JP2017156735A - Photosensitive transfer material and method for producing circuit wiring - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive transfer material that has excellent adhesion even when stuck on a substrate at low temperature and at high speed and can form circuit wiring in high resolution, and a method for producing a circuit wiring.SOLUTION: A photosensitive transfer material is prepared with a positive photosensitive resin layer 14 having a polymer that comprises constitutional unit A and a constitutional unit having an acid radical and has Tg of 90°C or less, and a photoacid generator.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photosensitive transfer material and a method for manufacturing circuit wiring.

In a display device (such as an organic EL display device and a liquid crystal display device) having a touch panel such as a capacitive input device, a conductive layer such as an electrode pattern corresponding to a sensor of a visual recognition part, a peripheral wiring part, and a wiring of a lead-out wiring part A pattern is provided inside the touch panel.
In general, a patterned layer is formed by a photosensitive resin composition layer provided on an arbitrary substrate using a photosensitive transfer material because the number of steps for obtaining a required pattern shape is small. On the other hand, a method is widely used in which exposure is performed through a mask having a desired pattern, development is performed after partial curing.

  For example, Patent Document 1 includes a support and a photosensitive resin composition layer, and the photosensitive resin composition layer includes a structural unit a1 having a group in which an acid group is protected by an acid-decomposable group. A photosensitive transfer material containing a polymer component containing a polymer and a photoacid generator and having a photosensitive resin composition having no ethylenic crosslinked structure, and a pattern forming method using the same are disclosed.

  Patent Document 2 discloses an acid generator, a resin having a group containing a lactone or sultone, which increases solubility in alkali by the action of an acid, and a positive photosensitive resin composition. A pattern forming method using a photosensitive resin composition is disclosed. Patent Document 2 describes that even if the film thickness is increased, a pattern having a good rectangular cross-sectional shape can be formed.

International Publication No. 2015/093271 JP-A-2015-194715

  In the circuit wiring for the touch panel, the electrode pattern corresponding to the sensor of the visual recognition portion and the wiring of the peripheral extraction portion (peripheral wiring portion and extraction wiring portion) do not intersect, and three-dimensional connection by a bridge or the like is not necessary. Therefore, in the technical field of the method of manufacturing circuit wiring for touch panels, a resist is not formed for each desired pattern as in a conventional pattern forming method using a photosensitive resin composition, and a plurality of types of patterns are formed by a single resist formation. It is expected that the circuit wiring including the conductive layer is formed and the process is omitted.

  Further, from the viewpoint of improving productivity and the like, a substrate for forming circuit wiring (hereinafter, sometimes referred to as “circuit wiring forming substrate”) without reducing the resolution of the circuit wiring to be patterned. It is desirable to perform exposure, development, and the like by laminating the photosensitive transfer material at a low temperature while being conveyed at high speed, for example, by roll-to-roll.

When the photosensitive transfer material disclosed in Patent Document 1 is bonded to a circuit wiring formation substrate at a low temperature and at a high speed, the adhesion is not sufficient and the photosensitive resin layer is also peeled off when the temporary support is peeled off. In some cases, a part of the photosensitive resin composition layer is unintentionally peeled off during the manufacturing process of the circuit wiring.
The photosensitive resin composition described in Patent Document 2 is a composition for forming a thick film layer by a coating method. In consideration of the configuration of the photosensitive resin composition used, when applied to a transfer material, There is a concern that sensitivity and resolution are not sufficient at the time of pattern formation.

  The present invention provides good adhesion even when bonded to a circuit wiring forming substrate at a low temperature and a high speed (for example, a roll temperature used for bonding is 130 ° C. or lower and a conveyance speed is 1 m / min or higher). It is an object of the present invention to provide a photosensitive transfer material capable of forming circuit wiring with high resolution and a method for manufacturing circuit wiring.

As a result of intensive studies by the present inventors, the photosensitive transfer material has a positive photosensitive resin layer containing a polymer having a specific structure and physical properties and a photoacid generator on a temporary support. It was found that the above object can be solved.
That is, the present invention includes the following embodiments.

<1> a temporary support;
A positive photosensitive resin layer containing a structural unit represented by the following general formula A and a structural unit having an acid group and having a glass transition temperature of 90 ° C. or less, and a photoacid generator;
A photosensitive transfer material.

In general formula A, 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. Alternatively, it represents an aryl group, and 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.

<2> The photosensitive transfer material according to <1>, wherein the polymer has a glass transition temperature of −20 ° C. or higher.
<3> The photosensitive transfer material according to <1> or <2>, wherein the polymer includes 20% by mass or more of the structural unit represented by the general formula A with respect to the total solid content of the polymer.
<4> The polymer according to any one of <1> to <3>, wherein the polymer contains 0.1% by mass to 20% by mass of a structural unit having an acid group with respect to the total solid content of the polymer. Transfer material.
<5> In any one of <1> to <4>, in the general formula A, the structural unit in which R ³⁴ is a hydrogen atom is 20% by mass or more with respect to the total amount of the structural unit represented by the general formula A. The photosensitive transfer material as described.
<6> The photosensitive transfer material according to any one of <1> to <5>, wherein the polymer has a weight average molecular weight Mw of 60,000 or less.
<7> The photosensitive transfer material according to any one of <1> to <6>, wherein the temporary support has light permeability.

<8> (A) A bonding step in which the positive photosensitive resin layer of the photosensitive transfer material according to <7> is bonded to the substrate and bonded to the substrate,
(B) An exposure process for pattern exposure of the positive photosensitive resin layer of the photosensitive transfer material after the bonding process;
(C) a development step of developing the positive photosensitive resin layer after the exposure step to form a pattern;
(D) A method for manufacturing a circuit wiring, which includes an etching process for etching a substrate in a region where no pattern is arranged in this order.

<9> (a) It has a base material and a plurality of conductive layers including a first conductive layer and a second conductive layer whose constituent materials are different from each other. On the surface of the base material, in order from the surface of the base material, A positive photosensitive resin layer of the photosensitive transfer material according to <7> is brought into contact with the first conductive layer with respect to the substrate on which the first conductive layer and the second conductive layer which are the outermost surface layers are laminated. Bonding process,
(B) a first exposure step of pattern-exposing the positive photosensitive resin layer via a temporary support of the photosensitive transfer material after the bonding step;
(C) First developing step of forming the first pattern by developing the positive photosensitive resin layer after the first exposure step after peeling the temporary support from the positive photosensitive resin layer after the first exposure step. ,
(D) a first etching step of etching at least the first conductive layer and the second conductive layer among the plurality of conductive layers in the region where the first pattern is not disposed;
(E) a second exposure step of pattern exposure of the first pattern after the first etching step with a pattern different from the first pattern;
(F) a second development step of developing the first pattern after the second exposure step to form a second pattern; and
(G) a second etching step of etching at least the first conductive layer among the plurality of conductive layers in the region where the second pattern is not disposed;
In this order.
<10> After the first etching step and before the second exposure step, the method further includes a step of attaching a protective film having optical transparency on the first pattern,
In the second exposure step, pattern exposure of the first pattern through the protective film,
<9> The method for manufacturing a circuit wiring according to <9>, wherein after the second exposure step, the protective film is peeled off from the first pattern, and then the second etching step is performed.

  According to the present invention, good adhesion even when bonded to a circuit wiring forming substrate at a low temperature and a high speed (for example, a roll temperature used for bonding is 130 ° C. or lower and a conveyance speed is 1 m / min or higher). And a photosensitive transfer material capable of forming a circuit wiring with high resolution and a method for manufacturing the circuit wiring.

It is the schematic which shows an example of the laminated constitution of the photosensitive transfer material of this embodiment. It is the schematic which shows an example of the manufacturing method of the circuit wiring for touchscreens using the photosensitive transfer material of this embodiment. It is the schematic of an example of the circuit wiring for touchscreens which can be manufactured with the manufacturing method of the circuit wiring of this embodiment. It is the schematic of an example of the circuit wiring for touchscreens which can be manufactured with the manufacturing method of the circuit wiring of this embodiment. It is the schematic which shows the structure of an example of the input device which has the circuit wiring formed by the manufacturing method of this embodiment. It is a schematic block 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 schematic block 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. FIG. 6 is a schematic diagram showing a pattern A. FIG. 6 is a schematic diagram showing a pattern B. FIG. 6 is a schematic diagram showing a pattern C.

Hereinafter, the photosensitive transfer material and the method for producing the circuit wiring of the present invention will be described. In addition, although it demonstrates referring an accompanying drawing, a code | symbol may be abbreviate | omitted.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acryl” represents both and / or acryl and methacryl, and “(meth) acrylate” represents both and / or acrylate and methacrylate.
Further, in the present specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
In this specification, the term “process” is not only an independent process, but is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.

[Photosensitive transfer material]
The photosensitive transfer material of the present embodiment includes a temporary support, a structural unit represented by the following general formula A and a structural unit having an acid group, and has a glass transition temperature (hereinafter sometimes referred to as Tg). And a positive photosensitive resin layer containing a photoacid generator.

In general formula A, 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. Alternatively, it represents an aryl group, and 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.
* In the general formula A indicates a connection position with an adjacent structural unit.

FIG. 1 schematically shows an example of the layer structure of the photosensitive transfer material of this embodiment. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 12, a positive photosensitive resin layer 14, and a cover film 16 are laminated in this order. The positive photosensitive resin layer 14 includes a polymer having a structural unit represented by the general formula A and a structural unit having an acid group, and having a glass transition temperature of 90 ° C. or lower, and a photoacid generator.
Hereinafter, constituent materials and the like of the photosensitive transfer material of the present embodiment will be described. In the present specification, the above configuration in the present invention may be referred to as follows.
The structural unit represented by Formula A may be referred to as “structural unit (a)”, and the structural unit having an acid group may be referred to as “structural unit (b)”.
A polymer having a structural unit represented by the general formula A and a structural unit having an acid group and having a glass transition temperature of 90 ° C. or lower may be referred to as a “specific polymer”.
The positive photosensitive resin layer may be referred to as “photosensitive resin layer”.

[Temporary support]
The temporary support 12 is a support that supports the positive photosensitive resin layer and is peelable from the positive photosensitive resin layer. The temporary support 12 used in the present embodiment preferably has light transmittance from the viewpoint that the positive photosensitive resin layer can be exposed through the temporary support when the positive photosensitive resin layer is subjected to pattern exposure.
Having light transmittance means that the transmittance of the main wavelength of pattern exposure is 50% or more, and the transmittance of the main wavelength of pattern exposure is preferably 60% or more from the viewpoint of improving sensitivity. % Or more is more preferable.
Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoints of strength and flexibility. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film, and among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of a temporary support body is not specifically limited, The range of 5 micrometers-200 micrometers is common, and the range of 10 micrometers-150 micrometers is especially preferable at points, such as handleability and versatility.
The temporary support may be selected according to the material in terms of strength as a support, flexibility required for bonding with a circuit wiring formation substrate, light transmittance required in the first exposure process, and the like. Good.

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

[Positive photosensitive resin layer]
The photosensitive transfer material 100 of the present embodiment has a positive photosensitive resin layer 14 disposed on the temporary support 12. The positive photosensitive resin layer 14 in this embodiment has a structural unit (a) represented by the general formula A and a structural unit (b) having an acid group, and has a glass transition temperature of 90 ° C. or lower. A polymer (specific polymer) and a photoacid generator are included.

<Polymer component>
[Specific polymer]
The positive photosensitive resin layer in this embodiment has a structural unit (a) represented by the general formula A and a structural unit (b) having an acid group as a polymer component, and has a glass transition temperature of 90. Includes specific polymers that are below ℃.
The specific polymer contained in the positive photosensitive resin layer may be only one type or two or more types.

(Structural unit (a))
The structural unit (a) represented by the general formula A is a structural unit containing a carboxy group protected with an acid-decomposable group, and is suitable as a structural unit containing a carboxy group protected with an acid-decomposable group, By including the structural unit (a) represented by Formula A, the specific copolymer has good sensitivity and resolution during pattern formation.

In General Formula A, when R ³¹ or R ³² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ³¹ or R ³² is an aryl group, a phenyl group is preferable. R ³¹ and R ³² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In General Formula A, 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. The alkyl group and aryl group in R ³³ may have a substituent.
In general formula A, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, and R ³¹ or R ³² and R ³³ 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 general formula A, X ⁰ represents a single bond or an arylene group, and a single bond is preferred. The arylene group may have a substituent.

In general formula A, R ³⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of lowering the Tg of the specific polymer.
More specifically, the structural unit in which R ³⁴ in the general formula A is a hydrogen atom is preferably 20% by mass or more based on the total amount of the structural unit (a) contained in the polymer.
In addition, the content (content ratio: mass ratio) of the structural unit in which R ³⁴ in the general formula A in the structural unit (a) is a hydrogen atom is calculated by a conventional method from 13C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity.

  Among the structural units (a) represented by the general formula A, a structural unit represented by the following general formula A1 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.

In General Formula A1, R ³⁴ represents a hydrogen atom or a methyl group, and R ^{35 to} R ⁴¹ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In general formula A1, R ³⁴ is preferably a hydrogen atom.
In general formula A1, R ^{35 to} R ⁴¹ are preferably hydrogen atoms.

Preferable specific examples of the structural unit (a) having a carboxylic acid group protected with an acid-decomposable group represented by the general formula A include the following structural units. R ³⁴ represents a hydrogen atom or a methyl group. —C (R ³¹ ) (R ³² ) —O—R ³³ in General Formula A corresponds to the acid-decomposable group.

The structural unit (a) contained in the specific copolymer may be one type or two or more types.
The content of the structural unit (a) represented by the general formula A in the specific polymer is preferably 20% by mass or more, more preferably 20% by mass to 90% by mass, and further 30% by mass to 70% by mass. preferable.
The content (content ratio: mass ratio) of the structural unit (a) in the specific polymer can be confirmed by the intensity ratio of peak intensity calculated by 13 C-NMR measurement by a conventional method.
Moreover, after decomposing | disassembling all the polymer components into a structural unit (monomer unit), the ratio of the structural unit (a) which has the protected carboxy group by which the acid group was protected by the acid-decomposable group is 5 mass%-80 The content is preferably not more than mass%, more preferably from 10 mass% to 80 mass%, particularly preferably from 30 mass% to 70 mass%.

(Structural unit (b))
The specific polymer of this embodiment contains the structural unit (b) which has an acid group. The structural unit (b) is a structural unit containing an acid group that is not protected by an acid-decomposable group, that is, an acid group that does not have an acid-decomposable group. When the specific polymer contains the structural unit (b), the specific copolymer has good sensitivity at the time of pattern formation, becomes easily soluble in an alkaline developer in the development process after pattern exposure, and shortens the development time. Can be achieved.
The acid group in this specification means a proton dissociable group having a pKa of 12 or less. The acid group is usually incorporated into the specific polymer as a structural unit [structural unit (b)] containing an acid group, using a monomer capable of forming an acid group. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. The pKa of the acid group is preferably −5 or more.

  The specific polymer contains, as a copolymerization component, a structural unit (a) having a specific structure protected by the above-described protecting group and a structural unit (b) having an acid group that is not protected by a protective device. By setting the transition temperature to 90 ° C. or lower, the positive photosensitive resin layer containing the specific polymer can maintain the transferability and the peelability from the temporary support at a good level, while at the time of pattern formation, Sensitivity is better.

The acid group that the specific polymer has is derived from an acid group derived from a carboxylic acid group, an acid group derived from a sulfonamide group, an acid group derived from a phosphonic acid group, an acid group derived from a sulfonic acid group, or a phenolic hydroxyl group And acid groups, sulfonamide groups, sulfonylimide groups and the like. Of these, at least one selected from an acid group derived from a carboxylic acid group and an acid group derived from a phenolic hydroxyl group is preferred.
The structural unit having an acid group can be introduced into the specific copolymer by copolymerizing a monomer having an acid group.
The structural unit containing an acid group as the structural unit (b) 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, and (meth) acrylic acid More preferably, it is a structural unit derived from.

As the structural unit (b) contained in the specific polymer, a structural unit having a carboxylic acid group and a structural unit having a phenolic hydroxyl group are preferable from the viewpoint of better sensitivity during pattern formation.
The monomer having an acid group that can form the structural unit (b) is not limited to the examples described above.

The structural unit (b) contained in the specific polymer may be only one type or two or more types.
It is preferable that a specific polymer contains 0.1 mass%-20 mass% of structural units [structural unit (b)] which have an acid group with respect to the total solid of a specific polymer.
As for content of the structural unit (b) in a specific polymer, 0.5 mass%-15 mass% are more preferable with respect to the total solid of a specific polymer, and 1 mass%-10 mass% are still more preferable.
When the content of the structural unit (b) is in the above range, the pattern formability becomes better.
The content (content ratio: mass ratio) of the structural unit (b) in the specific polymer can be confirmed by the intensity ratio of the peak intensity calculated from the 13C-NMR measurement by a conventional method.

(Other structural units)
A specific polymer is a range which does not impair the effect of this invention about other structural units (henceforth a structural unit (c)) other than the above-mentioned structural unit (a) and a structural unit (b). May be included.
There is no restriction | limiting in particular as a monomer used as a structural unit (c), For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid Diester, bicyclounsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, group having an aliphatic cyclic skeleton, etc. Mention may be made of unsaturated compounds.
Various characteristics of the specific polymer can be adjusted by adjusting at least one of the kind and the content using the other structural unit (c). In particular, the Tg of the specific polymer can be easily adjusted to 90 ° C. or lower by appropriately using the structural unit (c).
The other structural unit (c) may be included in the specific polymer alone or in combination of two or more.

  The other structural unit (c) is specifically styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinyl Ethyl benzoate, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) Isopropyl acrylate, 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 structural unit due to rate. In addition, the compounds described in paragraphs [0021] to [0024] of JP-A No. 2004-264623 can be exemplified.

  Further, as the other structural unit (c), an aromatic group, styrenes, and a group having an aliphatic cyclic skeleton are preferable from the viewpoint of improving the electrical characteristics of the obtained transfer material. Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Is mentioned.

  As the structural unit (c) that can be included in the specific polymer, for example, a (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Among them, (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

(Constituent unit content)
In the structural unit constituting the specific polymer, the content of the structural unit (c) is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less. The lower limit may be 0% by mass, but may be, for example, 1% by mass or more, and further 5% by mass or more.
The copolymerization ratio of the structural unit (c) in the specific polymer is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 60% by mass, and still more preferably 10% by mass to 50% by mass.
It is preferable to be within the above numerical range from the viewpoint of further improving resolution and adhesion.

It is also preferable to have a structural unit containing an acid group ester as the structural unit (c) from the viewpoint of optimizing the solubility in the developer and the physical properties of the positive photosensitive resin layer.
Among these, the specific polymer preferably contains a structural unit containing a carboxylic acid group as the structural unit (b), and further contains a structural unit (c) containing a carboxylic acid ester group as a copolymerization component. Component (b) derived from (meth) acrylic acid and component (c) derived from cyclohexyl (meth) acrylate or 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate The specific polymer contained as is more preferred.
Hereinafter, although the preferable example of the specific polymer which can be used for this embodiment is given, this embodiment is not limited to the following illustrations. In addition, the ratio of the structural unit and the weight average molecular weight in the following exemplary compounds are appropriately selected in order to obtain preferable physical properties.

(Glass transition temperature of specific polymer: Tg)
The glass transition temperature (Tg) of the specific polymer in this embodiment is 90 ° C. or less. When Tg is 90 ° C. or lower, a photosensitive transfer material having a positive photosensitive resin layer containing a specific polymer has high adhesion even when bonded at a low temperature and at a high speed. Tg is more preferably 60 ° C. or less, and further preferably 40 ° C. or less.
Although there is no restriction | limiting in particular in the lower limit of Tg of a specific polymer, -20 degreeC or more is preferable and -10 degreeC or more is more preferable. When the Tg of the specific polymer is −20 ° C. or higher, good pattern formability is maintained. For example, when a cover film is used, a decrease in peelability when the cover film is peeled is suppressed.

The glass transition temperature of the polymer can be measured using differential scanning calorimetry (DSC).
The specific measuring method was performed in accordance with the method described in JIS K 7121 (1987) or JIS K 6240 (2011). As the glass transition temperature in the present specification, an extrapolated glass transition start temperature (hereinafter sometimes referred to as Tig) is used.
The method for measuring the glass transition temperature will be described more specifically.
When determining the glass transition temperature, the apparatus is kept at a temperature about 50 ° C. lower than the expected Tg of the polymer until the apparatus is stabilized, and then heated at a rate of 20 ° C./min, about 30 times higher than the temperature at which the glass transition is completed. Heat to a higher temperature and draw a DTA or DSC curve.
The extrapolated glass transition start temperature (Tig), that is, the glass transition temperature Tg in the present specification, is a straight line obtained by extending the low-temperature base line in the DTA curve or DSC curve to the high-temperature side, and the step-like change portion of the glass transition. Calculated as the temperature of the intersection with the tangent drawn at the point where the slope of the curve is maximum.

As a method for adjusting the Tg of the specific polymer (copolymer) to the above-described preferred range, for example, from the Tg of the homopolymer of each constituent unit of the target specific polymer and the mass ratio of each constituent unit The Tg of the target specific polymer can be controlled using the FOX formula as a guideline.
Regarding the FOX formula, Tg of the homopolymer of the first structural unit contained in the specific polymer that is a copolymer is Tg1, the mass fraction in the copolymer of the first structural unit is W1, and the second structural unit When the Tg of the homopolymer of Tg2 is Tg2 and the mass fraction in the copolymer of the second structural unit is W2, the Tg0 of the copolymer containing the first structural unit and the second structural unit ( K) can be estimated according to the following equation:
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)
A copolymer having a desired Tg can be obtained by adjusting the type and mass fraction of each constituent unit contained in the copolymer using the FOX formula described above.
Moreover, it is also possible to adjust Tg of a specific polymer by adjusting a specific polymer weight average molecular weight.

(Molecular weight of specific polymer: Mw)
The molecular weight of the specific polymer contained in the positive photosensitive resin layer is preferably 60000 or less in terms of polystyrene-equivalent weight average molecular weight. When the weight average molecular weight of the specific polymer contained in the positive photosensitive resin layer is 60000 or less, the melt viscosity of the positive photosensitive resin layer is suppressed to a low level (for example, when bonded to the circuit wiring formation substrate) Bonding at 130 ° C. or lower) can be realized. In addition, if the weight average molecular weight of the specific polymer is too small, it becomes too soft when a positive photosensitive resin layer is formed on the temporary support, and it is easy to be scratched in the processing step, and due to excessive tackiness. The cover film may be difficult to peel off.
From this viewpoint, the weight average molecular weight of the specific polymer contained in the positive photosensitive resin layer is preferably in the range of 2000 to 60000, more preferably 3000 to 50000.
In addition, the weight average molecular weight of the specific polymer contained in the positive photosensitive resin layer can be measured by GPC (gel permeation chromatography), and various commercially available apparatuses can be used. The contents of the apparatus and the measuring techniques are known to those skilled in the art.
The measurement of the weight average molecular weight by gel permeation chromatography (GPC) uses HLC (registered trademark) -8220GPC (Tosoh Corp.) as a measuring device, TSKgel (registered trademark) Super HZM-M (4 .6 mmID × 15 cm, Tosoh Corporation), Super HZ4000 (4.6 mmID × 15 cm, Tosoh Corporation), Super HZ3000 (4.6 mmID × 15 cm, Tosoh Corporation), Super HZ2000 (4.6 mmID × 15 cm, One Tosoh Corporation) can be used, and THF (tetrahydrofuran) can be used as an eluent.
Further, the measurement conditions are 0.2 mass%, the flow rate is 0.35 ml / min, the sample injection amount is 10 μl, the measurement temperature is 40 ° C., and a differential refractive index (RI) detector is used. be able to.
The calibration curve is “Standard sample TSK standard, polystyrene” of Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A -2500 "," A-1000 ", and any one of the seven samples can be used.
The ratio (dispersity) between the number average molecular weight and the weight average molecular weight of the specific polymer is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

(Method for producing specific polymer)
The production method (synthesis method) of the specific polymer is not particularly limited. For example, a polymerizable monomer for forming the structural unit (a) represented by the general formula A, a structural unit having an acid group ( Polymerization is performed using a polymerization initiator in an organic solvent containing a polymerizable monomer for forming b) and, if necessary, a polymerizable monomer for forming other structural unit (c). Can be synthesized. It can also be synthesized by a so-called polymer reaction.

  The positive photosensitive resin layer in the present embodiment has a total solid content of the positive photosensitive resin layer from the viewpoint of developing good adhesion even when bonded to the circuit wiring formation substrate at low temperature and high speed. On the other hand, the specific polymer is preferably contained in a proportion of 50% by mass to 99.9% by mass, and more preferably in a proportion of 70% by mass to 98% by mass.

[Other polymers]
The positive photosensitive resin layer in the present embodiment does not contain the structural unit (a) represented by the general formula A as a polymer component in a range not impairing the effects of the present invention in addition to the specific polymer described above. It may further contain a polymer (sometimes referred to as “other polymer”). When the positive photosensitive resin layer contains another polymer, the blending amount of the other polymer is preferably 50% by mass or less and more preferably 30% by mass or less in the total polymer component. More preferably, it is 20% by mass or less.

  The positive photosensitive resin layer may contain only one type of other polymer in addition to the specific polymer, or may contain two or more types.

  As other polymers, for example, polyhydroxystyrene can be used, which is commercially available, SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (manufactured by Toagosei Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 678 (Above, manufactured by BASF) can also be used.

<Photo acid generator>
The positive photosensitive resin layer in this embodiment contains a photoacid generator. The photoacid generator used in the present embodiment is a compound capable of generating an acid when irradiated with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
The photoacid generator used in the present embodiment is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, and generates an acid, but is not limited to its chemical structure. 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 is not particularly defined, but can be set to -10.0 or more, for example.

  Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.

  Examples of nonionic photoacid generators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, the photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines and diazomethane derivatives include the compounds described in paragraphs [0083] to [0088] of JP2011-221494A.

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

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

In the compound containing an oxime sulfonate structure represented by the formula (B1), 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 Including a cyclic group, preferably a bicycloalkyl group), may be substituted with a halogen atom.
As the aryl group for R ^21, an aryl group having 6 to 18 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

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

In the 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 2 or 2 When X is 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 formula (B2), m4 is 1, X ¹⁰ is a methyl group, the substitution position of X ¹⁰ is an ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.

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

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

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

  Specific examples of the compound represented by the 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-toluene Sulfo) -4-methoxyphenyl] can be mentioned 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. It can also be used in combination with other types of photoacid generators.

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

Formula (OS-1)

In formula (OS-1), R ⁴¹¹ represents 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 heteroaryl. Represents a 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 —, and R ^{415 to} R ⁴¹⁷ represent an alkyl group. Or an aryl group.
R ^{421 to} R ⁴²⁴ are each independently 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. ^R421 ~
Two of R ⁴²⁴ may be bonded to each other to form a ring.
As R ^<421 > -R < ⁴²⁴ >, a hydrogen atom, a halogen atom, and an alkyl group are preferable, and the aspect in which at least 2 of R ^{< 421} > -R < ⁴²⁴ > couple | bond together and forms an aryl group is also mentioned preferably. Among these, an embodiment in which R ^{421 to} R ⁴²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

  Specific examples of the compound represented by the formula (OS-1) that can be suitably used in this embodiment include the compounds described in paragraphs [0128] to [0132] of JP2011-221494A (Exemplary Compound b). -1 to b-34), but this embodiment is not limited to these.

  In this invention, as a compound containing the oxime sulfonate structure represented by Formula (B1), the oxime represented by the following formula (OS-3), the following formula (OS-4), or the following formula (OS-5) A sulfonate compound is preferred.

In formula (OS-3) to 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.

In 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 formulas (OS-3) to (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ may be an alkyl group having 1 to 30 carbon atoms which may have a substituent. preferable.

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

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

In 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.
In formulas (OS-3) to (OS-5), it is preferable that 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 formulas (OS-3) to (OS-5), X ^{1 to} X ³ each independently represent O or S, and is preferably O.
In the 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 formulas (OS-3) to (OS-5), n ^{1 to} n ³ each independently represent 1 or 2, and when X ^{1 to} X ³ are O, n ^{1 to} n ³ are each independently 1 In addition, when X ^{1 to} X ³ are S, n ^{1 to} n ³ are each preferably 2 independently.

In 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. 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 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. preferable.

In 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. Is preferred.

In 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, preferably 0 or 1. Is more preferable and 0 is particularly preferable.
In addition, with respect to each substituent of formulas (OS-3) to (OS-5), (OS-3) to (OS-) described in paragraphs [0092] to [0109] of JP2011-221494A are disclosed. The preferred range of the substituent of 5) is likewise preferred.

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

In formulas (OS-6) to (OS-11), R ^{301 to} R ³⁰⁶ each independently represents 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 ³⁰⁸ 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 formulas (OS-6) to (OS-11) are those of (OS-6) to (OS-11) described in paragraphs [0110] to [0112] of JP2011-221494A. This is the same as the preferred range.

  Specific examples of the oxime sulfonate compound represented by the formula (OS-3) to the formula (OS-5) include compounds described in paragraphs [0114] to [0120] of JP2011-221494A. However, the present embodiment is not limited to these.

  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 formula (1).

In formula (1), R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ may each have a substituent,
Represents an alkyl group or an aromatic group, the alkyl group may form a ring connected to each other; X ^- represents a conjugate base.

The alkyl group in R ^{505, R 506} and ^{R 507,} preferably an alkyl group having 1 to 10 carbon atoms, which may have a substituent. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tertiary butyl group, a pentyl group, a neopentyl group, a hexyl group, a cyclohexyl group, a heptyl group, and an octyl group. . Among these, a methyl group, an ethyl group, or a tertiary butyl group is 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 preferred in the form containing a sulfur atom.
The aromatic group for R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ is preferably an aromatic group having 6 to 30 carbon atoms and may have a substituent. Such aromatic groups include phenyl, naphthyl, 4-methoxyphenyl, 4-chlorophenyl, 4-methylphenyl, 4-tertiarybutylphenyl, 4-phenylthiophenyl, 2,4 , 6-trimethylphenyl group, 4-methoxy-1-naphthyl group, or 4- (4′-diphenylsulfoniophenylthio) phenyl group.
In addition, the ionic photoacid generator represented by the formula (1) may be bonded with any of R ^{505 to} R ⁵⁰⁷ to form a multimer such as a dimer. For example, a 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 ^−. .

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 a substituent.

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 formula (3) or formula (4) is preferable, and a conjugate base of alkylsulfonic acid, a conjugate base of arylsulfonic acid, PY ₆ ⁻ , or formula (3) The monovalent anion represented by) is particularly preferred.

As the conjugated base of alkyl sulfonic acid and aryl sulfonic acid, a conjugated base of alkyl sulfonic acid having 1 to 7 carbon atoms is preferable, and a conjugated base of alkyl sulfonic acid having 1 to 4 carbon atoms is more preferable, and expressed in acid form. 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, and more preferably a fluorine atom.

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

In formula (3) and 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, and a cyclohexyl group. And octyl group. 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. Among 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 formulas (3) and (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, a butylene group, and 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 with an alkylene group having 2 to 6 carbon atoms, particularly having 2 to 4 carbon atoms. Bonding with an alkylene group having a fluorine atom is preferred.

  In addition, the ionic photoacid generator represented by the formula (1) is preferably a photoacid generator represented by the following 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 each independently represent a substituent. Represents a divalent aromatic group optionally having X ^1, and X ¹⁻ and X ²⁻ each independently represents a conjugate base.

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

The conjugate base in X ¹⁻ and X ²⁻ has the same meaning as the conjugate base represented by X ^{− in} formula (1),
The preferred embodiment is 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, Midori Chemical Co., Ltd.), GSID-26-1, Cyracure UVI-6976 (above, BASF Corp.).

  Diaryl iodonium salts used as an ionic photoacid generator are represented by the following formula (2).

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

In formula (2), the aromatic groups in R ⁵⁰⁸ and R ⁵⁰⁹ have the same meaning as the aromatic groups represented by R ⁵⁰⁵ , R ⁵⁰⁶ and R ⁵⁰⁷ in formula (1), and the preferred embodiments are also the same.
In formula (2), the conjugate base in X ^1- has the same meaning as the conjugate base represented by X ^{− in} formula (1), and the preferred embodiments are also the same.
The photoacid generator of the formula (2) ^is attached at R 508 ^{to R 509,} it may form multimers such as dimer. For example, a 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 ^−. .

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-p-toluenesulfonate, 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 (p-chlorophenyl) borate, tetramethyl Ammonium hexyltris (3-trifluoromethylphenyl) borate, benzyldimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3 -Trifluoromethylphenyl) borate and the like.

In addition to specific examples, specific examples of the photoacid generator include the following compounds, but the photoacid generator used in the present embodiment is not limited to these compounds.

  In the positive photosensitive resin layer, the photoacid generator is used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the positive photosensitive resin layer from the viewpoint of sensitivity and resolution. It is more preferable to use 0.5 to 5 parts by mass. Two or more kinds can be used in combination.

〔solvent〕
The positive photosensitive resin composition for forming the positive photosensitive resin layer (hereinafter sometimes referred to as “photosensitive resin composition”) is a component for forming the positive photosensitive resin layer. It is preferably prepared as a solution dissolved in a solvent.
As the solvent used in the positive photosensitive resin composition for forming the positive photosensitive resin layer, a known solvent can be used. Solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers And diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones and the like. Specific examples of the solvent used in the positive photosensitive resin composition for forming the positive photosensitive resin layer are described in paragraphs [0174] to [0178] of JP2011-221494A. Solvents are also included and their contents are incorporated herein.

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, -Solvents such as nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate can also be added.
Only 1 type may be used for a solvent and 2 or more types may be used for it.
The solvent which can be used for this embodiment may be used individually by 1 type, and it is more preferable to use 2 types together. When two or more solvents are used, for example, propylene glycol monoalkyl ether acetates and dialkyl ethers, diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates are used in combination. Is preferred.

Further, the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents 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 positive photosensitive resin composition for forming the positive photosensitive resin layer is 50 parts by mass to 1900 parts by mass per 100 parts by mass of the total solid content in the photosensitive resin composition. It is more preferable that it is 100 mass parts-900 mass parts.

<Other additives>
The positive photosensitive resin layer in the transfer material of this embodiment can contain a known additive as required in addition to the specific polymer and the photoacid generator.

[Plasticizer]
The positive photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity. In addition, since the positive photosensitive resin layer of this embodiment is excellent in plasticity by including the above-mentioned specific polymer, the inclusion of a plasticizer is not essential.
The plasticizer that can be contained in the positive photosensitive resin layer preferably has a weight average molecular weight smaller than that of the specific polymer.
The weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5000, and still more preferably 800 or more and less than 4000 from the viewpoint of imparting plasticity.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the specific polymer and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

  In said formula, R is a C2-C8 alkyl group and n represents the integer of 1-50. * Represents a bonding site with another atom.

  Note that, for example, even if the compound has an alkyleneoxy group (referred to as “compound X”), the positive photosensitive resin composition obtained by mixing the compound X, the specific polymer, and the photoacid generator, When plasticity does not improve compared with the positive photosensitive resin composition formed without containing the compound X, it does not correspond to the plasticizer in this embodiment. For example, an optional surfactant is not generally used in an amount that brings plasticity to the positive photosensitive resin composition, and thus does not fall under the plasticizer in this specification.

  Examples of the plasticizer that can be used in the present embodiment include compounds having the following structure, but are not limited thereto.

When using a plasticizer, the content of the plasticizer in the positive photosensitive resin layer is 1 part by mass with respect to 100 parts by mass of the total solid content in the positive photosensitive resin layer from the viewpoint of adhesion. It is preferably ˜50 parts by mass, and more preferably 2 parts by mass to 20 parts by mass.
When a positive photosensitive resin layer contains a plasticizer, only 1 type may be used and 2 or more types may be used.

[Sensitizer]
The positive photosensitive resin layer in this embodiment can further contain a sensitizer.
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.
Exposure sensitivity can be improved by containing a sensitizer.

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 a sensitizer which can be used for this embodiment, the compound as described in the paragraph [0139]-paragraph [0141] of international publication 2015/092731 can be mentioned.

  The content of the sensitizer in the positive photosensitive resin layer is preferably 0 to 10 parts by mass, and 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content. Is more preferable.

[Basic compounds]
The positive photosensitive resin layer in the present embodiment preferably further contains a basic compound. The basic compound can be arbitrarily selected from basic compounds 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 the compounds described in paragraphs [0204] to [0207] of JP2011-221494A, 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. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 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, 1,8-diazabicyclo [5.3.0] -7 -Undecene and the like.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

  The basic compound that can be used in this embodiment may be used alone or in combination of two or more.

  The content of the basic compound in the positive photosensitive resin layer is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total solid content in the positive photosensitive resin layer. More preferably, it is 005 parts by mass to 3 parts by mass.

[Heterocyclic compound]
The positive photosensitive resin layer in the present embodiment can include a compound containing a heterocyclic compound.
There is no restriction | limiting in particular in the heterocyclic compound in this embodiment. 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 cyclic ethers and cyclic esters (lactones), nitrogen-containing monomers such as cyclic amines and oxazolines Furthermore, a heterocyclic monomer having d electrons such as silicon, sulfur, and phosphorus can be added.

  The addition amount of the heterocyclic compound in the positive photosensitive resin layer is 0.01 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the positive photosensitive resin layer when the heterocyclic compound is transferred. It is preferable that it is 0.1 mass part-10 mass parts, It is more preferable that it is 1 mass part-5 mass parts. Addition within this range is preferable from the viewpoint of adhesion and etching resistance. Only 1 type may be used for a heterocyclic compound and it can also use 2 or more types together. When using 2 or more types together, the said preferable content points out the total content of 2 or more types of heterocyclic compounds.

  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.

A compound having an epoxy group in the molecule can be obtained as a commercial product. For example, JER828, JER1007, JER1
Examples include 57S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation), and other commercial products described in paragraph [0189] of JP2011-221494A.
Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (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-212 , EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX -121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (above, manufactured by Nagase Chemtech), YH-300, YH-301, YH-302, YH-315 YH-324, YH-325 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Eporide GT400, Cellbiners B0134, B0177 (above, Daicel Corporation).
The compound which has an epoxy group in a molecule | numerator may be used individually by 1 type, and may use 2 or more types together.

  Among compounds having an epoxy group in the molecule, 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. Preferably mentioned.

  Specific examples of the compound 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 Co., Ltd.) Can be used.

  Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

  Among the compounds having an oxetanyl group in the molecule, the positive photosensitive resin layer in the present embodiment is preferably a compound in which the heterocyclic compound has an epoxy group from the viewpoint of etching resistance and line width stability.

Moreover, the compound which has both an alkoxysilane structure and a heterocyclic structure in a molecule | numerator can also be used suitably. Examples include γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane. Of these, γ-glycidoxypropyltrialkoxysilane is more preferable.
The compounds having an alkoxysilane structure and a heterocyclic structure in the molecule may be used alone or in combination of two or more.

[Surfactant]
The positive photosensitive resin layer in the present embodiment preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic or amphoteric 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 (Manufactured by Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and the like.
Further, as a surfactant, it contains a structural unit A and a structural unit B represented by the following formula (I-1), and is converted to polystyrene measured by gel permeation chromatography when tetrahydrofuran (THF) is used as a solvent. A preferred example is a copolymer having a weight average molecular weight (Mw) of 1,000 or more and 10,000 or less.

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 carbon. 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 a numerical value of 10 mass% to 80 mass%. Q represents a numerical value of 20% to 90% by mass, 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 formula (I-2). R ⁴⁰⁵ in formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are 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 (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

  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.

Surfactant may be used individually by 1 type and may use 2 or more types together.
The addition amount of the surfactant in the positive photosensitive resin layer is preferably 10 parts by mass or less, and 0.001 part by mass to 10 parts by mass with respect to 100 parts by mass of the total solid content in the positive photosensitive resin layer. It is more preferable that it is a mass part, and it is still more preferable that it is 0.01 mass part-3 mass parts.

(Radiation absorber)
The positive photosensitive resin layer in this embodiment can contain a radiation absorber. As the radiation absorber, an ultraviolet absorber is preferable, and in particular, a radiation absorber exhibiting so-called photobleaching property in which the absorbance is reduced by ultraviolet absorption is preferably used. Specifically, photodecolorable materials such as naphthoquinone diazide derivatives, nitrones, and diazonium salts (for example, Japanese Examined Patent Publication No. 62-40697, M. Sasano et al., SPIE Sym. Proc., 631, 321 (1986)). Compound).
The above-described materials are used for the purpose of averaging the light intensity distribution in the photosensitive resin layer by the radiation absorber, and by providing a so-called internal enhancement type CEL (Contrast Enhancement Lithography) effect, pattern rectangularization and edge roughness (See Semiconductor process materials and chemicals, supervised by Masanori Sakamoto, CMC Publishing (2006)).

[Other ingredients]
In the positive photosensitive resin layer in the present embodiment, the metal oxide particles, a crosslinking agent other than the heterocyclic compound, an alkoxysilane compound, an antioxidant, a dispersant, an acid proliferating agent, a development accelerator, a conductive fiber, Known additives such as a colorant, a thermal radical generator, a thermal acid generator, a UV absorber, a thickener, and an organic or inorganic precipitation inhibitor can be added.
Preferred embodiments of the other components are described in paragraphs [0165] to [0184] of JP-A-2014-85643, the contents of which are incorporated herein.

<Thickness of positive photosensitive resin layer>
The thickness of the positive photosensitive resin layer is preferably 0.5 μm to 20 μm. When the thickness of the positive photosensitive resin layer is 20 μm or less, the pattern resolution is good, and when it is 0.5 μm or more, it is preferable from the viewpoint of pattern linearity.
The thickness of the positive photosensitive resin layer is more preferably 0.8 μm to 15 μm, and particularly preferably 1.0 μm to 10 μm.

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

The photosensitive transfer material of this embodiment which has a positive photosensitive resin layer on a temporary support body can be obtained by apply | coating the photosensitive resin composition to a temporary support body, and making it dry. The coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
In addition, the photosensitive resin composition layer can also be apply | coated on the laminated body of the temporary support body which has the other layer mentioned later on a temporary support body, and another layer.

<Other layers>
The photosensitive transfer material of the present embodiment may have a layer other than the positive photosensitive resin layer (hereinafter sometimes referred to as “other layer”). Examples of other layers include a contrast enhancement layer, an intermediate layer, a cover film, and a thermoplastic resin layer.

<Contrast enhancement layer>
The photosensitive transfer material of the present embodiment can have a contrast enhancement layer in addition to the positive photosensitive resin layer.
A contrast enhancement layer (CEL) is a material that absorbs light with respect to an exposure wavelength before exposure, but gradually decreases with exposure, that is, a material that increases light transmittance (photodecoloration). It is a layer containing a coloring pigment component). Known photodecolorable dye components include diazonium salts, stilbazolium salts, arylnitroso salts, and the like. A phenolic resin or the like is used as the film forming component.
In addition, as contrast enhancement layers, paragraphs [0004] to [0051] of JP-A-6-97065, paragraphs [0012] to [0055] of JP-A-6-332167, photopolymer handbook, photopolymer Materials described in the social gatherings, Industrial Research Committee (1989), Photopolymer Technology, Yamaoka, Nagamatsu, Nikkan Kogyo Shimbun (1988) can be used.

(Middle layer)
An intermediate layer may be formed on the positive photosensitive resin layer, and a contrast enhancement layer (hereinafter also referred to as “CEL” or “CE layer”) may be formed on the intermediate layer. The intermediate layer is provided to prevent mixing between the CEL and the positive photosensitive resin layer.

<Thermoplastic resin layer, cover film, etc.>
The photosensitive transfer material of the present embodiment can also have, for example, a temporary support, a thermoplastic resin layer, and a positive photosensitive resin layer in this order. Further, a cover film may be provided for the purpose of protecting the positive photosensitive resin layer.
Paragraphs [0189] to [0193] of JP-A-2014-85643 for preferred embodiments of the thermoplastic resin layer, and paragraphs [0194] to paragraphs of JP-A-2014-85643 for preferred embodiments of other layers. [0196] each of which is incorporated herein by reference.

When the photosensitive transfer material of this embodiment has other layers, such as a thermoplastic resin layer, the manufacturing method of the photosensitive transfer material as described in paragraph [0094] -paragraph [0098] of Unexamined-Japanese-Patent No. 2006-259138. It can produce according to.
For example, when producing the photosensitive transfer material of the present embodiment having a thermoplastic resin layer and an intermediate layer, a solution (thermoplasticity) in which a thermoplastic organic polymer and an additive are dissolved on a temporary support. Preparation which prepared by adding resin and an additive to the solvent which does not dissolve a thermoplastic resin layer on the obtained thermoplastic resin layer, after applying a coating liquid for resin layer), drying and providing a thermoplastic resin layer A liquid (intermediate layer coating liquid) is applied and dried to laminate the intermediate layer. On the formed intermediate layer, a positive photosensitive resin layer coating solution prepared using a solvent that does not dissolve the intermediate layer is further applied and dried to laminate the positive photosensitive resin layer. The photosensitive transfer material of the form can be suitably produced.

[Method of manufacturing circuit wiring]
A first embodiment of a circuit wiring manufacturing method using the photosensitive transfer material of this embodiment will be described.
The first embodiment of the circuit wiring manufacturing method is as follows:
(A) A bonding step in which a positive photosensitive resin layer of the photosensitive transfer material of the present embodiment in which the above-described temporary support has light permeability is bonded to the substrate to be bonded to the substrate,
(B) An exposure process for pattern exposure of the positive photosensitive resin layer of the photosensitive transfer material after the bonding process;
(C) a development process for developing the positive photosensitive resin layer after the exposure process to form a pattern, and (D) an etching process for etching the substrate in the region where the pattern is not disposed. It is a manufacturing method of circuit wiring.
The substrate in the first embodiment of the method for producing circuit wiring may be a substrate itself such as glass, silicon, or film, and may be a conductive layer or the like on the substrate such as glass, silicon, or film, if necessary. The board | substrate with which arbitrary layers of were provided may be sufficient.
According to the first embodiment of the circuit wiring manufacturing method, a fine pattern can be formed on the substrate surface.

The second embodiment of the circuit wiring manufacturing method is
(A) It has a base material and a plurality of conductive layers including a first conductive layer and a second conductive layer whose constituent materials are different from each other, and on the surface of the base material, the outermost surface layer in order from the surface of the base material The positive photosensitive resin layer of the photosensitive transfer material of the present embodiment described above is attached to the substrate on which the first conductive layer and the second conductive layer are stacked in contact with the first conductive layer. Matching process,
(B) a first exposure step of pattern-exposing the positive photosensitive resin layer via a temporary support of the photosensitive transfer material after the bonding step;
(C) First developing step of forming the first pattern by developing the positive photosensitive resin layer after the first exposure step after peeling the temporary support from the positive photosensitive resin layer after the first exposure step. ,
(D) a first etching step of etching at least the first conductive layer and the second conductive layer among the plurality of conductive layers in the region where the first pattern is not disposed;
(E) a second exposure step of pattern exposure of the first pattern after the first etching step with a pattern different from the first pattern;
(F) a second development step of developing the first pattern after the second exposure step to form a second pattern; and
(G) It is preferable to include a second etching step of etching at least the first conductive layer among the plurality of conductive layers in the region where the second pattern is not disposed in this order.

  Conventionally, photosensitive resin compositions are classified into a negative type in which a portion irradiated with actinic rays is left as an image and a positive type in which a portion not irradiated with actinic rays is left as an image due to differences in photosensitive systems. In the positive type, by irradiating actinic rays, for example, to improve the solubility of the exposed portion using a photosensitive agent that generates acid upon irradiation with actinic rays, both the exposed and unexposed portions are exposed at the time of pattern exposure. If the pattern shape obtained is not cured and the substrate is defective, the substrate can be reused (reworked) by full exposure or the like. Therefore, the positive type is preferable from the viewpoint of excellent so-called reworkability. Further, the technique of reexposing the remaining photosensitive resin layer to produce a different pattern can only be realized with a positive photosensitive resin layer.

  According to the second embodiment of the circuit wiring manufacturing method, even if a photosensitive transfer material is bonded to the circuit wiring forming substrate at a low temperature and at a high speed, high adhesion can be secured. In addition, since the circuit wiring manufacturing method of this embodiment can form circuit wiring including a plurality of types of conductive layers by bonding (laminating) in the circuit wiring manufacturing method of this embodiment once, the manufacturing efficiency can be increased. In addition, since it is not necessary to align the conductive layers of a plurality of types of patterns, it is suitable for use as an input device, particularly as a touch panel.

Hereinafter, the preferable aspect in 2nd Embodiment of the manufacturing method of circuit wiring is demonstrated in detail.
An example of a method for manufacturing a circuit wiring for a touch panel, which is one embodiment of the present invention, is schematically shown in FIG. Here, the circuit which has the conductive layer of two types of patterns using the base material 22 and the board | substrate 20 for circuit formation which has the 1st conductive layer 24 and the 2nd conductive layer 26 in order in the distance from one surface of the base material 22. A case where a wiring board is manufactured will be described.

A case where a conductive layer pattern of a capacitive input device is obtained by using a positive photosensitive resin layer in the photosensitive transfer material of this embodiment as an etching resist (etching pattern) will be described.
The capacitance-type input device has at least the following elements (2) to (5) on the non-contact side of the substrate (front plate or film substrate) and (2), ( Preferably, at least one of 3) and (5) is formed by the circuit wiring manufacturing method of the present embodiment.
(2) A plurality of first electrode patterns formed by extending a plurality of pad portions in the first direction through the connection portions (3) electrically insulated from the first electrode pattern, A plurality of second electrode patterns (4) formed of a plurality of pad portions extending in a direction intersecting the direction (4) Insulating layer for electrically insulating the first electrode pattern and the second electrode pattern ( 5) A conductive element that is electrically connected to at least one of the first electrode pattern and the second electrode pattern and is different from the first electrode pattern and the second electrode pattern. Details of each step will be described below. .

(A) Bonding Step First, in the bonding step, the substrate 22 has a plurality of conductive layers including the first conductive layer 24 and the second conductive layer 26 having different constituent materials. On the substrate (circuit wiring forming substrate) 20 on which the first conductive layer 24 and the second conductive layer 26 which are the outermost surface layers are laminated in order from the surface of the base material 22 on the upper side, the present embodiment described above. The positive photosensitive resin layer 14 of the photosensitive transfer material 100 in the form is brought into contact with the first conductive layer 24 and bonded thereto. Such a bonding of the circuit wiring forming substrate and the photosensitive transfer material may be referred to as “transfer” or “laminate”.

When the cover film 16 is provided on the positive photosensitive resin layer 14 of the photosensitive transfer material 100 as shown in FIG. 1, the cover film 16 is removed from the photosensitive transfer material 100 (positive photosensitive resin layer 14). After that, the positive photosensitive resin layer 14 of the photosensitive transfer material 100 is brought into contact with the first conductive layer 24 and bonded thereto.
Bonding (transferring) the photosensitive transfer material onto the first conductive layer is performed by stacking the positive photosensitive resin layer side of the photosensitive transfer material on the first conductive layer, and applying pressure and heating with a roll or the like. It is preferable to be performed. For laminating, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
When the base material of the circuit wiring forming substrate is a resin film, roll-to-roll bonding can also be performed.

(Base material)
As for the board | substrate with which the some electroconductive layer was laminated | stacked on the base material, it is preferable that a base material is a glass base material or a film base material, and it is more preferable that it is a film base material. When the circuit wiring manufacturing method of the present embodiment 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.
The refractive index of the substrate is preferably 1.5 to 1.52.
The base material may be composed of a light-transmitting base material such as a glass base material, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. Moreover, as the above-mentioned transparent substrate, the 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 substrate that is not optically distorted and a substrate having high transparency. Specific examples of the material include polyethylene terephthalate (PET), Examples thereof include polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

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

In the circuit wiring manufacturing method of the present embodiment, it is preferable that at least one of the plurality of conductive layers contains a metal oxide.
The conductive layer is preferably a first electrode pattern, a second electrode pattern, or another conductive element used in a capacitance type input device described later.
Other preferred modes of the conductive layer will be described later in the description of the capacitive input device.

(Circuit wiring formation board)
It is a board | substrate which has a conductive layer on the surface of a base material. Circuit wiring is formed by patterning the conductive layer. In this example, a film substrate such as PET is preferably provided with a plurality of conductive layers such as metal oxides and metals.

(B) 1st exposure process In a 1st exposure process, the positive type photosensitive resin layer 14 is pattern-exposed through the temporary support body 12 of the photosensitive transfer material after a bonding process.

  As examples of the exposure step, the development step, and other steps in the present embodiment, the method described in paragraphs [0035] to [0051] of JP-A-2006-23696 is preferably used in this embodiment. Can do.

For example, a mask 30 having a predetermined pattern is disposed above the photosensitive transfer material 100 disposed on the first conductive layer 24 (on the side opposite to the side in contact with the first conductive layer 24), and then the mask 30 And a method of exposing with ultraviolet rays from above the mask.
In the present embodiment, 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 an input device having circuit wiring manufactured according to the present embodiment and to reduce the area occupied by the extraction wiring as much as possible, at least a part of the pattern (particularly the touch panel The electrode pattern and the lead-out wiring portion) are preferably fine wires of 100 μm or less, and more preferably 70 μm or less.
Here, the light source used for exposure can be appropriately selected and used as long as it can irradiate light (for example, 365 nm, 405 nm, etc.) in a wavelength region where the exposed portion of the photosensitive transfer material can be dissolved in the developer. . Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned.
Energy of exposure generally ^5mJ / cm ^{2 ~200mJ} / cm 2 or so, preferably 10mJ ^/ cm ² ~100mJ ^/ cm 2 approximately.
It is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. By a process called PEB (Post Exposure Bake), pattern edge roughness due to standing waves generated in the photosensitive resin layer during exposure can be reduced.

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

(C) First development step In the first development step, the temporary support 12 is peeled off from the positive photosensitive resin layer 14 after the first exposure step, and then the positive photosensitive resin layer 14 after the first exposure step is removed. Development is performed to form the first pattern 14A.

The first development step is a step of forming a first pattern by developing the pattern-exposed positive photosensitive resin layer.
The development of the pattern-exposed positive photosensitive resin layer can be performed using a developer.
The developer is not particularly limited as long as the exposed portion of the positive photosensitive resin layer can be removed. For example, a known developer such as the developer described in JP-A-5-72724 can be used. it can. The developer is preferably a developer in which the exposed portion of the positive photosensitive resin layer exhibits a dissolution type development behavior. For example, an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is preferable. The developer may further contain an organic solvent miscible with water, a surfactant, and the like. Examples of the developer suitably used in the present embodiment include a developer described in paragraph [0194] of International Publication No. 2015/092731.

  The development method is not particularly limited, and any of paddle development, shower development, shower and spin development, dip development, and the like may be used. Here, the shower development will be described. The exposed portion can be removed by spraying a developer onto the positive photosensitive resin layer after exposure. 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 liquid temperature of the developer is preferably 20 ° C to 40 ° C.

Furthermore, you may have the post-baking process which heat-processes the pattern containing the positive photosensitive resin layer obtained by image development.
The post-baking is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably in an environment of 506.6 kPa or more. On the other hand, it is more preferable to carry out in an environment of 114.6 kPa or less, and it is particularly preferable to carry out in an environment of 101.3 kPa or less.
The post-baking temperature is preferably 80 ° C to 250 ° C, more preferably 110 ° C to 170 ° C, and particularly preferably 130 ° C to 150 ° C.
The post-bake time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
The post-bake may be performed in an air environment or a nitrogen substitution environment.

  You may have other processes, such as a post-exposure process.

(D) First Etching Step In the first etching step, at least the first conductive layer 24 and the second conductive layer 26 are etched among the plurality of conductive layers in the region where the first pattern 14A is not disposed. The first conductive layer 24A and the second conductive layer 26A having the same pattern are formed by etching.

  Etching of the conductive layer can be performed by a known method such as the method described in paragraph [0048] to paragraph [0054] of JP 2010-152155 A.

For example, as an etching method, a commonly performed wet etching method in which the substrate is immersed in an etching solution can be used. As an etchant used for wet etching, an acid type or alkaline type etchant may be appropriately selected in accordance with 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, and mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride, potassium permanganate, and the like. Is done. As the acidic component, a component obtained by combining a plurality of acidic components may be used.
Examples of alkaline type etchants include aqueous solutions of alkali components such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, salts of organic amines such as tetramethylammonium hydroxide, alkaline components and potassium permanganate. Examples thereof include a mixed aqueous solution of salt. As the alkali component, a component obtained by combining a plurality of alkali components may be used.

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

After the etching process, a cleaning process and a drying process may be performed as necessary to prevent contamination of the process line. For the washing step, for example, performed by washing 10 seconds to 300 seconds substrate with pure water at room temperature, the drying step, for example using air blow, air blow pressure ^{(0.1kg / cm 2 ~5kg / cm} 2 or so) The drying may be performed by appropriately adjusting the above.

(E) Second Exposure Step After the first etching step, the first pattern 14A after the first etching step is subjected to pattern exposure with a pattern different from the first pattern.

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

(F) Second development step In the second development step, the first pattern 14A after the second exposure step is developed to form a second pattern 14B.
By the development, the exposed portion of the first pattern in the second exposure step is removed.
In the second development step, the same method as the development in the first development step can be applied.

(G) Second Etching Step In the second etching step, at least the first conductive layer 24A among the plurality of conductive layers in the region where the second pattern 14B is not disposed is etched.

For the etching in the second etching step, the same method as the etching in the first etching step can be applied except that an etching solution corresponding to the conductive layer to be removed by etching is selected.
In the second etching step, it is preferable to selectively etch fewer conductive layers than in the first etching step, depending on the desired pattern. For example, as shown in FIG. 2, the first conductive layer is etched by using an etchant that selectively etches only the first conductive layer 24 </ b> B in a region where the positive photosensitive resin layer is not disposed. The pattern can be different from the pattern of the second conductive layer.
After the second etching step is completed, circuit wiring including conductive layers 24B and 26A having at least two types of patterns is formed.

(H) Positive photosensitive resin layer removing step After the second etching step, the second pattern 14B remains on a part of the first conductive layer 24B. If the positive photosensitive resin layer is unnecessary, all the remaining positive photosensitive resin layer 14B may be removed.

Although there is no restriction | limiting in particular as a method of removing the remaining positive type photosensitive resin layer, The method of removing by chemical processing can be mentioned.
As a method for removing the positive photosensitive resin layer, for example, a substrate having a positive photosensitive resin layer or the like in a peeling solution being stirred at 30 ° C. to 80 ° C., preferably 50 ° C. to 80 ° C., for 5 minutes to The method of immersing for 30 minutes is mentioned.

  Examples of the stripping solution include inorganic alkali components such as sodium hydroxide and potassium hydroxide, or organic alkali components such as tertiary amine and quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or Examples include stripping solutions dissolved in these mixed solutions. A stripping solution may be used and stripped by a spray method, a shower method, a paddle method, or the like.

  The circuit wiring manufacturing method of this embodiment may include other optional steps. For example, although the following processes are mentioned, it is not limited to these processes.

<Process for attaching protective film>
You may further have the process of affixing the protective film (not shown) which has a light transmittance on a 1st pattern before a 2nd exposure process after a 1st etching process.
In this case, it is preferable that in the second exposure step, the first pattern is subjected to pattern exposure via the protective film, and after the second exposure step, the protective film is peeled off from the first pattern, and then the second development step is performed.

<Step of reducing visible light reflectance>
The manufacturing method of the circuit wiring of this embodiment can include the process of reducing the visible light reflectance of some or all of the plurality of conductive layers on the substrate.
Examples of the treatment for reducing the visible light reflectance include an oxidation treatment. For example, the visible light reflectance can be reduced by blackening the copper by oxidizing copper.
With respect to a preferable embodiment of the process for reducing the visible light reflectance, paragraphs [0017] to [0025] of JP 2014-150118 A, paragraphs [0041] and paragraphs [0042] of JP 2013-206315 A, and so on. ], Paragraph [0048] and paragraph [0058], the contents of this publication are incorporated herein.

<Step of forming a new conductive layer on the insulating film>
The method for manufacturing a circuit wiring according to the present embodiment preferably includes a step of forming an insulating film on the formed circuit wiring and a step of forming a new conductive layer on the insulating film.
With such a configuration, a second electrode pattern described later can be formed while being insulated from the first electrode pattern.
There is no restriction | limiting in particular about the process of forming an insulating film, The method of forming a well-known permanent film can be mentioned. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.
There is no particular limitation on the process of forming a new conductive layer on the insulating film. A new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

  In the description with reference to FIG. 2, the case where circuit wirings having two different patterns are formed on a circuit wiring forming substrate having two conductive layers has been described. The number of conductive layers of the substrate to which the manufacturing method is applied is not limited to two layers, and a circuit wiring forming substrate in which three or more conductive layers are stacked is used, and the combination of the exposure step, the development step, and the etching step described above is used. By performing it three times or more, three or more conductive layers can be formed in different circuit wiring patterns.

  Although not shown in FIG. 2, the circuit wiring manufacturing method according to the present embodiment is such that the base material has a plurality of conductive layers on both surfaces, and the conductive layers are formed on both surfaces of the base material. It is also preferable to form circuits sequentially or simultaneously. With such a configuration, it is possible to form a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface. Moreover, it is also preferable to form the circuit wiring for touch panels of such a structure from both surfaces of a base material by roll-to-roll.

[Circuit wiring]
Although the use of the circuit wiring manufactured by the circuit wiring manufacturing method of the present embodiment is not limited, for example, the circuit wiring for a touch panel is preferable. A preferable aspect of the circuit wiring for the touch panel will be described later in the description of the capacitive input device.

FIG. 3 shows a schematic cross-sectional view of one embodiment of the circuit wiring that can be manufactured by the circuit wiring manufacturing method of the present embodiment. In the circuit wiring of this embodiment, the first electrode pattern 3 is formed on the circuit substrate 1, and another conductive element 6 is formed on the first electrode pattern 3. The circuit wiring for the touch panel shown in FIG. 3 has two types of patterns, that is, a conductive layer laminated portion in which another conductive element 6 is formed with the first electrode pattern 3 and a conductive portion having only the first electrode pattern 3. The circuit wiring includes the conductive portion.
When the touch-panel circuit wiring as shown in FIG. 3 is viewed obliquely from above in a plan view, the configuration shown in the schematic diagram of FIG. 4 is obtained. In the example of the circuit wiring for touch panel shown in FIG. 4, the dotted line portion in FIG. 4 is a conductive layer laminated portion in which another conductive element is formed with the first electrode pattern 3, and the portion in which the squares in FIG. Is a conductive part having only the first electrode pattern 3.
The circuit wiring manufacturing method of the present embodiment can easily manufacture a plurality of different circuit wirings. For example, as shown in FIG. 3 and FIG. 4, a circuit including a conductive laminated portion formed by laminating the conductive element 6 and the electrode pattern 3 and a conductive portion composed only of the electrode pattern 3 is easily formed. can do.

[Input device and display device]
An input device is an example of a device provided with circuit wiring manufactured by the circuit wiring manufacturing method of the present embodiment. The input device in the present embodiment is preferably a capacitive touch panel.
The display device in the present embodiment includes the input device in the present embodiment. The display device in the present embodiment is preferably an image display device.

<Capacitive Input Device and Image Display Device Comprising Capacitive Input Device>
An electrostatic capacitance type input device which is a preferable aspect of the input device and the display device in the present embodiment, and an image display device including the electrostatic capacitance type input device as a constituent element are “latest touch panel technology” (July 2009). (Technology Times, Inc.), supervised by Yuji Mitani, “Touch Panel Technology and Development”, CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. The disclosed configuration can be applied.

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

  The base material 1 is comprised by translucent board | substrates, such as a glass substrate, The tempered glass represented by the gorilla glass of Corning, etc. can be used. Moreover, in FIG. 5, the side in which each element of the base material (front surface layer) 1 is provided is called a non-contact surface. In the capacitive input device 10, input is performed by bringing a finger or the like into contact with the contact surface (the surface opposite to the non-contact surface) of the substrate 1.

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 side of the touch panel front plate, and is formed so that the lead wiring and the like are not visually observed from the glass substrate side.
In the capacitance-type input device 10, the mask layer 2 may be provided at a position that covers a partial region of the base material 1. Furthermore, the base material 1 can be provided with an opening in part. A mechanical switch by pressing can be installed in the opening.

On the 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 electrical A plurality of second transparent electrode patterns 4 comprising a plurality of pad portions formed extending in a direction intersecting the first direction, the first electrode pattern 3 and the second transparent electrode pattern An insulating layer 5 that electrically insulates 4 is formed. The first electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 to be described later are, for example, light-transmitting conductive materials such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide). It can be made of a conductive metal oxide film. Examples of the metal film include an ITO film; a metal film such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; a metal oxide film such as SiO ₂ . In the formation of the metal film, the film thickness of each element can be 10 nm to 200 nm. Further, since the amorphous ITO film is made into a polycrystalline ITO film by firing, the electrical resistance can be reduced.
The first electrode pattern 3 and the second transparent electrode pattern 4 are preferably formed using a positive photosensitive resin layer as an etching resist (etching pattern). For the formation of the second electrode layer for forming the second transparent electrode pattern, in addition to photolithography using a resist including the positive photosensitive resin layer used in the present embodiment, a known method is used. be able to. In addition, it can also manufacture using the photosensitive transfer material which has the photosensitive resin composition using an electroconductive fiber. In the case of forming the first conductive pattern or the like by using 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 transparent electrode pattern 4 is installed across both the non-contact surface of the substrate 1 and the region of the mask layer 2 opposite to the substrate 1. can do. In FIG. 5, a diagram is shown in which the second transparent electrode pattern is placed across both the non-contact surface of the substrate 1 and the region of the mask layer 2 opposite to the substrate 1. Yes.

  The first electrode pattern and the second electrode pattern 4 will be described with reference to FIGS. 6 and 7. 6 and 7 are also explanatory diagrams showing examples of the first electrode pattern and the second electrode pattern. As shown in FIGS. 6 and 7, 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 intersects the first direction (second direction in FIGS. 6 and 7: second The electrode pattern extends in the extending direction), and is formed by 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 transparent electrode are formed. The pattern 4 may be integrally formed (patterned). When the pad portion 3a and the second transparent electrode pattern 4 are integrally formed (patterned), as shown in FIGS. 6 and 7, a part of the connection part 3b and a part of the pad part 3a are connected, and Each layer is formed in a state where the first electrode pattern 3 and the second transparent electrode pattern 4 are electrically insulated by the insulating layer 5.

  In FIG. 5, another conductive element 6 is installed on the side 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 transparent electrode pattern 4, and is different from the first electrode pattern 3 and the second transparent electrode pattern 4. Is another element. FIG. 5 shows a diagram in which another conductive element 6 is connected to the second transparent electrode pattern 4.

Moreover, in FIG. 5, the transparent protective layer 7 is installed in the position which covers all the each component. The transparent protective layer 7 may be formed at a position covering 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. The material constituting the insulating layer 5 and the transparent protective layer 7 is preferably a material having good surface hardness and heat resistance, and known photosensitive siloxane resin materials, acrylic resin materials, etc. are used, and these are known to those skilled in the art. It is.
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 for manufacturing a capacitance-type input device, at least one of the first electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 has a positive photosensitive resin layer as an etching resist ( It is preferable that the etching pattern is formed by etching as an etching pattern. 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 transparent electrode pattern 4, and another conductive element 6 is formed by performing an etching process using a positive photosensitive resin layer as an etching resist (etching pattern). It is preferable that
When the first electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 are formed by etching, first, on the non-contact surface of the substrate 1 on which the black mask layer 2 and the like are formed. Then, at least an inorganic insulating layer is provided 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 positive photosensitive resin layer having a photocurable resin layer for etching as a 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 1st electrode pattern 3, the 2nd transparent electrode pattern 4, and another electroconductive element 6 using the photosensitive film which has an electroconductive photocurable resin layer, on the surface of the base material 1, It can be formed by providing at least an inorganic insulating layer for the portion provided with the black mask layer 2 and transferring the conductive photocurable resin layer on the non-contact surface of the substrate 1 or on the inorganic insulating layer.

  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 first or second transparent electrode pattern is formed on the substrate 1 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 surface. 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, except for the haze value (%) described later.

[Example 1]
A positive photosensitive resin composition 1 was produced according to the following formulation.
(Positive photosensitive resin composition 1: prescription)
-Specific polymer 1 (the following compound, weight average molecular weight 15,000) 9.66 parts (When Tg of the specific polymer 1 was measured by the above-mentioned method, it was -10 degreeC.)
Photo acid generator (compound A-1 below) 0.25 part Surfactant (surfactant C below) 0.01 part Additive (compound D below) 0.08 part propylene glycol monomethyl ether acetate [ Solvent] 90.00 parts In the following structure, the numerical value of each structural unit represents the content (% by mass) of the structural unit.

Compound A-1

Surfactant C: Perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC Corporation)

Compound D: Basic compound having the following structure (manufacturer: Toyo Kasei Kogyo Co., Ltd., product number: CMTU)

The produced positive photosensitive resin composition 1 was dried on a 50 μm-thick polyethylene terephthalate film (hereinafter referred to as “PET (A)”) as a temporary support using a slit-like nozzle. The coating amount was 0.0 μm.
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 pressure-bonded as a cover film to prepare a photosensitive transfer material 1.

  The total light haze of PET (A) was 0.19%. Film haze measured the total light haze value (%) of the base piece based on JIS-K-7136 using Suga Test Instruments Co., Ltd. haze meter HZ-2.

[Example 2]
A photosensitive transfer material 2 was produced in the same manner as in Example 1 except that the specific polymer 1 was replaced with the following specific polymer 2.
It was 20 degreeC when Tg of the specific polymer 2 was measured by the above-mentioned method. The weight average molecular weight measured by the GPC method described above was 15,000.

[Example 3]
A photosensitive transfer material 3 was produced in the same manner as in Example 1 except that the specific polymer 1 was replaced with the following specific polymer 3.
It was 40 degreeC when Tg of the specific polymer 3 was measured by the above-mentioned method. The weight average molecular weight measured by the GPC method described above was 15,000.

[Example 4]
A photosensitive transfer material 4 was produced in the same manner as in Example 1 except that the specific polymer 1 was replaced with the following specific polymer 4.
It was 50 degreeC when Tg of the specific polymer 4 was measured by the above-mentioned method. The weight average molecular weight measured by the GPC method described above was 15,000.

[Example 5]
A photosensitive transfer material 5 was produced in the same manner as in Example 1 except that the specific polymer 1 was replaced with the following specific polymer 5.
It was 56 degreeC when Tg of the specific polymer 5 was measured by the above-mentioned method. The weight average molecular weight measured by the GPC method described above was 15,000.

[Example 6]
A positive photosensitive resin composition 3 was produced in the same manner as in Example 1 except that the specific polymer 1 was replaced with the specific polymer 3. The produced positive photosensitive resin composition 3 was dried on a 50 μm-thick polyethylene terephthalate film (hereinafter referred to as PET (B)), which is a temporary support, using a slit-like nozzle. The coating was applied in an amount of 0 μm.
Thereafter, the film was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (OSM-N, manufactured by Tredegar) was pressure bonded as a cover film to prepare a photosensitive transfer material 6.
In addition, when the total light haze value (%) of PET (B) was measured by the same method as PET (A) in Example 1, the total light haze value was 0.78%.

[Comparative Example 1]
A photosensitive transfer material C1 of Comparative Example 1 was produced in the same manner as in Example 1 except that the specific polymer 1 was replaced with the following comparative polymer C1.
It was 100 degreeC when Tg of the comparative polymer C1 was measured by the above-mentioned method. The weight average molecular weight measured by the GPC method described above was 15,000.

[Evaluation]
A substrate was used in which a copper layer was formed by sputtering at a thickness of 500 nm on a 188 μm thick PET film.

<Laminate suitability evaluation>
The produced photosensitive transfer materials 1, 2 and C1 were cut into 50 cm squares, the cover film was peeled off, and a laminate roll temperature of 90 ° C., a linear pressure of 0.6 MPa, and a linear velocity (laminate velocity) of 3.6 m / min. It laminated on the PET board | substrate with a copper layer on condition. The area in which the photosensitive resin layer was in close contact with the copper layer was visually evaluated, and the area ratio in which the photosensitive resin layer was in close contact was determined by “area in which the photosensitive resin layer was in close contact / area of the cut transfer material” (%). Evaluation was made according to the following criteria A to C.
A: 95% or more B: 80% or more and less than 95% C: Less than 80%

<Resolution evaluation>
The produced photosensitive transfer materials 1 to 6 and C1 were laminated on a PET substrate with a copper layer under lamination conditions of a linear pressure of 0.6 MPa and a linear velocity of 3.6 m / min. When the roll temperature was 90 ° C. and the laminate suitability B or lower, a sample was prepared by raising the lami roll temperature until the laminate property was judged as A based on the above-described evaluation criteria.
In the photosensitive transfer materials of Examples 1 to 5 and C1, after exposure with an ultrahigh pressure mercury lamp through a line and space pattern (duty ratio 1: 1) mask with a line width of 3 μm to 20 μm without peeling off the temporary support. The temporary support was peeled off and developed. Development was performed by shower development for 30 seconds using a 1.0% sodium carbonate aqueous solution at 28 ° C.
In the photosensitive transfer material of Example 6, the temporary support was peeled from the photosensitive layer, and then exposed through a mask and developed in the same manner as in Example 1.
Of the obtained line and space patterns, the pattern having the highest resolution was defined as the ultimate resolution, and the following criteria A to C were evaluated.
A: Less than 7 μm B: 7 μm or more and less than 15 μm C: 15 μm or more The results are shown in Table 1 below.

  The photosensitive transfer material of the example was good in both laminating suitability and resolution evaluation. On the other hand, the photosensitive transfer material of Comparative Example 1 was inferior in laminate suitability.

[Example 7]
On a 100-micron-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited as a first conductive layer on the deposited second conductive layer to a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.

On the copper layer, the photosensitive transfer material 1 obtained in Example 1 was laminated after peeling the cover film (linear pressure 0.6 MPa, linear velocity 3.6 m / min, roll temperature 100 ° C.).
Without peeling off the temporary support, contact pattern exposure was performed using a photomask provided with pattern A shown in FIG. 8 having a configuration in which conductive layer pads are connected in one direction (first exposure step).
In the pattern A shown in FIG. 8, the solid line portion and the gray portion are light shielding portions, the portion other than the light shielding portion is an opening portion, and the dotted line portion virtually shows an alignment alignment frame. The solid line portion is a thin line of 70 μm or less. Thereafter, similar thin lines were formed in other examples and comparative examples.

  Thereafter, the temporary support is peeled off, and development using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution is performed (first development step). After the first development step, the first pattern ( A positive photosensitive resin layer having a pattern) shape which is the shape of the light shielding portion region of pattern A was obtained.

  Next, after etching the copper layer (first conductive layer) using a copper etchant (Kanto Chemical Co., Ltd., Cu-02), an ITO etchant (Kanto Chemical Co., Ltd., ITO-02) is used. By etching the ITO layer (second conductive layer), both the copper layer (first conductive layer) and the ITO layer (second conductive layer) are in the first pattern (pattern that is the shape of the light shielding part region of pattern A). A substrate drawn in (1) was obtained.

Next, also in the pattern B shown in FIG. 9 in a state of alignment, the solid line portion and the gray portion indicate the light shielding portion. According to the shape of the pattern B shown in FIG. 9, pattern exposure is performed using a photomask provided with an opening of the light-shielding portion and the light-shielding portion (second exposure step), and development using 2.38% TMAH aqueous solution is performed (first). 2 development step) and after the second development step, washing with water was performed to obtain a positive photosensitive resin layer having a second pattern (a pattern in which the light shielding part of pattern A and the light shielding part of pattern B overlap).
Also in the pattern B shown in FIG. 9, the gray portion indicates the light shielding portion, the portion other than the light shielding portion is the opening portion, and the dotted line portion virtually indicates the alignment alignment frame as described above.

Thereafter, the copper layer was etched using Cu-02, and the remaining photosensitive resin layer was peeled using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
As described above, a circuit wiring board having a pattern C shown in FIG. 10 was obtained. In FIG. 10, a region that is not a solid line (both white region and gray region) is a state in which the PET substrate is exposed. The solid line portion in the gray region in FIG. 10 is in a state where the ITO wiring is exposed. The other solid line portion is a peripheral wiring portion, and has a structure in which copper wiring is laminated on ITO wiring and shares the same circuit pattern.

Thereafter, by using Cu-02, only the first conductive layer (copper layer) in the region where the positive photosensitive resin layer having the second pattern is not disposed is etched (second etching step).
Furthermore, the remaining photosensitive resin layer was peeled off using a peeling liquid (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
As a result, a circuit wiring board having the wiring pattern C shown in FIG. 10 was obtained. In FIG. 10, a region that is not a solid line (both the opening portion shown in white and the region shown in gray) is a state where the PET substrate is exposed. The solid line portion in the gray region in FIG. 10 is in a state where the ITO wiring (second conductive layer) is exposed. The other solid line portion is a peripheral wiring portion, and has a structure in which a copper wiring (first conductive layer) is laminated on the ITO wiring and shares the same circuit pattern.
When the circuit of the obtained circuit wiring board was observed with a microscope, there was no peeling or chipping, and it was a clean pattern with high definition.

[Example 8]
On a 100-micron-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited as a first conductive layer on the deposited second conductive layer to a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
The photosensitive transfer material 1 was laminated on the copper layer (linear pressure 0.6 MPa, linear velocity 3.6 m / min, roll temperature 100 ° C.).
Pattern exposure was performed using a photomask provided with a pattern A having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support. After the exposure, the temporary support was peeled off, developed, and then washed with water to obtain a pattern A.
Next, after etching the copper layer using a copper etchant (Kanto Chemical Co., Ltd. Cu-02), the ITO layer is etched using an ITO etchant (Kanto Chemical Co., Ltd. ITO-02), A substrate on which both copper and ITO were drawn in pattern A was obtained.

Next, PET (A) was laminated again as a protective film on the remaining resist (positive photosensitive resin layer). In this state, pattern exposure was performed using a photomask provided with an opening of the pattern B in the aligned state, and after the PET (A) as a protective film was peeled off, development and washing were performed.
Thereafter, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Ltd.) to obtain a circuit wiring board.
As a result, a circuit wiring board having a pattern C was obtained.
When the circuit of the obtained circuit wiring board was observed with a microscope, there was no peeling or chipping, and it was a clean pattern with high definition.

DESCRIPTION OF SYMBOLS 1 Base material 2 Mask layer 3 Electrode pattern 3a Pad part 3b Connection part 4 Transparent electrode pattern 5 Insulating layer 6 Another electroconductive element 7 Transparent protective layer 10 Capacitive type input device 12 Temporary support body 14 Positive photosensitive resin layer 14A First pattern 14B Second pattern 16 Cover film 20 Circuit forming substrate 22 Base material 24 First conductive layer 24A First conductive layer (after the first etching step)
24B 1st conductive layer (after 2nd etching process)
26 2nd conductive layer 26A 2nd conductive layer (after 1st etching process and 2nd etching process)
30 mask 40 mask 100 photosensitive transfer material

Claims (10)

A temporary support;
A positive photosensitive resin layer containing a structural unit represented by the following general formula A and a structural unit having an acid group and having a glass transition temperature of 90 ° C. or less, and a photoacid generator;
A photosensitive transfer material.

In general formula A, 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. Alternatively, it represents an aryl group, and 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 photosensitive transfer material according to claim 1, wherein the polymer has a glass transition temperature of −20 ° C. or higher.   The photosensitive transfer material according to claim 1, wherein the polymer contains 20% by mass or more of the structural unit represented by the general formula A with respect to the total solid content of the polymer.   The photosensitivity according to any one of claims 1 to 3, wherein the polymer contains 0.1% by mass to 20% by mass of the structural unit having the acid group with respect to the total solid content of the polymer. Transfer material. 5. The structural unit in which R ³⁴ is a hydrogen atom in the general formula A is 20% by mass or more based on the total amount of the structural unit represented by the general formula A. 5. Photosensitive transfer material.   The photosensitive transfer material according to any one of claims 1 to 5, wherein the polymer has a weight average molecular weight Mw of 60,000 or less.   The photosensitive transfer material according to claim 1, wherein the temporary support has light permeability. (A) A bonding step in which the positive photosensitive resin layer of the photosensitive transfer material according to claim 7 is bonded to the substrate in contact with the substrate;
(B) An exposure step of pattern exposing the positive photosensitive resin layer of the photosensitive transfer material after the bonding step;
(C) a development step for developing the positive photosensitive resin layer after the exposure step to form a pattern;
(D) A method for manufacturing circuit wiring, which includes an etching process for etching a substrate in a region where the pattern is not disposed in this order. (A) a base material and a plurality of conductive layers including a first conductive layer and a second conductive layer having different constituent materials, and on the surface of the base material, in order of increasing distance from the surface of the base material; The positive photosensitive resin layer of the photosensitive transfer material according to claim 7 is used as the first conductive layer with respect to a substrate on which the first conductive layer and the second conductive layer which are surface layers are laminated. A pasting process for contacting and pasting,
(B) a first exposure step of pattern exposing the positive photosensitive resin layer via the temporary support of the photosensitive transfer material after the bonding step;
(C) After the temporary support is peeled from the positive photosensitive resin layer after the first exposure step, the positive photosensitive resin layer after the first exposure step is developed to form a first pattern. 1 development process,
(D) a first etching step of etching at least the first conductive layer and the second conductive layer among the plurality of conductive layers in a region where the first pattern is not disposed;
(E) a second exposure step of pattern-exposing the first pattern after the first etching step with a pattern different from the first pattern;
(F) a second development step of developing the first pattern after the second exposure step to form a second pattern; and
(G) A circuit wiring manufacturing method including a second etching step of etching at least the first conductive layer among the plurality of conductive layers in a region where the second pattern is not disposed in this order. After the first etching step and before the second exposure step, further comprising a step of attaching a protective film having light transmittance on the first pattern,
In the second exposure step, the pattern exposure of the first pattern through the protective film,
The method for manufacturing a circuit wiring according to claim 9, wherein after the second exposure step, the second etching step is performed after the protective film is peeled from the first pattern.