molecule, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak 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 Alonoxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, and PNOX (these are Toagosei Co., Ltd.) (Manufactured by K.K.).

It is preferable that the compound containing an oxetanyl group is used alone or in combination with a compound containing an epoxy group.

は In the positive photosensitive resin layer of the present disclosure, the heterocyclic compound is preferably a compound having an epoxy group from the viewpoint of etching resistance and line width stability.

(Alkoxysilane compound)
The positive photosensitive resin layer may contain an alkoxysilane compound. Preferred examples of the alkoxysilane compound include trialkoxysilane compounds.
Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriakoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxy Propyl trialkoxysilane, γ-methacryloxypropylalkyl dialkoxysilane, γ-chloropropyl trialkoxysilane, γ-mercaptopropyl trialkoxysilane, β- (3,4-epoxycyclohexyl) ethyl trialkoxysilane, vinyl trialkoxysilane Is mentioned. Among them, γ-glycidoxypropyl trialkoxysilane and γ-methacryloxypropyl trialkoxysilane are more preferable, γ-glycidoxypropyl trialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used alone or in combination of two or more.

(Surfactant)
The positive photosensitive resin layer preferably contains a surfactant from the viewpoint of uniformity of the film thickness. As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant (nonionic surfactant), and an amphoteric surfactant can be used, but a preferred surfactant is used. The surfactant is a non-ionic surfactant.
Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based, and fluorine-based surfactants. . In the following trade names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), Megafac (registered trademark, manufactured by DIC Corporation), Florard (Manufactured by Sumitomo 3M Limited), Asahi Guard (registered trademark, manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark, manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (Toray Dow) Corning Co., Ltd.).
Further, the surfactant contains a structural unit SA and a structural unit SB represented by the following formula I-1 and has a weight average in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) 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 each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or 1 carbon atom. L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are mass percentages representing a polymerization ratio, and p represents a numerical value of 10 mass% or more and 80 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.

L is preferably a branched alkylene group represented by the following formula I-2. R ⁴⁰⁵ in Formula I-2 represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the surface to be coated, and has 2 or more carbon atoms. 3 alkyl groups are more preferred. The sum of p and q (p + q) is preferably p + q = 100, that is, 100% by mass.

重量 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 paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362 can be used.

One surfactant may be used alone, or two or more surfactants may be used in combination.
The amount of the surfactant added is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and more preferably 0.1% by mass or less with respect to the total mass of the positive photosensitive resin layer. More preferably, the content is from 01% by mass to 3% by mass.

(Other components)
In the positive photosensitive resin layer of the present disclosure, metal oxide particles, an antioxidant, a dispersant, an acid multiplying agent, a development accelerator, a conductive fiber, a coloring agent, a thermal radical polymerization initiator, a thermal acid generator, Known additives such as an ultraviolet absorber, a thickener, a crosslinking agent, and an organic or inorganic suspending agent can be further added.
Preferred embodiments of the other components are described in paragraphs 0165 to 0184 of JP-A-2014-85643, respectively, and the contents of this publication are incorporated herein.

(Method of forming positive photosensitive resin layer)
The respective components and the solvent can be mixed at an arbitrary ratio and in an arbitrary method, and stirred and dissolved to prepare a photosensitive resin composition for forming a positive photosensitive resin layer. For example, a composition can be prepared by preparing a solution in which each component is dissolved in a solvent in advance, and then mixing the obtained solution at a predetermined ratio. The composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.
The solid components (for example, a polymer component, a photoacid generator, a basic compound, and a surfactant) in the photosensitive resin composition used in the present disclosure are uniform in the thickness of the positive photosensitive resin layer, In order to improve shape unevenness and the like, it is preferable to adjust by dissolving in the above-mentioned solvent.

A positive photosensitive resin layer can be formed by applying the photosensitive resin composition on a temporary support 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, or inkjet coating.
The photosensitive resin composition can be applied after forming an intermediate layer described later on the temporary support.

[Protective film]
The photosensitive transfer material according to the present disclosure has a protective film. The surface of the protective film on the side in contact with the positive photosensitive resin layer satisfies the following (A) and (B).
(A) The water contact angle is 75 ° or more.
(B) The surface roughness Ra is 45 nm or less.
By satisfying the above conditions (A) and (B), the surface energy of the surface of the protective film on the side in contact with the positive photosensitive resin layer can be reduced, and the unevenness can be reduced. And reduction of pattern failure can be achieved at the same time.

In the present disclosure, “the surface of the protective film that is in contact with the positive photosensitive resin layer” means the surface of the protective film to be bonded to the positive photosensitive resin layer (that is, the contact surface). Then, it means the surface of the protective film that is exposed by being separated from the positive photosensitive resin layer (that is, the peeled surface). Specific peeling conditions are as described below.

感光 The photosensitive transfer material according to the present disclosure is peelable at the interface between the protective film and the positive photosensitive resin layer. Here, “peelable at the interface between the protective film and the positive photosensitive resin layer” means that the protective film can be peeled from the positive photosensitive resin layer under the following peeling conditions. Further, when the protective film has an undercoat layer described below, and the undercoat layer is in contact with the positive photosensitive transfer material, the photosensitive transfer material according to the present disclosure, the protective film undercoat layer and the positive photosensitive resin layer At the interface with The presence of the undercoat layer in the peeled protective film can be confirmed by observing the cross section of the protective film. Specifically, the cross section of the protective film peeled off from the positive photosensitive resin layer under the following peeling conditions is observed using a scanning electron microscope. When a laminated structure including the base material of the protective film is observed in the observed image, it can be determined that the protective film has an undercoat layer.

(Peeling conditions)
The photosensitive transfer material is cut out to 4.5 cm wide by 9 cm long, and the surface on the temporary support side is stuck on a glass plate with a double-sided adhesive tape. A 4.5cm wide x 15cm long adhesive tape cut into the laminated photosensitive transfer material, the width direction of the adhesive tape is aligned with the width direction of the photosensitive transfer material, and the adhesive tape protrudes in the width direction. Instead, the adhesive tape is stuck so that the adhesive tape protrudes by 3 cm in the longitudinal direction. One end of the tape is gripped, and 180 ° peeling is performed at a peeling speed of 500 mm / min using a tensile tester. Here, the pressure-sensitive adhesive tape and the double-sided pressure-sensitive adhesive tape used are those described in JIS Z 0109: 2015, and the tensile tester is a tensile tester (tester grade 1: relative indication error) specified in JIS B 7721: 2009. ± 1.0%) or equivalent tensile tester is used.

(Water contact angle)
The water contact angle of the surface of the protective film on the side in contact with the positive photosensitive resin layer is 75 ° or more. By adjusting the water contact angle within the above numerical range, since the surface energy of the surface of the protective film on the side in contact with the positive photosensitive resin layer can be reduced, the peelability of the protective film can be improved. .
The water contact angle is preferably 78 ° or more, more preferably 82 ° or more, and may be 85 ° or more, or may be 100 ° or more, from the viewpoint of peelability.
The upper limit of the water contact angle is not limited. The water contact angle is preferably 150 ° or less, and more preferably 120 ° or less, from the viewpoint of adhesion.

The water contact angle can be measured by the following method.
Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DROPMASTER-501), the contact angle measured 7 seconds after 2 μL of purified water was dropped on the measurement surface at a temperature of 25 ° C. I do. When the protective film and the positive photosensitive resin layer are in contact with each other, the water contact angle is measured using the peeled surface exposed by peeling the protective film under the above peeling conditions as a measurement surface.

[Surface roughness Ra]
The surface roughness Ra of the surface of the protective film on the side in contact with the positive photosensitive resin layer is 45 nm or less. By adjusting the surface roughness Ra within the above numerical range, the occurrence of irregularities formed on the surface of the positive photosensitive resin layer can be reduced, so that pattern failure can be reduced.
The smaller the surface roughness Ra, the better from the viewpoint of reducing pattern failure. Specifically, the surface roughness Ra is preferably 42 nm or less, more preferably 25 nm or less, further preferably 20 nm or less, and particularly preferably 14 nm or less.
The lower limit of the surface roughness Ra is not limited. The surface roughness Ra is preferably 1 nm or more from the viewpoint of manufacturing.

The surface roughness Ra can be measured by the following method.
With respect to the measurement surface of the protective film, a surface profile of the protective film is obtained using a three-dimensional optical profiler (New View 7300, manufactured by Zygo) under the following conditions. The measurement and analysis software uses MicroScope Application 8.3.2. Next, a Surface Map screen is displayed by the analysis software (MetroPro 8.3.2-Microscope Application), and histogram data is obtained in the Surface Map screen. The arithmetic average roughness is calculated from the obtained histogram data, and is set as the Ra value. When the protective film and the positive photosensitive resin layer are in contact with each other, the surface roughness Ra is measured using the peeled surface exposed by peeling the protective film under the above peeling conditions as a measurement surface.
(Measurement condition)
Objective lens: 50 × Zoom: 0.5 × Measurement area: 1.00 mm × 1.00 mm
(Analysis conditions)
Removed: plane
Filter: off
FilterType: average
Remove spikes: on
Spike Height (xRMS): 7.5

〔Base material〕
As the base material of the protective film, a resin film is preferable. Examples of the resin film include a polyolefin film (eg, a polypropylene film), a polyester film (eg, a polyethylene terephthalate film), a cellulose triacetate film, a polycarbonate film, a polystyrene film, and the like. Among these, a polyolefin film is preferable, and a polypropylene film is more preferable as the base material of the protective film, from the viewpoints of peelability and reduction of pattern failure. As the polypropylene film, a commercially available product may be used, and for example, Trefane (registered trademark) 25KW37 (manufactured by Toray Industries, Inc.) or the like may be used. Further, as the base material of the protective film, from the viewpoint of smoothness, a polyester film is preferable, and a polyethylene terephthalate film is more preferable.

The resin film may be an unstretched film or a stretched film, but is preferably a stretched film. The stretched film may be a uniaxially stretched film, may be a biaxially stretched film, may be a multiaxially stretched film such as triaxially stretched, but is preferably a biaxially stretched film, From the viewpoint of smoothness, a biaxially oriented polypropylene film or a biaxially oriented polyethylene terephthalate film is more preferable.

厚み The thickness of the substrate is not particularly limited, but is preferably in the range of 5 μm to 200 μm, and more preferably in the range of 10 μm to 150 μm.

(Undercoat layer)
The protective film has a base material and an undercoat layer, and the outermost layer of the protective film on the side in contact with the positive photosensitive resin layer is preferably the above-mentioned undercoat layer. Since the surface energy of the protective film can be reduced by having the undercoat layer, the peelability of the protective film can be improved.
When the base material in the protective film is a resin film, the undercoat layer may be formed on an unstretched film, may be formed on a uniaxially stretched film, or may be formed on a biaxially stretched film. Is also good. The undercoat layer may be a stretched product stretched together with the unstretched film serving as the base material, or a stretched product stretched together with the uniaxially stretched film serving as the base material, from the viewpoint of adhesion to the base material. You may. The undercoat layer, which is a stretched product, can be formed, for example, by stretching a coating layer formed on a resin film as a base material together with the resin film, as described later.

As a more preferred embodiment, the protective film is a biaxially stretched film in which a uniaxially stretched film, which is a stretched product in the first stretching direction, is stretched along a film surface in a second stretching direction orthogonal to the first stretching direction; An undercoat layer that is a stretched product of the coating layer formed on one surface of the stretched film in the second stretching direction (hereinafter, may be simply referred to as “undercoat layer that is a stretched product”), and is a protective film. The outermost layer on the side in contact with the positive photosensitive resin layer is preferably the undercoat layer. By having a biaxially stretched film and an undercoat layer which is a stretched product, the surface energy of the protective film can be reduced to improve the peelability of the protective film, and further, the smoothness of the protective film surface and the base material ( That is, the adhesion between the biaxially stretched film) and the undercoat layer can be improved.
Here, the “biaxially stretched film” in the protective film having a biaxially stretched film and an undercoat layer that is a stretched product has a surface roughness Ra of one surface measured by the method described above of 45 nm. The following resin films are referred to.

In the present disclosure, the “undercoat layer that is a stretched product” refers to a material having an adhesive force with a biaxially stretched film measured by the following method of 0.098 N / cm or more.
The method for measuring the adhesion between the biaxially stretched film and the undercoat layer will be described below.
A tape (Printerc C, manufactured by Nitto Denko Corporation) is attached to the surface of the protective film having an undercoat layer on the undercoat layer side, and cut into 4.5 cm × 9 cm so that the width of the tape and the protective film match. Next, the tape is peeled at 180 ° at a peeling speed of 500 mm / min using a Tensilon universal tester (manufactured by A & D Corporation), and the adhesion is measured.

樹脂 Examples of the resin contained in the undercoat layer include polyolefin, acrylic polymer, polyester and the like. The undercoat layer preferably contains a modified resin, and more preferably contains at least one resin selected from the group consisting of an acid-modified resin and a silicone-modified resin, from the viewpoint of reducing releasability and pattern failure. . More specifically, the undercoat layer preferably contains at least one resin selected from the group consisting of a modified polyolefin and a modified acrylic polymer, from the viewpoint of reducing releasability and pattern failure, and comprises an acid-modified polyolefin and More preferably, it contains at least one resin selected from the group consisting of silicone-modified acrylic polymers, and particularly preferably it contains acid-modified polyolefin.

The acid-modified polyolefin is not limited as long as it is an acid-modified polyolefin, and is, for example, a terminal-modified or graft-modified polyolefin using a compound having an acid group (for example, an unsaturated carboxylic acid or the like) or an anhydride thereof. And the like. Examples of the acid group include a carboxy group, a sulfo group, and a phosphono group.

少なくとも At least one of the acid groups contained in the acid-modified polyolefin is preferably in the form of a salt (ie, a salt of an acid group). When at least one of the acid groups contained in the acid-modified polyolefin is in the form of a salt, excessive decomposition of the positive photosensitive resin can be reduced, so that the pattern shape can be improved. Examples of the salt include an alkali metal salt (for example, a sodium salt, a potassium salt, a lithium salt and the like), an amine salt, an ammonium salt and the like. Among these, at least one of the acid groups in the acid-modified polyolefin is preferably an alkali metal salt, and more preferably a sodium salt, from the viewpoint of the pattern shape.

Commercially available polyolefins such as acid-modified polyolefins may be used. For example, Chemipearl (registered trademark) S100, S120, S200, S300, S650, SA100 (all manufactured by Mitsui Chemicals, Inc.), Hardlen (registered trademark) AP-2, NZ1004, NZ1005 (all manufactured by Toyobo Co., Ltd.), Arrowbase (registered trademark) DA-1010, DB-4010, SB-1200, SD-1200, SE-1010, SE-1013 (all are Unitika) Co., Ltd.), Seixen (registered trademark) AC, A, L, NC, N (all manufactured by Sumitomo Seika Co., Ltd.), Sepolsion (registered trademark) G315, VA407 (all manufactured by Sumitomo Seika Co., Ltd.) ), Hitec S3121, S3148K (all manufactured by Toho Chemical Co., Ltd.).
Examples of the acid-modified polyolefin in which at least one of the acid groups is an amine salt include, for example, Sixen (registered trademark) L and the like.
Examples of the acid-modified polyolefin in which at least one of the acid groups is an ammonium salt include, for example, Sixen (registered trademark) AC.
Examples of the acid-modified polyolefin in which at least one of the acid groups is a sodium salt include Sixen (registered trademark) NC, Chemipearl (registered trademark) S120, and the like.

Silicone-modified acrylic polymer is an acrylic polymer having a silicone moiety. The silicone-modified acrylic polymer is not limited, and a known one can be used. A commercially available product may be used as the silicone-modified acrylic polymer, and examples thereof include Cymac (registered trademark) US-450 and US-480 (all manufactured by Toagosei Co., Ltd.).

樹脂 The resin contained in the undercoat layer may be used alone or in combination of two or more.

The content of the resin in the undercoat layer is preferably from 50% by mass to 100% by mass, and more preferably from 80% by mass to 100% by mass, based on the total mass of the undercoat layer, from the viewpoint of the releasability and the reduction in pattern failure. Is more preferable. In addition, the total content of at least one resin selected from the group consisting of the modified polyolefin and the modified acrylic polymer in the undercoat layer is, with respect to the total weight of the undercoat layer, from the viewpoint of reducing releasability and pattern failure. , 50% by mass to 100% by mass, more preferably 80% by mass to 100% by mass.

樹脂 The weight average molecular weight of the resin contained in the undercoat layer is preferably from 1,000 to 500,000 in terms of polystyrene in terms of releasability. The weight average molecular weight of the resin contained in the undercoat layer can be measured by the method described in the section of “Positive photosensitive resin layer” above.

The undercoat layer may further contain various additives as necessary. Examples of the additive include a surfactant, a crosslinking agent, an antioxidant, a preservative, and the like.

Examples of the surfactant include known surfactants such as a cationic surfactant, a nonionic surfactant, and an anionic surfactant. Among these, as the surfactant, an anionic surfactant is preferable. Examples of anionic surfactants include Lapizol (registered trademark) A-90, A-80, BW-30, B-90, and C-70 (all manufactured by NOF Corporation), and NIKKOL (registered trademark). OTP-100 (all manufactured by Nikko Chemical Co., Ltd.), Kohakuur (registered trademark) ON, L-40, Phosphanol (registered trademark) 702 (all manufactured by Toho Chemical Industry Co., Ltd.), Beaulite (registered trademark) ) A-5000, SSS (all manufactured by Sanyo Chemical Industries, Ltd.) and the like.

Examples of the crosslinking agent include known crosslinking agents such as epoxy, isocyanate, melamine, carbodiimide, and oxazoline.

The thickness of the undercoat layer is not limited, and is preferably from 10 nm to 550 nm, more preferably from 10 nm to 500 nm, still more preferably from 10 nm to 100 nm, from the viewpoint of reducing peeling and pattern failure. It is particularly preferably from 10 nm to 60 nm.

The method for forming the undercoat layer is not limited. For example, an undercoat layer can be formed by applying a coating liquid for forming an undercoat layer containing a solid content of the undercoat layer on a base material and drying.
The coating method is not limited, and a known method such as slit coating, spin coating, curtain coating, or inkjet coating can be applied.
The drying method is not limited, and a known method such as a heater or hot air can be applied.
The undercoat layer may be formed by an inline coating method using a coating solution for forming an undercoat layer. The in-line coating method is a method of applying a coating liquid for forming an undercoat layer at a stage before winding the manufactured base material, and an off-line coating method of separately applying after winding the manufactured base material. Be distinguished. As an example of a method of forming an undercoat layer by an inline coating method, one surface of a resin film stretched in the first stretching direction was coated with an undercoat layer formation coating solution, and the undercoat layer formation coating solution was applied. A method of forming an undercoat layer by stretching the resin film in a second stretching direction orthogonal to the first stretching direction along the resin film surface is preferable. By stretching in the second stretching direction in a state where the undercoat layer forming coating liquid is applied to one surface of the resin film stretched in the first stretching direction, the adhesion between the resin film and the undercoat layer serving as the base material is improved. And the smoothness of the protective film surface can be improved.
The stretching method is not limited, and a known method can be applied.
The stretching temperature may be appropriately selected according to the glass transition temperature (Tg) of the substrate, and is preferably equal to or higher than Tg, and is equal to or lower than 80 ° C. higher than Tg, and is higher by 5 ° C. than Tg. It is more preferable that the temperature is equal to or higher than the temperature and equal to or lower than the temperature higher by 60 ° C. than the Tg.
The stretching ratio is preferably 2.5 times to 5.0 times, more preferably 3.0 times to 4.5 times. The stretching ratio refers to the ratio of the length after stretching to the length before stretching.
After the biaxial stretching, the stretched film may be subjected to heat treatment such as heat setting and thermal relaxation.

(Overcoat layer)
The protective film may have an overcoat layer on the outermost layer on the side opposite to the side in contact with the positive photosensitive resin layer. By having the overcoat layer, for example, the slipperiness with a mask used at the time of exposure can be improved.

Examples of the resin contained in the overcoat layer include polyolefin, acrylic polymer, polyester, polyurethane, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl pyrrolidone, polyvinyl acetal, polyvinyl alcohol, polyamide, butadiene-styrene thermoplastic polymer, Epoxy resins, melamine resins and the like can be mentioned. Among these, an acrylic polymer is preferable as the resin contained in the overcoat layer from the viewpoint of slipperiness.
It is preferable that a surfactant, a wax, a matting agent, resin particles, inorganic particles, and the like are further added to the overcoat layer from the viewpoint of slipperiness. In particular, from the viewpoint of transportability, the overcoat layer preferably contains inorganic particles. The particle diameter of the inorganic particles is preferably in the range of 0.03 μm to 1 μm, more preferably in the range of 0.05 μm to 0.5 μm.

The thickness of the overcoat layer is not limited, and is preferably from 10 nm to 500 nm, and more preferably from 10 nm to 100 nm, from the viewpoint of slipperiness.
[Intermediate layer]
The photosensitive transfer material according to the present disclosure may have an intermediate layer between the temporary support and the positive photosensitive resin layer. As the intermediate layer, a water-soluble resin layer is preferable. By having the water-soluble resin layer, the adhesion between the temporary support and the positive photosensitive resin layer can be improved.

(Water-soluble resin layer)
The water-soluble resin layer is a layer containing a water-soluble resin. The water-soluble resin is not limited as long as it is a water-soluble resin, and examples thereof include polyvinyl alcohol, cellulose, polyacrylamide, polyethylene oxide, vinyl ether, polyamide, and copolymers thereof. Among these, cellulose is preferable as the water-soluble resin from the viewpoint of adhesion.
In the present disclosure, “water-soluble” means a property of dissolving 1 g or more in 100 g of water at 25 ° C.

From the viewpoint of adhesion, the content of the water-soluble resin in the water-soluble resin layer is preferably 20% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass based on the total mass of the water-soluble resin layer. % Is more preferable.

から The thickness of the water-soluble resin layer is preferably from 1 μm to 10 μm, more preferably from 1 μm to 5 μm, from the viewpoint of adhesion.

表面 The surface of the protective film on the side in contact with the positive photosensitive resin layer may be subjected to surface modification from the viewpoint of peelability. The surface modification method is not limited as long as the surface energy of the protective film is reduced, and examples thereof include a corona treatment, a plasma treatment, a laser treatment, and an ultraviolet treatment.

<Method of manufacturing circuit wiring>
The method for manufacturing a circuit wiring according to the present disclosure includes a step of peeling the protective film of the photosensitive transfer material (hereinafter, may be referred to as a “peeling step”) and a step of removing the protective film of the photosensitive transfer material from the temporary support. On the other hand, a step of bonding the outermost layer on the side having the positive photosensitive resin layer to the substrate having the conductive layer (hereinafter, may be referred to as a “bonding step”), and the photosensitivity after the bonding step. A step of pattern-exposing the positive photosensitive resin layer of the transfer material (hereinafter, may be referred to as an “exposure step”), and developing the positive photosensitive resin layer after the pattern exposure step to form a resin pattern. (Hereinafter, may be referred to as “development step”) and a step of etching the substrate in a region where the resin pattern is not disposed (hereinafter, referred to as “etching step”). That it includes. A), the.
According to the method for manufacturing a circuit wiring according to the present disclosure, since the photosensitive transfer material is used, a circuit wiring with reduced pattern failure can be manufactured.

Hereinafter, a method for manufacturing a circuit wiring according to the present disclosure will be described in detail.

[Peeling step]
The method for manufacturing a circuit wiring according to the present disclosure includes a step of peeling off the protective film of the photosensitive transfer material. The method for peeling the protective film is not limited, and a known method can be applied.

[Lamination process]
The method for manufacturing a circuit wiring according to the present disclosure includes a step of bonding the outermost layer of the photosensitive transfer material having the positive photosensitive resin layer to the temporary support to a substrate having a conductive layer. .

(2) An example of the bonding step is schematically shown in FIG. The substrate 20 (circuit wiring forming substrate) 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. The first conductive layer 24 and the second conductive layer 26, which are the outermost layers, are laminated in order from the farthest from the surface of the base material 22. In the bonding step, the positive photosensitive resin layer 14 of the photosensitive transfer material 100 according to the present disclosure is brought into contact with the first conductive layer 24 and bonded to the substrate 20 (substrate for forming circuit wiring). Note that such bonding of the circuit wiring forming substrate and the photosensitive transfer material may be referred to as “transfer” or “laminate”.

Lamination of the photosensitive transfer material to the substrate is performed by superposing the outermost layer of the photosensitive transfer material on the side having the positive photosensitive resin layer with respect to the temporary support on the substrate, and applying pressure and heating using a roll or the like. It is preferably performed. For lamination, a known laminator such as a laminator, a vacuum laminator, or an auto-cut laminator that can further increase the productivity can be used. When the base material constituting the substrate is a resin film, it is also possible to perform roll-to-roll bonding.

The substrate has a conductive layer on a substrate such as glass, silicon, or a film, and an optional layer may be formed as necessary.
Preferably, the substrate is transparent.
The base material preferably has a refractive index of 1.50 to 1.52.
The base material may be composed of a light-transmitting base material such as a glass base material, and tempered glass represented by gorilla glass of Corning and the like can be used. Further, as the above-mentioned transparent substrate, the materials used in JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be preferably used.
When a film substrate is used as the substrate, it is more preferable to use a substrate having small optical distortion and a substrate having high transparency, and a resin film is more preferable. Specific materials include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

基板 In a substrate having a conductive layer on a substrate, the substrate is preferably a glass substrate or a film substrate, more preferably a film substrate, and particularly preferably a resin film. In the method for producing a circuit wiring according to the present disclosure, when the circuit wiring is for a touch panel, it is particularly preferable that the substrate is a sheet-shaped resin composition.

As the conductive layer formed on the base material, any conductive layer used for general circuit wiring or touch panel wiring can be exemplified.
The conductive layer is preferably a metal layer, and at least one layer selected from the group consisting of conductive metal oxide layers, from the viewpoint of conductivity and fine line forming properties, and is a metal layer. Is more preferable, and a copper layer is particularly preferable.
Further, the base material may have one conductive layer or two or more conductive layers. In the case of two or more layers, it is preferable to have conductive layers of different materials.
Examples of the material of the conductive layer include a metal and a conductive metal oxide.
Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, and Mo.
Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ . In addition, “conductive” in the present disclosure refers to a volume resistivity of less than 1 × 10 ⁶ Ωcm, and preferably a volume resistivity of less than 1 × 10 ⁴ Ωcm.

In the method for manufacturing a circuit wiring according to the present disclosure, when a substrate having a plurality of conductive layers on a base material is used, at least one of the plurality of conductive layers preferably contains a conductive metal oxide.
The conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition unit used in a capacitive touch panel, or a wiring of a peripheral extraction unit.

[Exposure process]
The method for manufacturing a circuit wiring according to the present disclosure includes a step of pattern-exposing the positive photosensitive resin layer of the photosensitive transfer material after the bonding step.

FIG. 2 (b) schematically shows an example of the exposure step. For example, in the exposure step shown in FIG. 2B, the positive photosensitive resin layer 14 is subjected to pattern exposure via the temporary support 12 of the photosensitive transfer material. For example, a mask 30 having a predetermined pattern is disposed above the photosensitive transfer material 100 disposed on the first conductive layer 24 (the side opposite to the side in contact with the first conductive layer 24), and thereafter, the mask 30 And a method of exposing to ultraviolet light from above the mask through the mask.

において In the present disclosure, the detailed arrangement and specific size of the pattern are not particularly limited. In order to improve the display quality of a display device (for example, a touch panel) provided with an input device having circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure, and to reduce the area occupied by the extracted wiring as much as possible, At least a part (particularly, the part of the electrode pattern and the lead-out wiring of the touch panel) is preferably a fine line of 100 μm or less, and more preferably a fine line of 70 μm or less.

(4) The light source used for the exposure can be appropriately selected and used as long as the exposed portion of the positive photosensitive resin layer can be irradiated with light (for example, 365 nm, 405 nm, etc.) in a wavelength range that can be dissolved in the developer. Specifically, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp and the like can be mentioned.

The exposure amount is ^preferably from 5mJ / cm 2 ~ 200mJ / cm 2, more preferably 10mJ / cm 2 ~ 100mJ / cm 2.

In the exposure step, pattern exposure may be performed after the temporary support is separated from the photosensitive resin layer, and before the temporary support is separated, pattern exposure is performed through the temporary support, and then the temporary support is separated. May be. In order to prevent mask contamination due to the 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 perform pattern exposure without removing the temporary support. The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.

[Development step]
The method for manufacturing a circuit wiring according to the present disclosure includes a step of forming a resin pattern by developing the positive photosensitive resin layer after the step of pattern exposure.

FIG. 2C schematically shows an example of the developing step. In the developing step, the temporary support 12 is separated from the positive photosensitive resin material layer 14 after the exposure step, and then the positive photosensitive resin layer 14 after the exposure step is developed to form a first pattern 14A.

The development of the pattern-exposed positive photosensitive resin layer can be performed using a developer.
The developer is not particularly limited as long as the exposed portion of the positive photosensitive resin layer can be removed. For example, a known developer such as a developer described in JP-A-5-72724 may be used. it can. The developing solution is preferably a developing solution in which the exposed portion of the photosensitive resin layer has a developing behavior of a dissolving type. For example, an alkali aqueous solution-based developer containing a compound having a pKa of 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. As the developer suitably used in the present disclosure, for example, a developer described in paragraph 0194 of International Publication No. 2015/093271 is exemplified.

The development system is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development. Here, the shower development will be described. By exposing the photosensitive resin layer after exposure to a developer by spraying, the exposed portion can be removed. After the development, it is preferable to remove a development residue while spraying a detergent or the like with a shower and rubbing with a brush or the like. The liquid temperature of the developer is preferably from 20 ° C to 40 ° C.

Further, the method may include a post-baking step of heating a pattern including the photosensitive resin layer obtained by development.
Post-baking is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably in an environment of 506.6 kPa or more. On the other hand, the heating of the post bake is more preferably performed in an environment of 114.6 kPa or less, and particularly preferably performed in an environment of 101.3 kPa or less.
The post-baking temperature is preferably from 80 ° C. to 250 ° C., more preferably from 110 ° C. to 170 ° C., and particularly preferably from 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 in a nitrogen-substituted environment.

Also, other steps such as a post-exposure step may be provided before the etching step described later.

[Etching process]
The method of manufacturing a circuit wiring according to the present disclosure includes a step of etching a substrate in a region where the resin pattern is not arranged.

(2) An example of the etching step is schematically shown in FIG. In the etching step, at least the first conductive layer 24 and the second conductive layer 26 of the plurality of conductive layers in the region where the first pattern 14A is not arranged are etched. By etching, a first conductive layer 24A and a second conductive layer 26A having the same pattern as the first pattern 14A are formed.

(4) As a method of the etching treatment, a known method such as a method described in paragraphs 0048 to 0054 of JP-A-2010-152155, a known dry etching method such as plasma etching, or the like can be applied.

For example, as a method of the etching treatment, there is a commonly-used wet etching method of immersing in an etching solution. As an etchant used for wet etching, an acidic type or alkaline type etchant may be appropriately selected in accordance with an etching target.
Examples of the acidic type etchant 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. Illustrated. As the acidic component, a component obtained by combining a plurality of acidic components may be used.
Examples of the alkaline type etchant include aqueous solutions of alkali components alone such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, salts of organic amines such as tetramethylammonium hydroxide, and alkali components and potassium permanganate. Examples thereof include a mixed aqueous solution with a salt. As the alkali component, a component obtained by combining a plurality of alkali components may be used.

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

After the etching step, a washing step and a drying step may be performed as necessary to prevent contamination of the process line.
As the cleaning liquid used in the cleaning step, pure water, an organic solvent soluble in pure water, or an aqueous solution in which a surfactant is mixed can be used. From the viewpoint of suppressing peeling unevenness due to droplets remaining on the substrate surface and improving removability, it is preferable to use an organic solvent that can be dissolved in pure water, or an aqueous solution in which a surfactant is mixed, as the cleaning liquid. It is more preferable to use an aqueous solution in which both an organic solvent soluble in water and a surfactant are mixed.

The water-soluble organic solvent to be mixed with water is not particularly limited, but preferably has a boiling point of 50 ° C to 250 ° C, more preferably 55 ° C to 200 ° C, from the viewpoint of the volatility of the solvent. More preferably, the temperature is from 60 ° C to 150 ° C.
Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, and ethylene glycol, 2-acetoxy-2-phenylethanol, 3-methoxy-3-methylethanol, and 3-methoxy-3-methylethanol. Butanol, alkoxy alcohols such as 2-butoxyethoxyethanol, ketones such as acetone and methyl ethyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, glycol ethers such as ethylene glycol dimethyl ether, tetrahydrofuran, acetonitrile, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, 1,3-dioxolan, and the like can be mentioned.
Among the above, methanol, ethanol, propanol, isopropanol, 3-methoxy-3-methylbutanol, 2-acetoxy-2-phenylethanol, tetrahydrofuran, and dimethylsulfoxide are preferred.

は The water-soluble organic solvent to be mixed with water may be used alone or in combination of two or more.

The content of the water-soluble organic solvent to be mixed with water is preferably 0.01% by mass to 95% by mass, and more preferably 0.01% by mass to 20% by mass, based on the total mass of the aqueous solution. More preferably, the content is 0.01% by mass to 10% by mass, and particularly preferably 0.01% by mass to 5% by mass.

The surfactant to be mixed with water is not particularly limited as long as it is water-soluble, and an anionic surfactant, a cationic surfactant, a nonionic surfactant (nonionic surfactant), or Any of the amphoteric surfactants can be used. From the viewpoint of suppressing foaming of the cleaning liquid, a nonionic surfactant is preferable.
Examples of the anionic surfactant include carboxylate, sulfonate, sulfate, phosphate and the like.
Examples of the cationic surfactant include amine salts and quaternary ammonium salts.
Examples of amphoteric surfactants include betaine types.
Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, alkylbenzene polyalkylene glycols, polyoxyalkylene glycols, and silicone-based surfactants. Activators and fluorinated surfactants can be mentioned.
In the following trade names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by JEMCO), Megafac (manufactured by DIC), Florard (Sumitomo 3M) Asahi Guard, Surflon (made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA), Surfynol (made by Nissin Chemical Industry Co., Ltd.), and SH-8400 (Toray Dow Corning Co., Ltd.) Series).

は The surfactant may be used alone, or two or more surfactants may be used in combination, and it is preferable to use two or more surfactants in combination.

The content of the surfactant mixed with water is preferably 10% by mass or less, more preferably 0.001% by mass to 5% by mass, and more preferably 0.01% by mass with respect to the total mass of the aqueous solution. % To 3% by mass.

The surface tension of an aqueous solution in which a water-soluble organic solvent or a surfactant is mixed is preferably 50 mN / m or less, and more preferably 10 mN / m, from the viewpoint of suppressing uneven peeling due to droplets remaining on the substrate surface and improving the removability. / M to 50 mN / m, more preferably 15 mN / m to 40 mN / m, and most preferably 20 mN / m to 40 mN / m.

The washing time in the washing step is not particularly limited, and it is preferable to wash the substrate, for example, for 10 seconds to 300 seconds. In the drying step, for example, an air blow is used, and an air blow pressure (preferably 0.1 kg / cm ^{2) is used.} (About 5 kg / cm ² ) may be appropriately adjusted for drying.

好ましい Further, two preferable embodiments are shown below as a method of manufacturing a circuit wiring according to the present disclosure.

The method for manufacturing a circuit wiring according to the present disclosure includes a step of exposing the entire surface of the positive photosensitive resin layer after the etching step (hereinafter, may be referred to as an “entire exposure step”) and a step of exposing the entire positive photosensitive resin layer. And a step of removing the photosensitive resin layer (hereinafter, sometimes referred to as a “removing step”).
In a conventional method for manufacturing a circuit wiring, when an etching mask removing liquid is used for a long time, the etching mask removing property may gradually decrease. After the etching step, by exposing the entire surface of the positive photosensitive resin layer used as an etching mask, the solubility in the removing solution and the permeability of the removing solution are improved, and the removing solution is removed even when the removing solution is used for a long time. Excellent in nature.
Further, a circuit wiring is manufactured by repeatedly applying the method for manufacturing a circuit wiring to a substrate having a base material and a plurality of conductive layers including a first conductive layer and a second conductive layer having different constituent materials. You can also.

The method for producing a circuit wiring according to the present disclosure includes a step of peeling a protective film of the photosensitive transfer material, and an outermost layer of the photosensitive transfer material having a positive photosensitive resin layer with respect to the temporary support. 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 on the surface of the base material, A step of bonding the first conductive layer and the second conductive layer, which are surface layers, to a substrate on which the first conductive layer and the second conductive layer are stacked, and pattern exposure of the positive photosensitive resin layer of the photosensitive transfer material after the bonding step. A first exposure step, a first development step of developing the positive photosensitive resin layer after the first exposure step to form a first pattern, and the plurality of the plurality of areas in a region where the first pattern is not arranged. At least the first conductive layer and the conductive layer A first etching step of etching the second conductive layer, a second exposure step of pattern-exposing the first pattern after the first etching step with a pattern different from the first pattern, and a second exposure step A second developing step of developing the first pattern to form a second pattern, and etching at least the first conductive layer among the plurality of conductive layers in a region where the second pattern is not arranged. A second etching step, a step of exposing the entire surface of the second pattern (hereinafter, may be referred to as an “entire exposure step”), and a step of removing the second pattern (hereinafter, referred to as a “removing step”). ) Are preferably included in this order.
As an embodiment of the method of manufacturing the circuit wiring, WO 2006/190405 can be referred to, and the contents thereof are incorporated herein.

Hereinafter, the above-described two preferred embodiments will be described as a method of manufacturing a circuit wiring according to the present disclosure. Note that the embodiments such as the conditions described in the above-described steps can be applied to the embodiments such as the conditions in the steps not described below.

[Second exposure step]
An example of the second exposure step is schematically shown in FIG.
After the first etching step, the first pattern 14A after the first etching step is subjected to pattern exposure with a pattern different from the first pattern 14A.

In the second exposure step, the first pattern 14A remaining on the first conductive layer is exposed to at least a portion corresponding to a portion of the first conductive layer to be removed in a second developing step described later.
For the pattern exposure in the second exposure step, the same method as the pattern exposure in the above-described exposure step can be applied except that a mask 40 having a different pattern from the mask 30 used in the first exposure step is used.

[Second developing step]
An example of the second developing step is schematically shown in FIG.
In the second development step, the first pattern 14A after the second exposure step is developed to form a second pattern 14B.
By development, a portion of the first pattern 14A that has been exposed in the second exposure step is removed.
In the second development step, the same method as the development in the development step described above can be applied.

[Second etching step]
An example of the second etching step is schematically shown in FIG.
In the second etching step, at least the first conductive layer 24A of the plurality of conductive layers in the region where the second pattern 14B is not arranged is etched.

For the etching in the second etching step, the same method as the etching in the above-described etching step can be applied, except that an 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 in accordance with a desired pattern than in the above-described etching step. For example, as shown in FIG. 2G, the first conductive layer 24B is etched by using an etchant that selectively etches only the first conductive layer 24B in a region where the photosensitive resin layer is not disposed. May be different from the pattern of the second conductive layer.
After completion of the second etching step, a circuit wiring including at least two types of

conductive layers

24B and 26A is formed.

[Overall exposure process]
In the whole-surface exposure step, all of the positive-type photosensitive resin layer that causes an afterimage by development may be exposed, and the portion without the positive-type photosensitive resin layer may or may not be exposed. From the viewpoint of simplicity, for example, it is preferable to expose the entire surface of the substrate on the side having the positive photosensitive resin layer.

光源 The light source used for the exposure in the entire surface exposure step is not particularly limited, and a known exposure light source can be used.から From the viewpoint of removability, it is preferable to use a light source containing light having the same wavelength as in the above-mentioned exposure step.

The exposure amount in the overall exposure step, from the viewpoint of removability is ^preferably 5mJ / cm 2 ~ 1,000mJ / cm 2, more preferably 10mJ / cm 2 ~ 800mJ / cm 2, 100mJ / It is particularly preferred that the density be from cm ² to 500 mJ / cm ² .

露光 From the viewpoint of removability, the exposure amount in the entire surface exposure step is preferably equal to or more than the exposure amount in the exposure step, and more preferably greater than the exposure amount in the exposure step.

<Heating process>
The method of manufacturing a circuit wiring according to the present disclosure includes a step of heating the entire surface exposed positive photosensitive resin layer during the entire surface exposure step, after the exposure step, or both, and before the removal step described below. (Hereinafter, may be referred to as a “heating step”). By including the heating step, the reaction rate of the photoacid generator and the reaction rate between the generated acid and the positive photosensitive resin can be improved, and as a result, the removal performance can be improved.

[Removal step]
An example of the removing step is schematically shown in FIG.
After the end of the second etching step, the second pattern 14B remains on a part of the first conductive layer 24B. What is necessary is just to remove the remaining second pattern 14B which is the positive photosensitive resin layer.
The removal in the removing step includes, for example, dissolving and dispersing the positive photosensitive resin layer in a removing liquid.

The method of removing the remaining positive-type photosensitive resin layer is not particularly limited, but a method of removing by a chemical treatment can be mentioned, and the use of a removing liquid is particularly preferable.
As a method for removing the positive type photosensitive resin layer, the substrate having the photosensitive resin layer or the like in the removal solution with stirring at preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C., is used for 1 minute to 30 minutes. An immersion method may be used.

In the removal step, from the viewpoint of removability, it is preferable to use a removal liquid containing 30% by mass or more of water, more preferably use a removal solution containing 50% by mass or more of water, and contain 70% by mass or more of water. It is more preferable to use a removing liquid that performs the removal.
The removing solution is preferably a removing solution containing an inorganic alkali component and / or an organic alkali component. Examples of the inorganic alkali component include sodium hydroxide, potassium hydroxide, magnesium hydroxide, aluminum hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia and the like. Examples of the organic alkali component include a primary amine compound, a secondary amine compound, a tertiary amine compound, a quaternary ammonium salt compound, and the like. Specifically, tetramethylammonium hydroxide, diethylamine, Examples include triethylamine, alkanolamine (eg, monomethylethanolamine, dimethylethanolamine, monoethanolamine, 2-amino-2-methyl-1-propanol, etc.), and aromatic amine (eg, pyridine, quinoline, etc.).
Above all, from the viewpoint of removability, a removal solution containing an organic alkali component is more preferred, and a removal solution containing an amine compound is particularly preferred.
The content of the alkali component may be appropriately selected from the viewpoint of the basic strength and solubility of the alkali component. %, More preferably 0.1 to 10% by mass.

The removal liquid preferably contains an organic solvent.
Examples of the organic solvent include esters such as ethyl acetate and ethyl lactate, ketones such as acetone, alcohols such as methanol, ethanol, diacetone alcohol and ethylene glycol, amides such as dimethylformamide and dimethylacetamide, methyl cellosolve, and propylene. Preferred examples include glycol ethers such as glycol methyl ether, tetrahydrofuran, γ-butyrolactone, acetonitrile, dioxane, dimethyl sulfoxide, N-methylpyrrolidone, and the like.

The removal liquid preferably contains a surfactant from the viewpoint of removability.
The surfactant is not particularly limited, and a known surfactant can be used. The content of the surfactant is preferably from 0.1% by mass to 10% by mass with respect to the total mass of the removing solution from the viewpoint of removability.
The removal liquid may contain a rust inhibitor, an acid, an ionic liquid, a polymer dispersant, or the like according to the purpose.

In the removing step, a method of removing the positive photosensitive resin by a spray method, a shower method, a paddle method, or the like using a removing liquid is preferable.

回路 The method for manufacturing a circuit wiring according to the present disclosure may include other arbitrary steps. For example, the following steps may be mentioned, but it is not limited to these steps.

[Process of attaching protective film]
After the first etching step and before the second exposure step, the method may further include a step of attaching a light-transmissive protective film (not shown) on the first pattern.
In this case, in the second exposure step, it is preferable that the first pattern is subjected to pattern exposure through the protective film, and after the second exposure step, the protective film is removed from the first pattern, and then the second development step is performed.

[Step of lowering visible light reflectance]
The method for manufacturing a circuit wiring according to the present disclosure can include a step of performing a process of reducing visible light reflectance of a part or all of a plurality of conductive layers on a base material.
An example of the treatment for lowering the visible light reflectance includes an oxidation treatment. For example, by oxidizing copper to form copper oxide, blackening can reduce visible light reflectance.
Preferred embodiments of the process for reducing the visible light reflectance are described in paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048, and 0058 of JP-A-2013-206315. And the contents of this publication are incorporated herein.

[Step of forming insulating film, step of forming new conductive layer on insulating film]
The method for manufacturing a circuit wiring according to the present disclosure preferably also 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-described second electrode pattern can be formed while being insulated from the first electrode pattern.
There is no particular limitation on the step of forming the insulating film, and a known method of forming a permanent film can be used. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
There is no particular limitation on the step of forming a new conductive layer on the insulating film. A new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

[Roll-to-roll method]
The method for manufacturing circuit wiring according to the present disclosure is preferably performed by a roll-to-roll method.
The roll-to-roll method uses a substrate that can be wound and unwound as a substrate, and unwinds the substrate or a structure including the substrate before any of the steps included in the circuit wiring manufacturing method ( Hereinafter, it may be referred to as a “unwinding step”), and after any of the steps, a step of winding up a structure including a substrate or a substrate (hereinafter, sometimes referred to as a “winding step”). And a method in which at least one step (preferably all steps or all steps other than the heating step) is performed while transporting a structure including a base material or a substrate.
The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and a known method may be used in a manufacturing method using a roll-to-roll method.

方法 Also, as examples of the exposure step, the development step, and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present disclosure.

FIG. 2 shows a case in which circuit wiring having two different patterns is formed on a circuit wiring forming substrate having two conductive layers, but a substrate to which the circuit wiring manufacturing method according to the present disclosure is applied. Is not limited to two layers. By using a substrate for circuit wiring formation in which three or more conductive layers are stacked and performing the above-described combination of the exposure step, the developing step, and the etching step three or more times, the three or more conductive layers are respectively different circuit wiring patterns. Can also be formed.

Although not shown in FIG. 2, the method for manufacturing a circuit wiring according to the present disclosure uses a substrate having a plurality of conductive layers on both surfaces of a base material, respectively, and a conductive layer formed on both surfaces of the base material. It is also preferable to form circuits sequentially or simultaneously. With such a configuration, it is possible to form a circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the base material and the second conductive pattern is formed on the other surface. In addition, it is also preferable that the circuit wiring for a touch panel having such a configuration is formed on both sides of the base material by roll-to-roll.

回路 The circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure can be applied to various devices. Examples of the device provided with the circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure include an input device and the like, and a capacitance touch panel is preferable. Further, the input device can be applied to a display device such as an organic EL display device and a liquid crystal display device.

<Touch panel manufacturing method>
The method for manufacturing a touch panel according to the present disclosure includes a step of peeling off the protective film of the photosensitive transfer material (hereinafter, may be referred to as a “peeling step”), and a step of removing the photosensitive transfer material from the temporary support. Bonding the outermost layer on the side having the positive photosensitive resin layer to the substrate having the conductive layer (hereinafter, sometimes referred to as a “bonding step”); and the photosensitive transfer after the bonding step. A step of pattern-exposing the positive photosensitive resin layer of the material (hereinafter, may be referred to as an “exposure step”), and developing the positive photosensitive resin layer after the pattern exposure step to form a resin pattern. A step of forming (hereinafter, sometimes referred to as a “development step”) and a step of etching a substrate in a region where the resin pattern is not arranged (hereinafter, referred to as an “etching step”). Including, that there.) I am.
According to the method for manufacturing a touch panel according to the present disclosure, since the photosensitive transfer material is used, a touch panel with reduced pattern failure can be manufactured.

Specific modes of the peeling step, the bonding step, the exposing step, the developing step, and the etching step in the method for manufacturing a touch panel according to the present disclosure will be described in the above section “Method for Manufacturing Circuit Wiring”. The same applies to the preferred embodiments.

A touch panel according to the present disclosure is a touch panel having at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure. Further, the touch panel according to the present disclosure preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
The detection method in the touch panel according to the present disclosure may be any of known methods such as a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the capacitance type is preferable.
As the touch panel type, a so-called in-cell type (for example, those described in JP-A-2012-517051 shown in FIGS. 5, 6, 7, and 8) and a so-called on-cell type (for example, JP-A-2013-168125) Japanese Unexamined Patent Publication No. 19-89102, Japanese Unexamined Patent Publication No. 2012-89102, and FIGS. 1 and 5), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, No. 2013-54727, FIG. 2), other configurations (for example, those described in FIG. 6 of JP-A-2013-164871), various out-cell types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.).
As the touch panel according to the present disclosure, “Latest Touch Panel Technology” (July 6, 2009, Techno Times Co., Ltd.), supervised by Yuji Mitani, “Technology and Development of Touch Panel”, CMC Publishing (2004, 12) , FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, and the like.

<Production method of resin pattern>
The method for producing a resin pattern according to the present disclosure includes a step of peeling the protective film of the photosensitive transfer material (hereinafter, may be referred to as a “peeling step”) and a step of removing the protective film of the photosensitive transfer material from the temporary support. On the other hand, a step of bonding the outermost layer on the side having the positive photosensitive resin layer to the substrate (hereinafter, sometimes referred to as a "bonding step"), and the above-described step of bonding the photosensitive transfer material after the bonding step. A step of pattern-exposing the positive photosensitive resin layer (hereinafter sometimes referred to as an “exposure step”), and a step of developing the positive photosensitive resin layer after the pattern exposure step to form a resin pattern (Hereinafter, may be referred to as “developing step”). According to the method for manufacturing a resin pattern according to the present disclosure, since the photosensitive transfer material is used, a resin pattern with reduced pattern failure can be manufactured.

In the method for manufacturing a resin pattern according to the present disclosure, the specific modes of the peeling step, the bonding step, the exposing step, and the developing step are as described in the above section “Method for manufacturing circuit wiring”. And the preferred embodiment is also the same. In addition, the substrate in the method for manufacturing a resin pattern according to the present disclosure may be a substrate itself such as glass, silicon, or a film, or a substrate such as glass, silicon, or a film, and if necessary, a conductive layer. May be a substrate on which an arbitrary layer is formed.

<Film>
The film according to the present disclosure is a biaxially stretched polyethylene terephthalate film in which a uniaxially stretched polyethylene terephthalate film, which is a stretched product in the first stretching direction, is stretched along a film surface in a second stretching direction orthogonal to the first stretching direction. And an undercoat layer which is a stretched product of the coating layer formed on one surface of the uniaxially stretched polyethylene terephthalate film in the second stretching direction. The surface of the undercoat layer has the following (A) and (B) Meet).
(A) The water contact angle is 75 ° or more.
(B) The surface roughness Ra is 45 nm or less.

Since the film according to the present disclosure satisfies the above conditions (A) and (B), the surface energy of the film surface can be reduced and the unevenness can be reduced. Transfer of unevenness can be reduced.

Furthermore, the film according to the present disclosure has a biaxially stretched polyethylene terephthalate film and an undercoat layer that is a stretched product, and by further reducing the surface energy of the film, the peelability of the film can be further improved. The surface smoothness and the adhesion between the biaxially oriented polyethylene terephthalate film and the undercoat layer can also be improved.

上記 The biaxially stretched polyethylene terephthalate film in the film according to the present disclosure refers to a polyethylene terephthalate film having one surface having a surface roughness Ra of 45 nm or less measured by the method described above.

上記 The undercoat layer in the film according to the present disclosure is synonymous with the undercoat layer which is a stretched product described in the section “undercoat layer”.

好ましい A preferred embodiment of the film according to the present disclosure is the same as the preferred embodiment of the protective film described in the section of “Photosensitive Transfer Material” above.

Further, as another embodiment, a film according to the present disclosure has a first resin layer and a second resin layer provided on the first resin layer, and the first resin layer is made of polyester. And the surface of the second resin layer satisfies the following (A) and (B).
(A) The water contact angle is 75 ° or more.
(B) The surface roughness Ra is 45 nm or less.

The first resin layer contains polyester, and may contain other components as needed. The polyester is preferably polyethylene terephthalate from the viewpoint of smoothness.

厚み The thickness of the first resin layer is preferably from 5 μm to 200 μm, more preferably from 10 μm to 150 μm, further preferably from 10 μm to 100 μm, particularly preferably from 10 μm to 50 μm.

樹脂 The resin contained in the second resin layer is not particularly limited, and examples thereof include polyolefin, acrylic polymer, and polyester. The second resin layer preferably contains a modified resin from the viewpoint of releasability and reduction of pattern failure, and contains at least one resin selected from the group consisting of an acid-modified resin and a silicone-modified resin. Is more preferred. More specifically, the second resin layer preferably contains at least one resin selected from the group consisting of a modified polyolefin and a modified acrylic polymer, from the viewpoint of peelability and reduction of pattern failure, It is more preferable to contain at least one resin selected from the group consisting of a modified polyolefin and a silicone-modified acrylic polymer, and it is particularly preferable to contain an acid-modified polyolefin.

Preferred examples of the acid-modified polyolefin are the same as the acid-modified polyolefin described in the section of “Undercoat layer”.

樹脂 The resin contained in the second resin layer may be used alone or in combination of two or more.

The thickness of the second resin layer is not limited, and is preferably from 10 nm to 550 nm, more preferably from 10 nm to 500 nm, and more preferably from 10 nm to 100 nm, from the viewpoints of peelability and reduction in pattern failure. More preferably, it is particularly preferably from 10 nm to 60 nm.

フィルム The method for producing a film according to the present disclosure is not particularly limited as long as the second resin layer can be provided on the first resin layer. The second resin layer may be provided on the first resin layer by a coating method, and the first resin layer and the second resin layer may be provided by a co-extrusion method.

In the method for producing a film according to the present disclosure, a first resin layer is formed by film forming, and then a coating liquid for forming a second resin layer is applied on the first resin layer, and a biaxial stretching process is performed. May be performed. Further, in the method for producing a film according to the present disclosure, a first resin layer is formed by film forming, and after performing a uniaxial stretching treatment, a coating liquid for forming a second resin layer is applied. A method of performing another uniaxial stretching treatment may be used. In addition, the method for producing a film according to the present disclosure is a method in which a first resin layer is formed by film forming, a biaxial stretching process is performed, and then a coating liquid for forming a second resin layer is applied. There may be.

Further, the method for producing a film according to the present disclosure is a method in which a raw material for forming a first resin layer and a raw material for forming a second resin layer are co-extruded and then biaxially stretched. It may be. Note that the stretching process may be omitted as appropriate.

フィルム The film according to the present disclosure can protect the surface of an object by being attached to various objects. That is, the protective film is preferably used. The film according to the present disclosure is excellent in releasability, and can reduce the transfer of unevenness to the adherend surface, for example, a member that needs to avoid deformation of the surface shape (for example, a member having high smoothness, And a member having a characteristic surface shape). Further, the protective film according to the present disclosure is more preferably used for protecting various photosensitive transfer materials (dry film resists), and for protecting a photosensitive transfer material having a positive photosensitive resin layer. It is particularly preferred that they be used.

Hereinafter, the present disclosure will be described in detail with reference to Examples, but the present disclosure is not limited thereto. Unless otherwise specified, “parts” and “%” are based on mass.

<Production Example 1>
According to the following procedure, the following coating liquid 1 for forming an undercoat layer was applied to one surface of polyethylene terephthalate (PET) used as a substrate, and then stretched to obtain a protective film of Production Example 1.

[Preparation of Undercoat Layer-Forming Coating Solution 1]
The following components were mixed together to obtain a coating liquid 1 for forming an undercoat layer. The obtained coating solution 1 for forming an undercoat layer was subjected to filtration with a 6 μm filter (F20, manufactured by Mare Filter Systems Co., Ltd.) and membrane deaeration (2 × 6 radial flow superphobic, manufactured by Polypore).
-Acid-modified polyolefin (Siixen L, manufactured by Sumitomo Seika Co., Ltd., solid content: 25% by mass): 16.7 parts-Anionic surfactant (Lapisol A-90, manufactured by NOF Corporation, solid content: 1 mass%) % Water dilution): 5.6 parts, water: 77.7 parts

[Extrusion molding]
After drying polyethylene terephthalate (PET) pellets using a titanium compound described in Japanese Patent No. 5575671 as a polymerization catalyst to a water content of 50 ppm or less, the pellets were put into a hopper of a single-screw kneading extruder having a diameter of 30 mm. And extruded. This melt (melt) was passed through a filter (pore size: 3 μm) and then extruded from a die to a cooling roll at 25 ° C. to obtain an unstretched film. Note that the extruded melt was brought into close contact with a cooling roll by using an electrostatic application method.

[Stretching, coating]
The unstretched film extruded and solidified on the cooling roll by the above method is subjected to sequential biaxial stretching by the following method, and has a 25 μm-thick base material (polyester film) and a 50 nm-thick undercoat layer. I got

(A) Longitudinal stretching The unstretched film was passed between two pairs of nip rolls having different peripheral speeds and stretched in the longitudinal direction (that is, the transport direction). The stretching was performed at a preheating temperature of 75 ° C., a stretching temperature of 90 ° C., a stretching ratio of 3.4 times, and a stretching speed of 1300% / sec.

(B) Coating An undercoat layer forming coating liquid 1 was coated on one surface of the longitudinally stretched film by a bar coater so that the thickness after film formation was 50 nm.

(C) Lateral stretching The film that had been longitudinally stretched and applied was laterally stretched using a tenter under the following conditions.
-conditions-
Preheating temperature: 110 ° C
Stretching temperature: 120 ° C
Stretching ratio: 4.2 times Stretching speed: 50% / sec

[Heat fixation, thermal relaxation]
Subsequently, the stretched film after the completion of the longitudinal stretching and the transverse stretching was heat-set under the following conditions. Furthermore, after heat setting, the width of the tenter was reduced and the heat was relaxed under the following conditions.
-Thermal process conditions-
Heat setting temperature: 227 ° C
Heat setting time: 6 seconds-Thermal relaxation condition-
Thermal relaxation temperature: 190 ° C
Thermal relaxation rate: 4%

[Take-up]
After heat fixation and thermal relaxation, both ends were trimmed, and after extruding (knurling) the ends at a width of 10 mm, they were wound up at a tension of 40 kg / m. In addition, the width of the film roll was 1.5 m, and the winding length was 6,300 m. The obtained film roll was used as the protective film of Production Example 1.
The substrate of the obtained protective film has a haze of 0.2, and has a heat shrinkage of 1.0% in MD (Machine Direction) and 0 in TD (Transverse Direction) when heated at 150 ° C. for 30 minutes. 0.2%. The thickness of the undercoat layer measured from a cross-sectional TEM (Transmission Electron Microscope) photograph was 50 nm.

<Production Examples 2 to 7>
Except that the composition of the undercoat layer forming coating liquid 1 was changed according to the description in Table 1, and that the thickness of the undercoat layer after film formation was changed according to the description in Table 1 by adjusting the bar during coating, In the same manner as in Production Example 1, protective films of Production Examples 2 to 7 were obtained.

<Production Example 8>
Except that the following undercoat layer forming coating liquid 2 was used in place of the undercoat layer forming coating liquid 1 and that the thickness of the undercoat layer after film formation was changed to 80 nm by adjusting the bar at the time of coating, the production was carried out. A protective film of Production Example 8 was obtained in the same manner as in Example 1.
(Coating solution 2 for forming undercoat layer)
-Urethane polymer (Elastron H3DF, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content 28% by mass): 16.5 parts-Blocked isocyanate (Duranate WM44-L70G, manufactured by Asahi Kasei Corporation, solid content 70% by mass): 1 0.5 parts anionic surfactant (Lapisol A-90, manufactured by NOF CORPORATION, solid content 1% by mass in water): 4.2 parts sodium hydrogen carbonate (Asahi Glass Co., Ltd., solid content 5%) % Water dilution): 0.3 part Carnauba wax dispersion (Cerosol 524, manufactured by Chukyo Yushi Co., Ltd., solid content 30% by mass): 0.5 part Organosin water dispersion (Elastron Cat21, Daiichi Kogyo Pharmaceutical Co., Ltd.) (Manufactured by Corporation, solid content 1% by mass diluted with water): 3.3 parts, water: 73.7 parts

<Production Example 9>
A protective film of Production Example 9 was obtained in the same manner as in Production Example 1, except that the coating liquid for forming an undercoat layer was not applied.

<Production Example 10>
In the coating step, the following coating liquid for forming an overcoat layer is further coated on the surface of the longitudinally stretched film opposite to the surface to which the coating liquid 1 for forming an undercoat layer is applied so that the thickness after film formation is 60 nm. Except for the application, a protective film of Production Example 10 was obtained in the same manner as in Production Example 1.
(Coating liquid for overcoat layer formation)
Acrylic polymer (AS-563A, manufactured by Daicel Finechem Co., Ltd., solid content: 27.5% by mass): 16.7 partsNonionic surfactant (Naroacty CL95, manufactured by Sanyo Chemical Industry Co., Ltd., solid content: 100) % By mass): 0.07 parts Anionic surfactant (Lapisol A-90, manufactured by NOF CORPORATION, solid content: 1% by mass in water): 11.44 parts Carnauba wax dispersion (Cerosol 524, Chukyo) 0.7 parts of a carbodiimide compound (Carbodilite V-02-L2, manufactured by Nisshinbo Industries, diluting with a solid content of 10% by weight in water): 2.09 parts Snowtex XL, manufactured by Nissan Chemical Co., Ltd., solid content: 40% by mass): 0.28 parts, water: 69.0 parts

<Abbreviation>
In the following examples, the following abbreviations represent the following compounds, respectively.
ATHF: 2-tetrahydrofuranyl acrylate (synthetic product)
MMA: Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
EA: ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
CHA: cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
PMPMA: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
PGMEA (propylene glycol monomethyl ether acetate): (manufactured by Showa Denko KK)
V-601: dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

<Example 1>
[Synthesis of ATHF]
Acrylic acid (72.1 g, 1.0 mol) and hexane (72.1 g) were added to a three-neck flask and cooled to 20 ° C. After dropwise addition of camphorsulfonic acid (7.0 mg, 0.03 mmol) and 2-dihydrofuran (77.9 g, 1.0 mol), the mixture was stirred at 20 ° C. ± 2 ° C. for 1.5 hours, and then heated to 35 ° C. And stirred for 2 hours. After spreading Kyoward 200 (aluminum hydroxide adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (hydrotalcite-based adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) in order on Nutsche, the reaction solution was filtered. Then, a filtrate was obtained. Hydroquinone monomethyl ether (MEHQ, 1.2 mg) was added to the obtained filtrate, and the mixture was concentrated at 40 ° C. under reduced pressure to obtain 140.8 g of 2-tetrahydrofuranyl acrylate (ATHF) as a colorless oil. Rate 99.0%).

[Synthesis of Polymer A1]
PGMEA (75.0 g) was charged into a three-necked flask and heated to 90 ° C. under a nitrogen atmosphere. ATHF (29.0 g), CHA (5.0 g), EA (30.0 g), MMA (35.0 g), PMPMA (1.0 g), V-601 (4.1 g), PGMEA (75.0 g) Was added dropwise over 2 hours to a three-neck flask solution maintained at 90 ° C. ± 2 ° C. After completion of the dropwise addition, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain a polymer A1 (solid content: 40.0%).

[Preparation of photosensitive resin composition 1]
Photosensitive resin composition 1 was prepared according to the following formulation.
-Polymer A1: 93.9 parts-Photoacid generator (B-1 below): 2.0 parts-Surfactant (C-1 below): 0.1 parts-Additive (D-1 below): 0.2 parts ・ PGMEA: 900 parts

[Preparation of photosensitive transfer material]
The photosensitive resin composition 1 was applied on a 25 μm-thick polyethylene terephthalate film serving as a temporary support using a slit-shaped nozzle so that the dry film thickness became 3.0 μm. After drying for 2 minutes in a convection oven at 100 ° C., the undercoat layer side of the protective film of Production Example 1 was brought into contact with the photosensitive resin composition layer and pressure-bonded to produce a photosensitive transfer material. The obtained photosensitive transfer material was used as the photosensitive transfer material of Example 1.

<Examples 2 to 4, 7 to 11>
The photosensitive transfer materials of Examples 2 to 4 and 7 to 11 were produced in the same manner as in Example 1 except that the protective film was changed as described in Table 2.

<Example 5>
[Preparation of Composition 1 for Intermediate Layer]
Composition 1 for an intermediate layer was prepared according to the following formulation.
-Distilled water: 137.0 parts-Methanol: 319.0 parts-NISSO HPC-SSL (manufactured by Nippon Soda Co., Ltd.): 20.6 parts-Snowtex O (manufactured by Nissan Chemical Industries, Ltd.): 68.5 Department

[Preparation of photosensitive transfer material]
The composition 1 for an intermediate layer is slit-coated on a 25 μm-thick polyethylene terephthalate film serving as a temporary support so as to have a dry film thickness of 2.0 μm, and then dried in a convection oven at 100 ° C. for 2 minutes. Thus, a water-soluble resin layer serving as an intermediate layer was formed. Next, the photosensitive resin composition 1 was applied onto the water-soluble resin layer using a slit-shaped nozzle so that the dry film thickness became 3.0 μm. After drying in a convection oven at 100 ° C. for 2 minutes, the protective film of Production Example 3 was pressed to produce a photosensitive transfer material. The obtained photosensitive transfer material was used as the photosensitive transfer material of Example 5.

<Example 6>
A photosensitive transfer material of Example 6 was produced in the same manner as in Example 3, except that the following photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.

[Preparation of photosensitive resin composition 2]
Photosensitive resin composition 2 was prepared according to the following formulation.
-Novolak resin (meta-cresol: para-cresol = 30:70, molecular weight 5,500): 79.9 parts-Photosensitizer: naphthoquinonediazide compound (1): 20 described on page 4 of JP-A-4-22955 0.0 part ・ Surfactant (C-1 below): 0.1 part ・ PGMEA: 900 parts

<Comparative Example 1>
A photosensitive transfer material of Comparative Example 1 was obtained in the same manner as in Example 1, except that the film of Production Example 8 was used instead of the protective film of Production Example 1.

<Comparative Example 2>
A photosensitive transfer material of Comparative Example 2 was obtained in the same manner as in Example 1, except that the film of Production Example 9 was used instead of the protective film of Production Example 1.

<Comparative Example 3>
A photosensitive transfer material of Comparative Example 3 was obtained in the same manner as in Example 1, except that the following film 2 was used instead of the protective film of Production Example 1.

<Measurement of water contact angle>
The water contact angle was measured using the peeled surface exposed by peeling the protective film from each of the photosensitive transfer materials of Examples 1 to 11 and Comparative Examples 1 to 3 under the following peeling conditions as a measurement surface. Specifically, using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DROPMASTER-501), the contact angle 7 seconds after dropping 2 μL of purified water on the measurement surface at a temperature of 25 ° C. was measured. It was measured by the drop method. Table 2 shows the measurement results.

[Peeling conditions]
The photosensitive transfer material was cut out to 4.5 cm wide by 9 cm long, and the surface on the temporary support side was bonded to a glass plate with a double-sided adhesive tape. An adhesive tape cut to 4.5 cm wide and 15 cm long is attached to the pasted photosensitive transfer material, the width direction of the adhesive tape is aligned with the width direction of the photosensitive transfer material, and the adhesive tape protrudes in the width direction. Instead, the pieces were bonded so that the adhesive tape protruded by 3 cm before and after the length direction. One end of the tape was gripped, and 180 ° peeling was performed at a peeling speed of 500 mm / min using a tensile tester. Here, the pressure-sensitive adhesive tape and the double-sided pressure-sensitive adhesive tape used are those described in JIS Z 0109: 2015, and the tensile tester is a tensile tester (tester grade 1: relative indication error) specified in JIS B 7721: 2009. ± 1.0%) or equivalent tensile tester.

<Measurement of surface roughness Ra>
A three-dimensional optical profiler (New View 7300, manufactured by Zygo) was used for the peeled surface exposed by peeling the protective film from each of the photosensitive transfer materials of Examples 1 to 11 and Comparative Examples 1 to 3 under the above peel conditions. The surface profile of the protective film was obtained under the following conditions. The measurement and analysis software uses MicroScope Application 8.3.2. Next, a Surface Map screen is displayed by the analysis software (MetroPro 8.3.2-Microscope Application), and histogram data is obtained in the Surface Map screen. The arithmetic average roughness was calculated from the obtained histogram data, and was defined as an Ra value. Table 2 shows the measurement results.
[Measurement condition]
Objective lens: 50 × Zoom: 0.5 × Measurement area: 1.00 mm × 1.00 mm
[Analysis conditions]
Removed: plane
Filter: off
FilterType: average
Remove spikes: on
Spike Height (xRMS): 7.5

<Evaluation of peelability of protective film>
After the photosensitive transfer materials of Examples 1 to 11 and Comparative Examples 1 to 3 were stored at a temperature of 23 ° C. and a relative humidity of 55% for 2 months, the protective film was peeled off under the above peeling conditions. The peelability of the protective film was evaluated according to the following criteria. Table 2 shows the evaluation results. In addition, 2 is a practical range.

[Standard]
2: Only the protective film can be peeled off 1: The positive photosensitive resin layer adheres to the peeled protective film.

<Pattern shape evaluation>
In the pattern shape evaluation, a polyethylene terephthalate (PET) substrate with a copper layer (hereinafter, referred to as a “PET substrate with a copper layer”) in which a copper layer was formed on a 188 μm-thick PET film with a thickness of 500 nm by a sputtering method. .)It was used.
After storing the photosensitive transfer materials of Examples 1 to 11 and Comparative Examples 1 to 3 at a temperature of 23 ° C. and a relative humidity of 55% for 2 months, the protective film of each photosensitive transfer material was peeled off and the copper Lamination was performed on a layered PET substrate under the conditions of 100 ° C., 2 m / min, and 0.6 MPa to produce a laminate in which a positive resist layer was laminated on a copper layer.
The laminated body was exposed to a contact pattern using a photomask provided with a line and space wiring pattern having a line width of 10 μm (the width ratio of the opening portion to the light shielding portion was 1: 1) without peeling the temporary support. went. For exposure, a high-pressure mercury lamp using i-ray (365 nm) as a main exposure wavelength was used.
After leaving for 5 hours after exposure, the temporary support was peeled off and developed. The development was performed by using a 1.0% aqueous sodium carbonate solution at 28 ° C. for 40 seconds by shower development. A 10 μm line-and-space pattern was formed by the above method, an exposure amount at which the ratio of the line width to the space width was 1: 1 was obtained, and a pattern was formed on the sample with the exposure amount. The form of this pattern was observed by SEM (Scanning Electron Microscope, 20,000 times magnification), and the form of the pattern was evaluated based on the following criteria. Table 2 shows the evaluation results. In addition, 2 or more is a practicable level.
[Standard]
3: Tapered shape without undercut.
2: There is a part where an undercut exists or a part where a pattern is missing.
1: There is a portion where no pattern remains.

As can be seen from Table 2, the photosensitive transfer materials of Examples 1 to 11 have good cover releasability, and the patterns manufactured using these photosensitive transfer materials have reduced pattern failure and excellent pattern shape. I understand. Compared with the photosensitive transfer materials of Examples 1 and 2, the photosensitive transfer material of Example 3 has a good pattern without undercut since the acid group contained in the acid-modified polyolefin is a sodium salt. Obtained.

On the other hand, when the photosensitive transfer materials of Comparative Examples 1 and 2 were stored at 23 ° C. and 55% (relative humidity) for 2 months, the protective film could not be peeled off normally, and it was difficult to use them as photosensitive transfer materials. Further, the photosensitive transfer material of Comparative Example 3 had a portion where no pattern remained, and was not at a practical level.

<Photoacid generator>
B-1: Compound having the structure shown below (the compound described in paragraph 0227 of JP-A-2013-047765, which was synthesized according to the method described in paragraph 0204).

<Surfactant>
C-1: Megafac F552 (manufactured by DIC Corporation)

<Additives>
D-1: Compound having the structure shown below

<Protective film>
Film 1: Polypropylene film Torayfan 25KW37 (manufactured by Toray Industries, Inc.)
Film 2: Polypropylene film Alphan E-501 (manufactured by Oji F-Tex Corporation)

<Example 101>
On a PET substrate having a thickness of 100 μm, ITO was formed as a second conductive layer by sputtering to a thickness of 150 nm, and copper was formed thereon as a first conductive layer to a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
The photosensitive transfer material 1 obtained in Example 1 was laminated on the copper layer (roll temperature: 120 ° C., linear pressure: 0.8 MPa, linear velocity: 1.0 m / min.). Contact pattern exposure was performed using a photomask provided with a pattern A shown in FIG. 3 having a configuration in which conductive layer pads were connected in one direction without removing the temporary support. In the pattern A shown in FIG. 3, a solid line portion SL and a gray portion G are light shielding portions, and a dotted line portion DL is a virtual frame for alignment. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Next, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.) A substrate on which both copper and ITO were drawn in pattern A was obtained.
Next, pattern exposure was performed using a photomask provided with an opening of pattern B shown in FIG. 4 in an aligned state, and development and washing were performed. In the pattern B shown in FIG. 4, a gray portion G is a light-shielding portion, and a dotted line portion DL virtually shows a frame for alignment.
Thereafter, the copper layer was etched using Cu-02, and the entire surface of the remaining photosensitive resin layer was exposed to light (300 mJ / cm ² ) using an ultra-high pressure mercury lamp. It was removed using BONDERITE C-AK P123 (manufactured by Co., Ltd.) to obtain a circuit wiring.
Observation of the obtained circuit wiring with a microscope revealed no peeling or chipping and a beautiful pattern.

<Example 102>
On a PET substrate having a thickness of 100 μm, ITO was formed as a second conductive layer by sputtering to a thickness of 150 nm, and copper was formed thereon as a first conductive layer to a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
The photosensitive transfer material 1 obtained in Example 1 was laminated on the copper layer (roll temperature: 120 ° C., linear pressure: 0.8 MPa, linear velocity: 1.0 m / min.).
Pattern exposure was performed using a photomask provided with a pattern A shown in FIG. 3 having a configuration in which conductive layer pads were connected in one direction without removing the temporary support. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Next, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.) A substrate on which both copper and ITO were drawn in pattern A was obtained.
Next, PET (A) was laminated as a protective layer on the remaining resist. In this state, pattern exposure was performed using a photomask provided with an opening for pattern B shown in FIG. 4 in an aligned state, and PET (A) was peeled off, followed by development and washing with water.
Thereafter, the copper wiring was etched using Cu-02, the entire surface of the remaining photosensitive resin layer was exposed to light (300 mJ / cm ² ) using an ultra-high pressure mercury lamp, and after being exposed to light for 10 seconds, the removal solution (Henkel ( It was removed using BONDERITE C-AK P123 (manufactured by Co., Ltd.) to obtain a circuit wiring.
Observation of the obtained circuit wiring with a microscope revealed no peeling or chipping and a beautiful pattern.

The disclosures of Japanese Patent Application No. 2018-170973 filed on September 12, 2018 and Japanese Patent Application No. 2019-057423 filed on March 25, 2019 are incorporated herein by reference in their entirety. Is included in the book. In addition, all documents, patent applications, and technical standards described herein are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. , Incorporated herein by reference.

Claims

A temporary support,
A positive photosensitive resin layer,
Protective film,
In this order, and the surface of the protective film in contact with the positive photosensitive resin layer satisfies the following (A) and (B).
(A) The water contact angle is 75 ° or more.
(B) The surface roughness Ra is 45 nm or less.
感光 The photosensitive transfer material according to claim 1, wherein the surface roughness Ra is 25 nm or less.
The said protective film has a base material and an undercoat layer, The outermost layer of the said protective film in contact with the said positive photosensitive resin layer is the said undercoat layer, Claim 1 or Claim 2. The photosensitive transfer material as described in the above.
The protective film,
A biaxially stretched film in which a uniaxially stretched film that is a stretched product in the first stretching direction is stretched in a second stretching direction orthogonal to the first stretching direction along the film surface,
An undercoat layer, which is a stretched product in the second stretching direction of the coating layer formed on one surface of the uniaxially stretched film,
Has,
The photosensitive transfer material according to claim 1, wherein an outermost layer of the protective film on a side in contact with the positive photosensitive resin layer is the undercoat layer.
The photosensitive transfer material according to claim 3 or 4, wherein the undercoat layer contains an acid-modified polyolefin.
6. The photosensitive transfer material according to claim 5, wherein the acid-modified polyolefin has an acid group, and at least one of the acid groups is an alkali metal salt.
The photosensitive transfer material according to any one of claims 3 to 6, wherein the undercoat layer has a thickness of 10 nm to 550 nm.
8. The photosensitive transfer material according to claim 1, further comprising a water-soluble resin layer between the temporary support and the positive photosensitive resin layer.
The photosensitive transfer material according to any one of claims 1 to 8, wherein the positive photosensitive resin layer contains an acid-decomposable resin.
10. The positive photosensitive resin layer according to claim 1, wherein the positive photosensitive resin layer contains a polymer component at a ratio of 80% by mass to 98% by mass based on the total solid content of the positive photosensitive resin layer. 3. The photosensitive transfer material according to item 1.
Removing the protective film of the photosensitive transfer material according to any one of claims 1 to 10,
A step of bonding the outermost layer of the photosensitive transfer material on the side having the positive photosensitive resin layer to the temporary support to a substrate having a conductive layer,
Pattern exposure of the positive photosensitive resin layer of the photosensitive transfer material after the bonding step,
Developing the positive photosensitive resin layer after the pattern exposure step to form a resin pattern,
A step of etching the substrate in a region where the resin pattern is not arranged,
And a method for manufacturing a circuit wiring.
Removing the protective film of the photosensitive transfer material according to any one of claims 1 to 10,
A step of bonding the outermost layer on the side having the positive photosensitive resin layer to the temporary support of the photosensitive transfer material, to a substrate having a conductive layer,
Pattern exposure of the positive photosensitive resin layer of the photosensitive transfer material after the bonding step,
Developing the positive photosensitive resin layer after the pattern exposure step to form a resin pattern,
A step of etching the substrate in a region where the resin pattern is not arranged,
A method for manufacturing a touch panel, comprising:
Removing the protective film of the photosensitive transfer material according to any one of claims 1 to 10,
A step of bonding the outermost layer of the photosensitive transfer material on the side having the positive photosensitive resin layer to the temporary support to a substrate,
Pattern exposure of the positive photosensitive resin layer of the photosensitive transfer material after the bonding step,
Developing the positive photosensitive resin layer after the pattern exposure step to form a resin pattern,
A method for producing a resin pattern, comprising:
A biaxially stretched polyethylene terephthalate film in which a uniaxially stretched polyethylene terephthalate film which is a stretched product in the first stretching direction is stretched along a film surface in a second stretching direction orthogonal to the first stretching direction,
An undercoat layer that is a stretched product in the second stretching direction of a coating layer formed on one surface of the uniaxially stretched polyethylene terephthalate film,
Has,
A film wherein the surface of the undercoat layer satisfies the following (A) and (B).
(A) The water contact angle is 75 ° or more.
(B) The surface roughness Ra is 45 nm or less.
The film according to claim 14, wherein the undercoat layer contains an acid-modified polyolefin.
A first resin layer, and a second resin layer provided on the first resin layer;
The first resin layer contains polyester,
A film in which the surface of the second resin layer satisfies the following (A) and (B).
(A) The water contact angle is 75 ° or more.
(B) The surface roughness Ra is 45 nm or less.
17. The film according to claim 16, wherein the thickness of the first resin layer is 5 μm to 200 μm, and the thickness of the second resin layer is 10 nm to 550 nm.
The film according to any one of claims 14 to 17, which is a protective film.