WO2017057616A1

WO2017057616A1 - Dry film resist, manufacturing method for circuit wiring, circuit wiring, input device, and display device

Info

Publication number: WO2017057616A1
Application number: PCT/JP2016/078890
Authority: WO
Inventors: 晃男片山; 崇一郎長田
Original assignee: 富士フイルム株式会社
Priority date: 2015-09-30
Filing date: 2016-09-29
Publication date: 2017-04-06
Also published as: JPWO2017057616A1; JP6574846B2

Abstract

This positive dry film resist having a resist layer on a temporary supporting body and satisfying condition (1) and/or condition (2) enables manufacturing of circuit wiring having high pattern linearity. Condition (1): the temporary supporting body has a transmittance of not higher than 80% with respect to an exposure main wavelength for the resist layer. Condition (2): a light absorption layer having a transmittance of not higher than 80% with respect to the exposure main wavelength for the resist layer is included between the temporary supporting body and the resist layer. Also provided are a manufacturing method for circuit wiring, circuit wiring, an input device, and a display device.

Description

Dry film resist, circuit wiring manufacturing method, circuit wiring, input device and display device

The present invention relates to a dry film resist, a circuit wiring manufacturing method, circuit wiring, an input device, and a display device.

In a display device (such as an organic EL display device or a liquid crystal display device) equipped with a touch panel such as a capacitance-type input device, an electrode pattern corresponding to a sensor in a visual recognition part, or a conductive pattern such as a wiring in a peripheral wiring part or a lead-out wiring part Is provided inside the touch panel.
In general, a patterned conductive layer is formed by using a dry film resist as a photosensitive transfer material and a resist provided on an arbitrary circuit formation substrate because the number of steps for obtaining a required pattern shape is small. A layer (photosensitive resin composition layer) is exposed through a mask having a desired pattern, the resist layer is partially cured or dissolved, and developed to obtain a circuit pattern, and then etched to form a conductive layer In addition, a method of forming a circuit pattern by transfer is widely used.

Here, the resist layer is roughly classified into a negative type and a positive type from the reaction method with light or electron beam. When exposed to a negative resist layer, the solubility in the developer decreases, leaving an exposed portion after development. When the positive resist layer is exposed, the solubility in the developer increases, and the exposed portion is removed after development. Since there is an advantage that a high-resolution pattern can be easily formed as compared with a negative resist, a positive dry film resist is required.

For example, positive dry film resists described in

Patent Documents

1 and 2 are known as positive dry film resists.

Patent Document 1 describes a multilayer resist in which an intermediate layer having photobleaching properties and / or light absorption properties is provided between a lower photoresist layer and an upper photoresist layer. Patent Document 1 also describes providing a multilayer resist with improved multi-contrast exposure controllability and improved multi-contrast exposure effect.

Patent Document 2 describes a film-type photodegradable transfer material including a support film; a photodegradable photoresist layer; and a reflection suppressing layer formed on a surface to be laminated on a circuit forming substrate.

Japanese Patent Laid-Open No. 5-66568 JP 2009-282522 A

When the present inventors examined circuit formation using the positive-type dry film resists described in

Patent Documents

1 and 2, when pattern exposure was performed without peeling off the temporary support, exposure was caused by light diffusion caused by the temporary support. It was found that light diffuses and the pattern linearity of the resulting pattern is degraded. In the positive resist, the exposed portion dissolves to form a mask image, so that the remaining pattern portion is not cured, and peeling is likely to occur particularly in a thin line pattern when the pattern linearity is lowered. Therefore, circuit quality degradation, circuit disconnection, and short circuit may occur. Therefore, it has been found that this is a more prominent problem when a high resolution pattern is formed using a positive dry film resist than when a high resolution pattern is formed using a negative resist.

The problem to be solved by the present invention is to provide a dry film resist that is capable of producing a circuit wiring having a high pattern linearity that is easy to form a high resolution pattern.
Further, the problem to be solved by the present invention is to provide a positive-type circuit wiring that can easily form a high-resolution pattern and a high pattern linearity, and a method for manufacturing the circuit wiring.
Another problem to be solved by the present invention is to provide an input device using the circuit wiring and a display device including the input device.

As a result of intensive studies by the present inventors, it has been found that the above problem can be solved when a temporary support is a dry film resist having a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer.
Further, the present inventors have found that the above problem can be solved in the same manner as when a dry film resist having a light absorption layer having a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer is used between the temporary support and the resist layer. It was. In addition, since the transfer material described in Patent Document 2 uses a mechanism that prevents halation of exposure light reflected by the metal substrate by the reflection suppression layer, the transfer surface in contact with the target substrate in the case of transfer is It is necessary to laminate the temporary support, the resist layer, and the reflection suppressing layer in this order from the opposite side.
The present invention, which is a specific means for solving the above problems, and preferred ranges of the present invention are as follows.

[1] A positive dry film resist having a resist layer on a temporary support,
A dry film resist satisfying at least one of the following conditions (1) and (2);
Condition (1): The temporary support has a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer;
Condition (2): A light absorption layer having a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer is provided between the temporary support and the resist layer.
[2] In the dry film resist according to [1], the resist layer includes a photosensitizer,
It is preferable that the extinction coefficient of the resist layer of the photosensitive agent with respect to the main exposure wavelength is less than 12,000 cm ⁻¹ M ⁻¹ .
[3] In the dry film resist according to any one of [1] and [2], the total light haze of the temporary support is preferably 3.0% or less.
[4] In the dry film resist according to any one of [1] to [3], the resist layer preferably contains a naphthoquinonediazide compound and a resin having a phenolic hydroxyl group.
[5] In the dry film resist according to any one of [1] to [3], the resist layer includes (A) a component and (B) a photoacid generator,
The component (A) is preferably a polymer having a group in which an acid group is protected with an acid-decomposable group.
[6] In the dry film resist according to [5], the component (A) is a polymer component including a polymer having an acid structural unit a1 in which a carboxy group or a phenolic hydroxyl group is protected in the form of an acetal. Is preferred.
[7] In the dry film resist according to [5] or [6], the component (A) is preferably a polymer having a structural unit represented by the following general formula A1 or general formula A1 ′;
General formula A1

In general formula A1, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or Represents an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, and R ⁴ represents a hydrogen atom or a methyl group;
General formula A1 '

In General 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 an aryl group, and R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, and each R ¹⁴ independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, An alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group or a cycloalkyl group is represented.
[8] In the dry film resist according to any one of [5] to [7], the resist layer contains two or more types of component (A), and
As the component (A), it is preferable to contain a polymer having a structural unit represented by the following general formula A2 ′;
General formula A2 '

In general formula A2 ′, 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 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, and X ⁰ represents a single bond or an arylene group. .
[9] In the dry film resist according to any one of [1] to [8], it is preferable that the resist layer further includes (C) a heterocyclic compound.
[10] In the dry film resist according to any one of [1] to [9], the resist layer preferably further contains a basic compound.
[11] In the dry film resist according to any one of [1] to [10], the resist layer preferably further contains a radiation absorber.
[12] A circuit wiring manufacturing method including the following steps (a), (b), (c) and (d);
(A) a laminating step of laminating the dry film resist according to any one of [1] to [11] on a circuit forming substrate having a base material and a conductive layer;
(B) a pattern exposure step of exposing a contact pattern with a pattern for pattern exposure without peeling off the temporary support of the dry film resist;
(C) a development step in which the temporary support is peeled and then developed to form a pattern exposure pattern on the resist layer;
(D) An etching step of forming a pattern exposure pattern on the circuit forming substrate by etching.
[13] In the circuit wiring manufacturing method according to [12], the step (b) is the following step (b1),
(C) The process is the following (c1) process,
(D) The process is the following (d1) process,
Further, it preferably includes the following steps (e1), (f1) and (g);
(B1) A pattern exposure step of exposing the contact pattern with the first pattern without peeling off the temporary support of the dry film resist;
(C1) A development step of peeling the temporary support and developing to form a first pattern on the resist layer;
(D1) an etching step of forming a first pattern on the circuit forming substrate by etching;
(E1) A pattern exposure step of exposing the contact pattern with the second pattern without removing the resist layer to which the first pattern is transferred in the step (c1);
(F1) A development step of developing and forming a second pattern different from the first pattern on the resist layer;
(G) An etching step of forming the second pattern on the circuit formation substrate by etching.
[14] In the circuit wiring manufacturing method according to [12], the step (b) is the following step (b1),
(C) The process is the following (c1) process,
(D) The process is the following (d2) process,
Furthermore, it is preferable to include a step (e2), a step (f2) and a step (g);
(B1) A pattern exposure step of exposing the contact pattern with the first pattern without peeling off the temporary support of the dry film resist;
(C1) A development step of peeling the temporary support and developing to form a first pattern on the resist layer;
(D2) After forming the first pattern on the circuit formation substrate by etching, a cover film is pasted on the remaining resist layer without peeling off the resist layer on which the first pattern was formed in the step (c1). Attaching etching process;
(E2) A pattern exposure step of exposing the contact pattern with the second pattern without peeling off the cover film attached in the step (d2);
(F2) A development step in which the cover film attached in step (d2) is peeled and then developed to form a second pattern different from the first pattern on the resist layer;
(G) An etching step of forming the second pattern on the circuit formation substrate by etching.
[15] A circuit wiring manufactured by the circuit wiring manufacturing method according to any one of [12] to [14].
[16] An input device using the circuit wiring according to [15].
[17] In the input device according to [16], the input device is preferably a capacitive touch panel.
[18] A display device comprising the input device according to [16] or [17].

ADVANTAGE OF THE INVENTION According to this invention, the dry film resist which can manufacture the circuit wiring which is a positive type which is easy to form a high resolution pattern, and has high pattern linearity can be provided.
In addition, according to the present invention, it is possible to provide a positive-type circuit wiring that can easily form a high-resolution pattern and a high pattern linearity and a method for manufacturing the circuit wiring.
Further, according to the present invention, it is possible to provide an input device using the circuit wiring and a display device including the input device.

It is a schematic diagram which shows an example of the manufacturing method of circuit wiring. It is a cross-sectional schematic diagram of an example of circuit wiring which is one of the embodiments of the present invention obtained when x is 2. It is a schematic diagram of an example of circuit wiring which is one of the embodiments of the present invention obtained when x is 2. 4 is a schematic diagram showing a pattern A. FIG. 4 is a schematic diagram showing a pattern B. FIG. 6 is a schematic diagram showing a pattern C. FIG. It is a cross-sectional schematic diagram which shows an example of arrangement | positioning of the connection part of a 1st electrode pattern, and a 2nd electrode pattern. It is a schematic diagram which shows an example of arrangement | positioning of the pad part and connection part of a 1st electrode pattern, and a 2nd electrode pattern. It is a cross-sectional schematic diagram which shows a structure of an example of the input device of this invention.

Hereinafter, a dry film resist, a method for manufacturing circuit wiring, circuit wiring, an input device, in particular, an input device that is a touch panel, and a display device using the input device will be described.
The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to the embodiments and specific examples. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Dry film resist]
The dry film resist of the present invention is a positive dry film resist having at least a resist layer on a temporary support,
The dry film resist satisfies at least one of the following conditions (1) and (2).
Condition (1): The temporary support has a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer;
Condition (2): A light absorption layer having a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer is provided between the temporary support and the resist layer.
Since it is said structure, the dry film resist of this invention is a positive type which is easy to form a high resolution pattern, and can manufacture circuit wiring with high pattern linearity. Here, when the dry film resist is exposed through the temporary support, the pattern linearity is lowered by the light diffusion of the exposure light caused by the temporary support. Although not bound by any theory, the problem that the pattern linearity decreases is presumably caused mainly by light diffusion of exposure light caused by fillers and other temporary supports in the temporary support and / or the surface. Is done. When the energy of the exposure light after being diffused by the temporary support exceeds the resist sensitivity (activation energy of the photosensitizer of the resist layer, that is, the required exposure amount), the portion that should be the unexposed portion in the desired pattern is diffused The pattern is exposed to light and the pattern linearity is lowered. On the other hand, if the exposure light energy after diffusion does not exceed the resist sensitivity (necessary exposure amount), the portion that should be an unexposed part in the desired pattern is not actually exposed with the diffused light, and the pattern linearity decreases. Can be suppressed.
In order to avoid a decrease in pattern linearity due to light diffusion of exposure light on the temporary support, (i) suppression of light diffusion on the temporary support due to, for example, suppressing haze of the temporary support, ii) Techniques such as absorption of diffused light that has passed through the temporary support in the temporary support or other members disposed until reaching the resist layer, and (iii) low sensitivity of the resist layer are conceivable.
In the present invention, paying attention to the absorption of the diffused light that has passed through the temporary support in the temporary support or other members disposed until reaching the resist layer, the condition (1) and / or the condition ( The configuration satisfies 2).
In addition, it can also be used as a preferable means to suppress the linearity degradation by combining a plurality of aspects (i) to (iii).

<Configuration>
The dry film resist of the present invention has at least a resist layer on a temporary support. When the dry film resist of this invention satisfy | fills conditions (2), it has further the light absorption layer which has the transmittance | permeability of 80% or less with respect to the exposure dominant wavelength of a resist layer between a temporary support body and a resist layer.
The dry film resist of the present invention preferably has a temporary support, a thermoplastic resin layer, and a resist layer in this order, and may further have other layers such as a protective film. Regarding preferred modes of the thermoplastic resin layer, [0189] to [0193] of JP-A-2014-85643, and for preferable modes of other layers, refer to [0194] to [0196] of JP-A-2014-85643, respectively. The contents of this publication are incorporated herein.

The dry film resist of the present invention is a positive dry film resist in which exposed portions are dissolved in a developer. A positive dry film resist has an advantage that a high-resolution pattern can be easily formed as compared with a negative resist.
Further, in the positive type, by irradiating actinic light, for example, a photosensitive agent that generates acid upon irradiation with actinic light is used to increase the solubility of the exposed part. None of them are cured, and when the obtained pattern shape is defective, the circuit-formed substrate can be reused (reworked) by full exposure or the like. Therefore, the positive type is preferably used from the viewpoint of excellent so-called reworkability.
Further, the technique of reexposing the remaining resist to produce different patterns can only be realized with a positive type.

More preferably, the dry film resist of the present invention satisfies at least one of the following conditions (1) and (2) and satisfies the condition (1).
Condition (1): The temporary support has a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer;
Condition (2): A light absorption layer having a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer is provided between the temporary support and the resist layer.
When the condition (1) is satisfied, it is preferable that the following condition (1A) is satisfied.
Condition (1A): The temporary support has a transmittance of more than 10% and 80% or less with respect to the exposure main wavelength of the resist layer.
When the condition (2) is satisfied, it is preferable that the following condition (2A) is satisfied.
Condition (2A): A light absorption layer having a transmittance of more than 10% and 80% or less with respect to the exposure main wavelength of the resist layer is provided between the temporary support and the resist layer.
When the condition (2) or the condition (2A) is satisfied, the temporary support, the light absorbing layer, and the light-receiving layer are formed from the side opposite to the laminate surface in contact with the target substrate when the dry film resist is laminated (for example, transferred) to the target substrate. A resist layer can be provided in this order.
Here, Japanese Patent Application Laid-Open No. 2009-282522 describes that the reflection suppressing layer preferably has an absorptance of 90% or more for light having a wavelength in the range of 200 nm to 700 nm. In the temporary support or the light absorption layer, if the light absorption of the exposure dominant wavelength of the resist layer is excessive, it requires pressure on the resist design due to containing a large amount of the photosensitive agent in the resist layer or a large amount of exposure. In practice, it is preferable to use a temporary support or a light absorption layer having a transmittance of more than 10% and 80% or less with respect to the exposure main wavelength of the resist layer.

(Temporary support)
The dry film resist of the present invention has a temporary support.
When the dry film resist of the present invention satisfies the condition (1), the temporary support preferably has a transmittance of 80% or less and a transmittance of 60% or less with respect to the exposure main wavelength of the resist layer. More preferably, the transmittance is 50% or less.
The dry film resist of the present invention preferably has a temporary support having a haze (total light haze) of 3.0% or less, more preferably 2.0% or less, and 1.5% or less. Is particularly preferred. The lower limit of the haze is not particularly limited. For example, in the case of a PET film, a filler added to the film or coated on the surface of the film is a main haze source. This causes problems such as deterioration of properties and blocking during storage. Therefore, considering that the minimum filler is necessary, it is practical to be 0.05% or more. Needless to say, in a film other than PET, the practical minimum haze can take different values, and is not limited to the above value of 0.05% or more in any sense.
There is no restriction | limiting in particular as a temporary support body. Preferred embodiments of the temporary support are described in JP-A-2014-85643, [0017] to [0018], and the contents of this publication are incorporated herein.

(Resist layer)
The dry film resist of the present invention has a resist layer.
In the dry film resist of the present invention, the resist layer preferably contains a photosensitizer, and the extinction coefficient of the photosensitizer with respect to the main exposure wavelength of the resist layer is preferably less than 12,000 cm ⁻¹ M ⁻¹ . Note that 1 cm ⁻¹ M ⁻¹ is converted to 1 × 10 ² L · m ⁻¹ mol ⁻¹ .
More preferably extinction coefficient with respect to the exposure main wavelength of the resist layer of photosensitive agent is less than 10,000 cm ^-1 M ^-1, and particularly preferably less than 5,000 cm ^-1 M ^-1. The lower limit of the extinction coefficient is not particularly limited, but if the absorbance is too small, a large amount of exposure is required, resulting in a decrease in throughput, and a dry film resist can be added by adding a large amount of photosensitizer to correct the sensitivity decrease. Therefore, it is practical to be 30 cm ⁻¹ M ⁻¹ or more.
Examples of the photosensitizer include a naphthoquinone diazide compound described below and a photoacid generator described below.

As a preferred embodiment of the resist layer, the first preferred embodiment containing a naphthoquinone diazide compound and a resin having a phenolic hydroxyl group, the resist layer contains (A) component and (B) a photoacid generator, and (A) component However, the 2nd preferable aspect which is a polymer in which an acid group has the group protected by the acid-decomposable group is mentioned. The second preferred embodiment is more preferable than the first preferred embodiment from the viewpoint of improving the linearity of the pattern by improving the solubility of the resist layer resulting from the chemical amplification type.
Hereinafter, the material of the resist layer used in each preferred embodiment will be described.

-First preferred embodiment of resist layer-
First, the 1st preferable aspect of a resist layer is demonstrated.
In the dry film resist of the present invention, the resist layer preferably contains a naphthoquinonediazide compound and a resin having a phenolic hydroxyl group. Especially, it is especially preferable that a resist layer contains two types, a cresol novolak resin and a naphthoquinone diazide derivative, from a viewpoint with wide development latitude.

--Resin having phenolic hydroxyl group--
Examples of the resin having a phenolic hydroxyl group include a phenol novolac resin and a cresol novolac resin.

As the phenol novolak resin, those having a molar ratio of formaldehyde to phenol of about 0.5 to 1.0 are preferred, and those of about 0.8 to 1.0 are more preferred from the viewpoint of developability and image sticking. The weight average molecular weight of the phenol novolac resin is preferably 300 to 4000, and particularly preferably 400 to 800.
The phenol novolac resin may be a derivative thereof.
The phenol novolac resin may be used alone or in combination of two or more different weight average molecular weights, and other cresol novolac resins may be used as long as the object of the present invention is not impaired. You may mix and use resin.
The content of the phenol novolac resin is preferably 40 to 90% by mass, and more preferably 60 to 80% by mass with respect to the total solid content in the positive photosensitive layer.

The cresol novolak resin preferably has a molar ratio of formaldehyde to cresol of about 0.7 to 1.0, more preferably about 0.8 to 1.0. The weight average molecular weight of the cresol novolak resin is preferably 800 to 8,000, more preferably 1000 to 6000.
The isomer ratio (ortho / meta / para molar ratio) of the cresol novolak resin is not particularly limited and can be appropriately selected according to the purpose. Is preferably 10 mol% or more, more preferably 20 mol% or more.

The said cresol novolak resin may be used individually by 1 type, and can be used as a 2 or more types of mixture. In this case, it may be used by mixing with other resins such as phenol novolac.
In the present invention, as the cresol novolak resin, a derivative of a cresol novolak resin such as a reaction product with naphthoquinone diazide sulfonate may be used.
The amount of the cresol novolac resin is preferably 0.1 ~ 10g / ^{m 2,} more preferably 0.5 ~ 5g / ^{m 2.}

--Naphthoquinonediazide compound--
The naphthoquinonediazide compound is not particularly limited and may be appropriately selected depending on the intended purpose, but it is particularly preferable to use in combination with a cresol novolac resin. The naphthoquinonediazide compound may be a monofunctional compound, a bifunctional or higher functional compound, and a mixture thereof.
Examples of the monofunctional naphthoquinonediazide compound include naphthoquinone-4-sulfonic acid chloride or an ester compound obtained by reacting naphthoquinone-5-sulfonic acid chloride with a substituted phenol.

As the bifunctional or higher naphthoquinone diazide compound, for example, an ester compound obtained by reacting naphthoquinone-4-sulfonic acid chloride or naphthoquinone-5-sulfonic acid chloride with a compound having a plurality of phenolic hydroxyl groups is preferable. Examples of the compound having a plurality of phenolic hydroxyl groups include polyphenols such as bisphenols, trisphenols and tetraquinosphenols; polyfunctional phenols such as dihydroxybenzene and trihydroxybenzene; bis-type or tris-type dihydroxybenzene or Examples thereof include trihydroxybenzene, asymmetric polynuclear phenol, and a mixture thereof.
Examples of the compound having a plurality of phenolic hydroxyl groups include 4-t-butylphenol, 4-isoamylphenol, 4-t-octylphenol, 2-isopropyl-5-methylphenol, 2-acetylphenol, 4-hydroxybenzophenone, 3 -Chlorophenol, 4-benzyloxycarbonylphenol, 4-dodecylphenol, resorcinol, 4- (1-methyl-1-phenylethyl) -1,3-benzenediol, phloroglucinol, 4,4'-dihydroxybenzophenone, Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-4-hydroxyphenyl) methane, 2,3,4,4′-tetrahydroxy Benzophenone, 4,4 '-[ 4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], and the like.

Examples of the naphthoquinonediazide compound include 4′-t-octylphenylnaphthoquinonediazide-4-sulfonate, 4′-t-octylphenylnaphthoquinonediazide-5-sulfonate, 4′-benzoylphenylnaphthoquinonediazide-5-sulfonate, , 3,4,4′-tetrahydroxybenzophenone and a reaction product of 1,2-naphthoquinonediazide-5-sulfonic acid chloride. These may be used alone or in combination of two or more. A naphthoquinone diazide compound described in JP-A-4-22955 may be used, and the contents of this publication are incorporated herein.

The addition amount of the naphthoquinone diazide compound in the resist layer is preferably 1 to 200 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the cresol novolac resin.

In the first preferred embodiment of the other resist layer, materials described in [0072] to [0083] of Japanese Patent Application Laid-Open No. 2007-24969 may be used as an additive. Incorporated into.
Moreover, you may use the material as described in the 2nd preferable aspect of the below-mentioned resist layer for the 1st preferable aspect of a resist layer.

-Second Preferred Embodiment of Resist Layer-
A second preferred embodiment of the resist layer will be described.
In the present invention, the resist layer preferably contains (A) component and (B) a photoacid generator, and (A) component is a polymer having a group in which an acid group is protected by an acid-decomposable group. .

<(A) component: a polymer having an acid group protected by an acid-decomposable group>
The component (A) is preferably a polymer having a group in which an acid group is protected with an acid-decomposable group.
In the dry film resist of the present invention, the component (A) is more preferably a polymer component including a polymer having an acid structural unit a1 in which a carboxy group or a phenolic hydroxyl group is protected in the form of an acetal.
The resist layer may further contain a polymer other than these.

<< Structural Unit (a1) >>
The component (A) has an acid constituent unit a1 in which an acid group is protected with an acid-decomposable group, preferably a carboxy group or a phenolic hydroxyl group is protected in the form of an acetal. It can be.
As the acid group and the acid-decomposable group in the “group in which the acid group is protected with an acid-decomposable group” in the present invention, 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 preferably include a carboxy group and a phenolic hydroxyl group. Examples of the acid-decomposable group include groups that are relatively easily decomposed by an acid (for example, an ester structure of a group represented by the formula (A1) or the formula (A1 ′) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl group. An acetal functional group such as an ester group) or a group that is relatively difficult to be decomposed by an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group). be able to.

The structural unit (a1) having a group in which the acid group is protected with an acid-decomposable group is a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group, or a protected carboxy protected with an acid-decomposable group. A structural unit having a group is preferred.
In the resist layer, the structural unit (a1) having a group in which the acid group is protected with an acid-decomposable group is a structural unit having a group in which a carboxy group or a phenolic hydroxyl group is protected in the form of an acetal. preferable.
Hereinafter, the structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group and the structural unit having a protected carboxy group protected with an acid-decomposable group will be described in order.

<<< Structural Unit Having Protected Phenolic Hydroxyl Group Protected with Acid-Decomposable Group >>>
The structural unit having a protected phenolic hydroxyl group protected by an acid-decomposable group is a structural unit having a protected phenolic hydroxyl group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below. It is.
As the structural unit having a phenolic hydroxyl group, a structural unit in which the hydroxyl group of a structural unit derived from hydroxystyrene or α-methylhydroxystyrene (for example, a structural unit in a novolak resin) is protected by an acid-decomposable group is used. From the viewpoint of improving the resolution, a polymer having a structural unit represented by the following general formula A1 or general formula A1 ′ is more preferable.

General formula A1

In general formula A1, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or Represents an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, and R ⁴ represents a hydrogen atom or a methyl group.
In the general formula A1, when R ¹ and R ² are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably at least one is a hydrogen atom.
In the general formula A1, R ³ 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.
R ¹ or R ² and R ³ may be linked to form a cyclic ether, and R ¹ or R ² and R ³ are preferably 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 general formula A1, R ⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

General formula A1 '

In General 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 an aryl group, and R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, and each R ¹⁴ independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, An alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group or a cycloalkyl group is represented.
In the general formula A1 ′, when R ¹¹ and R ¹² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹¹ and R ¹² are aryl groups, a phenyl group is preferred. R ¹¹ and R ¹² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably at least one is a hydrogen atom.
In the general formula A1 ′, R ¹³ 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 ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether.
In the general formula A1 ′, R ¹⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

As the acid-decomposable group that can be used for the structural unit having a protected phenolic hydroxyl group protected with the acid-decomposable group, a known one can be used, and is not particularly limited. Among the acid-decomposable groups, a structural unit having a protected phenolic hydroxyl group protected with acetal is preferable from the viewpoint of basic physical properties of the resist layer, particularly sensitivity, pattern shape, and storage stability of the resist layer. Furthermore, among the acid-decomposable groups, the phenolic hydroxyl group is more preferably a protected phenolic hydroxyl group protected in the form of an acetal represented by the following general formula (a1-10) from the viewpoint of sensitivity. When the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the following general formula (a1-10), the entire protected phenolic hydroxyl group is —Ar—O—CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ). Ar represents an arylene group.

Formula (a1-10)

(In formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms, and R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.

In the general formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, and R ¹⁰³ represents an alkyl group. The alkyl group may be linear, branched or cyclic. Here, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

In the general formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be linear, branched or cyclic.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are haloalkyl groups, and when it has an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are aralkyl groups.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an α-methylphenyl group, and a naphthyl group. Examples of the entire alkyl group substituted with an aryl group, ie, an aralkyl group, include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
In addition, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is linear Alternatively, when it is a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ can be bonded together to form a ring together with the carbon atoms to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ¹⁰³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.

Note that in the general formula (a1-10), any one of R ¹⁰¹ and R ¹⁰² is preferably a hydrogen atom or a methyl group.

Preferred examples of the acetal ester structure of a phenolic hydroxyl group include the case where R ¹⁰¹ = methyl group, R ¹⁰² = hydrogen atom, R ¹⁰³ = ethyl group, or R ¹⁰¹ = methyl group, R ¹⁰² = hydrogen atom, R ¹⁰³ = ethyl group. And when R ¹⁰¹ and R ¹⁰³ are bonded to each other to form a 5-membered ring, R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group, or R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl The case of a group can be illustrated.

Examples of the polymerizable monomer used to form a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include, for example, paragraph No. 0042 of JP2011-215590A. And the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.

Specific examples of the acetal protecting group for the phenolic hydroxyl group include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group. 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 And -benzyloxyethyl group. These may be used alone or in combination of two or more.

As the polymerizable monomer used to form the structural unit having a protected phenolic hydroxyl group protected by the acid-decomposable group, a commercially available monomer may be used, or a monomer synthesized by a known method may be used. You can also. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.

As preferred specific examples of the structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group, the following structural units can be exemplified, but the present invention is not limited thereto.

The copolymerization ratio of the structural unit having a protected phenol group protected with an acid-decomposable group in the polymer having the structural unit (a1) having a group protected with an acid-decomposable group is the acid-decomposable group. It is preferably 10 to 50 mol%, more preferably 20 to 40 mol%, and more preferably 25 to 40 mol% based on the polymer containing a structural unit having a protected phenol group protected with. Particularly preferred.
In addition, all the polymer components (when the polymer component is a mixture of two or more polymers, all polymers included) are decomposed into structural units (monomer units) and then all the components The ratio of the structural unit (a1) having a protected phenol group in which the acid group is protected with an acid-decomposable group to the number of moles of the unit is preferably 0 to 40 mol%, and preferably 10 to 35 mol%. Is more preferable, and 15 to 30 mol% is particularly preferable.

<<< Structural Unit Having Protected Carboxy Group Protected with Acid-Decomposable Group >>>
The structural unit having a protected carboxy group protected with an acid-decomposable group is a structural unit in which the carboxy group of the structural unit having a carboxy group has a protected carboxy group protected by an acid-decomposable group described in detail below. It is.
There is no restriction | limiting in particular as a structural unit which has the said carboxy group which can be used for the structural unit which has the protected carboxy group protected by the said acid-decomposable group, A well-known structural unit can be used. For example, a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxy group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid, And a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
Hereinafter, a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxy group in the molecule, an ethylenically unsaturated group, and an acid, which are used as the structural unit having a carboxy group. The structural unit (a1-1-2) having both an anhydride-derived structure will be described in turn.

<<< constituent unit (a1-1-1) derived from unsaturated carboxylic acid having at least one carboxy group in the molecule >>>
Examples of the unsaturated carboxylic acid used in the present invention as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxy group in the molecule include those listed below. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, and 2- (meth) acryloyloxy. Examples thereof include ethyl hexahydrophthalic acid and 2- (meth) acryloyloxyethyl-phthalic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxy group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2- (meth) acryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the unsaturated carboxylic acid, acrylic acid 2-carboxyethyl ester, methacrylic acid 2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among them, from the viewpoint of developability, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxy group in the molecule, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, or an anhydride of an unsaturated polycarboxylic acid may be used. Acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid are more preferable.
The structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxy group in the molecule may be composed of one kind alone or two or more kinds. It may be.

<<<< Structural Unit (a1-1-2) Having Both Ethylenically Unsaturated Group and Acid Anhydride Structure >>>>>
The structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride is obtained by reacting a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride. A unit derived from the obtained monomer is preferred.
As the acid anhydride, known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, phthalic anhydride, tetrahydrophthalic anhydride and succinic anhydride are preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.

The acid-decomposable group that can be used for the structural unit having a protected carboxy group protected by the acid-decomposable group is used for a structural unit having a protected phenol group protected by the acid-decomposable group. Possible acid-decomposable groups can be used.
Among these acid-decomposable groups, a protected carboxy group in which the carboxy group is protected in the form of an acetal is preferable from the viewpoint of basic physical properties of the resist layer, particularly sensitivity and pattern shape, and storage stability of the resist layer. Furthermore, among the acid-decomposable groups, the carboxy group is more preferably a protected carboxy group protected in the form of an acetal represented by the general formula (a1-10) from the viewpoint of sensitivity. When the carboxy group is a protected carboxy group protected in the form of an acetal represented by the general formula (a1-10), the entire protected carboxy group is — (C═O) —O—CR ¹⁰¹ The structure is R ¹⁰² (OR ¹⁰³ ).

As the polymerizable monomer used to form the structural unit having a protected carboxy group represented by the above general formula (a1-10), a commercially available monomer may be used, or one synthesized by a known method Can also be used. For example, it can be synthesized by the synthesis method described in paragraph numbers 0037 to 0040 of JP2011-212494A.

Among the structural units having a protected carboxy group protected by the acid-decomposable group, a structural unit represented by the following general formula A2 ′ is preferable from the viewpoint of increasing sensitivity. In the dry film resist of the present invention, the resist layer contains two or more types of the component (A), and a polymer having a structural unit represented by the following general formula A2 ′ as the component (A). Is preferred.

(In General Formula A2 ′, 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. 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, and X ⁰ represents a single bond or an arylene group. To express.)
In the general formula A2 ′, when R ³¹ and R ³² are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferable. When R ³¹ and R ³² are aryl groups, a phenyl group is preferred. R ³¹ and R ³² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the general formula A2 ′, 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.
In the above general formula A2 ′, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, or R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether. Is preferred. 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 general formula A2 ′, R ³⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the general formula A2 ′, X ⁰ represents a single bond or an arylene group, and a single bond is preferable.

Among the structural units represented by the general formula A2 ′, a structural unit represented by the following general formula A2 ″ is more preferable from the viewpoint of further increasing sensitivity.

(Wherein R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹²² to R ¹²⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
In the general formula A2 ″, R ¹²¹ is preferably a hydrogen atom or a methyl group.
In the general formula A2 ″, R ¹²² to R ¹²⁸ are preferably hydrogen atoms.

As preferred specific examples of the structural unit having a protected carboxy group protected with an acid-decomposable group, the following structural units can be exemplified. R represents a hydrogen atom or a methyl group.

The copolymerization ratio of the structural unit having a protected carboxy group protected by an acid-decomposable group in the polymer having the structural unit (a1) having a group protected by an acid-decomposable group is the acid-decomposable group. It is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, particularly preferably 30 to 50 mol%, based on the polymer containing a structural unit having a protected carboxy group protected with.
Moreover, after decomposing all the polymer components into structural units (monomer units), the structural unit (a1) having a protected carboxy group in which the acid group is protected with an acid-decomposable group with respect to the number of moles of all the structural units. Is preferably 0 to 60 mol%, more preferably 10 to 50 mol%, and particularly preferably 15 to 25 mol%.

<< Other structural units (a3) >>
The component (A) of the resist layer has a structural unit (a3) other than these in addition to the structural unit (a1) having a group in which the acid group is protected with an acid-decomposable group. Also good. These other structural units (a3) are a copolymer of the polymer used for the component (A), that is, a polymer having a structural unit (a1) having a group in which an acid group is protected by an acid-decomposable group. It may be included as a component. In addition to the polymer containing the structural unit (a1) having a group in which the acid group used in the component (A) is protected with an acid-decomposable group, the acid group is substantially protected with an acid-decomposable group. The polymer having other structural units without including the structural unit (a1) having the group formed may have other structural units (a3).

There is no restriction | limiting in particular as a monomer used as another structural unit (a3), For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to. Moreover, you may have the structural unit which has an acid group so that it may mention later. The monomer which becomes another structural unit (a3) can be used individually or in combination of 2 or more types.

The structural unit (a3) specifically includes styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid. Ethyl, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid Isopropyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate Mention may be made of a constituent unit derived from, such as the door. In addition, compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

Further, as other structural unit (a3), styrenes and groups having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical characteristics. Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.

Furthermore, (meth) acrylic acid alkyl ester is preferable as another structural unit (a3) from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.
In the structural unit constituting the polymer containing the structural unit (a1) having a group in which the acid group is protected with an acid-decomposable group, the content of the structural unit (a3) is preferably 60 mol% or less, 50 mol% or less is more preferable, and 40 mol% or less is still more preferable. As a lower limit, although 0 mol% may be sufficient, it can be set as 1 mol% or more, for example, Furthermore, it can be set as 5 mol% or more. If the numerical value is within the above range, various characteristics of the resist layer are improved.

It is preferable to have a structural unit containing an acid group as the other structural unit (a3). When the component (A) has a structural unit containing an acid group, the component (A) is easily dissolved in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa (power of Ka; Ka is an acid dissociation constant) of 10 or less. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including the structural unit containing an acid group in the polymer, the component (A) tends to be easily dissolved in an alkaline developer.
As the acid group of the structural unit containing an acid group used for the above other structural units, those derived from a carboxylic acid group, those derived from a sulfonamide group, those derived from a phosphonic acid group, those derived from a sulfonic acid group Examples thereof include those derived from phenolic hydroxyl groups, sulfonamide groups, sulfonylimide groups and the like, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
The structural unit containing an acid group used for the above other structural units is a structural unit obtained by substituting an acid group for a structural unit derived from styrene or a structural unit derived from a vinyl compound, or (meth) acrylic acid. More preferably, it is a structural unit derived from.

Furthermore, it is preferable to have a structural unit containing an ester of an acid group from the viewpoint of optimizing the solubility in a developer and the physical properties of the film.

In the present invention, it is particularly preferable from the viewpoint of sensitivity that the other structural unit (a3) contains a structural unit having a carboxy group or a structural unit having a phenolic hydroxyl group.
As the structural unit (a1) having a group in which the acid group is protected with an acid-decomposable group, the polymer having a structural unit having a protected phenol group protected with the acid-decomposable group includes the above other structural units ( Among a3), it is preferable to contain a structural unit derived from a phenolic hydroxyl group as a copolymerization component. As the structural unit (a1) having a group in which the acid group is protected with an acid-decomposable group, a polymer having a structural unit having a protected phenol group protected with the acid-decomposable group is hydroxystyrene or α-methyl. It is more preferable to include a structural unit derived from hydroxystyrene as a copolymerization component, and it is particularly preferable to include a structural unit derived from hydroxystyrene as a copolymerization component.
In the polymer having a structural unit having a protected phenol group protected with an acid-decomposable group, the copolymerization ratio of the structural unit containing an acid group is protected by this acid-decomposable group when the acid group is a phenolic hydroxyl group. The amount of the polymer having a structural unit having a protected phenol group is preferably 50 to 90 mol%, more preferably 60 to 75 mol%.
Further, when the acid group is a carboxy group, it is preferably 0 to 30 mol%, more preferably 5 to 10 mol%, based on the polymer having a structural unit having a protected phenol group protected with this acid-decomposable group. .
The copolymerization ratio of the structural unit containing an ester of an acid group in the polymer having a structural unit having a protected phenol group protected with an acid-decomposable group is a structure having a protected phenol group protected with this acid-decomposable group. The amount is preferably 0 to 30 mol%, more preferably 0 to 10 mol%, particularly preferably 0 mol%, based on the polymer having units.

As the structural unit (a1) having a group in which the acid group is protected with an acid-decomposable group, a polymer having a structural unit having a protected carboxy group protected with the acid-decomposable group includes the above other structural units ( Among a3), it is preferable to contain a structural unit derived from a carboxylic acid group and / or an ester thereof as a copolymerization component. As the structural unit (a1) having a group in which the acid group is protected by an acid-decomposable group, a polymer having a structural unit having a protected carboxy group protected by the acid-decomposable group is (meth) acrylic acid, More preferably, a structural unit derived from benzyl (meth) acrylate or 2-hydroxyethyl (meth) acrylate is included as a copolymerization component.
In the polymer having a structural unit having a protected carboxy group protected with an acid-decomposable group, the copolymerization ratio of the structural unit containing an acid group is protected by this acid-decomposable group when the acid group is a phenolic hydroxyl group. The amount of the polymer having a constitutional unit having a carboxy group is preferably 50 to 90 mol%, more preferably 60 to 75 mol%.
Further, when the acid group is a carboxy group, it is preferably 0 to 30 mol%, more preferably 5 to 10 mol%, based on the polymer having a structural unit having a carboxy group protected by this acid-decomposable group.
The copolymerization ratio of the structural unit containing an ester of an acid group in the polymer having a structural unit having a protected carboxy group protected with an acid-decomposable group is a structure having a protected carboxy group protected with this acid-decomposable group. The amount is preferably 10 to 80 mol%, more preferably 30 to 70 mol%, particularly preferably 40 to 60 mol%, based on the polymer having units.

<Preferred embodiment of polymer component>
The structural unit having a protected carboxy group protected with an acid-decomposable group develops faster (development speed) than the structural unit having a protected phenolic hydroxyl group protected with the acid-decomposable group. Therefore, when it is desired to develop the resist layer rapidly after exposure, a structural unit having a protected carboxy group protected with an acid-decomposable group is preferred. Conversely, when it is desired to slow development, it is preferable to use a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group.

In the resist layer, in the component (A), the polymer having the structural unit (a1) having a group in which an acid group is protected by an acid-decomposable group may be one type or two or more types. The resist layer preferably contains two or more types of polymers having the structural unit (a1) having a group in which the acid group is protected with an acid-decomposable group as the polymer component. Among them, the polymer component contains a polymer having a structural unit having a protected phenolic hydroxyl group protected by the acid-decomposable group and a structural unit having a protected carboxy group protected by the acid-decomposable group. It is more preferable to contain a polymer.
The resist layer contains two or more kinds of polymers having the structural unit (a1) having a group in which the acid group is protected with an acid-decomposable group as the polymer component, and the acid group is an acid-decomposable group. As the polymer having the structural unit (a1) having a group protected with a, it is particularly preferable to contain a polymer having the structural unit represented by the general formula A2 ′ from the viewpoint of increasing sensitivity. That is, in the dry film resist of the present invention, the resist layer contains two or more types of the component (A) and a polymer having a structural unit represented by the general formula A2 ′ as the component (A). It is preferable.
The resist layer contains two or more kinds of polymers having the structural unit (a1) having a group in which the acid group is protected with an acid-decomposable group as the polymer component, and the acid group is an acid-decomposable group. As the polymer having the structural unit (a1) having a group protected with, at least one of the polymers having the structural unit represented by the general formula A1 or the general formula A1 ′, and the general formula A2 ′ It is particularly preferable to contain a polymer having a structural unit represented from the viewpoint of increasing both sensitivity and resolution.

When the polymer component contains two or more kinds of the polymer having the structural unit (a1) having a group in which the acid group is protected with an acid-decomposable group, a protected phenolic hydroxyl group protected with the acid-decomposable group The ratio of the polymer having a structural unit having a structural unit having a structural unit having a protected carboxy group protected by the acid-decomposable group is preferably 10:90 to 100: 0 by mass, It is more preferably 30:70 to 60:40, and particularly preferably 1: 1.

<< Molecular Weight of Polymer Containing Constituent Unit (a1) having a Group Protected with Acid-Decomposable Group >>
The weight average molecular weight of the polymer containing the structural unit (a1) having a group in which the acid group is protected with an acid-decomposable group is a polystyrene-equivalent weight average molecular weight, preferably 1,000 to 200,000. The range is preferably 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value.
The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

<< (A) Component Production Method >>
Various methods for synthesizing the component (A) are also known. As an example, a polymerizable monomer mixture containing a polymerizable monomer used to form at least the structural units represented by the above (a1) and (a3) is added to a polymerization initiator in an organic solvent. It can synthesize | combine by superposing | polymerizing using. It can also be synthesized by a so-called polymer reaction.

The resist layer preferably contains the component (A) in a proportion of 50 to 99.9 parts by mass, more preferably 70 to 98 parts by mass with respect to 100 parts by mass of the total solid content.

<< Other polymer components >>
In addition to the polymer containing the structural unit (a1) having a group in which the acid group used in the component (A) is protected with an acid-decomposable group, the acid group is substantially protected with an acid-decomposable group. You may have the polymer which does not contain the structural unit (a1) which has the group formed, and has another structural unit. In addition to the polymer used for the component (A), a polymer having other structural unit is included without substantially including the structural unit (a1) having a group in which an acid group is protected by an acid-decomposable group. In this case, the blending amount of the polymer is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in all polymer components.

The polymer having the other structural unit (a3) without substantially including the structural unit (a1) in the resist layer may be included in only one kind or in two or more kinds. .

As a polymer which does not contain these structural units (a1) but has other structural units (a3), for example, polyhydroxystyrene can be used and is commercially available, SMA 1000P, SMA 2000P, SMA 3000P. , SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (Sartomer) As described above, manufactured by Toagosei Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, manufactured by BASF) and the like can also be used.

<(B) component: Photoacid generator>
The resist layer preferably contains (B) a photoacid generator. As the photoacid generator (also referred to as “component (B)”) used in the present invention, an acid can be generated by irradiation with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. A compound. The photoacid generator (B) used in the present invention is preferably a compound that generates an acid in response to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm. (B) The chemical structure of the photoacid generator is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The pKa value of the acid generated upon irradiation with radiation is preferably 4.0 or less, more preferably 3.0 or less. The lower limit value is not particularly defined, but can be set to -10.0 or more, for example.

Examples of the (B) photoacid generator include ionic photoacid generators and nonionic photoacid generators.

Examples of nonionic photoacid generators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, from the viewpoint of insulating properties, it is preferable that the (B) photoacid generator in the resist layer is an oxime sulfonate compound. These photoacid generators can be used alone or in combination of two or more. Specific examples of trichloromethyl-s-triazines and diazomethane derivatives include the compounds described in JP-A 2011-212494, paragraphs 0083 to 0088, the contents of which are incorporated herein.

Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1).

General formula (B1)

(In the general formula (B1), R ²¹ represents an alkyl group or an aryl group. The wavy line represents a bond with another group.)

Any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. 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, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like). It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
The aryl group for R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

The above compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B2).

(In the general formula (B2), R ⁴² represents an alkyl group or an aryl group, X ¹⁰ represents an alkyl group, an alkoxy group, or a halogen atom, m4 represents an integer of 0 to 3, and m4 represents When it is 2 or 3, the plurality of X ¹⁰ may be the same or different.)

The alkyl group as X ¹⁰ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X ¹⁰ is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X ¹⁰ is preferably a chlorine atom or a fluorine atom. m4 is preferably 0 or 1. In the above general formula (B2), m4 is 1, X ¹⁰ is a methyl group, the substitution position of X ¹⁰ is the ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound that is a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

The compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B3).

(In the general formula (B3), R ⁴³ has the same meaning as R ⁴² in the general formula (B2), and X ¹¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Represents a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the general formula (B3) is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, or a perfluoro-n-propyl group. Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is particularly preferable.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
n4 is preferably from 0 to 2, particularly preferably from 0 to 1.

Specific examples of the compound represented by the general formula (B3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino). ) Benzyl cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4- Methoxyphenyl] acetonitrile, α-[(4 It can be given toluenesulfonyl) -4-methoxyphenyl] acetonitrile.

Specific examples of preferred oxime sulfonate compounds include the following compounds (i) to (viii) and the like, and one kind can be used alone, or two or more kinds can be used in combination. Compounds (i) to (viii) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.

The compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably a compound represented by the following general formula (OS-1).

In the general formula (OS-1), R ⁴¹¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group. R ⁴¹² represents an alkyl group or an aryl group.
X ⁴⁰¹ represents —O—, —S—, —NH—, —NR ⁴¹⁵ —, —CH ₂ —, —CR ⁴¹⁶ H—, or —CR ⁴¹⁵ R ⁴¹⁷ —, wherein R ⁴¹⁵ to R ⁴¹⁷ are alkyl groups. Or an aryl group.
R ⁴²¹ to R ⁴²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R ⁴²¹ to R ⁴²⁴ may be bonded to each other to form a ring.
R ⁴²¹ to R ⁴²⁴ are preferably a hydrogen atom, a halogen atom and an alkyl group, and an embodiment in which at least two of R ⁴²¹ to R ⁴²⁴ are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which all of R ⁴²¹ to R ⁴²⁴ are hydrogen atoms is more preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

The compound represented by the general formula (OS-1) is more preferably a compound represented by the following general formula (OS-2).

In the general formula (OS-2), R ⁴⁰¹ , R ⁴⁰² , R ⁴²¹ to R ⁴²⁴ are respectively synonymous with those in the formula (OS-1), and preferred examples are also the same.
Among these, an embodiment in which R ⁴⁰¹ in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and is represented by the general formula (OS-2). , R ⁴⁰¹ is most preferably a cyano group, a phenyl group, or a naphthyl group.

In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.

Specific examples of the compound represented by the general formula (OS-1) that can be suitably used in the present invention include compounds described in paragraph numbers 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to b-34), but the present invention is not limited thereto.

In the present invention, the compound containing the oxime sulfonate structure represented by the above general formula (B1) includes the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-5). It is preferable that it is an oxime sulfonate compound represented by these.

(In General Formula (OS-3) to General Formula (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ¹ to X ³ each independently represents an oxygen atom or a sulfur atom, n ¹ to n ³ each independently represents 1 or 2, and m ¹ to m ³ each independently represents an integer of 0 to 6 Represents.)

In the general formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.
In the above formulas (OS-3) to (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.

In the general formulas (OS-3) to (OS-5), the aryl group in R ²² , R ²⁵ and R ²⁸ is an aryl group having 6 to 30 carbon atoms which may have a substituent. preferable.

In the general formulas (OS-3) to (OS-5), the heteroaryl group in R ¹ is preferably a heteroaryl group having 4 to 30 carbon atoms in total which may have a substituent.

In the general formulas (OS-3) to (OS-5), at least one ring of the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be a heteroaromatic ring. For example, a heteroaromatic ring and benzene The ring may be condensed.

In the general formulas (OS-3) to (OS-5), R ²³ , R ²⁶ and R ²⁹ are preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group. preferable.
In the general formulas (OS-3) to (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ present in the compound are an alkyl group, an aryl group or a halogen atom. It is more preferable that one is an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.

The alkyl group for R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.

The aryl group for R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.

In the general formulas (OS-3) to (OS-5), X ¹ to X ³ each independently represents O or S, and is preferably O.
In the general formulas (OS-3) to (OS-5), the ring containing X ¹ to X ³ as a ring member is a 5-membered ring or a 6-membered ring.
In the general formulas (OS-3) to (OS-5), n ¹ to n ³ each independently represents 1 or 2, and when X ¹ to X ³ are O, n ¹ to n ³ are each independently In addition, when X ¹ to X ³ are S, it is preferable that n ¹ to n ³ are each independently 2.

In the general formulas (OS-3) to (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. To express. Among them, R ²⁴ , R ²⁷ and R ³⁰ are preferably each independently an alkyl group or an alkyloxy group.
The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.
In the general formulas (OS-3) to (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyl group having 1 to 30 carbon atoms which may have a substituent. It is preferable.

In the general formulas (OS-3) to (OS-5), the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. Preferably there is.

In the general formulas (OS-3) to (OS-5), m ¹ to m ³ each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, More preferably, it is particularly preferably 0.
In addition, with respect to each of the substituents of (OS-3) to (OS-5) described above, the substitution of (OS-3) to (OS-5) described in paragraph numbers 0092 to 0109 of JP2011-221494A The preferred range of groups is likewise preferred.

The compound containing the oxime sulfonate structure represented by the general formula (B1) is particularly an oxime sulfonate compound represented by any of the following general formulas (OS-6) to (OS-11). preferable.

(In the formulas (OS-6) to (OS-11), R ³⁰¹ to R ³⁰⁶ represent an alkyl group, an aryl group, or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ³⁰⁸ to R ³¹⁰ , R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group; R ³¹¹ and R ³¹⁴ each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group.)

Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. It is the same.

Specific examples of the oxime sulfonate compounds represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. However, the present invention is not limited to these.

In the resist layer, (B) the nonionic photoacid generator is used in an amount of 0.1 to 100 parts by weight with respect to 100 parts by weight of the total resin components (preferably the total solid content, more preferably the total polymer) in the resist layer. It is preferable to use 10 parts by mass, and it is more preferable to use 0.5 to 10 parts by mass. Two or more types can be used in combination.

Examples of the ionic photoacid generator include diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts and the like. Of these, triarylsulfonium salts and diaryliodonium salts are preferred.

Triarylsulfonium salts used as an ionic photoacid generator are represented by the following general formula (1).
General formula (1)

(In the general formula (1), R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ each represents an alkyl group or an aromatic group which may have a substituent, and in the case of an alkyl group, they are linked to each other to form a ring. X ⁻ represents a conjugate base.

As the alkyl group for R ⁵⁰⁵ , R ⁵⁰⁶ and R ^507, an alkyl group having 1 to 10 carbon atoms is preferable and may have a substituent. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tertiary butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group and octyl group. Can be mentioned. Of these, a methyl group, an ethyl group, and a tertiary butyl group are preferable. In addition, when two or more of R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ are alkyl groups, it is preferable that the two or more alkyl groups are connected to each other to form a ring. A 5-membered ring (thiacyclopentane) and a 6-membered ring (thiacyclohexane) are preferable.
The aromatic group in R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ is preferably an aromatic group having 6 to 30 carbon atoms and may have a substituent. Examples of the aromatic group having 6 to 30 carbon atoms include phenyl group, naphthyl group, 4-methoxyphenyl group, 4-chlorophenyl group, 4-methylphenyl group, 4-tertiarybutylphenyl group, 4-phenylthiophenyl group, Examples include 2,4,6-trimethylphenyl group, 4-methoxy-1-naphthyl group, and 4- (4′-diphenylsulfoniophenylthio) phenyl group.
Further, the ionic photoacid generator represented by the general formula (1) may be bound by any of R ⁵⁰⁵ to R ⁵⁰⁷ to form a multimer such as a dimer. For example, the 4- (4′-diphenylsulfoniophenylthio) phenyl group is an example of a dimer, and the counter anion in the 4- (4′-diphenylsulfoniophenylthio) phenyl group is the same as X ^−. It is.

The substituent which the alkyl group and aromatic group in R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ may have is preferably an aromatic group, specifically a phenyl group, 4-methoxyphenyl group, 4-chlorophenyl group. 4- (4′-diphenylsulfoniophenylthio) phenyl group is particularly preferred. These substituents may be further substituted with the above substituents.

As the conjugate base in X ^−, a conjugate base of alkylsulfonic acid, a conjugate base of arylsulfonic acid, BY ₄ ⁻ (Y represents a halogen atom, the same applies to the following), PY ₆ ⁻ , AsY ₆ ⁻ , SbY ₆ ⁻ , or a monovalent anion represented by the following general formula (3) or general formula (4) is preferable, and a conjugate base of alkylsulfonic acid, a conjugate base of arylsulfonic acid, PY ₆ ⁻ , or A monovalent anion represented by the formula (3) is particularly preferable.

As the conjugate base of alkylsulfonic acid and arylsulfonic acid, a conjugate base of alkylsulfonic acid having 1 to 7 carbon atoms is preferable, and a conjugate base of alkylsulfonic acid having 1 to 4 carbon atoms is more preferable. For example, methanesulfonic acid, trifluoromethanesulfonic acid, n-propanesulfonic acid, and heptanesulfonic acid are particularly preferable.
Examples of the conjugate base of aryl sulfonic acid include benzene sulfonic acid, chlorobenzene sulfonic acid, and paratoluene sulfonic acid when expressed in the form of an acid.

Y in BY ₄ ⁻ , PY ₆ ⁻ , AsY ₆ ⁻ and SbY ₆ ^— in X ⁻ is preferably a fluorine atom or a chlorine atom, particularly preferably a fluorine atom.

(In General Formula (3) and General Formula (4), R ⁵²¹ , R ⁵²² and R ⁵²³ are each independently an alkyl group having 1 to 10 carbon atoms or an alkyl group having a fluorine atom having 1 to 10 carbon atoms. Alternatively, R ⁵²¹ and R ⁵²² represent a ring in which the alkylene group having 2 to 6 carbon atoms or the alkylene group having 2 to 6 carbon atoms is bonded to each other.

In general formula (3) and general formula (4), examples of the alkyl group having 1 to 10 carbon atoms in R ⁵²¹ , R ⁵²² and R ⁵²³ include a methyl group, an ethyl group, a butyl group, a tertiary butyl group, A cyclohexyl group, an octyl group, etc. can be mentioned. Examples of the alkyl group having a fluorine atom having 1 to 10 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a dodecafluoropentyl group, and a perfluorooctyl group. Can be mentioned. Of these, R ⁵²¹ , R ⁵²² and R ⁵²³ are preferably alkyl groups having 1 to 10 carbon atoms and particularly preferably alkyl groups having 1 to 6 carbon atoms.
In general formula (3) and general formula (4), when R ⁵²¹ and R ⁵²² are bonded to each other to form a ring, the alkylene group having 2 to 6 carbon atoms includes an ethylene group, a propylene group, and a butylene group. , Pentylene group, hexylene group and the like. Examples of the alkylene group having 2 to 6 carbon atoms include a tetrafluoroethylene group, a hexafluoropropylene group, an octafluorobutylene group, a decafluoropentylene group, and an undecafluorohexylene group. it can. Among these, when R ⁵²¹ and R ⁵²² are bonded to each other to form a ring, they are preferably bonded by an alkylene group having a fluorine atom having 2 to 6 carbon atoms, particularly having 2 to 4 carbon atoms. Bonding with an alkylene group having a fluorine atom is preferred.

The ionic photoacid generator represented by the general formula (1) is preferably a photoacid generator represented by the following general formula (5).

(In the formula, R ⁵¹⁰ , R ⁵¹¹ , R ⁵¹² and R ⁵¹³ each independently represents an alkyl group or an aromatic group which may have a substituent, and Ar ³ and Ar ⁴ are each independently substituted. Represents a divalent aromatic group which may have a group, and X ¹⁻ and X ²⁻ each independently represents a conjugate base.)

Alkyl groups and the aromatic groups in ^{^R ^510,} R 511, R ⁵¹² and ^{R 513} has the same meaning as the alkyl group and the aromatic group represented by ^R ^{505, R 506} and ^{R 507} in formula (1), preferred embodiments are also It is the same. Moreover, the substituent which may have is the same.

X ^1- and ^{X 2-in} the conjugate bases of general formula (1) X ^- has the same meaning as conjugate bases represented, preferable embodiments thereof are also the same.

The divalent aromatic group in Ar ³ and Ar ⁴ is preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group.

Specific examples of triarylsulfonium salts used as ionic photoacid generators include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyl. Examples thereof include diphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, and 4-phenylthiophenyldiphenylsulfonium trifluoroacetate.
Commercially available compounds include TPS-102, 103, 105, 106, 109, 300, 1000, MDS-103, 105, 109, 205, 209, BDS-109, DTS-103, 105, MNPS-109, HDS-109 (above, manufactured by Midori Chemical Co., Ltd.), GSID-26-1, Cyracure UVI-6976 (above, manufactured by BASF).

The diaryl iodonium salts used as the ionic photoacid generator are represented by the following general formula (2).
General formula (2)

(In General Formula (2), R ⁵⁰⁸ and R ⁵⁰⁹ each independently represents an aromatic group which may have a substituent, and X ⁻ represents a conjugate base.)

In General Formula (2), the aromatic groups in R ⁵⁰⁸ and R ⁵⁰⁹ are synonymous with the aromatic groups represented by R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ in General Formula (1), and the preferred embodiments are also the same.
In the general formula (2), X ^- in the conjugate base of the general formula of (1) X ^- has the same meaning as conjugate bases represented, preferable embodiments thereof are also the same.
In addition, the photoacid generator represented by the general formula (2) may be bound by R ⁵⁰⁸ to R ⁵⁰⁹ to form a multimer such as a dimer. For example, the 4- (4′-diphenylsulfoniophenylthio) phenyl group is an example of a dimer, and the counter anion in the 4- (4′-diphenylsulfoniophenylthio) phenyl group is the above-mentioned X ⁻ and It is the same thing.

Specific examples of diaryliodonium salts used as ionic photoacid generators include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trioxide. Fluoroacetate, phenyl, 4- (2′-hydroxy-1′-tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2′-hydroxy-1′-tetradecaoxy) phenyliodonium hexafluoroantimonate, phenyl , 4- (2′-hydroxy-1′-tetradecaoxy) phenyliodonium-paratoluenesulfonate, and the like.
Commercially available compounds include DPI-105, 106, 109, 201, BI-105, MPI-105, 106, 109, BBI-102, 103, 105, 106, 109, 110, 201, 300, 301 ( As mentioned above, Midori Chemical Co., Ltd.) can be mentioned.

Specific examples of quaternary ammonium salts used as ionic photoacid generators include tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (parachlorophenyl) borate, tetramethylammonium Hexyltris (3-trifluoromethylphenyl) borate, benzyldimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (parachlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-tri Fluoromethylphenyl) borate and the like.

In addition to the above specific examples, specific examples of the component (B) include the following compounds, but the present invention is not limited thereto.

The content of component B in the resist layer is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymer component. When the content of component B is 0.1 parts by mass or more, desired sensitivity (higher sensitivity) is easily obtained, and when it is 10 parts by mass or less, the transparency of the coating film is easily secured.
Moreover, it is preferable that the addition amount of a nonionic photoacid generator is 1 mass% or less, and the aspect which does not contain a nonionic photoacid generator substantially is preferable.

<Solvent>
The photosensitive resin composition for forming the resist layer is preferably prepared as a solution in which a predetermined component is dissolved in a solvent (component (D)).
As the solvent used in the photosensitive resin composition for forming the resist layer, known solvents can be used, 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 Examples include glycol monoalkyl ether acetates, esters, ketones, amides, lactones, etc. That. Specific examples of the solvent used in the photosensitive resin composition for forming the resist layer include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A, and the contents thereof are as follows. Incorporated in the description.

In addition, 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, 1-nonanol as required for these solvents. , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ethers. It is more preferable to use together with acetates.

Component D is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
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 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.

The content of the solvent in the resist layer for forming the resist layer is preferably 50 to 95 parts by weight, and preferably 60 to 90 parts by weight, per 100 parts by weight of the total resin components in the photosensitive resin composition. Is more preferable.

<Sensitizer>
In the dry film resist, the resist layer preferably further contains a sensitizer. The resist layer can contain a sensitizer in order to promote its decomposition in combination with the (B) photoacid generator, and in particular when using a nonionic photoacid generator, It is preferable to contain. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid.
Inclusion of a sensitizer further improves exposure sensitivity, and uses a nonionic photoacid generator with low visible light absorptivity, or exposure light source is a mixed line of g-line and h-line Is particularly effective.

As the sensitizer, anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, base styryl derivatives, and distyrylbenzene derivatives are preferable, and anthracene derivatives are more preferable.
Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 , 10-dibromoanthracene, 2-ethylanthracene and 9,10-dimethoxyanthracene are preferred.
As the acridone derivative, acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone and N-ethyl-2-methoxyacridone are preferable.
As the thioxanthone derivative, thioxanthone, diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and 2-chlorothioxanthone are preferable.
As the coumarin derivatives, coumarin-1, coumarin-6H, coumarin-110 and coumarin-102 are preferable.
Examples of the base styryl derivative include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole, and 2- (4-dimethylaminostyryl) naphthothiazole.
Examples of the distyrylbenzene derivative include distyrylbenzene, di (4-methoxystyryl) benzene, and di (3,4,5-trimethoxystyryl) benzene.

Specific examples of the sensitizer include the following, but the present invention is not limited thereto. In the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

The content of the sensitizer in the resist layer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymerizable component. Desirable sensitivity can be easily obtained by setting the content of the sensitizer to 0.1 parts by mass or more, and transparency of the coating film can be easily ensured by setting the content to 10 parts by mass or less.

<Basic compound>
In the dry film resist of the present invention, the resist layer preferably further contains a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. And ethanolamine, dicyclohexylamine, dicyclohexylmethylamine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea (abbreviation CHMETU), and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 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 (abbreviation DBN), 1,8-diazabicyclo [5.3. 0] -7-undecene That.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.

The basic compounds that can be used in the present invention may be used alone or in combination of two or more.

The content of the basic compound in the resist layer is preferably 0.001 to 3 parts by mass and more preferably 0.005 to 1 part by mass with respect to 100 parts by mass of the total solid content in the resist layer. preferable.

<(C): Heterocyclic compound>
In the dry film resist of the present invention, the resist layer preferably contains (C) a heterocyclic compound. By adding the heterocyclic compound, the cured film obtained from the resist layer can be made stronger.
There is no restriction | limiting in particular as a heterocyclic compound except a polymer component. For example, compounds having an epoxy group or oxetanyl group in the molecule described below, alkoxymethyl group-containing heterocyclic compounds, other oxygen-containing monomers such as various types of cyclic ethers and cyclic esters (lactones), cyclic amines and oxazolines Nitrogen-containing monomers and heterocyclic monomers having d electrons such as silicon, sulfur and phosphorus can be added.

The addition amount of the heterocyclic compound in the resist layer is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the resist layer. More preferably, it is 1 to 5 parts by mass. By adding in this range, a cured film having excellent mechanical strength can be obtained, and a cured film having excellent chemical resistance can be obtained. A plurality of heterocyclic compounds can be used in combination, and in that case, the heterocyclic compounds are added together to calculate the content.

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

These are available as commercial products. Examples thereof include commercially available products described in paragraph No. 0189 of JP2011-212494, such as JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation), and the like.
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX- 832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX- 14L, 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 (manufactured by Nagase ChemteX Corporation), YH-300, YH-301, YH-302, YH-315 YH-324, YH-325 (manufactured by Nippon Steel Chemical Co., Ltd.), Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolide GT400, Cellbiners B0134, B0177 (manufactured by Daicel Corporation).
These can be used alone or in combination of two or more.

Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, aliphatic epoxy, and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.

Specific examples of compounds having an oxetanyl group in the molecule include Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei) Can be used.

In addition, the compound containing an oxetanyl group is preferably used alone or mixed with a compound containing an epoxy group.

Among these, the (C) heterocyclic compound is preferably a compound having an epoxy group from the viewpoint of etching resistance and line width stability.

A compound having both an alkoxysilane structure and a heterocyclic structure in the molecule can also be suitably used for the resist layer. Examples thereof include γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane. Of these, γ-glycidoxypropyltrialkoxysilane is more preferred. These can be used alone or in combination of two or more.

<Surfactant>
The resist layer may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and the like.
In addition, the surfactant contains the structural unit A and the structural unit B represented by the following general formula (I-1), and is converted to polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A copolymer having a weight average molecular weight of 1,000 or more and 10,000 or less can be mentioned as a preferred example.

Formula (I-1)

(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 C represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. A numerical value is represented, q represents a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 to 18 and s represents an integer of 1 to 10)

L is preferably a branched alkylene group represented by the following general formula (I-2). R ⁴⁰⁵ in the general 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 coated surface. A

number

2 or 3 alkyl group is more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

Formula (I-2)

The weight average molecular weight of the copolymer is more preferably from 1,500 to 5,000.

In addition, surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362 can also be used.

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the surfactant in the resist layer is preferably 10 parts by mass or less, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the resist layer. More preferably, it is 0.01 to 3 parts by mass.

<Radiation absorber>
The positive photosensitive material used in the present invention preferably contains a radiation absorber. As the radiation absorber, an ultraviolet absorber is preferable. An ultraviolet absorber exhibiting a so-called photobleaching property in which the absorbance is decreased by ultraviolet absorption is more preferably used. Specifically, photobleachable materials such as naphthoquinonediazide derivatives, nitrones and diazonium salts (for example, Japanese Patent Publication No. 62-40697, M. Sasano et al., SPIE Symp. Proc., 631, 321 (1986)). Described compounds).
The radiation absorber is used for the purpose of averaging the light intensity distribution in the resist layer, and brings about the so-called internal enhancement type CEL (Contrast Enhancement Lithography) effect, thereby making the pattern rectangular and pattern linearity (line edge). Roughness can be improved (see Semiconductor Process Materials and Chemicals, supervised by Masanori Sakamoto, CM Publishing (2006)).

<Other ingredients>
In addition to the above components, the resist layer further includes metal oxide particles, cross-linking agents other than heterocyclic compounds, alkoxysilane compounds, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, and colorants. Well-known additives such as plasticizers, thermal radical generators, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic precipitation inhibitors can be added.
Preferred embodiments of the other components are described in [0165] to [0184] of JP-A-2014-85643, the contents of which are incorporated herein.

<Compound having an ethylenically unsaturated bond>
In the dry film resist, the amount of the compound having an ethylenically unsaturated bond in the resist layer is preferably 0% by mass from the viewpoint of resolution. Note that 0 mass% may include an aspect that is contained in a minute amount (for example, 1 mass% or less in the resist layer) to the extent that the resolution effect is not impaired.

<Resist layer thickness>
The thickness of the resist layer is preferably 0.5 to 10 μm. When the film thickness of the resist layer is 10 μm or less, the resolution of the pattern is good, and when it is 0.5 μm or more, it is preferable from the viewpoint of pattern linearity.
The thickness of the resist layer is more preferably 0.8 to 5 μm, and particularly preferably 1.0 to 3.0 μm.

<Method for forming resist layer>
A photosensitive resin composition for forming a resist layer can be prepared by mixing each component at a predetermined ratio and by any method, stirring and dissolving. For example, a resin composition can be prepared by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

(Light absorption layer)
When satisfying the condition (2), the dry film resist of the present invention has a light absorption layer having a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer between the temporary support and the resist layer.
When the dry film resist of the present invention satisfies the condition (2), the light absorption layer preferably has a transmittance of 60% or less, and more preferably has a transmittance of 55% or less.

The light absorption layer will be described. The light absorption layer is provided between the resist layer and the temporary support in order to absorb unnecessary light out of the exposure light diffused by the temporary support and suppress resist exposure.
The light absorption layer preferably contains a light absorber and a resin.

The light absorber is selected from ultraviolet absorbers, dyes, and the like, and may or may not have a so-called photobleaching property that absorbs exposure light and decreases the absorbance.
Photobleaching materials include photobleachable materials such as naphthoquinone diazide derivatives, nitrones and diazonium salts (for example, Japanese Patent Publication No. 62-40697, M. Sasano et al., SPIE Symp. Proc., 631, 321 (1986). ), Stilbazolium salts, aryl nitroso salts, formazan dyes, oxonol dyes, and the like. More specific examples include formazan dyes such as nitro blue tetrazolium, MTT formazan, 1,3,5-triphenyl formazan and INT formazan, and oxonol dyes such as oxonol yellow K and oxonol 805 blue.
As a light absorber that is not photobleached, a known ultraviolet absorber or the like can be used. Representative structures include benzotriazole, benzophenone, triazine, cyanoacrylate, oxanilide, formamidine, and the like. More specific examples include benzotriazoles such as TINUVIN 384, 900, and 928 (all manufactured by BASF), ADK STAB LA-29 and LA-36 (all manufactured by ADEKA), and TINUVIN 400 and 460 (all manufactured by BASF). And benzophenone compounds such as Adeka Stub 1413 (manufactured by ADEKA) and the like.

The resin constituting the light absorption layer is preferably an alkali-soluble resin because both the resist and the resist must be lost by alkali development. The alkali-soluble resin is preferably a linear organic polymer and is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of the linear organic high molecular polymer include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, The methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer described in JP-A-59-53836 and JP-A-59-71048 Examples thereof include polymers and partially esterified maleic acid copolymers. Similarly, acidic cellulose derivatives having a carboxylic acid in the side chain are useful.
In addition to those described above, alkali-soluble resins include those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth) Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include chain butyl (meth) acrylate or phenoxyhydroxypropyl (meth) acrylate.

In addition to the above substances, substances such as surfactants, antioxidants, antifoaming agents, development accelerators, and plasticizers may be added to the light absorption layer to improve the properties.

<Preparation method of dry film resist>
The dry film resist can be produced according to the method for producing a photosensitive transfer material described in paragraphs [0094] to [0098] of JP-A-2006-259138. The resist layer is preferably formed using a positive photosensitive resin composition.
Specifically, when forming a dry film resist having an intermediate layer, a solution (addition liquid for thermoplastic resin layer) in which an additive is dissolved together with a thermoplastic organic polymer is applied on a support and dried. After providing a thermoplastic resin layer, a prepared solution (intermediate layer coating solution) prepared by adding a resin or an additive to a solvent that does not dissolve the thermoplastic resin layer is applied onto this thermoplastic resin layer and dried. Then, an intermediate layer is laminated, and a resist layer coating solution prepared using a solvent that does not dissolve the intermediate layer is further applied onto the intermediate layer, dried, and then the resist layer is laminated. be able to.

[Method of manufacturing circuit wiring]
The circuit wiring manufacturing method of the present invention is a circuit wiring manufacturing method including the following steps (a), (b), (c) and (d).
(A) a laminating step of laminating the dry film resist of the present invention on a circuit-forming substrate having a base material and a conductive layer;
(B) a pattern exposure step of exposing a contact pattern with a pattern exposure pattern (preferably a photomask having a pattern exposure pattern shape) without peeling off the temporary support of the dry film resist;
(C) A development step of forming a pattern exposure pattern (preferably a resist pattern having a pattern exposure pattern shape) on the resist layer by developing after peeling the temporary support;
(D) An etching step of forming a pattern exposure pattern (preferably a conductive layer pattern (circuit wiring) having a pattern exposure pattern shape) on the circuit forming substrate by etching.
In the present specification, “pattern exposure pattern” means “pattern exposure pattern shape” unless otherwise specified. When the pattern exposure pattern is developed on the resist layer after pattern exposure, it means that a resist pattern having the same shape as the “pattern exposure pattern shape” used for pattern exposure is formed. When a pattern exposure pattern is formed on a circuit forming substrate by etching, this means that a conductive layer pattern having the same shape as the “pattern exposure pattern shape” used for pattern exposure is formed.
The circuit wiring of the present invention is suitable for an input device, particularly for a touch panel. In the circuit wiring manufacturing method of the present invention, the circuit wiring is preferably a circuit wiring of the input device. Furthermore, in the method for manufacturing circuit wiring of an input device according to the present invention, the input device is preferably a touch panel.
Hereinafter, preferred embodiments of the method for producing circuit wiring of the present invention will be described.

In the method for manufacturing a circuit wiring of the present invention, the step (b) is the following step (b1),
(C) The process is the following (c1) process,
(D) The process is the following (d1) process,
Further, the following steps (e1), (f1) and (g) are preferably included from the viewpoint of forming a circuit wiring including a conductive layer having two types of patterns;
(B1) A pattern exposure step of exposing the contact pattern with the first pattern without peeling off the temporary support of the dry film resist;
(C1) A development step of peeling the temporary support and developing to form a first pattern on the resist layer;
(D1) an etching step of forming a first pattern on the circuit formation substrate (substantially a conductive layer of the circuit formation substrate) by etching;
(E1) A pattern exposure step of exposing the contact pattern with the second pattern without removing the resist layer to which the first pattern is transferred in the step (c1);
(F1) A development step of developing and forming a second pattern different from the first pattern on the resist layer;
(G) An etching step of forming a second pattern on the circuit formation substrate (substantially a conductive layer of the circuit formation substrate) by etching.

In the method for manufacturing a circuit wiring of the present invention, the step (b) is the following step (b1),
(C) The process is the following (c1) process,
(D) The process is the following (d2) process,
Furthermore, it is preferable to include the step (e2), the step (f2), and the step (g) from the viewpoint of forming a circuit wiring including a conductive layer having two types of patterns and more easily suppressing process contamination;
(B1) A pattern exposure step of exposing the contact pattern with the first pattern without peeling off the temporary support of the dry film resist;
(C1) A development step of peeling the temporary support and developing to form a first pattern on the resist layer;
(D2) After transferring the first pattern to the circuit formation substrate (substantially the conductive layer of the circuit formation substrate) by etching, without removing the resist layer on which the first pattern was formed in the step (c1) An etching step of attaching a cover film on the remaining resist layer;
(E2) A pattern exposure step of exposing the contact pattern with the second pattern without peeling off the cover film attached in the step (d2);
(F2) A development step in which the cover film attached in step (d2) is peeled and then developed to form a second pattern different from the first pattern on the resist layer;
(G) An etching step of forming a second pattern on the circuit formation substrate (substantially a conductive layer of the circuit formation substrate) by etching.

In the method of manufacturing circuit wiring, it is also preferable that the base material has conductive layers on both surfaces, and the base material is sequentially or simultaneously formed on the conductive layers formed on both surfaces. With this configuration, it is possible to form a touch panel circuit wiring in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the other surface. Moreover, it is also preferable to form the circuit wiring for touch panels of this structure from both surfaces of a base material by roll-to-roll.

A case where a conductive pattern of a capacitive input device is obtained using a resist layer as an etching resist (etching pattern) will be described.
The capacitance type input device has a base material (also referred to as a front plate) and at least the following elements (2) to (5) on the non-contact surface side of the base material: (2), (3) It is preferable that at least one of (5) is formed by the circuit wiring manufacturing method of the present invention.
(2) A plurality of first electrode patterns formed by extending a plurality of pad portions in a first direction via connecting portions. (3) The first electrode patterns are electrically insulated from the first electrode patterns, and the first A plurality of second electrode patterns including a plurality of pad portions and connection portions formed extending in a direction crossing one direction; and (4) electrically connecting the first electrode pattern and the second electrode pattern. Electrically insulating layer (5) electrically connected to at least one of the first electrode pattern and the second electrode pattern, and having a different conductivity from the first electrode pattern and the second electrode pattern Hereinafter, details of each step will be described.

<(A) Process>
(A) A laminating process for laminating the dry film resist of the present invention on a circuit forming substrate having a base material and a conductive layer will be described.
Lamination (transfer, bonding) of the dry film resist onto the circuit forming substrate is carried out by applying the resist layer on the circuit forming substrate (preferably on the conductive layer, and when there are two or more conductive layers, the first layer of the conductive layer is formed. It is preferably carried out using a method of layering, pressing and heating on the layer). For laminating, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.

(Base material)
The substrate is preferably a glass substrate or a film substrate, and more preferably a film substrate. When the circuit wiring manufacturing method of the present invention is a circuit wiring for a touch panel, the substrate is particularly preferably a sheet-shaped resin composition.
Moreover, it is preferable that a base material is transparent.
In this specification, the term “transparent” means that the average transmittance of visible light having a wavelength of 400 nm to 700 nm is 80% or more. Therefore, the transparent layer refers to a layer having an average transmittance of visible light having a wavelength of 400 nm to 700 nm of 80% or more. The average transmittance of visible light having a wavelength of 400 nm to 700 nm of the transparent layer is preferably 90% or more.
The refractive index of the substrate is particularly preferably from 1.50 to 1.52.
The substrate may be composed of a transparent substrate such as a glass substrate. As the base material, tempered glass represented by Corning gorilla glass can be used. Further, as the above-mentioned transparent substrate, materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
When a film substrate is used as the substrate, it is more preferable to use a material that is not optically distorted or highly transparent. Specific examples of the material include polyethylene terephthalate (PET) and polyethylene naphthalate. , Polycarbonate, triacetyl cellulose, and cycloolefin polymer.

(Conductive layer)
As a conductive layer, the arbitrary conductive layers used for general circuit wiring and touch-panel wiring can be mentioned.
Examples of the material for the conductive layer include metals and metal oxides.
The multilayer conductive layers may be made of the same material or different materials, but preferably contain different materials.

It is preferable that at least one of the multilayer conductive layers contains a metal oxide.
Examples of the metal oxide used in this case include metal oxide films such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ . The metal oxide will be described later.
The conductive layer is preferably a material for a first electrode pattern, a second electrode pattern, and another conductive element described below, which are used in a capacitive input device described later.
Other preferred modes of the conductive layer will be described later in the description of the capacitive input device.

<(B) Process>
(B) A pattern exposure process for exposing a contact pattern with a pattern for pattern exposure without peeling off the temporary support of the dry film resist will be described.
The step (b) is preferably a pattern exposure step in which the contact pattern is exposed with the first pattern without peeling the temporary support of (b1) dry film resist.

As examples of the exposure step, the development step (c) described later, and other steps, the method described in paragraphs [0035] to [0051] of JP-A-2006-23696 is preferably used in the present invention. Can be used.

Specifically, above the resist layer formed on the circuit forming substrate (preferably on the conductive layer, or on the first layer of the conductive layer if there are two or more conductive layers), and temporarily support Examples include a method in which a predetermined mask is arranged at a position in direct contact with the body, and then a contact pattern is exposed from a light source above the mask through the mask and a temporary support.
In the present invention, 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) including the input device of the present invention and to reduce the area occupied by the extraction wiring as much as possible, at least a part of the pattern (particularly the electrode pattern of the touch panel and the extraction wiring portion). ) Is preferably a fine wire of 100 μm or less, more preferably 70 μm or less, and particularly preferably 10 μm or less.
Here, as the light source for the exposure, a light source capable of irradiating light in a wavelength region (for example, 365 nm, 405 nm, etc.) that allows the exposed portion of the resist layer to be dissolved in the developer is appropriately selected and used. it can. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. The exposure amount is usually about 5 to 200 mJ / cm ² , preferably about 10 to 100 mJ / cm ² .
It is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and pattern linearity of the pattern after exposure. By this process called so-called PEB (Post Exposure Bake), it is possible to reduce the roughness of the resist pattern edge due to standing waves generated in the resist layer during exposure.

Pattern exposure is performed before the temporary support is peeled off. Thereafter, the support may be peeled off. Exposure through a mask or digital exposure using a laser or the like may be used. The pattern exposure is preferably exposure through a mask. When exposure is performed through a mask, the pattern exposure pattern is also referred to as a mask pattern.

<(C) Process>
A development process for forming a pattern exposure pattern on the resist layer after peeling off the temporary support will be described.
The step (c) is preferably a development step (c1) in which the temporary support is peeled and then developed to form a first pattern on the resist layer.

The development step is a step of developing the pattern-exposed resist layer.
The development can be performed using a developer. The developer is not particularly limited, and known developers such as those described in JP-A-5-72724 can be used. The developer preferably has a development behavior in which the resist layer has a dissolution type. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable, but is further miscible with water. A small amount of an organic solvent having Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol And acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
Further, a known surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

The development method may be any of paddle development, shower development, shower & spin development, dip development, and the like. Here, the shower development will be described. The exposed portion can be removed by spraying a developing solution onto the resist layer after exposure. When a thermoplastic resin layer or an intermediate layer is provided, a cleaning solution having a low solubility of the resist layer may be sprayed by a shower or the like before development to remove the thermoplastic resin layer or the intermediate layer. preferable. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

Further, it may have a post-baking step of heat-treating the pattern including the resist layer obtained by the development, and obtained by the development after the step of removing the thermoplastic resin layer and the intermediate layer. A step of performing post-baking for heat-treating the pattern made of the resist layer may be included.
By the post-baking step, elimination of the protecting group using an acid in the resist layer can be promoted. In the structural unit (a1) having a group in which the acid group in the resist layer is protected with an acid-decomposable group, protecting the carboxy group with an acetal reduces the activation energy for protecting group elimination, and This is preferable from the viewpoint of avoiding heat treatment.

(C) You may have other processes, such as a post exposure process, before or after a process.

<(D) Process>
(D) An etching process for forming a pattern exposure pattern on the circuit forming substrate by etching will be described.
Step (d) includes (d1) etching to form a first pattern on the circuit formation substrate, or (d2) etching to form the first pattern on the circuit formation substrate and then the remaining resist. It is preferable that it is an etching process which affixes a cover film on a layer.
(D2) After the first pattern is formed on the circuit forming substrate by etching, the cover film is formed on the remaining resist layer without peeling off the resist layer on which the first pattern is formed in the above-described step (c1). In the etching step of attaching the film, it is preferable to use again the temporary support once peeled off in the step (c) as the cover film.

For the etching, a known etching method such as the method described in paragraphs [0048] to [0054] of JP 2010-152155 A can be applied.

For example, as an etching method, there is a commonly performed wet etching method of dipping in an etching solution. As an etching solution used for wet etching, an acid type or an alkaline type may be appropriately selected according to an object to be etched. Examples of acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid; mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride, potassium permanganate, etc. Is done. As the acidic component, a combination of a plurality of acidic components may be used. In addition, alkaline type etching solutions include aqueous solutions containing only alkali components such as salts of organic amines such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, tetramethylammonium hydroxide; alkaline components and potassium permanganate, etc. A mixed aqueous solution of a salt of A combination of a plurality of alkali components may be used as the alkali component.

The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower. The resist layer used as an etching mask (etching pattern) in the present invention preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in the above temperature range. Therefore, the resist layer is prevented from being peeled off during the etching process, and the portion where the resist layer does not exist is selectively etched.
After the etching, a cleaning process and / or a drying process may be performed as necessary to prevent line contamination. For example, the cleaning process is performed by cleaning the substrate with pure water at room temperature for 10 to 300 seconds. For the drying process, an air blow is used and an air blow pressure (about 0.1 to 5 kg / cm ² ) is appropriately set. Adjust and do.

<(E1) step and (e2) step>
(E1) a pattern exposure step of exposing the contact pattern with the second pattern without peeling off the resist layer on which the first pattern has been formed in the step (c1), and (e2) in the step (d2). A pattern exposure process for exposing the contact pattern with the second pattern without peeling off the attached cover film will be described.
For the contact pattern exposure in the steps (e1) and (e2), the same method as the contact pattern exposure in the step (b) can be used.

<(F1) process and (f2) process>
(F1) a development step of developing and forming a second pattern different from the first pattern on the resist layer; and (f2) the cover film attached in the step (d2) is peeled off and then developed. A developing process for forming a second pattern different from the first pattern on the resist layer will be described.
The development in step (f1) and (f2) can use the same method as the development in step (c).

<(G) Process>
(G) An etching process for forming the second pattern on the circuit formation substrate by etching will be described.
For the etching in the step (g), the same method as the etching in the step (d) can be used.
In step (g), it is preferable to selectively etch fewer conductive layers than in step (d), depending on the desired pattern.

<Method for Forming Circuit Wiring Containing Two Types of Conductive Layers>
When forming a circuit wiring including a conductive layer having at least two types of patterns, the following (Xa) process, (Xb) process, (Xc) process, (Xd) process, (Xe) process, and (Xz) process are performed as follows. It is also preferable to implement in combination with each step of the method for manufacturing a circuit wiring of the invention.
(Xa) where x is an integer of 2 or more, the first layer of the conductive layer with respect to the circuit forming substrate having the base material and the conductive layers from the x-th layer to the first layer in order from one surface of the base material A laminating step for forming a resist layer in which the exposed portion is dissolved in a developer;
(Xb) A pattern exposure and development process in which a resist layer is formed into a first pattern by pattern exposure and development on the circuit-formed substrate on which the resist layer is formed;
(Xc) An etching process for etching from the first layer to the i-th layer of the conductive layer in the region where the resist layer having the first pattern in the (Xb) process is not formed, where i is an integer of 1 to x ;
(Xd) A pattern exposure and development step in which the resist layer remaining in the step (Xb) is subjected to pattern exposure and development in a pattern different from that of the remaining resist layer, and the resist layer is used as a second pattern;
(Xe) An etching process in which j is an integer of 1 or more and less than i, and etching is performed from the first layer to the jth layer of the conductive layer in the region where the resist layer formed as the second pattern in the (Xd) process is not formed. ;
(Xz) A remaining resist layer removing step of removing all the remaining resist layers to form circuit wiring including conductive layers having at least two types of patterns.

FIG. 1 shows an example of a method for manufacturing a circuit wiring for a touch panel when forming a circuit wiring including a conductive layer having at least two types of patterns.
In the example of the method for manufacturing the circuit wiring for touch panel shown in FIG. 1, in addition to the (Xa) process, the (Xb) process, the (Xc) process, the (Xd) process, the (Xe) process, and the (Xz) process, Step (Xf) is described.
In the step (Xa), a resist layer is formed on the first layer of the conductive layer. This resist layer remains at least partially in the subsequent (Xa) step, (Xb), (Xc), (Xd), (Xe), and (Xf), and finally remains in the (Xz) step. All the resist layers to be removed are removed to form a circuit wiring including at least two types of conductive layers. That is, a circuit wiring including a plurality of types of conductive layers can be formed by a single resist formation.
In step (Xb), pattern exposure and development are performed to make the resist layer the first pattern.
In the step (Xc), the first layer to the i-th layer of the conductive layer in the region where the resist layer having the first pattern in the step (Xb) is not formed are etched. In FIG. 1, i = x is set in step (Xc), and all the conductive layers from the first layer to the x-th layer are etched and removed.
The pattern from the first layer to the i-th layer of the conductive layer obtained in the (Xc) process does not remain when all the resist layers are removed by going to the (Xz) process, and in the (Xe) process. Etching in step (Xf), which can be performed as needed, forms another pattern. In the configuration shown in FIG. 1, the pattern from the first layer to the i-th layer of the conductive layer obtained in the step (Xc) is described as seven columns, but the third, fourth, and fifth columns from the right Is a different pattern in the etching in the (Xe) process, and the first, second and sixth pillars from the right also have a different pattern in the etching in the (Xf) process, and the final (Xz) When all the resist layers are removed through the process, only the seventh column from the right is a pattern from the first layer to the i-th layer of the conductive layer.
In the step (Xd), the resist layer remaining in the step (Xb) is subjected to pattern exposure and development in a pattern different from that of the remaining resist layer, so that the resist layer becomes a second pattern.
In the (Xe) process, the first to jth layers of the conductive layer in the region where the resist layer having the second pattern formed in the (Xd) process is not formed are etched. In FIG. 1, in step (Xe), j = x−1 and j = i−1, the conductive layers from the first layer to the x−1th layer (jth layer) are removed by etching, Only the x layer is left.
Although details of the (Xf) process are omitted in FIG. 1, the (Xf) process can be repeated as many times as necessary.
In the step (Xz), all remaining resist layers are removed to form circuit wiring including conductive layers having at least two types of patterns. FIG. 1 shows that the entire resist layer was finally removed after the (Xz) step.

(Step (Xa))
(Xa) Step: The first conductive layer is formed on a circuit-formed substrate having a base material and conductive layers from the x-th layer to the first layer in order from one surface of the base material, where x is an integer of 2 or more. A laminating process for laminating a resist layer in which a portion exposed on the layer is dissolved in a developer will be described.

(Xa) The step is preferably a step of laminating the resist layer of the dry film resist from which the protective film has been removed on the first layer of the conductive layer.

x is an integer of 2 or more, preferably 2 or 3, and more preferably 2.
FIG. 2 shows a schematic cross-sectional view of an example of circuit wiring for a touch panel, which is one of the embodiments of the present invention obtained when x is 2. In FIG. 2, the first electrode pattern 3 is formed on the substrate 1, and another conductive element 6 is formed on the first electrode pattern. The circuit wiring for the touch panel shown in FIG. 2 has two types of patterns: a conductive layer laminate in which another conductive element is formed with the first electrode pattern 3 and a conductive layer having only the first electrode pattern 3. The circuit wiring includes a conductive layer.
FIG. 3 shows the circuit wiring for the touch panel in FIG. In the example of the circuit wiring for the touch panel shown in FIG. 3, the dotted line portion in FIG. 3 is a conductive layer laminated body in which another conductive element is formed with the first electrode pattern 3, and the portion where the squares in FIG. Is a conductive layer having only the first electrode pattern 3. As shown in FIG. 3, among the conductive layers having different types of patterns included in the circuit wiring, the conductive layer having at least one type of pattern includes a conductive layer stack of two or more layers sharing the same circuit pattern. Is preferred.

(Step (Xb))
Process (Xb): A pattern exposure and development process in which a resist layer is formed into a first pattern by pattern exposure and development on a circuit-formed substrate on which a resist layer is formed will be described.
The pattern exposure and development in the step (Xd) can use the same methods as the pattern exposure and development in the steps (b) and (c).

(Step (Xc))
(Xc) Process: Etching is performed from the first layer to the i-th layer of the conductive layer in the region where the resist layer having the first pattern in the (Xb) process is not formed, where i is an integer of 1 to x. The etching process will be described.
For the etching process in the step (Xc), the same method as the etching process in the process (d) can be used.

(Step (Xd))
Process (Xd): The pattern exposure and development process in which the resist layer remaining in the process (Xb) is subjected to pattern exposure and development in a pattern different from the remaining resist layer to make the resist layer a second pattern will be described.
The pattern exposure and development in the step (Xd) can use the same methods as the pattern exposure and development in the step (Xb).

(Step (Xe))
(Xe) Process: Etching is performed from the first layer to the jth layer of the conductive layer in the region where the resist layer having the second pattern in the (Xd) process is not formed, where j is an integer of 1 or more and less than i. The etching process will be described.
The same method as the etching in the (Xc) process can be used for the etching in the (Xe) process.
In step (Xe), it is preferable to selectively etch fewer conductive layers than in step (Xc), depending on the desired pattern.

(Step (Xf))
It is preferable that the method for manufacturing circuit wiring further includes the following step (Xf).
Step (Xf): pattern exposure and development of the remaining resist layer in a pattern different from the remaining resist layer, and any less than j from the first layer of the conductive layer in the region where the resist layer is not formed after development Pattern exposure and development process in which the conductive layer is patterned by etching up to the layer.
Hereinafter, the step (Xf) will be described.
In the method for manufacturing a circuit wiring of the present invention, it is also preferable not to perform the step (Xf). That is, in the method for manufacturing a circuit wiring of the present invention, it is preferable that the circuit wiring includes a conductive layer having only two types of patterns.
The number of repetitions of the step (Xf) is not particularly limited, and can be repeated according to the desired pattern shape. Among these, it is preferable that the number of repetitions of the (Xf) step is one.
In the method for manufacturing a circuit wiring of the present invention, it is preferable that the (Xf) step includes the following (Xf1) step and (Xf2) step, and includes a conductive layer having at least three types of patterns.
(Xf1) A pattern exposure and development process in which the resist layer remaining in the (Xe) process is subjected to pattern exposure and development in a pattern different from the remaining resist layer, and the resist layer is used as a third pattern;
(Xf2) Pattern exposure in which k is an integer of 1 or more and less than j, and etching is performed from the first layer to the k-th layer of the conductive layer in the region where the resist layer formed as the third pattern in the step (f1) is not formed And development process.
Other preferred embodiments of the step (Xf) are the same as those in the steps (Xd) and (Xe).

((Xz) process)
Step (Xz): The remaining resist layer removing step for removing all the remaining resist layers to form circuit wiring including conductive layers having at least two types of patterns will be described.
Although there is no restriction | limiting in particular as a method of removing all the resist layers which remain | survive after the said etching process, The method of removing by a chemical process can be mentioned.
Examples of the method for removing the resist layer include a method of immersing a substrate having a resist layer or the like in a stripping solution being stirred at 30 to 80 ° C., preferably 50 to 80 ° C. for 5 to 30 minutes. The resin pattern used as an etching mask may exhibit excellent chemical resistance at 45 ° C. or lower, but preferably exhibits a property of swelling with an alkaline stripping solution when the chemical temperature is 50 ° C. or higher. Due to the above properties, when the stripping process is performed using a stripping solution of 50 to 80 ° C., there are advantages that the process time is shortened and the resist layer stripping residue is reduced. That is, by providing a difference in chemical temperature between the etching step and the step of removing the resist layer, the resist layer used as an etching mask exhibits good chemical resistance in the etching step, while the removal step In this case, good releasability is exhibited, and both contradictory properties of chemical resistance and releasability can be satisfied.

Examples of the stripping solution include inorganic alkali components such as sodium hydroxide and potassium hydroxide, organic alkali components such as tertiary amine and quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or these. What was melt | dissolved in this mixed solution is mentioned. You may peel by the spray method, the shower method, the paddle method etc. using said peeling liquid.

[Circuit wiring]
The circuit wiring of the present invention is a circuit wiring manufactured by the circuit wiring manufacturing method of the present invention. The circuit wiring of the present invention is preferably a touch panel circuit wiring. A preferable aspect of the circuit wiring for the touch panel will be described later in the description of the capacitive input device.

[Input device and display device]
The input device of the present invention is an input device using the circuit wiring of the present invention. In the present invention, the input device is preferably a capacitive touch panel.
The display device of the present invention includes the input device of the present invention. The display device of the present invention is preferably an image display device.

<Capacitive Input Device and Image Display Device Comprising Capacitive Input Device>
A capacitive input device which is a preferred embodiment of the input device and display device of the present invention, and an image display device including this capacitive input device as a constituent element are “latest touch panel technology” (July 6, 2009). (Published by Techno Times Co., Ltd.), Yuji Mitani, Yoshio Itakura, "Technology and Development of Touch Panel" (CMC Publishing, 2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292 The configuration disclosed in the above can be applied.

First, the configuration of the capacitive input device will be described. FIG. 9 is a cross-sectional view showing the configuration of the capacitive input device. In FIG. 9, the capacitive input device 10 includes a base material 1, a mask layer 2, a first electrode pattern 3, a second electrode pattern 4, an insulating layer 5, and another conductive element 6. , And a transparent protective layer 7.

In FIG. 9, the side on which each element of the base material 1 is provided is referred to as a non-contact surface. In the capacitance-type input device 10, input is performed by bringing a finger or the like into contact with the contact surface of the substrate 1 (the surface opposite to the non-contact surface). Hereinafter, the base material may be referred to as a “front plate”.

A mask layer 2 is provided on the non-contact surface of the substrate 1. The mask layer 2 is a frame-like pattern around the display area formed on the non-contact surface side of the base material 1 (for example, the touch panel front plate), and is formed so as to hide the lead wiring and the like.
The capacitive input device 10 may be provided with a mask layer 2 that covers a partial region of the substrate 1. Furthermore, the base material 1 can be provided with an opening in part. A mechanical switch that operates by pressing can be installed in the opening.

On the non-contact surface of the substrate 1, a plurality of first electrode patterns 3 formed by extending a plurality of pad portions in the first direction via connection portions, and the first electrode pattern 3 and the electric A plurality of second electrode patterns 4 including a plurality of pad portions and connection portions formed so as to extend in a direction intersecting the first direction, and the first electrode pattern 3 and the second electrode pattern An insulating layer 5 that electrically insulates the electrode pattern 4 is formed. The first electrode pattern 3, the second electrode pattern 4, and another conductive element 6 to be described later can be made of a transparent conductive metal oxide film such as ITO or IZO, for example. Examples of the conductive film include metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as ITO, IZO, and SiO ₂ . At this time, the film thickness of each element can be 10 to 200 nm. Further, by baking, the amorphous ITO film can be changed to a polycrystalline ITO film, and the electrical resistance can be reduced.
The first electrode pattern 3 and the second electrode pattern 4 are preferably formed using a resist layer as an etching resist (etching pattern). For the formation of the second electrode layer for forming the second electrode pattern, a known method can be used in addition to photolithography using a resist including the resist layer used in the present invention. In addition, it can also manufacture using the photosensitive transfer material which has the photosensitive resin composition using an electroconductive fiber. When the first electrode pattern or the like is formed of ITO or the like, paragraphs [0014] to [0016] of Japanese Patent No. 4506785 can be referred to.

In addition, at least one of the first electrode pattern 3 and the second electrode pattern 4 is disposed across both the non-contact surface of the base material 1 and the surface of the mask layer 2 opposite to the base material 1. be able to. FIG. 9 shows an aspect in which the second electrode pattern 4 is disposed across both the non-contact surface of the substrate 1 and the surface of the mask layer 2 opposite to the substrate 1. Yes.

7 and 8, the first electrode pattern and the second electrode pattern 4 will be described. 7 and 8 are also explanatory diagrams showing examples of the first electrode pattern and the second electrode pattern. As shown in FIG. 8, the first electrode pattern is formed such that the pad portion 3a extends in the first direction via the connection portion 3b. The second electrode pattern 4 is electrically insulated by the first electrode pattern and the insulating layer 5 and is formed to extend in a direction intersecting the first direction (second direction). It is composed of a plurality of pad portions. Here, when the first electrode pattern 3 is formed, the pad portion 3a and the connection portion 3b may be manufactured integrally, or only the connection portion 3b is manufactured, and the pad portion 3a and the second electrode are formed. The pattern 4 may be integrally formed (patterned). When the pad portion 3a and the second electrode pattern 4 are integrally formed (patterned), as shown in FIGS. 7 and 8, a part of the connection portion 3b and one of the pad portions 3a (not shown in FIG. 7). Each layer is formed such that the first electrode pattern 3 and the second electrode pattern 4 are electrically insulated by the insulating layer 5.

In FIG. 9, another conductive element 6 is provided on the surface of the mask layer 2 opposite to the base 1. Another conductive element 6 is electrically connected to at least one of the first electrode pattern 3 and the second electrode pattern 4 and is different from the first electrode pattern 3 and the second electrode pattern 4. Is an element. FIG. 9 shows a diagram in which another conductive element 6 is connected to the second electrode pattern 4.

Moreover, in FIG. 9, the transparent protective layer 7 which covers all of each component is installed. The transparent protective layer 7 may be configured to cover only a part of each component. The insulating layer 5 and the transparent protective layer 7 may be made of the same material or different materials. As the material constituting the insulating layer 5 and the transparent protective layer 7, those having high surface hardness and high heat resistance are preferable, and known photosensitive siloxane resin materials, acrylic resin materials, and the like are used, and these are known to those skilled in the art. is there.
As a method for patterning the insulating layer, a known method such as ink jet or screen can be used in addition to the photolithography method.

In the method of manufacturing the capacitance-type input device, at least one of the first electrode pattern 3, the second electrode pattern 4, and another conductive element 6 is formed by etching a resist layer (etching pattern). It is preferable to form by etching using. In addition, at least one element of the black mask layer 2, the insulating layer 5, and, if necessary, the transparent protective layer 7 also has a temporary support, a thermoplastic resin layer, and a photocurable resin layer in this order. It is also preferable to form using a film.

At least one of the first electrode pattern 3, the second electrode pattern 4, and another conductive element 6 is preferably formed by etching using a resist layer as an etching resist (etching pattern). .
When forming the first electrode pattern 3, the second electrode pattern 4, and another conductive element 6 by etching, first, on the non-contact surface of the substrate 1 on which the black mask layer 2 is formed, An inorganic insulating layer is provided at least on the portion where the black mask layer 2 is provided, and a transparent electrode layer such as ITO is formed on the non-contact surface of the substrate 1 or on the inorganic insulating layer by sputtering. Next, an etching pattern is formed by exposure and development using a resist layer having an etching photocurable resin layer as the photocurable resin layer on the transparent electrode layer. Thereafter, the transparent electrode layer is etched to pattern the transparent electrode, and the etching pattern is removed, whereby the first electrode pattern 3 and the like can be formed.

When forming the first electrode pattern 3, the second electrode pattern 4, and another conductive element 6 using a photosensitive film having a photocurable resin layer containing a conductive material, the surface of the substrate 1 On the portion where the black mask layer 2 is provided, at least an inorganic insulating layer is provided, and the photocurable resin layer containing the conductive material is transferred onto the non-contact surface of the substrate 1 or onto the inorganic insulating layer. It can be formed using a method such as (laminate).

The mask layer 2, the insulating layer 5, and the transparent protective layer 7 can be formed by transferring a photocurable resin layer to the substrate 1 using a photosensitive film. For example, when the black mask layer 2 is formed, the black photocurable resin layer is transferred onto the surface of the substrate 1 using a photosensitive film having a black photocurable resin layer as the photocurable resin layer. Can be formed. When the insulating layer 5 is formed, the surface of the substrate 1 on which the first or second electrode pattern is formed using a photosensitive film having an insulating photocurable resin layer as the photocurable resin layer. It can be formed by transferring a photocurable resin layer to the film. When the transparent protective layer 7 is formed, a photocurable resin layer is used on the surface of the substrate 1 on which each element is formed using a photosensitive film having a transparent photocurable resin layer as the photocurable resin layer. It can be formed by transferring.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.
The following symbols represent the following compounds, respectively.
MATHF: 2-tetrahydrofuranyl methacrylate MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
PHS: parahydroxystyrene PHS-EVE: 1-ethoxyethyl protector of parahydroxystyrene PHS-THF: 2-tetrahydrofuranyl protector of parahydroxystyrene PGMEA: propylene glycol monomethyl ether acetate

[Evaluation method of material properties]
Below, the evaluation method of a material characteristic is described.

<Total light haze of temporary support>
Using a haze meter HZ-2 manufactured by Suga Test Instruments Co., Ltd., the total light haze (%) of the small piece of the temporary support was measured in accordance with JIS (Japan Industrial Standards) K7136.

<Transmittance of temporary support or light absorption layer>
A transmission spectrum of a light absorption layer sample prepared by peeling the temporary support from a small piece of the temporary support or a laminate in which the light absorption layer is formed on the temporary support, is converted into an 8453 ultraviolet-visible spectrophotometer (Agilent The transmittance at a wavelength of 365 nm which is the same as the exposure main wavelength of the resist layer was determined.

<Absorption coefficient of photosensitizer>
A 0.01 mol / L acetonitrile solution of each photosensitizer was prepared, and the absorbance at 365 nm, which is the same as the exposure main wavelength of the resist layer, was measured with the above-mentioned 8453 ultraviolet-visible spectrophotometer using a 0.1 mm quartz cell. The extinction coefficient per 1 cm of optical path length was calculated | required from the obtained value.

[Example 1]
A positive photosensitive resin composition was prepared according to the following formulation.
Novolac resin (metacresol: paracresol = 30: 70, molecular weight 5,500): 79.9 parts Photosensitizer: naphthoquinonediazide compound (1) described on page 4 of JP-A-4-22955 Part / surfactant (surfactant 1 below): 0.1 part / PGMEA: 900 parts surfactant 1: F-554, perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (manufactured by DIC) )

The absorption coefficient (365 nm) in acetonitrile of the used photosensitizer was 12,100 cm ⁻¹ M ⁻¹ .

The prepared positive type photosensitive resin composition is dried on a colored polyethylene terephthalate film (hereinafter referred to as colored PET (A)) having a film thickness of 75 μm to be a temporary support, using a slit-like nozzle. It apply | coated so that it might be set to 0 micrometer. Thereafter, the film was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (manufactured by Tredegar, OSM-N) was pressed as a protective film to prepare a dry film resist. The obtained dry film resist was used as the dry film resist of Example 1.
The colored PET (A) was prepared by the method described in [0060] of JP-A-6-306192. Dialresin Blue G (manufactured by Mitsubishi Chemical Corporation) was used as the coloring dye, and the dye amount was adjusted so as to have a transmittance of 60% for light having a wavelength of 365 nm. The total light haze of the colored PET (A) was 2.6%.

Next, copper was formed as a conductive layer with a thickness of 200 nm on a PET substrate having a thickness of 100 μm by a vacuum deposition method to obtain a circuit formation substrate.
In each Example and Comparative Example, the protective film was peeled off from the dry film resist of Example 1, and then the (a) laminating step described later was performed. The dry film resist of Example 1 was laminated and transferred onto the copper layer to produce a positive resist layer (a) A lamination process was performed.
A photomask provided with a mask pattern of line-and-space wiring with a line width of 5 μm (opening portion: light-shielding portion has a 1: 1 pattern exposure pattern) without peeling off the temporary support from the resist layer is used. Then, a photomask was brought into contact with the temporary support and contact pattern exposure was performed (b) A pattern exposure step was performed. For the exposure, a high pressure mercury lamp having i-line (365 nm) as an exposure dominant wavelength was used.
After removing the temporary support from the exposed circuit-formed substrate, development using 2.38% by mass of TMAH aqueous solution and washing with water were performed to obtain a resist layer on which a wiring pattern was formed (c) A development step was performed.
Next, an etching (d) process for forming a pattern for pattern exposure on the circuit forming substrate by etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.) was obtained, thereby obtaining a copper wiring substrate. . The obtained circuit wiring was used as the circuit wiring of Example 1.

[Example 2]
A dry film resist of Example 2 was prepared in the same manner as in Example 1 except that the temporary support used was colored PET (B) having a transmittance of 40% for light having a wavelength of 365 nm. Further, a copper wiring board as a circuit wiring of Example 2 was produced in the same manner as in Example 1 except that the dry film resist of Example 2 was used as the dry film resist. The colored PET (B) was adjusted to have the above transmittance by using the same material as the colored PET (A) and adjusting the amount of dye. The total light haze of the colored PET (B) was 3.2%.

[Example 3]
<Synthesis Example 1: Synthesis of PHS-EVE>
20 g of alkali-soluble resin (VP-8000 manufactured by Nippon Soda Co., Ltd.) and 320 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask and distilled under reduced pressure, and water and PGMEA were distilled off azeotropically. After confirming that the water content was sufficiently low, 24 g of ethyl vinyl ether and 0.35 g of paratoluenesulfonic acid were added and stirred at room temperature for 1 hour. Thereto, 0.28 g of triethylamine was added to stop the reaction. After adding ethyl acetate to the reaction solution and further washing with water, ethyl acetate, water and azeotropic PGMEA were distilled off under reduced pressure to obtain PHS-EVE which is an alkali-soluble resin protected with an acid-decomposable group. It was. The weight average molecular weight of the obtained resin was 12,000. The polydispersity was 1.21.
The structure of PHS-EVE is as shown below, and is a 1-ethoxyethyl protected paraparastyrene / parahydroxystyrene copolymer (30 mol% / 70 mol%) of parahydroxystyrene.

Using the synthesized PHS-EVE, a positive photosensitive composition was prepared according to the following formulation.
-PHS-EVE: 97.9 parts-Photoacid generator (PAG-1 below): 2 parts-Surfactant (surfactant 1 above): 0.1 part-PGMEA: 900 parts PAG-1: WO2014 / Compound B-9 according to 020984.
The absorption coefficient (365 nm) in acetonitrile of PAG-1 was 15,500 cm ⁻¹ M ⁻¹ .
The positive photosensitive composition is slit-coated on colored PET (A) as a temporary support so as to have a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally a protective film. A dry film resist was prepared by pressure-bonding a polyethylene film (OSM-N, manufactured by Tredegar). The obtained dry film resist was used as the dry film resist of Example 3.
A copper wiring board as a circuit wiring of Example 3 was produced in the same manner as in Example 1 except that the dry film resist of Example 3 was used as the dry film resist.

[Example 4]
A dry film resist of Example 4 was produced in the same manner as Example 3 except that colored PET (B) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 4 was produced in the same manner as in Example 1 except that the dry film resist of Example 4 was used as the dry film resist.

[Example 5]
A dry film resist of Example 5 was prepared in the same manner as Example 3 except that PAG-2 (Compound A-1 described in [0227] of JP2013-047765 A) was used instead of PAG-1. did. Further, a copper wiring board as a circuit wiring of Example 5 was produced in the same manner as in Example 1 except that the dry film resist of Example 5 was used as the dry film resist. The absorption coefficient (365 nm) in acetonitrile of PAG-2 was 7,800 cm ⁻¹ M ⁻¹ .

[Example 6]
A dry film resist of Example 6 was produced in the same manner as Example 5 except that colored PET (B) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 6 was produced in the same manner as in Example 1 except that the dry film resist of Example 6 was used as the dry film resist.

[Example 7]
A dry film resist of Example 7 was prepared in the same manner as in Example 3 except that CPI-210S manufactured by San Apro Co., Ltd. was used instead of PAG-1. Further, a copper wiring board as a circuit wiring of Example 7 was produced in the same manner as in Example 1 except that the dry film resist of Example 7 was used as the dry film resist. The extinction coefficient (365 nm) of CPI-210S in acetonitrile was 85 cm ⁻¹ M ⁻¹ .

[Example 8]
In place of PAG-1, compound No. described in [0079] of WO201408269 A dry film resist of Example 8 was produced in the same manner as Example 3 except that 10 was used. Further, a copper wiring board as a circuit wiring of Example 8 was produced in the same manner as in Example 1 except that the dry film resist of Example 8 was used as the dry film resist. The absorption coefficient (365 nm) of this compound in acetonitrile was 11,700 cm ⁻¹ M ⁻¹ .

[Example 9]
A dry film resist of Example 9 was produced in the same manner as Example 3 except that the film described in [0057] and [0058] of Japanese Patent No. 4036068 was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 9 was produced in the same manner as in Example 1 except that the dry film resist of Example 9 was used as the dry film resist.

[Example 10]
<Synthesis Example 2: Synthesis of PHS-THF>
15.6 g of alkali-soluble resin (VP-8000 manufactured by Nippon Soda Co., Ltd.) and 100 g of propylene glycol monomethyl ether acetate (PGMEA) were dissolved in a flask and distilled under reduced pressure, and water and PGMEA were distilled off azeotropically. After confirming that the water content was sufficiently low, 2.7 g of 2,3-dihydrofuran and 0.015 g of paratoluenesulfonic acid were added and stirred at room temperature for 2 hours. Thereto was added 0.090 g of triethylamine to stop the reaction. Ethyl acetate was added to the reaction solution, and the mixture was further washed with water. Then, ethyl acetate and water were distilled off under reduced pressure to obtain PHS-THF, a soluble resin having a protection rate of 25 mol%. The weight average molecular weight of the obtained resin was 12,000. The polydispersity was 1.13.
The structure of PHS-THF is shown below, and is a 2-tetrahydrofuranyl protected form of parahydroxystyrene / parahydroxystyrene copolymer (30 mol% / 70 mol%).

Using the synthesized PHS-THF, a positive photosensitive composition was prepared according to the following formulation.
-PHS-THF: 97.9 parts-Photoacid generator (PAG-2): 2 parts-Surfactant (surfactant 1): 0.1 parts-PGMEA: 900 parts

The positive photosensitive composition is slit-coated on colored PET (A) as a temporary support so as to have a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally a protective film. A dry film resist was prepared by pressure-bonding a polyethylene film (OSM-N, manufactured by Tredegar). The obtained dry film resist was used as the dry film resist of Example 10.
A copper wiring board as the circuit wiring of Example 10 was produced in the same manner as in Example 1 except that the dry film resist of Example 10 was used as the dry film resist.

[Example 11]
A dry film resist of Example 11 was produced in the same manner as Example 10 except that colored PET (B) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 11 was produced in the same manner as in Example 1 except that the dry film resist of Example 11 was used as the dry film resist.

[Example 12]
<Synthesis Example 3: Synthesis of polymer novolak-EVE (1-ethoxyethyl protected product)>
A polymer novolak-EVE (1-ethoxyethyl protector. The ratio of constituent units is a molar ratio) was synthesized in the same manner as in Example 1 of JP-A-2003-98671. The weight average molecular weight of the obtained resin was 5,000. The polydispersity was 7.0. The structure of the polymer novolak-EVE (1-ethoxyethyl protector) is shown below.

Using the synthesized polymer novolak-EVE, a positive photosensitive composition was prepared according to the following formulation.
-Polymer novolak-EVE: 97.9 parts-Photoacid generator (PAG-2): 2 parts-Surfactant (surfactant 1): 0.1 part-PGMEA: 900 parts

The positive photosensitive composition is slit-coated on colored PET (A) as a temporary support so as to have a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally a protective film. A dry film resist was prepared by pressure-bonding a polyethylene film (OSM-N, manufactured by Tredegar). The obtained dry film resist was used as the dry film resist of Example 12.
A copper wiring board as the circuit wiring of Example 12 was produced in the same manner as in Example 1 except that the dry film resist of Example 12 was used as the dry film resist.

[Example 13]
A dry film resist of Example 13 was produced in the same manner as Example 12 except that colored PET (B) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 13 was produced in the same manner as in Example 1 except that the dry film resist of Example 13 was used as the dry film resist.

[Example 14]
<Synthesis Example 4: Synthesis of MATHF copolymer>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2,3-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a residual yellow oily product. Distillation under reduced pressure gave 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oil (yield 80 mol%) in a fraction having a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.
A MATHF copolymer was prepared in the same manner as in Example 1 of JP-A-2003-98671 except that tetrahydro-2H-furan-2-yl methacrylate was used instead of 1-ethoxyethyl methacrylate. Synthesized.
The weight average molecular weight measured by gel permeation chromatography (GPC) of the obtained MATH copolymer was 14,000. The structure of the MATHH copolymer (ratio of constituent units is molar ratio) is shown below.

Using the synthesized MATHF copolymer, a positive photosensitive composition was prepared according to the following formulation.
MATH copolymer: 97.9 parts Photoacid generator (PAG-2): 2 parts Surfactant (surfactant 1): 0.1 parts PGMEA: 900 parts Positive photosensitivity The composition is slit coated on the colored PET (A), which is a temporary support, so as to have a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (Tredeger as a protective film). A dry film resist was prepared by pressure bonding OSM-N). The obtained dry film resist was used as the dry film resist of Example 14.
A copper wiring board as the circuit wiring of Example 14 was produced in the same manner as in Example 1 except that the dry film resist of Example 14 was used as the dry film resist.

[Example 15]
A dry film resist of Example 15 was produced in the same manner as Example 14 except that colored PET (B) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 15 was produced in the same manner as in Example 1 except that the dry film resist of Example 15 was used as the dry film resist.

[Example 16]
A positive photosensitive composition was prepared according to the following formulation.
-MATHH copolymer: 69.1 parts-PHS-THF: 28.8 parts-Photoacid generator (PAG-2): 2 parts-Surfactant (surfactant 1): 0.1 Parts / PGMEA: 900 parts The positive photosensitive composition is slit-coated on a colored PET (A) as a temporary support so as to have a dry film thickness of 2.0 μm and dried in a convection oven at 100 ° C. for 2 minutes. Finally, a polyethylene film (manufactured by Tredegar, OSM-N) was pressure-bonded as a protective film to prepare a dry film resist. The obtained dry film resist was used as the dry film resist of Example 16.
A copper wiring board as the circuit wiring of Example 16 was produced in the same manner as in Example 1 except that the dry film resist of Example 16 was used as the dry film resist.

[Example 17]
A dry film resist of Example 17 was produced in the same manner as Example 16 except that colored PET (B) was used as a temporary support. Further, a copper wiring board as a circuit wiring of Example 17 was produced in the same manner as in Example 1 except that the dry film resist of Example 17 was used as the dry film resist.

[Example 18]
A positive photosensitive composition was prepared according to the following formulation.
-MATH copolymer: 97.7 parts-Photoacid generator (PAG-2): 2 parts-Basic compound (N-cyclohexyl-N '-[2- (4-morpholinyl) ethyl] thiourea, Abbreviation CHMETU): 0.2 part ・ Surfactant (Surfactant 1): 0.1 part ・ PGMEA: 900 parts

The positive photosensitive composition is slit-coated on colored PET (A) as a temporary support so as to have a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally a protective film. A dry film resist was prepared by pressure-bonding a polyethylene film (OSM-N, manufactured by Tredegar). The obtained dry film resist was used as the dry film resist of Example 18.
A copper wiring board as the circuit wiring of Example 18 was produced in the same manner as in Example 1 except that the dry film resist of Example 18 was used as the dry film resist.

[Example 19]
A positive photosensitive composition was prepared according to the following formulation.
-MATH copolymer: 97.8 parts-Photoacid generator (PAG-2): 2 parts-Basic compound (1,5-diazabicyclo [4.3.0] -5-nonene, abbreviated as DBN) : 0.1 part-Surfactant (Surfactant 1): 0.1 part-PGMEA: 900 parts

The positive photosensitive composition is slit-coated on colored PET (A) as a temporary support so as to have a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally a protective film. A dry film resist was prepared by pressure-bonding a polyethylene film (OSM-N, manufactured by Tredegar). The obtained dry film resist was used as the dry film resist of Example 19.
A copper wiring board as the circuit wiring of Example 19 was produced in the same manner as in Example 1 except that the dry film resist of Example 19 was used as the dry film resist.

[Example 20]
A positive photosensitive composition was prepared according to the following formulation.
-MATH copolymer: 93.1 parts-Photoacid generator (PAG-2): 2 parts-Surfactant (surfactant 1): 0.1 part-Heterocyclic compound (Denacol EX-321L) (Nagase ChemteX Co., Ltd.)): 4.8 parts / PGMEA: 900 parts The above positive photosensitive composition is dried to a thickness of 2.0 μm on colored PET (A) as a temporary support. The film was slit-coated, dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (OSM-N, manufactured by Tredegar) was pressure bonded as a protective film to prepare a dry film resist. The obtained dry film resist was used as the dry film resist of Example 20.
A copper wiring board as a circuit wiring of Example 20 was produced in the same manner as in Example 1 except that the dry film resist of Example 20 was used as the dry film resist.

[Example 21]
A positive photosensitive composition was prepared according to the following formulation.
• MATH copolymer: 93.0 parts • Photoacid generator (PAG-2): 2 parts • Surfactant (surfactant 1): 0.1 part • Heterocyclic compound (3-glycid Xylpropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)): 4.8 parts, PGMEA: 900 parts

The positive photosensitive composition is slit-coated on colored PET (A) as a temporary support so as to have a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally a protective film. A dry film resist was prepared by pressure-bonding a polyethylene film (OSM-N, manufactured by Tredegar). The obtained dry film resist was used as the dry film resist of Example 21.
A copper wiring board as the circuit wiring of Example 21 was produced in the same manner as in Example 1 except that the dry film resist of Example 21 was used as the dry film resist.

[Example 22]
A positive photosensitive composition was prepared according to the following formulation.
-MATH copolymer: 97.8 parts-Photoacid generator (PAG-2): 2 parts-Radiation absorber (UV absorber 1 having the following structure): 0.1 part-Surfactant (the interface) Activator 1): 0.1 part PGMEA: 900 parts UV absorber 1

The positive photosensitive composition is slit-coated on colored PET (A) as a temporary support so as to have a dry film thickness of 2.0 μm, dried in a convection oven at 100 ° C. for 2 minutes, and finally a protective film. A dry film resist was prepared by pressure-bonding a polyethylene film (OSM-N, manufactured by Tredegar). The obtained dry film resist was used as the dry film resist of Example 22.
A copper wiring board as the circuit wiring of Example 22 was produced in the same manner as in Example 1 except that the dry film resist of Example 22 was used as the dry film resist.

[Example 23]
A positive photosensitive composition having the same composition as in Example 1 was prepared.

Next, the composition for light absorption layers was prepared with the following compositions.
・ 1,3,5-triphenylformazan: 20 parts ・ Copolymer polymer of polyvinyl pyrrolidone 60 mass% and polyacrylic acid 40 mass%: 80 parts ・ Pure water: 900 parts

The PET composition having a film thickness of 75 μm was slit coated with the above composition for a light absorbing layer so as to have a dry film thickness of 1.0 μm, and dried in a convection oven at 100 ° C. for 5 minutes. Note that the transmittance of the manufactured light absorption layer with respect to light having a wavelength of 365 nm was 55%.
The positive photosensitive resin composition was slit coated on the light absorbing layer so as to have a dry film thickness of 2.0 μm, and dried in a convection oven at 100 ° C. for 5 minutes. Finally, a polyethylene film (Tradegar, OSM-N) was pressure bonded as a protective film to prepare a dry film resist. The obtained dry film resist was used as the dry film resist of Example 23.
Next, a copper wiring substrate as a circuit wiring of Example 23 was obtained in the same manner as in Example 1 except that the dry film resist of Example 23 was used as the dry film resist.

[Example 24]
A dry film resist was produced in the same manner as in Example 23 except that the light absorption layer had the following composition. The obtained dry film resist was used as the dry film resist of Example 24.
A copper wiring board as the circuit wiring of Example 24 was obtained in the same manner as in Example 1 except that the dry film resist of Example 24 was used as the dry film resist. The manufactured light absorption layer had a transmittance of 63% with respect to light having a wavelength of 365 nm.
-Copolymer polymer of polyvinyl pyrrolidone 60% by mass and polyacrylic acid 40% by mass: 70 parts-Pure water: 900 parts-The following specific naphthoquinone diazide compound: 30 parts

[Example 25]
A dry film resist of Example 25 was produced in the same manner as in Example 23, except that the positive photosensitive composition was the same as that used in Example 10. Further, a copper wiring substrate as a circuit wiring of Example 25 was obtained in the same manner as in Example 1 except that the dry film resist of Example 25 was used as the dry film resist.

[Example 26]
A dry film resist of Example 26 was prepared in the same manner as in Example 23 except that the positive photosensitive composition was the same as that used in Example 12. Further, a copper wiring board as a circuit wiring of Example 26 was obtained in the same manner as in Example 1 except that the dry film resist of Example 26 was used as the dry film resist.

[Example 27]
A dry film resist of Example 27 was produced in the same manner as in Example 23, except that the positive photosensitive composition was the same as that used in Example 14. Further, a copper wiring board as a circuit wiring of Example 27 was obtained in the same manner as in Example 1 except that the dry film resist of Example 27 was used as the dry film resist.

[Example 28]
A dry film resist of Example 28 was prepared in the same manner as in Example 23 except that the positive photosensitive composition was the same as that used in Example 16. Further, a copper wiring board as a circuit wiring of Example 28 was obtained in the same manner as in Example 1 except that the dry film resist of Example 28 was used as the dry film resist.

[Example 29]
On a PET substrate having a thickness of 100 μm, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by vacuum evaporation to a thickness of 200 nm. A film was formed with a film thickness to obtain a circuit forming substrate.
After the protective film was peeled off from the dry film resist of Example 14, the dry film resist of Example 14 was laminated and transferred onto the copper layer to produce a positive resist layer (a) A lamination process was performed.
The resist layer is temporarily supported using a photomask provided with the pattern A (first pattern) shown in FIG. 4 having a configuration in which conductive pads are connected in one direction without peeling off the temporary support. (B1) A pattern exposure step was performed in which a photomask was contacted to expose the contact pattern. In the pattern A shown in FIG. 4, the solid line portion and the gray portion are light shielding portions, the other portions are openings, and the dotted line portion virtually shows an alignment alignment frame. For the exposure, a high pressure mercury lamp having i-line (365 nm) as an exposure dominant wavelength was used.
Thereafter, the temporary support was peeled off, and development using 1.0% sodium carbonate aqueous solution and washing with water were performed to obtain a resist layer on which pattern A was formed (c1).
Next, after etching the first layer (copper layer) using a copper etchant (Cu-02 manufactured by Kanto Chemical Co., Ltd.), the second layer using an ITO etchant (ITO-02 manufactured by Kanto Chemical Co., Inc.). Etching (IT1 layer) was performed to form a first pattern on the circuit formation substrate (d1). By etching in this way, the first to second layers of the conductive layer in the region where the resist layer is not formed are etched, and the first pattern in the region where the resist layer having the first pattern is not formed. A circuit-formed substrate was obtained in which both the first layer (copper layer) and the second layer (ITO layer) were drawn with a first pattern (a pattern having a shape of a region (negative) in which no pattern A was present).
Next, a pattern exposure step (e1) was performed in which pattern exposure was performed using a photomask provided with openings of the pattern B (second pattern) shown in FIG. In the pattern B shown in FIG. 5, the gray portion is a light shielding portion, the other portion is an opening portion, and the dotted line portion virtually shows an alignment alignment frame. For the exposure, a high pressure mercury lamp having i-line (365 nm) as an exposure dominant wavelength was used.
Development and washing with 1.0% by mass of an aqueous sodium carbonate solution were performed to transfer a second pattern different from the first pattern (the pattern where the light shielding part of pattern A and the light shielding part of pattern B overlap). A resist layer was obtained (f1).
Thereafter, by etching only the wiring of the first layer (copper layer) using Cu-02, the first layer of the conductive layer in the region where the resist layer having the second pattern is not formed is etched. (G) The etching process which forms the pattern for pattern exposure on a circuit formation board | substrate was performed. By etching in this way, a circuit forming substrate including a conductive layer having only two types of patterns was obtained. Specifically, the obtained conductive layer has a pattern A (existence of the first pattern) in which both the first layer (copper layer) and the second layer (ITO layer) in the region where the resist layer having the second pattern is formed. The second layer (ITO layer) in the region where the resist layer which is the second pattern is not formed and the second pattern is not present is drawn. It was drawn with a pattern having the shape of (negative).
The remaining resist layer was removed by peeling using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Ltd.), and a circuit wiring including a conductive layer of two types of patterns was formed on the substrate. 29 circuit wirings were obtained. The circuit wiring of Example 29 has the circuit wiring of the pattern C shown in FIG. The wiring portion included in the gray region in FIG. 6 is in a state where the second layer (ITO wiring) is exposed. A dotted line portion in FIG. 6 virtually shows an alignment alignment frame. The other part is a peripheral wiring part and has a structure including two or more conductive layer laminates in which the first layer (copper wiring) is laminated on the second layer (ITO wiring) and shares the same circuit pattern. ing. FIGS. 2 and 3 are schematic diagrams showing a structure including two or more conductive layer stacks sharing the same circuit pattern. In the circuit wiring of Example 29, the first layer (copper wiring) overlapped the second layer (ITO wiring) in the dotted line portion of FIG.

[Example 30]
On a PET substrate having a thickness of 100 μm, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by vacuum evaporation to a thickness of 200 nm. A film was formed with a film thickness to obtain a circuit forming substrate.
After the protective film was peeled off from the dry film resist of Example 14, the dry film resist of Example 14 was laminated and transferred onto the copper layer to produce a positive resist layer (a) A lamination process was performed.
The resist layer is contacted with the temporary support using a photomask provided with a pattern A (first pattern) having a configuration in which conductive pads are connected in one direction without peeling off the temporary support. (B1) A pattern exposure step was performed to expose the contact pattern. For the exposure, a high pressure mercury lamp having i-line (365 nm) as an exposure dominant wavelength was used.
Thereafter, the temporary support was peeled off, and development using 1.0% sodium carbonate aqueous solution and washing with water were performed to obtain a resist layer on which pattern A was formed (c1).
Next, after etching the first layer (copper layer) using a copper etchant (Cu-02 manufactured by Kanto Chemical Co., Ltd.), the second layer using an ITO etchant (ITO-02 manufactured by Kanto Chemical Co., Inc.). The pattern exposure pattern was transferred to the circuit forming substrate by etching the (ITO layer). By etching in this way, the first to second layers of the conductive layer in the region where the resist layer is not formed are etched, and the first pattern in the region where the resist layer having the first pattern is not formed. A circuit-formed substrate was obtained in which both the first layer (copper layer) and the second layer (ITO layer) were drawn with a first pattern (a pattern having a shape of a region (negative) in which no pattern A was present). Next, an etching process was performed (d2) in which colored PET (A) used as a temporary support was again laminated as a cover film on the remaining resist layer.
(D2) Contact the photomask with the cover film using the photomask provided with the opening of the pattern B (second pattern) in a state where the alignment is aligned in a state where the cover film attached in the step is not peeled off (E2) A pattern exposure step was performed to expose the contact pattern. For the exposure, a high pressure mercury lamp having i-line (365 nm) as an exposure dominant wavelength was used.
(D2) After the cover film attached in the etching step is peeled off, development using 1.0% aqueous sodium carbonate solution and washing with water are performed, and a second pattern different from the first pattern (light shielding portion of pattern A) And a pattern in which the light-shielding portion of pattern B overlaps) (f2) A development step was performed to obtain a resist layer to which the pattern layer was transferred.
Thereafter, the copper wiring is etched using Cu-02. Only the wiring of the first layer (copper layer) is etched, whereby the first layer of the conductive layer in the region where the resist layer having the second pattern is not formed. (G) The etching process which forms the pattern for pattern exposure on a circuit formation board | substrate by etching up to was performed.
The remaining resist layer was removed by peeling using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Ltd.), and a circuit wiring including a conductive layer of two types of patterns was formed on the substrate. 30 circuit wirings were obtained. The circuit wiring of Example 30 has the circuit wiring of the pattern C shown in FIG.

[Comparative Example 1]
A positive photosensitive resin composition prepared in the same manner as in Example 1 was applied on a 75 μm-thick PET film serving as a temporary support using a slit nozzle so that the dry film thickness was 2.0 μm. did. Thereafter, the film was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (manufactured by Tredegar, OSM-N) was pressed as a protective film to prepare a dry film resist. The obtained dry film resist was used as the dry film resist of Comparative Example 1. The 75 μm-thick PET has a transmittance of 85% for light having a wavelength of 365 nm and a total light haze of 2.0%.
Next, a copper wiring board as a circuit wiring of Comparative Example 1 was obtained in the same manner as in Example 1 except that the dry film resist of Comparative Example 1 was used as the dry film resist.

[Comparative Example 2]
A dry film resist was prepared in the same manner as in Comparative Example 1 except that the positive photosensitive composition was the same as that used in Example 14. The obtained dry film resist was used as the dry film resist of Comparative Example 2.
A copper wiring substrate was produced as the circuit wiring of Comparative Example 2 in the same manner as in Example 1 except that the dry film resist of Comparative Example 2 was used as the dry film resist.

[Comparative Example 3]
A copper wiring substrate which is a circuit wiring of Comparative Example 3 was obtained in the same manner as Comparative Example 2, except that the temporary support was peeled off during contact pattern exposure and the photomask was brought into contact with the resist layer to expose the contact pattern. .

[Comparative Example 4]
Comparative Example 4 is the same as Comparative Example 2 except that a proxy mask is exposed with a gap of 75 μm between the temporary support and the photomask at the time of exposure instead of contacting the photomask with the temporary support and exposing the contact pattern. The copper wiring board which is the circuit wiring of was obtained.

[Evaluation]
<Pattern linearity (LWR)>
Twenty pattern widths were measured at locations selected at random from the line-and-space patterns of the wiring boards having the circuit wirings of the obtained examples and comparative examples. A standard deviation σ was determined from the obtained line width data, and a value obtained by multiplying the standard deviation σ by 3 was defined as LWR (Line Width Roughness), which was used as an index of pattern linearity.
By definition, the smaller the LWR, the smaller the line width variation, which is preferable. For a pattern with a line width of 5 μm, the value is evaluated as follows according to the value of LWR.
1.0 ≦ LWR: Unsuitable because the line width variation is large and leads to circuit failure 0.5 ≦ LWR <1.0: Usable as a wiring board LWR <0.5: Very preferable Table 1 shows the evaluation results. .

<Process contamination>
The presence or absence of contamination of the photomask due to transfer of the resist to the photomask during exposure was evaluated according to the following criteria.
A: No photomask contamination during exposure.
B: Photomask is contaminated during exposure.
The evaluation results are shown in Table 1 below.

From Table 1 above, it was found that according to the dry film resist of the present invention, it is possible to manufacture a circuit wiring that is a positive type that easily forms a high-resolution pattern and that has high pattern linearity. The circuit wiring having high pattern linearity is suitable as the circuit wiring for the input device and the display device. Moreover, according to the circuit wiring manufacturing method of the present invention, it has been found that circuit wiring with high pattern linearity can be manufactured without process contamination.
As shown in Comparative Examples 1 and 2, when pattern exposure is performed through a temporary support having a high transmittance with respect to the exposure main wavelength, the pattern linearity is very low, and it is not suitable as a circuit wiring for an input device or a display device. I understood that. This is the same even when proxy exposure is performed using a temporary support having a high transmittance with respect to the exposure main wavelength as in Comparative Example 4, and the pattern linearity is very low. Further, as shown in Comparative Example 3, high pattern linearity can be obtained if the exposure is performed by peeling off the temporary support, but it is not preferable because resist transfer to the mask occurs and process contamination occurs.
From Table 1 above, (i) suppression of light diffusion in the temporary support due to, for example, suppressing haze of the temporary support, and (ii) temporary support of diffused light that has passed through the temporary support. Regarding the absorption by other members arranged in the body or before reaching the resist layer, the magnitude relationship of the improvement effect of each pattern linearity can be read. For example, the reason why the effect of improving pattern linearity is higher in Example 6 than in Example 5 is that the temporary support is caused by the fact that the transmittance of the temporary support is lower in Example 6 than in Example 5. The effect of improving the linearity of the pattern due to the absorption of the diffused light passing through the temporary support within the temporary support is due to the fact that the temporary support has a lower haze in Example 5 than in Example 6. It can be read that this is because the effect of improving the linearity of the pattern due to the suppression of light diffusion in the temporary support due to the suppression of the above was exceeded. Further, the reason why the effect of improving pattern linearity is higher in Example 9 than in Example 5 is that the temporary support is caused by the fact that the haze of the temporary support is lower in Example 9 than in Example 5. The effect of improving the linearity of the pattern due to suppression of light diffusion in the temporary support due to suppression of haze and the like is due to the fact that the transmittance of the temporary support is lower in Example 5 than in Example 9. It can be read that this is because the effect of improving the pattern linearity due to the absorption of the diffused light passing through the temporary support within the temporary support was exceeded.

1: Base material 2: Mask layer 3: First electrode pattern 3a: Pad portion 3b: Connection portion 4: Second electrode pattern 5: Insulating layer 6: Another conductive element (peripheral wiring portion and lead-out wiring portion)
7: Transparent protective layer 10: Capacitance type input device

Claims

A positive dry film resist having a resist layer on a temporary support,
A dry film resist satisfying at least one of the following conditions (1) and (2);
Condition (1): The temporary support has a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer;
Condition (2): A light absorption layer having a transmittance of 80% or less with respect to the exposure main wavelength of the resist layer is provided between the temporary support and the resist layer.
The resist layer contains a photosensitizer;
2. The dry film resist according to claim 1, wherein an extinction coefficient of the photosensitive agent with respect to an exposure principal wavelength of the resist layer is less than 12,000 cm −1 M −1 .
The dry film resist according to claim 1 or 2, wherein the total light haze of the temporary support is 3.0% or less.
The dry film resist according to any one of claims 1 to 3, wherein the resist layer contains a naphthoquinonediazide compound and a resin having a phenolic hydroxyl group.
The resist layer contains (A) component and (B) photoacid generator,
The dry film resist according to any one of claims 1 to 3, wherein the component (A) is a polymer having an acid group protected by an acid-decomposable group.
6. The dry film resist according to claim 5, wherein the component (A) is a polymer component including a polymer having an acid structural unit a1 in which a carboxy group or a phenolic hydroxyl group is protected in the form of an acetal.
The dry film resist according to claim 5 or 6, wherein the component (A) is a polymer having a structural unit represented by the following general formula A1 or general formula A1 '.
General formula A1

In general formula A1, R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 is an alkyl group or Represents an aryl group, R 1 or R 2 and R 3 may be linked to form a cyclic ether, and R 4 represents a hydrogen atom or a methyl group;
General formula A1 '

In General 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 an aryl group, and R 11 or R 12 and R 13 may be linked to form a cyclic ether, and each R 14 independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, An alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group or a cycloalkyl group is represented.
The resist layer contains two or more types of the component (A), and
The dry film resist according to any one of claims 5 to 7, which contains a polymer having a structural unit represented by the following general formula A2 'as the component (A);
General formula A2 '

In general formula A2 ′, 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 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, and X 0 represents a single bond or an arylene group. .
The dry film resist according to any one of claims 1 to 8, wherein the resist layer further comprises (C) a heterocyclic compound.
The dry film resist according to claim 1, wherein the resist layer further contains a basic compound.
The dry film resist according to any one of claims 1 to 10, wherein the resist layer further contains a radiation absorber.
A circuit wiring manufacturing method including the following steps (a), (b), (c) and (d);
(A) a laminating step of laminating the dry film resist according to any one of claims 1 to 11 on a circuit-forming substrate having a base material and a conductive layer;
(B) A pattern exposure step of exposing a contact pattern with a pattern for pattern exposure without peeling off the temporary support of the dry film resist;
(C) A development step of peeling off the temporary support and developing to form the pattern exposure pattern on the resist layer;
(D) An etching step of forming the pattern exposure pattern on the circuit forming substrate by etching.
The step (b) is the following step (b1),
The step (c) is the following step (c1),
The step (d) is the following step (d1),
Furthermore, the manufacturing method of the circuit wiring of Claim 12 including the following (e1) process, (f1) process, and (g) process;
(B1) A pattern exposure step of exposing the contact pattern with the first pattern without peeling off the temporary support of the dry film resist;
(C1) A development step of peeling the temporary support and developing to form the first pattern on the resist layer;
(D1) an etching step of forming the first pattern on the circuit forming substrate by etching;
(E1) A pattern exposure step of exposing a contact pattern with a second pattern without peeling off the resist layer on which the first pattern has been formed in the step (c1);
(F1) A development step of developing and forming a second pattern different from the first pattern on the resist layer;
(G) An etching step of forming the second pattern on the circuit forming substrate by etching.
The step (b) is the following step (b1),
The step (c) is the following step (c1),
The step (d) is the following step (d2),
Furthermore, the manufacturing method of the circuit wiring of Claim 12 including the process (e2), the process (f2), and the process (g);
(B1) A pattern exposure step of exposing the contact pattern with the first pattern without peeling off the temporary support of the dry film resist;
(C1) A development step of peeling the temporary support and developing to form the first pattern on the resist layer;
(D2) After the first pattern is formed on the circuit forming substrate by etching, the resist layer on which the first pattern is formed in the step (c1) without peeling off the remaining resist layer. Etching process to attach a cover film on top;
(E2) A pattern exposure step of exposing the contact pattern with a second pattern without peeling off the cover film attached in the step (d2);
(F2) A development step in which the cover film attached in the step (d2) is peeled and then developed to form a second pattern different from the first pattern on the resist layer;
(G) An etching step of forming the second pattern on the circuit forming substrate by etching.
A circuit wiring manufactured by the circuit wiring manufacturing method according to any one of claims 12 to 14.
An input device using the circuit wiring according to claim 15.
The input device according to claim 16, wherein the input device is a capacitive touch panel.
A display device comprising the input device according to claim 16 or 17.