WO2019225460A1

WO2019225460A1 - Photosensitive transfer material, circuit wiring manufacturing method, and touch panel manufacturing method

Info

Publication number: WO2019225460A1
Application number: PCT/JP2019/019460
Authority: WO
Inventors: 一真両角; 克己篠田; 漢那　慎一; 知樹松田; 壮二石坂
Original assignee: 富士フイルム株式会社
Priority date: 2018-05-22
Filing date: 2019-05-16
Publication date: 2019-11-28
Also published as: JPWO2019225460A1; CN112136081A; TW202003598A

Abstract

Provided is a photosensitive transfer material comprising a temporary support and a photosensitive resin layer that includes a polymer having a glass transition temperature of 90°C or lower and including a structural unit having an acid group protected by an acid-decomposable group, a photoacid generator, and a benzotriazole compound. Provided also is the application of the photosensitive transfer material.

Description

Photosensitive transfer material, circuit wiring manufacturing method, and touch panel manufacturing method

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

Generally, a photolithography technique using a photosensitive resin composition is used for forming wirings and electrodes on a semiconductor element, a printed circuit board, and the like. In the photolithography technique, a pattern is formed by forming a layer of a photosensitive resin composition on a substrate, then exposing and developing.

As a photosensitive resin composition, for example, a chemically amplified photoresist composition containing a resin whose alkali solubility is changed by an acid, a compound which generates an acid upon irradiation with radiation, and a rust inhibitor is known (for example, special No. 2004-347951).

Further, a chemically amplified positive resist composition containing a polymer compound, photoacid generator, carboxylic acid compound, and benzotriazole and / or imidazole compound that is soluble in an alkaline aqueous solution by the action of an acid is known ( For example, see JP-A-2017-32983).

However, when a resin pattern is formed using a conventionally proposed photosensitive resin composition, the designed pattern shape is not reproduced due to, for example, a residue generated by development, that is, the resin pattern shape is designed. May not match. For this reason, when a conductive pattern is formed using a resin pattern with inferior shape reproducibility, a conductive pattern is formed along the resin pattern, and thus there is a problem that a conductive wiring excellent in linearity cannot be obtained.

This indication is made in view of the above-mentioned situation, and makes it a subject to solve the object shown below.
An object of one embodiment of the present disclosure is to provide a photosensitive transfer material that is excellent in resin pattern shape reproducibility and improves the linearity of conductive wiring when applied to the formation of a conductive pattern.
Another embodiment of the present disclosure aims to provide a method of manufacturing a circuit wiring that is excellent in linearity of a conductive wiring in a conductive pattern.
Still another embodiment of the present disclosure aims to provide a method for manufacturing a touch panel having circuit wiring excellent in linearity of conductive wiring in a conductive pattern.

Means for solving the above problems include the following aspects.
<1> A polymer, a photoacid generator, and a benzotriazole compound, each including a temporary support and a structural unit having a group in which an acid group is protected by an acid-decomposable group and having a glass transition temperature of 90 ° C. or less And a photosensitive resin layer containing a photosensitive transfer material.
<2> The photosensitive transfer material according to <1>, wherein the benzotriazole compound is a compound represented by the following formula (1).

In formula (1), P represents a hydrogen atom or a substituent, Q represents a substituent, n represents an integer of 0 to 4, and when n is 2 or more, a plurality of Q are the same But it can be different. However, a benzotriazole compound having at least one functional group selected from the group consisting of a sulfonic acid group, a thiol group, and a thioether group is excluded.

<3> In the above formula (1), P is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, a carboxy group, an alkylamino group, a dialkylamino group, or The photosensitive transfer material according to <2>, wherein Z represents an alkylene group, Z represents an alkylene group, and Y represents a hydroxy group, a carboxy group, an alkylamino group, or a dialkylamino group.
<4> In the above formula (1), Q is a halogen atom, hydroxy group, alkyl group, aryl group, heterocyclic group, acyl group, amino group, —ZY group, alkoxy group, carboxy group, or alkoxyacyl. The photosensitive transfer material according to <2> or <3>, wherein Z represents an alkylene group, and Y represents a hydroxy group, a carboxy group, an alkylamino group, or a dialkylamino group.
<5> In the above formula (1), P is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, an amino group, or a —ZY group. , Z represents an alkylene group having 1 or 2 carbon atoms which may be substituted with a carboxy group, Y represents a hydroxy group, a carboxy group, or a dialkylamino group having 1 to 10 carbon atoms in each alkyl group Q is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, an amino group, an alkoxy group having 1 to 6 carbon atoms, a carboxy group, or carbon <2> The photosensitive transfer material according to <2>, wherein the number is an alkoxyacyl group having 1 to 6 and n is 0 or 1.
<6> In the above formula (1), P represents a hydrogen atom or a -ZY group, Z represents an alkylene group having 1 or 2 carbon atoms which may be substituted with a carboxy group, Y represents a dialkylamino group having 1 to 10 carbon atoms in each alkyl group, Q is an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and n is 0 Or the photosensitive transfer material as described in <5> which is 1.
<7> The photosensitive composition according to any one of <1> to <6>, wherein the content of the benzotriazole compound is 0.01% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer. Transfer material.
<8> The photosensitive transfer according to any one of <1> to <7>, wherein a mass ratio of the content of the benzotriazole compound to the content of the polymer is 0.001 to 0.1. material.
<9> The photosensitive transfer according to any one of <1> to <8>, wherein the mass ratio of the content of the benzotriazole compound to the content of the photoacid generator is 0.01 to 5. material.
<10> The content of the structural unit having a group in which the acid group in the polymer is protected with an acid-decomposable group is 20% by mass to 50% by mass with respect to the total mass of the polymer. <1> The photosensitive transfer material according to any one of <9>.
<11> The structural unit according to any one of <1> to <10>, wherein the structural unit having a group in which the acid group is protected with an acid-decomposable group is a structural unit represented by the following formula (A1): Photosensitive transfer material.

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

<12> The photosensitive transfer material according to any one of <1> to <11>, wherein the photosensitive resin layer further contains an amine compound other than the benzotriazole compound.
<13> The photosensitive transfer material according to any one of <1> to <12>, wherein the polymer further includes a structural unit having a pKaH of 3 or more.
<14> The photosensitive transfer material according to any one of <1> to <13>, further comprising an intermediate layer between the temporary support and the photosensitive resin layer.
<15> A step of bonding the outermost layer on the photosensitive resin layer side of the temporary support of the photosensitive transfer material according to any one of <1> to <14> to a substrate;
The step of pattern exposure of the photosensitive resin layer of the photosensitive transfer material after the step of pasting, the step of developing the photosensitive resin layer after the step of pattern exposure to form a pattern, and the arrangement of the pattern And a step of etching a substrate in a region that has not been formed.
<16> The method for producing circuit wiring according to <15>, wherein the substrate is a substrate containing copper.
<17> A step of bonding the outermost layer on the photosensitive resin layer side of the temporary support of the photosensitive transfer material according to any one of <1> to <14> to the substrate, and the step of bonding A step of pattern exposing the photosensitive resin layer of the photosensitive transfer material later, a step of developing the photosensitive resin layer after the pattern exposing step to form a pattern, and an area where the pattern is not disposed And a step of etching the substrate in the method.

According to an embodiment of the present disclosure, it is possible to provide a photosensitive transfer material that has excellent resin pattern shape reproducibility and improves the linearity of conductive wiring when applied to the formation of a conductive pattern.
According to another embodiment of the present disclosure, it is possible to provide a circuit wiring manufacturing method that is excellent in linearity of conductive wiring in a conductive pattern.
According to still another embodiment of the present disclosure, it is possible to provide a method for manufacturing a touch panel having circuit wiring excellent in linearity of conductive wiring in a conductive pattern.

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

Hereinafter, embodiments of the present disclosure will be described in detail. In addition, this indication is not restrict | limited at all to the following embodiment, In the range of the objective of this indication, it can add and implement suitably.

In the present disclosure, 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 a numerical range described in stages in the present disclosure, an upper limit value or a lower limit value described in a numerical range may be replaced with an upper limit value or a lower limit value in another numerical range. Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
In this disclosure, “(meth) acryl” represents both and / or acryl and methacryl, and “(meth) acrylate” means both and / or acrylate and methacrylate. .
In the present disclosure, the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. .
In the present disclosure, the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. .
In the notation of a group (atomic group) in the present disclosure, the notation that does not indicate substitution and non-substitution includes those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present disclosure, “mass%” and “weight%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In the present disclosure, the chemical structural formula may be described as a simplified structural formula in which a hydrogen atom is omitted.

<Photosensitive transfer material>
The photosensitive transfer material of the present disclosure includes a temporary support, a polymer including a structural unit having a group in which an acid group is protected by an acid-decomposable group, and a glass transition temperature of 90 ° C. or less, photoacid generation And a photosensitive resin layer containing a benzotriazole compound.
FIG. 1 schematically shows an example of the layer structure of the photosensitive transfer material of the present disclosure. In the photosensitive transfer material 100A shown in FIG. 1, a temporary support 10, a photosensitive resin layer 12, and a cover film 16 are laminated in this order.

In the present disclosure, the “acid group” refers to a proton dissociable group having a pKa of 12 or less.
In the present disclosure, the “group in which an acid group is protected with an acid-decomposable group” refers to a group having a structure in which an acid group is protected with an acid-decomposable group. For example, when the acid group is a carboxy group, the group in which the acid group is protected with an acid-decomposable group is a structure in which the carboxy group is protected with an acid-decomposable group, that is, the hydrogen atom of the carboxy group is acid-decomposable. A group having a structure substituted with a group.

According to the photosensitive transfer material of the present disclosure, the resin pattern has excellent shape reproducibility (hereinafter sometimes simply referred to as “shape reproducibility”), and when applied to the formation of a conductive pattern, the linearity of the conductive wiring. (Hereinafter simply referred to as “linearity”) is improved. The reason why the photosensitive transfer material of the present disclosure exhibits such an effect is not clear, but is presumed as follows.
The photoacid generator contained in the photosensitive resin layer can generate an acid upon exposure. The acid generated by the exposure can act with a group in which the acid group is protected by an acid-decomposable group, which is contained in the structural unit of the polymer. The acid-decomposable group can be removed from the group in which the acid group is protected by the acid-decomposable group by the action of the acid. For this reason, in the exposed photosensitive resin layer, the acid decomposition reaction of the photosensitive resin occurs, and the solubility in the developer increases.
It is considered that the same principle as described above is also used for the photolithography technique using the photosensitive resin composition disclosed in Japanese Patent Application Laid-Open No. 2004-347951 or 2017-32983. However, as described above, when a resin pattern is formed using a conventional photosensitive resin composition, the shape of the resin pattern may not match the designed pattern shape due to, for example, a residue generated by development. As one of the factors that cause a residue in development, inhibition of the acid decomposition reaction of the photosensitive resin caused by a metal component such as copper oxide present on a transfer target (for example, a support) can be considered. That is, it is considered that a metal component such as copper oxide present in the transferred material acts on the acid generated by exposure and inhibits the acid decomposition reaction of the photosensitive resin, so that a residue is generated during development. For example, in Japanese Patent Application Laid-Open No. 2004-347951, although a rust inhibitor is added to a chemically amplified photoresist composition, a polymer having a high glass transition temperature is used. It can still be inhibited by metal components present in the transcript. For the same reason, Japanese Patent Application Laid-Open No. 2017-32983 uses a carboxylic acid compound in combination with a benzotriazole and / or imidazole compound, but the acid decomposition reaction of the photosensitive resin is a metal component present in the transferred object. Can still be inhibited.
In contrast to the prior art, in the photosensitive transfer material of the present disclosure, the photosensitive resin layer contains the above components, so that the benzotriazole compound in the photosensitive resin layer contains a polymer having a low glass transition temperature. It is considered that it easily moves in the conductive resin layer and coordinates to the surface of the transfer material. It is considered that the action of the metal component of the transferred body on the acid is reduced by the coordination of the benzotriazole compound on the surface of the transferred body. For this reason, according to the photosensitive transfer material of the present disclosure, the shape reproducibility of the resin pattern is excellent, and it is considered that the linearity of the conductive wiring is improved when applied to the formation of the conductive pattern.

[Temporary support]
The photosensitive transfer material of the present disclosure has a temporary support.
The temporary support is a support that supports the photosensitive resin layer and can be peeled off from an adherend such as the photosensitive resin layer.

Examples of the temporary support include a glass substrate, a resin film, and paper, and a resin film is preferable from the viewpoint 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. Among these, a biaxially stretched polyethylene terephthalate film is preferable.

The thickness of the temporary support is not limited, and is preferably 5 μm to 200 μm, more preferably 10 μm to 150 μm, from the viewpoints of ease of handling and versatility.

From the viewpoint of exposing the photosensitive resin layer through the temporary support when the photosensitive resin layer is subjected to pattern exposure, the temporary support preferably has light transmittance. Here, “having light transmittance” means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more. The transmittance of the main wavelength of light used for pattern exposure is preferably 60% or more, more preferably 70% or more, from the viewpoint of improving exposure sensitivity. As a measuring method of the transmittance, a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd. can be mentioned.

A preferred embodiment of the temporary support is described, for example, in paragraphs 0017 to 0018 of JP-A-2014-85643, and the contents of this publication are incorporated in this specification.

[Photosensitive resin layer]
The photosensitive transfer material of the present disclosure includes a polymer having a structural unit having an acid group protected with an acid-decomposable group, and a glass transition temperature of 90 ° C. or less, a photoacid generator, and a benzotriazole It has the photosensitive resin layer containing a compound.

[Benzotriazole compound]
The photosensitive resin layer in the present disclosure contains a benzotriazole compound. The benzotriazole skeleton in the benzotriazole compound is effective in reducing the action of the metal component of the transferred material on the acid described above.

The benzotriazole compound is not limited as long as it is a compound having a benzotriazole skeleton, and a known benzotriazole compound can be used.
Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 5-carboxybenzotriazole, 1- (hydroxymethyl) -1H. -Benzotriazole, 1-acetyl-1H-benzotriazole, 1-aminobenzotriazole, 9- (1H-benzotriazol-1-ylmethyl) -9H-carbazole, 1-chloro-1H-benzotriazole, 1- (2- Pyridinyl) benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1- (1′-hydroxyethyl) benzotriazole, 1- (2′-hydroxyethyl) benzotriazole, 1-propyl Benzoto Azole, 1- (1′-hydroxypropyl) benzotriazole, 1- (2′-hydroxypropyl) benzotriazole, 1- (3′-hydroxypropyl) benzotriazole, 4-hydroxy-1H-benzotriazole, 5-methyl -1H-benzotriazole, methylbenzotriazole-5-carboxylate, ethylbenzotriazole-5-carboxylate, t-butyl-benzotriazole-5-carboxylate, cyclopentylethyl-benzotriazole-5-carboxylate, 1H-benzo Triazole-4-sulfonic acid, 1H-benzotriazole-1-acetonitrile, 1H-benzotriazole-1-carboxaldehyde, 2-methyl-2H-benzotriazole, and 2-ethyl-2H-benzotri An azole is mentioned.

The benzotriazole compound is preferably a compound represented by the following formula (1) from the viewpoint of shape reproducibility and linearity.

In the formula (1), examples of the substituent represented by P include a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, a carboxy group, an alkylamino group, and a dialkylamino group. , And -ZY groups.

In the formula (1), examples of the halogen atom represented by P include a chlorine atom, a bromine atom, and an iodine atom.

In formula (1), the alkyl group represented by P may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, iso-propyl group, butyl group, tert-butyl group, hexyl group, cyclohexyl group, octyl group, decyl group, and dodecyl. Groups.

In formula (1), the aryl group represented by P may be a monocyclic aryl group or a condensed ring aryl group. The aryl group is preferably an aryl group having 6 to 18 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a terphenyl group, and a fluorenyl group.

In the formula (1), the heterocyclic group represented by P may be an aliphatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group represented by P may be a monocyclic heterocyclic group or a condensed heterocyclic group. The heterocyclic group is preferably a heterocyclic group having 1 to 18 carbon atoms, and more preferably a heterocyclic group having 3 to 12 carbon atoms. Examples of the heterocyclic group having 1 to 18 carbon atoms include a furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridinyl group, pyrazinyl group, pyrimidinyl group, indolyl group, isoquinolyl group, carbazolyl group, phenanthridinyl group And phenanthrolinyl group.

In formula (1), the acyl group represented by P is preferably an acyl group having 1 to 12 carbon atoms, more preferably an acyl group having 1 to 8 carbon atoms, and still more preferably a carbon number. An acyl group having 1 to 6 carbon atoms, particularly preferably an acyl group having 2 to 4 carbon atoms. Examples of the acyl group having 1 to 12 carbon atoms include acetyl group, propionyl group, butanoyl group, and benzoyl group.

In formula (1), the alkyl group in the alkylamino group represented by P may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. The alkylamino group is preferably an alkylamino group having 1 to 10 carbon atoms, more preferably an alkylamino group having 3 to 10 carbon atoms, and particularly preferably an alkylamino group having 6 to 10 carbon atoms. It is an amino group. Examples of the alkyl group in the alkylamino group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, and a cyclohexyl group. , An octyl group, and a decyl group.

In formula (1), each alkyl group in the dialkylamino group represented by P may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. In addition, each alkyl group in the dialkylamino group may be the same or different. The dialkylamino group is preferably a dialkylamino group having 1 to 10 carbon atoms in each alkyl group, more preferably a dialkylamino group having 3 to 10 carbon atoms in each alkyl group, particularly preferably Each alkyl group is a dialkylamino group having 6 to 10 carbon atoms. Examples of the alkyl group in the dialkylamino group having 1 to 10 carbon atoms of each alkyl group include, for example, methyl group, ethyl group, propyl group, iso-propyl group, butyl group, tert-butyl group, hexyl group, 2-ethylhexyl Group, cyclohexyl group, octyl group, and decyl group.

In the formula (1), in the —ZY group represented by P, Z represents an alkylene group, and Y represents a hydroxy group, a carboxy group, an alkylamino group, or a dialkylamino group.
The alkylene group represented by Z is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably an alkylene group substituted with a carboxy group. Preferred is an alkylene group having 1 or 2 carbon atoms, particularly preferably an unsubstituted alkylene group having 1 or 2 carbon atoms, and most preferably an unsubstituted methylene group. Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.
Y is preferably a hydroxy group or a dialkylamino group having 1 to 10 carbon atoms in each alkyl group, more preferably a dialkylamino group having 1 to 10 carbon atoms.
The alkyl group in the alkylamino group and dialkylamino group represented by Y may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. In addition, each alkyl group in the dialkylamino group may be the same or different. The alkylamino group is preferably an alkylamino group having 1 to 10 carbon atoms, more preferably an alkylamino group having 3 to 10 carbon atoms, and particularly preferably an alkylamino group having 6 to 10 carbon atoms. An amino group. The dialkylamino group is preferably a dialkylamino group having 1 to 10 carbon atoms in each alkyl group, more preferably a dialkylamino group having 3 to 10 carbon atoms in each alkyl group, particularly preferably Each alkyl group is a dialkylamino group having 6 to 10 carbon atoms. Examples of the alkyl group in the alkylamino group having 1 to 10 carbon atoms and the dialkylamino group in which each alkyl group has 1 to 10 carbon atoms include, for example, methyl group, ethyl group, propyl group, iso-propyl group, butyl group Tert-butyl group, hexyl group, 2-ethylhexyl group, cyclohexyl group, octyl group, and decyl group.

In formula (1), P is preferably a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, a carboxy group, an alkylamino group, a dialkylamino group, or — A ZY group, more preferably a hydrogen atom, a hydroxy group, an alkyl group, an acyl group, an amino group, or a -ZY group, still more preferably a hydrogen atom, an alkyl group, or -ZY group. A group, particularly preferably a hydrogen atom or a -ZY group.

In the formula (1), examples of the substituent represented by Q include a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, a —ZY group, an alkoxy group, a carboxy group, and the like. Groups and alkoxyacyl groups.

In the formula (1), a halogen atom represented by Q, an alkyl group, an aryl group, a heterocyclic group, an acyl group, and a —ZY group are each a halogen atom represented by P in the above formula (1). , An alkyl group, an aryl group, a heterocyclic group, an acyl group, and a -ZY group, and the preferred range is also the same.

In the formula (1), the alkoxy group represented by Q may be a linear alkoxy group or a branched alkoxy group. The alkoxy group represented by Q is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, and a dodecyloxy group.

In formula (1), the alkoxy group in the alkoxyacyl group represented by Q may be a linear alkoxy group or a branched alkoxy group. The alkoxyacyl group represented by Q is preferably an alkoxyacyl group having 1 to 12 carbon atoms, and more preferably an alkoxyacyl group having 1 to 6 carbon atoms. Examples of the alkoxyacyl group having 1 to 12 carbon atoms include a methoxyacyl group (namely, methoxycarbonyl group), ethoxyacyl group (namely, ethoxycarbonyl group), butoxyacyl group (namely, butoxycarbonyl group), tert- Butoxyacyl group (ie butoxycarbonyl group), pentyloxyacyl group (ie pentyloxycarbonyl group), hexyloxyacyl group (ie hexyloxycarbonyl group), octyloxyacyl group (ie octyloxycarbonyl group), and A dodecyloxyacyl group (that is, a dodecyloxycarbonyl group) may be mentioned.

In the formula (1), Q is preferably a halogen atom, hydroxy group, alkyl group, aryl group, heterocyclic group, acyl group, amino group, —ZY group, alkoxy group, carboxy group, or alkoxyacyl group. And more preferably a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an acyl group, an amino group, a carboxy group, or an alkoxyacyl group, and particularly preferably an alkyl group or an alkoxy group.

Preferable combinations of P and Q in the formula (1) include an embodiment in which a group group arbitrarily selected from the following (a) and a group group arbitrarily selected from the following (b) are combined.
(A) P is preferably a hydrogen atom, a hydroxy group, an alkyl group, an acyl group, an amino group, or a —ZY group, and more preferably a hydrogen atom, an alkyl group, or a —ZY group. And particularly preferably a hydrogen atom or a —ZY group.
(B) Q is preferably a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an acyl group, an amino group, a carboxy group, or an alkoxyacyl group, and more preferably an alkyl group or an alkoxy group.

More preferable combinations of P and Q in the formula (1) include an embodiment in which a group of groups arbitrarily selected from the following (a) and a group of groups arbitrarily selected from the following (b) are combined.
(A) P is preferably a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, an amino group, or a -ZY group, and Z is An alkylene group having 1 or 2 carbon atoms, which may be substituted with a carboxy group, Y is a hydroxy group, a carboxy group, or a dialkylamino group having 1 to 10 carbon atoms in each alkyl group; Preferably, it is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a -ZY group, and Z is an alkylene group having 1 or 2 carbon atoms, which may be substituted with a carboxy group, Y is a dialkylamino group having 1 to 10 carbon atoms in each alkyl group, more preferably a hydrogen atom or a -ZY group, and Z is a carbon that may be substituted with a carboxy group. An alkylene group having a number of 1 or 2, and Y is A dialkylamino group having 1 to 10 carbon atoms in the alkyl group, particularly preferably a hydrogen atom or a -ZY group, and Z is an unsubstituted alkylene group having 1 or 2 carbon atoms. , Y is a dialkylamino group having 1 to 10 carbon atoms in each alkyl group.
(B) Q is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, an amino group, an alkoxy group having 1 to 6 carbon atoms, a carboxy group Or an alkoxyacyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

In the formula (1), n represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

In the present disclosure, the benzotriazole compound may be used alone or in combination of two or more.

The content of the benzotriazole compound is preferably 0.01% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer, and more preferably from the viewpoint of transferability, shape reproducibility, and linearity. It is 0.05 mass% to 10 mass%, more preferably 0.05 mass% to 2 mass%, and particularly preferably 0.05 mass% to 1 mass%.

The mass ratio of the content of the benzotriazole compound to the content of the following polymer is preferably 0.001 to 0.1, more preferably 0.001 to 0, from the viewpoint of shape reproducibility and linearity. .05, particularly preferably 0.001 to 0.01.

The mass ratio of the content of the benzotriazole compound to the content of the structural unit having a group in which the acid group in the photosensitive resin layer is protected with an acid-decomposable group is preferable from the viewpoint of shape reproducibility and linearity. Is 0.003 to 0.3, more preferably 0.003 to 0.15, and particularly preferably 0.003 to 0.03.

The mass ratio of the content of the benzotriazole compound to the content of the photoacid generator is preferably 0.01 to 5, more preferably 0.01 to 0.8 from the viewpoint of shape reproducibility and linearity. Particularly preferred is 0.05 to 0.3.

(Polymer)
The photosensitive resin layer in the present disclosure includes a polymer (hereinafter referred to as “polymer A”) having a structural unit having a group in which an acid group is protected by an acid-decomposable group and having a glass transition temperature of 90 ° C. or less. May be referred to)).

(Structural unit having an acid group protected with an acid-decomposable group)
The polymer A includes a structural unit having a group in which an acid group is protected with an acid-decomposable group.

Examples of the acid group in the group in which the acid group is protected with an acid-decomposable group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxy group, and a sulfonylimide group. The acid group in the group in which the acid group is protected with an acid-decomposable group is preferably at least one acid group selected from the group consisting of a carboxy group and a phenolic hydroxy group.
The acid-decomposable group in the group in which the acid group is protected with an acid-decomposable group is not limited as long as it can be eliminated by the action of an acid, and a known acid-decomposable group can be used. Examples of the acid-decomposable group include an acid-decomposable group that protects an acid group by forming a skeleton such as ester, acetal, or ether. Specific examples of the acid-decomposable group include a tert-butyl group, a benzyl group, a methoxymethyl group, and a tetrahydropyranyl group. The acid-decomposable group is preferably an acid-decomposable group that protects the acid group by forming an acetal structure.

The structural unit having an acid group protected by an acid-decomposable group is preferably a structural unit represented by the following formula (A1) from the viewpoint of sensitivity and resolution. The structural unit represented by the formula (A1) is a structural unit having a group in which a carboxy group that is an acid group is protected by an acid-decomposable group.

In the formula (A1), the alkyl group represented by R ³¹ and R ³² is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, iso-propyl group, butyl group, tert-butyl group, hexyl group, cyclohexyl group, octyl group, and decyl group. It is done.

In the formula (A1), the aryl group represented by R ³¹ and R ³² is preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, particularly preferably Is a phenyl group. The aryl group may be a monocyclic aryl group or a condensed ring aryl group. Examples of the aryl group having 1 to 18 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, and a terphenyl group.

In formula (A1), R ³¹ and R ³² are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In formula (A1), R ³³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
In the formula (A1), examples of the alkyl group having 1 to 10 carbon atoms represented by R ³³ include a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, a tert-butyl group, a hexyl group, Examples include a cyclohexyl group, an octyl group, and a decyl group.
In the formula (A1), the aryl group represented by R ³³ is preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may be a monocyclic aryl group or a condensed ring aryl group. Examples of the aryl group having 1 to 18 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, and a terphenyl group.

In formula (A1), R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, and preferably linked to form a cyclic ether. The number of ring members of the cyclic ether is not limited, and is preferably 5 or 6, more preferably 5.

In the formula (A1), R ³⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature of the polymer A can be further lowered.

In the formula (A1), the content of the structural unit in which R ³⁴ is a hydrogen atom is preferably 20% by mass or more based on the total mass of the structural unit having a group in which an acid group is protected by an acid-decomposable group. .
In the formula (A1), the content of the structural unit in which R ³⁴ is a hydrogen atom can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. .

In Formula (A1), X ⁰ represents a single bond or a linking group, and preferably a single bond. The linking group represented by X ⁰ is preferably an alkylene group, an arylene group, —C (═O) O—, —C (═O) NR ^N —, —O—, or a combination thereof. An alkylene group or an arylene group is more preferable, and an arylene group is particularly preferable. ^RN represents an alkyl group or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a hydrogen atom.

Specific examples of the structural unit represented by the formula (A1) include the following structural units. R ³⁴ represents a hydrogen atom or a methyl group.

Among the structural units represented by the formula (A1), the structural unit represented by the following formula (A2) is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.

In the formula (A2), R ³⁴ represents a hydrogen atom or a methyl group, and R ³⁵ to R ⁴¹ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula (A2), R ³⁴ is preferably a hydrogen atom. In the formula (A2), R ³⁵ to R ⁴¹ are preferably hydrogen atoms.

The structural unit having an acid group protected by an acid-decomposable group is preferably a structural unit represented by the following formula (A3) from the viewpoint of suppressing deformation of the pattern shape. The structural unit represented by the formula (A3) is a structural unit having a group in which a phenolic hydroxy group which is an acid group is protected with an acid-decomposable group.

In formula (A3), R ^B1 and R ^B2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of R ^B1 and R ^B2 is an alkyl group or an aryl group , R ^B3 represents an alkyl group or an aryl group, and R ^B1 or R ^B2 and R ^B3 may be linked to form a cyclic ether, R ^B4 represents a hydrogen atom or a methyl group, X ^B represents a single bond or a divalent linking group, R ^B12 represents a substituent, and n represents an integer of 0 to 4.

In formula (A3), the alkyl group in R ^B1 and R ^B2 has the same meaning as the alkyl group represented by R ³¹ and R ³² in formula (A1), and the preferred range is also the same.

In formula (A3), the aryl group in R ^B1 and R ^B2 has the same meaning as the aryl group represented by R ³¹ and R ³² in formula (A1), and the preferred range is also the same.

In formula (A3), R ^B1 and R ^B2 are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In formula (A3), R ^B3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

In formula (A3), R ^B1 or R ^B2 and R ^B3 may be linked to form a cyclic ether, or R ^B1 or R ^B2 and R ^B3 may be linked to form a cyclic ether. preferable. The number of ring members of the cyclic ether is not limited and is preferably 5 or 6, and more preferably 5.

In formula (A3), R ^B4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature of the polymer A can be further lowered.

In the formula (A3), the content of the structural unit in which R ^B4 is a hydrogen atom is preferably 20% by mass or more based on all structural units having a group in which an acid group is protected with an acid-decomposable group.
In the formula (A3), the content of the structural unit in which R ^B4 is a hydrogen atom can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. .

In the formula (A3), X ^B represents a single bond or a divalent linking group, and preferably a single bond, an alkylene group, —C (═O) O—, —C (═O) NR ^N —, —O— or a combination thereof, and more preferably a single bond. The alkylene group may be linear, may have a branch or a cyclic structure, and may have a substituent. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. ^RN represents an alkyl group or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a hydrogen atom. When X ^B contains —C (═O) O—, an embodiment in which the carbon atom contained in —C (═O) O— and the carbon atom bonded to R ^B4 are directly bonded is preferable. When ^{containing, -C (= O) NR N} - - is ^{X B -C (= O) NR} N and carbon atoms contained in ^a mode in which the carbon atom ^{to which R B4} is bonded is directly bonded is preferable.

In the formula (A3), the group containing R ^B1 to R ^B3 (that is, —OCR ^B1 R ^B2 (OR ^B3 )) and X ^B are preferably bonded to each other at the para position.

In formula (A3), R ^B12 represents a substituent, preferably an alkyl group or a halogen atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 4.

In the formula (A3), n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

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

In formula (A4), R ^B4 represents a hydrogen atom or a methyl group, R ^B5 to R ^B11 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^B12 represents Represents a substituent, and n represents an integer of 0 to 4.

In formula (A4), R ^B4 is preferably a hydrogen atom.
In formula (A4), R ^B5 to R ^B11 are preferably hydrogen atoms.
In formula (A4), R ^B12 represents a substituent, preferably an alkyl group or a halogen atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 4.
In formula (A4), n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

Preferable specific examples of the structural unit represented by the formula (A4) include the following structural units. R ^B4 represents a hydrogen atom or a methyl group.

In the present disclosure, the structural unit having a group in which an acid group is protected by an acid-decomposable group may be used alone or in combination of two or more.

The content of the structural unit having a group in which the acid group in the polymer A is protected with an acid-decomposable group is preferably 20% by mass or more, more preferably 20% by mass with respect to the total mass of the polymer A. % To 90% by mass, more preferably 20% to 70% by mass, and particularly preferably 20% to 50% by mass. The content of the structural unit having a group in which the acid group in the polymer A is protected with an acid-decomposable group can be confirmed by the intensity ratio of peak intensity calculated by ¹³ C-NMR measurement by a conventional method. it can.

(Other structural units)
-Constitutional unit in which pKaH has 3 or more groups-
The polymer A can further include a structural unit having a pKaH group of 3 or more. The polymer A further includes a structural unit having a pKaH group of 3 or more, thereby suppressing excessive diffusion of the acid generated from the photoacid generator, and resulting from the tailing of the resin pattern during development. The decline in sex can be suppressed. Further, the polymer A further includes a structural unit having a pKaH group of 3 or more, so that the resin obtained even when the photosensitive transfer material is developed after a certain amount of time has passed after exposure. Thinning of the line width of the pattern or the like can be suppressed (hereinafter, sometimes referred to as “retention time dependency suppression”).

In the present disclosure, “pKaH” refers to the pKa of a conjugate acid.
In the present disclosure, the “group having a pKaH of 3 or more” refers to a group having a pKa of a conjugate acid of the group of 3 or more. For example, the pKaH value of “—NH ₂ ” is the pKa value of “—NH ₃ ⁺ ”. Here, the value of “pKaH” is a calculated value obtained by ACD / ChemSketch (ACD / Labs 8.00 Release Product Version 8.08). Specifically, from the chemical structure of the structural unit having a specific functional group, the above-mentioned ACD / ChemSketch is used to calculate the pKaH value of the specific functional group.

The group having a pKaH of 3 or more is preferably a group having a pKaH of 4 or more, more preferably a group having a pKaH of 5 or more, and a pKaH of 5 or more from the viewpoint of resolution and retention time-dependent inhibition. More preferably, it is a group of 15 or less, and particularly preferably a group having a pKaH of 6 or more and 10 or less. In other words, the polymer A preferably includes a structural unit having a pKaH of 4 or more, more preferably includes a structural unit having a pKaH of 5 or more, and a group having a pKaH of 5 or more and 15 or less. It is more preferable to include a structural unit, and it is particularly preferable to include a polymer A having at least a structural unit having a pKaH group of 6 to 10.

The group having pKaH of 3 or more is preferably a group having a nitrogen atom from the viewpoint of resolution and retention time-dependent suppression, and is an aliphatic amino group, aromatic amino group, or nitrogen-containing heteroaromatic ring. It is more preferably a group, more preferably an aliphatic amino group or a nitrogen-containing heteroaromatic group, and particularly preferably an aliphatic amino group.
The aliphatic amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group, but from the viewpoint of resolution and retention time-dependent suppression, A primary amino group or a tertiary amino group is preferred.
The aromatic amino group is preferably an anilino group, a monoalkylanilino group, or a dialkylanilino group, and more preferably a monoalkylanilino group or a dialkylanilino group.
The nitrogen-containing heteroaromatic ring in the nitrogen-containing heteroaromatic group is preferably a pyridine ring, an imidazole ring, or a triazole ring, more preferably a pyridine ring or an imidazole ring, and particularly preferably a pyridine ring. preferable.
The nitrogen-containing heteroaromatic group may further have a substituent on the nitrogen-containing heteroaromatic ring. The substituent is not particularly limited, but is preferably an alkyl group, and more preferably a methyl group.

In addition, the group having a pKaH of 3 or more is particularly preferably a group having an alkylamine structure from the viewpoint of resolution and retention time-dependent suppression.
Examples of the alkylamine structure include dialkylamine and trialkylamine. Specifically, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, 1,2,2,6,6- Examples thereof include a pentaalkyl-4-piperidyl group and a 2,2,6,6-tetraalkyl-4-piperidyl group.
Preferred examples of the monomer that forms the structural unit having the alkylamine structure include the following.

The structural unit having a pKaH group of 3 or more is preferably a structural unit represented by the following formula (B1) or formula (B2) from the viewpoints of resolution and retention time-dependent inhibition properties. The structural unit represented by (B1) is more preferable.

In formulas (B1) and (B2), R ¹ represents a hydrogen atom or a methyl group, and Z represents a single bond, a methylene group, an arylene group, —O—, —C (═O) —NH—, or —C (═O) —O—, wherein R ² is a single bond or at least one selected from the group consisting of an ether bond, a urethane bond, a urea bond, an amide bond, an ester bond, and a carbonate bond. Represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms which may have a group, and R ³ and R ⁴ each independently represents a hydrogen atom, an ether bond or a thioether bond. , A hydroxyl group, a formyl group, an acetoxy group, a cyano group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond, and at least one group selected from the group consisting of aromatic groups Yo Represents a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ² and R ³ , R ² and R ⁴ , or R ³ and R ⁴ are bonded to each other to form a ring. Q ¹ represents an aromatic group having a nitrogen atom or a nitrogen-containing heteroaromatic group.

Z in the formula (B1) is a single bond, an arylene group, —C (═O) —NH—, or —C (═O) — from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. It is preferably O—, more preferably an arylene group, —C (═O) —NH—, or —C (═O) —O—, —C (═O) —NH—, or — Particularly preferred is C (═O) —O—.
Z in the formula (B2) is preferably a single bond, an arylene group, or —C (═O) —O— from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. More preferably.
R ² in Formula (B1) has at least one group selected from the group consisting of an ether bond, a urethane bond, and a urea bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. It is preferably a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms which has at least one group selected from the group consisting of an ether bond, a urethane bond and a urea bond. It is more preferably a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms, particularly a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms. preferable.
R ² in Formula (B2) is preferably a single bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis.

R ³ and R ⁴ in the formula (B1) are each independently a hydrogen atom or carbon that may have an ether bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. It is preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. .
Further, in the formula (B1), R ² , R ³ and R ⁴ in the formula (B1) are bonded to form a nitrogen-containing aliphatic ring from the viewpoint of resolution and retention time-dependent suppression. An embodiment is preferred, and an embodiment in which a piperidine ring is formed is more preferred.
Q ¹ in formula (B2) is preferably a nitrogen-containing heteroaromatic group from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis, and includes a pyridyl group, a methylpyridyl group, an imidazolyl group, a methyl group. It is more preferably an imidazolyl group or a triazolyl group, further preferably a pyridyl group, and particularly preferably a 4-pyridyl group.

Examples of the structural unit in which pKaH has a group of 3 or more are derived from the structural unit described in paragraph 0140 of JP-A-2015-187634 and the monomers described in paragraphs 0068 to 0070 of JP-A-2011-039266. A structural unit is mentioned.

Examples of the monomer that forms a structural unit having a pKaH group of 3 or more include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2- (dimethylamino) ethyl methacrylate, acrylic acid 2 , 2,6,6-Tetramethyl-4-piperidyl, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, methacrylic acid 2- (diethylamino) ethyl, 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate, N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino) propyl acrylate, methacrylate 2- (diisopropylamino) ethyl acid, 2-morpholinoethyl methacrylate, 2-morpholinoethyl acrylate, N- [3- (dimethylamino) propyl] acrylamide, allylamine, 4-aminostyrene, 4-vinylpyridine, 2- Examples include vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, and 1-vinyl-1,2,4-triazole.

In addition, monomers having an amino group or a nitrogen-containing heterocyclic group described in JP-A-2015-187634 or JP-A-2011-39266 are also included.

The content of the structural unit having a pKaH group of 3 or more in the polymer A is preferably 0.01 mass with respect to the total mass of the polymer A from the viewpoint of resolution and retention time-dependent suppression. % To 30% by mass, more preferably 0.05% to 20% by mass, still more preferably 0.1% to 10% by mass, and particularly preferably 0.4% to 4% by mass. Most preferably, it is 0.6 mass% to 2 mass%.

-Structural unit having an acid group-
The polymer A can further include a structural unit having an acid group. When the polymer A further includes a structural unit having an acid group, the photosensitive resin layer in the present disclosure has good sensitivity at the time of pattern formation, and is easily dissolved in an alkaline developer in the development step after pattern exposure. Development time can be shortened.

The acid group is incorporated into the polymer A as a structural unit having an acid group using, for example, a monomer capable of forming an acid group. The introduction of the structural unit having an acid group into the polymer A is, for example, by copolymerizing a monomer having an acid group, copolymerizing a monomer having an acid anhydride structure, and hydrolyzing the acid anhydride. It can be carried out.

From the viewpoint of improving sensitivity, the upper limit of the pKa of the acid group is preferably 10 or less, more preferably 6 or less. Further, the lower limit of the pKa of the acid group is preferably −5 or more.

Examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxy group, and a sulfonylimide group. Among these, at least one acid group selected from the group consisting of a carboxy group and a phenolic hydroxy group is preferable.

The structural unit having an acid group is more preferably a structural unit derived from a styrene compound, a structural unit obtained by introducing an acid group into a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid. .

In the present disclosure, the structural unit having an acid group may be used alone or in combination of two or more.

The content of the structural unit having an acid group in the polymer A is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass with respect to the total mass of the polymer A. % By mass, particularly preferably 1% by mass to 10% by mass. When the content of the structural unit having an acid group is within the above range, the pattern formability is further improved. The content of the structural unit having an acid group can be confirmed by the intensity ratio of the peak intensity calculated by ¹³ C-NMR measurement by a conventional method.

-Other structural units-
The polymer A can further contain a constituent unit other than the constituent units described above (hereinafter, may be referred to as “constituent unit Z”) as long as the effects of the photosensitive transfer material of the present disclosure are not impaired. . Various characteristics of the polymer A can be adjusted by adjusting at least one of the type and content of the structural unit Z. In particular, the glass transition temperature of the polymer A can be easily adjusted by appropriately using the structural unit Z. By setting the glass transition temperature of the polymer A to 90 ° C. or lower, the photosensitive resin layer containing the polymer A can maintain the transferability and the peelability from the temporary support at a good level while forming a pattern. Better resolution and sensitivity.

Examples of the structural unit Z include styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, Mention may be made of unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated dicarboxylic acid anhydrides. Specific examples of the structural unit Z include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meta ) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth And a structural unit formed by polymerizing benzyl acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, or cyclohexyl (meth) acrylate. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be given.

As the structural unit Z, a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical characteristics of the obtained transfer material. Specific examples of the monomer that forms the structural unit Z include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl ( Examples include meth) acrylate and benzyl (meth) acrylate. Among these, as the structural unit Z, a structural unit derived from cyclohexyl (meth) acrylate is preferable.

Further, as the monomer forming the structural unit Z, for example, (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.

In the present disclosure, the structural unit Z may be used alone or in combination of two or more.

The upper limit of the content of the structural unit Z in the polymer A is preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass with respect to the total mass of the polymer A. It is as follows. The lower limit of the content of the structural unit Z may be 0% by mass or more with respect to the total mass of the polymer A, preferably 1% by mass or more, and more preferably 5% by mass or more. When the content of the structural unit Z is within the above range, the resolution and adhesion are further improved. The content of the structural unit Z can be confirmed by the intensity ratio of peak intensity calculated by ¹³ C-NMR measurement by a conventional method.

Hereinafter, although the preferable example of the polymer A in this indication is given, this indication is not restrict | 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.

In the present disclosure, the polymer A may be used alone or in combination of two or more.

The content of the polymer A in the photosensitive resin layer is preferably 50% by mass to 99.9% with respect to the total mass of the photosensitive resin layer, from the viewpoint of developing good adhesion to the transfer target. % By mass, more preferably 70% by mass to 98% by mass.

(Glass transition temperature: Tg)
The glass transition temperature (Tg) of the polymer A is 90 ° C. or less. When the glass transition temperature of the polymer A is 90 ° C. or less, shape reproducibility, linearity, and adhesion of the photosensitive resin layer to the transfer target are improved.

The upper limit of the glass transition temperature (Tg) of the polymer A is preferably 60 ° C. or less, more preferably 40 ° C., from the viewpoints of shape reproducibility, linearity, and adhesion of the photosensitive resin layer to the transfer target. It is as follows.
The lower limit of the glass transition temperature of the polymer A is not limited, and is preferably −20 ° C. or lower, more preferably −10 ° C. or higher. When the temperature is −20 ° C. or higher, good pattern formability is maintained, and, 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 A can be measured using differential scanning calorimetry (DSC). A specific measuring method can be performed in accordance with the method described in JIS K 7121 (1987). The glass transition temperature in the present disclosure uses an extrapolated glass transition start temperature (hereinafter sometimes referred to as Tig).
Hereinafter, the measuring method of the glass transition temperature of the polymer A will be described more specifically.
When determining the glass transition temperature, after maintaining the apparatus at a temperature about 50 ° C. lower than the Tg of the expected polymer A until the apparatus is stabilized, the heating rate is about 20 ° C./minute, and is about the temperature at which the glass transition is completed. Heat to a temperature 30 ° C higher and draw a DTA or DSC curve.
The extrapolated glass transition start temperature, that is, the glass transition temperature in the present disclosure, has a maximum slope of a straight line obtained by extending the base line on the low temperature side in the DTA curve or DSC curve to the high temperature side and the curve of the stepped change portion of the glass transition. Calculated as the temperature of the intersection with the tangent drawn at the point.

Examples of a method for adjusting the glass transition temperature of the polymer A to the above-described preferable range include a method using the FOX formula as a guide. According to the FOX formula, the glass transition temperature of the target polymer A can be estimated from the glass transition temperature of the homopolymer of each constituent unit of the target polymer A and the mass ratio of each constituent unit. It is.
The FOX formula will be described below using a polymer containing a first structural unit and a second structural unit as an example.
The glass transition temperature of the homopolymer of the first structural unit is Tg1, the mass fraction of the first structural unit in the polymer is W1, the glass transition temperature of the homopolymer of the second structural unit is Tg2, When the mass fraction of the second structural unit in the coalescence is W2, and the glass transition temperature of the polymer containing the first structural unit and the second structural unit is Tg0, Tg0 is in accordance with the following FOX formula: It is possible to estimate. The unit of glass transition temperature used in the FOX formula is Kelvin (K).
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)
As described above, a polymer having a desired glass transition temperature can be obtained by adjusting the type and mass fraction of each structural unit contained in the polymer A using the FOX formula.
It is also possible to adjust the glass transition temperature of the polymer A by adjusting the weight average molecular weight of the polymer A.

(Weight average molecular weight: Mw)
The weight average molecular weight (Mw) of the polymer A is a polystyrene equivalent weight average molecular weight, preferably 60,000 or less, more preferably 2,000 to 60,000, and particularly preferably 3,000 to 50. , 000. When the polymer A has a weight average molecular weight of 60,000 or less, the melt viscosity of the photosensitive resin layer is kept low, and bonding at a low temperature (for example, 130 ° C. or less) is realized when bonding to the transfer target. can do.

The weight average molecular weight and number average molecular weight (Mn) of the polymer A can be measured by gel permeation chromatography (GPC). Various commercially available apparatuses can be used as the measuring apparatus, and the contents of the apparatus and measuring techniques are known to those skilled in the art.
For the measurement of the weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by Tosoh Corp.) was used as a measuring device, and TSKgel (registered trademark) Super HZM-M (4 .6 mmID × 15 cm, manufactured by Tosoh Corporation), Super HZ4000 (4.6 mmID × 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mmID × 15 cm, manufactured by Tosoh Corporation), and Super HZ2000 (4. 6 mm ID × 15 cm, manufactured by Tosoh Corporation), one each connected in series, and THF (tetrahydrofuran) can be used as an eluent. Further, the measurement conditions are as follows: the sample concentration is 0.2% by 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” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It can be created using any of the seven samples “A-2500” and “A-1000”.

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

(Method for producing polymer)
The manufacturing method of the polymer A is not restrict | limited, The polymer A can be synthesize | combined by superposing | polymerizing the polymerizable monomer for forming each said structural unit based on a well-known method. For example, in an organic solvent containing a polymerizable monomer for forming a structural unit having a group in which an acid group is protected with an acid-decomposable group, and further, if necessary, a polymerizable monomer for forming the structural unit Z, It can synthesize | combine by superposing | polymerizing using a polymerization initiator. It can also be synthesized by a so-called polymer reaction.

[Photoacid generator]
The photosensitive resin layer in the present disclosure contains a photoacid generator.

The photoacid generator is not limited as long as it is a compound capable of generating an acid by irradiation with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams, and a known photoacid generator is used. Can do.

As the photoacid generator, a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 nm to 450 nm and generates an acid is preferable, but its chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.

The photoacid generator is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a light that generates an acid having a pKa of 2 or less. Acid generators are particularly preferred. The lower limit value of pKa is not particularly defined, but is preferably −10 or more, for example.

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

Examples of the nonionic photoacid generator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, an oxime sulfonate compound is preferable from the viewpoints of sensitivity, resolution, and adhesion. Specific examples of trichloromethyl-s-triazines and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP 2011-212494A.

As the oxime sulfonate compound, a compound represented by the following formula (L1) is preferable.

In Formula (L1), R ²¹ represents an alkyl group or an aryl group, and * represents a bonding site with another atom or another group. In the compound having an oxime sulfonate structure represented by the formula (L1), any group may be substituted. The alkyl group represented by R ²¹ may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. The alkyl group represented by R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R ²¹ may be substituted with an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group, or a halogen atom. Here, the cycloalkyl group includes a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group. The cycloalkyl group is preferably a bicycloalkyl group.

The aryl group represented by R ²¹ is preferably an aryl group having 6 to 18 carbon atoms, more preferably a phenyl group or a naphthyl group.
The aryl group represented by R ²¹ may be substituted with at least one group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom.

The compound represented by the formula (L1) is also preferably a compound represented by the following formula (L2).

In the formula (L2), 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 When X is 3, the plurality of X ¹⁰ may be the same or different.

The alkyl group represented by X ¹⁰ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X ¹⁰ is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X ¹⁰ is preferably a chlorine atom or a fluorine atom. m4 is preferably 0 or 1. In the formula (L2), 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 represented by the formula (L1) is also preferably a compound represented by the following formula (L3).

In the formula (L3), R ⁴³ represents an alkyl group or an aryl group, X ¹¹ represents a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and n4 represents an integer of 0 to 5.

In the formula (L3), R ⁴³ is preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, or perfluoro-n-propyl. Group, perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group, or pentafluorophenyl group, more preferably n-octyl group.
In the formula (L3), X ¹¹ is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group.
In the formula (L3), n4 is preferably an integer of 0 to 2, more preferably 0 or 1.

Examples of the compound represented by the formula (L3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) benzyl cyanide. Nido, 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, and α-[(4-to En sulfonyl) -4-methoxyphenyl] include acetonitrile.

Specific examples of preferable oxime sulfonate compounds include the following compounds (i) to (viii), and the like may be used alone or in combination of two or more. 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 represented by the formula (L1) is also preferably a compound represented by the following formula (OS-1).

In the 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 a heteroaryl group Represents.
In formula (OS-1), R ⁴¹² represents an alkyl group or an aryl group.
In the formula (OS-1), X ⁴⁰¹ represents —O—, —S—, —NH—, —NR ⁴¹⁵ —, —CH ₂ —, —CR ⁴¹⁶ H—, or —CR ⁴¹⁵ R ⁴¹⁷ —.
In formula (OS-1), R ⁴¹⁵ to R ⁴¹⁷ each independently represents an alkyl group or an aryl group.
In the formula (OS-1), R ⁴²¹ to R ⁴²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, An amide group, a sulfo group, a cyano group, or an aryl group is represented. Two of R ⁴²¹ to R ⁴²⁴ may be bonded to each other to form a ring.
In the formula (OS-1), R ⁴²¹ to R ⁴²⁴ are preferably each independently a hydrogen atom, a halogen atom, or an alkyl group, and more preferably a hydrogen atom. An embodiment in which at least two of R ⁴²¹ to R ⁴²⁴ are bonded to each other to form an aryl group is also preferable.

Preferable specific examples of the compound represented by the formula (OS-1) include compounds described in paragraphs 0128 to 0132 of JP2011-212494A (exemplary compounds b-1 to b-34). However, it is not limited to these.

As the compound represented by the formula (L1), the compound represented by the following formula (OS-3), the compound represented by the formula (OS-4), or the formula (OS-5) A compound is preferred.

In the formulas (OS-3) to (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, or an alkyloxy group. Represents 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, and n1 to n3 each independently represents 1 or 2 M1 to m3 each independently represents an integer of 0 to 6.

In formulas (OS-3) to (OS-5), the alkyl group, aryl group, or heteroaryl group represented by 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 is preferably an alkyl group having 1 to 30 carbon atoms.
In the formulas (OS-3) to (OS-5), the aryl group represented by R ²² , R ²⁵ , and R ²⁸ is preferably an aryl group having 6 to 30 carbon atoms.
In the formulas (OS-3) to (OS-5), the heteroaryl group represented by R ²² , R ²⁵ and R ²⁸ is preferably a heteroaryl group having 4 to 30 carbon atoms. In the formulas (OS-3) to (OS-5), the heteroaryl group represented by R ²² , R ²⁵ , and R ²⁸ suffices if at least one ring is a heteroaromatic ring. The ring and the benzene ring may be condensed.

In formulas (OS-3) to (OS-5), R ²³ , R ²⁶ and R ²⁹ are each independently preferably a hydrogen atom, an alkyl group or an aryl group, and a hydrogen atom or an alkyl group It is more preferable that

In Formula (OS-3) to Formula (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ present in each 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 represented by R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

The aryl group represented by R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 carbon atoms.

In the formulas (OS-3) to (OS-5), X ¹ to X ³ each independently represents O or S, preferably O.
In 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 represents 1 or 2, and when X1 to X3 are O, n1 to n3 are each independently In addition, when X1 to X3 are S, it is preferable that n1 to n3 are each independently 2.

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 Represents an alkoxysulfonyl group. Among these, 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 represented by R ²⁴ , R ²⁷ , and R ³⁰ may have a substituent.

In the formulas (OS-3) to (OS-5), the alkyl group represented by R ²⁴ , R ²⁷ , and R ³⁰ is preferably an alkyl group having 1 to 30 carbon atoms.

In formulas (OS-3) to (OS-5), the alkyloxy groups represented by R ²⁴ , R ²⁷ and R ³⁰ are preferably alkyloxy groups having 1 to 30 carbon atoms.

In the formulas (OS-3) to (OS-5), m1 to m3 each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, particularly preferably 0.
Further, with respect to the substituents of the formulas (OS-3) to (OS-5), the formulas (OS-3) to (OS-5) described in paragraphs 0092 to 0109 of JP2011-221494A are disclosed. The preferred range of substituents of

The compound containing an oxime sulfonate structure represented by the formula (L1) is particularly preferably an oxime sulfonate compound represented by any of the following formulas (OS-6) to (OS-11).

In the formulas (OS-6) to (OS-11), R ³⁰¹ to R ³⁰⁶ each independently represents an alkyl group, an aryl group, or a heteroaryl group, and R ³⁰⁷ represents a hydrogen atom or a bromine atom R ³⁰⁸ to R ³¹⁰ , R ³¹³ , R ³¹⁶ , and R ³¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, or 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 represents a hydrogen atom or a methyl group.

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

Specific examples of the oxime sulfonate compounds represented by the formulas (OS-3) to (OS-5) include the compounds described in paragraphs 0114 to 0120 of JP2011-221494A. The form is not limited to these.

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

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

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

[Other polymers]
The photosensitive resin layer in the present disclosure is a polymer that does not contain a structural unit having a group in which an acid group is protected by an acid-decomposable group, as long as the effect of the photosensitive transfer material of the present disclosure is not impaired. It may be referred to as a “polymer of”).

The structural unit contained in the other polymer is not limited as long as the structural unit is a structural unit other than the structural unit having an acid group protected by an acid-decomposable group. For example, the structural unit having a pKaH of 3 or more. And a structural unit having an acid group.

As another polymer, for example, polyhydroxystyrene can be used. Commercially available products include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON. UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncry 690, Joncry 678, Joncry 67, and Joncry 586 (above, BASF) can also be used. .

In the present disclosure, other polymers may be used alone or in combination of two or more.

When the photosensitive resin layer contains another polymer, the content of the other polymer is preferably 50% by mass or less with respect to the total mass of the polymer A and the total mass of the other polymer. More preferably, it is 30 mass% or less, Most preferably, it is 20 mass% or less.

[Other ingredients]
(Amine compounds other than benzotriazole compounds)
The photosensitive resin layer in the present disclosure may further contain an amine compound other than the benzotriazole compound (hereinafter sometimes referred to as “amine compound”).

The amine compound is not limited as long as it does not have a benzotriazole skeleton, and a known amine compound can be used. Examples of amine compounds include trimethylamine, diethylamine, triethylamine, trioctylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine. , Dicyclohexylamine, dicyclohexylmethylamine, 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, quino , 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, 1,3-dimethylthiourea, trimethylthiourea, 1,3-dicyclohexylthiourea, and 1-cyclohexyl-3- (2-morpholinoethyl) thiourea.

The amine compound is preferably at least one compound selected from an aliphatic amine and an aromatic amine, and more preferably an aliphatic amine. The aliphatic amine is preferably an aliphatic amine having 1 to 30 carbon atoms, more preferably an aliphatic amine having 10 to 30 carbon atoms, and particularly preferably an aliphatic amine having 10 to 30 carbon atoms. It is at least one amine selected from secondary amines and tertiary aliphatic amines having 10 to 30 carbon atoms. Aliphatic amines and aromatic amines may contain atoms other than carbon and nitrogen atoms, for example, oxygen atoms or sulfur atoms. The aliphatic amine may be a chain amine compound or a cyclic amine compound.

In the present disclosure, amine compounds may be used alone or in combination of two or more.

The content of the amine compound is preferably 0.001% by mass to 5% by mass and more preferably 0.005% by mass to 3% by mass with respect to the total mass of the photosensitive resin layer.

(Surfactant)
The photosensitive resin layer in the present disclosure can further contain a surfactant from the viewpoint of film thickness uniformity.

As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used, and a nonionic surfactant is preferable.

Nonionic surfactants include, for example, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. Can be mentioned. In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (manufactured by Toray Dow Corning Co., Ltd.).

The surfactant preferably contains a structural unit X and a structural unit Y represented by the following formula (S1), and has a polystyrene equivalent weight measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A copolymer having an average molecular weight (Mw) of 1,000 to 10,000. The measurement of the weight average molecular weight by gel permeation chromatography is as described above.

In formula (S1), 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 hydrogen. Represents an atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10% by mass Represents a numerical value of ˜80% by mass, q represents a numerical value of 20% by mass to 90% by mass, r represents an integer of 1 to 18, s represents an integer of 1 to 10, and * represents other Represents a binding site to the structure of

In formula (S1), L is preferably a branched alkylene group represented by the following formula (S2). In the formula (S2), R ⁴⁰⁵ 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 with respect to the coated surface. Preferably, it is an alkyl group having 2 or 3 carbon atoms. The sum of p and q is preferably 100, that is, 100% by mass.

The weight average molecular weight (Mw) of the copolymer containing the structural unit X and the structural unit Y represented by the formula (S1) is preferably 1,500 to 5,000.

As the surfactant, surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362 can also be used.

In the present disclosure, the surfactant may be used alone or in combination of two or more.

The content of the surfactant in the photosensitive resin layer is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer. The content is particularly preferably 0.01% by mass to 3% by mass.

(solvent)
The photosensitive resin layer in the present disclosure may contain a solvent.

The solvent is not limited, and a known solvent can be used. Examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl. Examples include ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP2011-212494A, the contents of which are incorporated herein.

In addition to the solvents described above, 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, if necessary It may further contain a solvent such as 1-nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate.

In the present disclosure, the solvent may be used alone or in combination of two or more. When two or more solvents are used, for example, combined use of propylene glycol monoalkyl ether acetates and dialkyl ethers, combined use of diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates A combination with the above is preferred.

In addition, 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.
Examples of the solvent 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.). And propylene glycol methyl-n-propyl ether (boiling point 131 ° C.).
Examples of the solvent having a boiling point of 160 ° C. or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), 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 mono Ethyl ether acetate (boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), and 1,3-butylene glycol diacetate (boiling point) 32 ° C.) and the like.

The content of the solvent in the photosensitive resin layer is preferably 2% by mass or less, more preferably 1% by mass or less, and 0.5% by mass or less with respect to the mass of the photosensitive resin layer. It is particularly preferred.

(Plasticizer)
The photosensitive resin layer of the present disclosure can further contain a plasticizer for the purpose of improving plasticity.

The plasticizer preferably has a weight average molecular weight smaller than that of the 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 5,000, and particularly preferably 800 or more and less than 4,000 from the viewpoint of imparting plasticity.

The plasticizer is not particularly limited as long as it is a compound that is compatible with the above polymer and exhibits plasticity. However, from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

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

For example, even if the compound has an alkyleneoxy group having the above structure (hereinafter sometimes referred to as “compound X”), the photosensitive resin composition containing compound X does not contain compound X. When plasticity does not improve compared to the resin composition, it does not fall under the plasticizer in the present disclosure. For example, an optionally added surfactant is not used as an amount of plasticizer in the present disclosure because it is generally not used in an amount that brings plasticity to the photosensitive resin composition.

Examples of the plasticizer having an alkyleneoxy group having the above structure include compounds having the following structure, but are not limited thereto.

In the present disclosure, the plasticizer may be used alone or in combination of two or more.

The content of the plasticizer is preferably 1% by mass to 50% by mass and more preferably 2% by mass to 20% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of adhesion. .

(Other additives)
In addition to the above components, the photosensitive resin layer in the present disclosure includes a sensitizer, an alkoxysilane compound, metal oxide particles, an antioxidant, a dispersant, an acid proliferator, a development accelerator, a conductive fiber, a colorant, It may further contain known additives such as a thermal radical polymerization initiator, a thermal acid generator, an ultraviolet absorber, a thickener, a crosslinking agent, and an organic or inorganic precipitation inhibitor. Preferred embodiments of these additives are described in JP-A No. 2014-85643, paragraphs 0148 to 156, paragraphs 0165 to 0184, and paragraphs 0139 to 0141 of WO2015 / 092731, respectively. Is incorporated herein by reference.

[Average film thickness of photosensitive resin layer]
The lower limit of the average film thickness of the photosensitive resin layer is preferably 0.5 μm or more, more preferably 2.0 μm or more, and particularly preferably 5.0 μm or more from the viewpoint of transferability (laminability). . The upper limit of the average film thickness of the photosensitive resin layer is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 5 μm or less from the viewpoint of production suitability. Moreover, it is preferable to calculate the average film thickness of the photosensitive resin layer by measuring the thickness of 10 places of the photosensitive resin layer. Specific examples include surface shape measurement, cross-sectional optical microscope or electron microscope observation, and the like. In addition, Bruker's Dektak series can be suitably used for surface shape measurement. Moreover, a scanning electron microscope (SEM) can be used suitably for cross-sectional observation.

[Middle layer]
The photosensitive transfer material of the present disclosure preferably further includes an intermediate layer between the temporary support and the photosensitive resin layer from the viewpoint of shape reproducibility, linearity, and adhesiveness of the photosensitive resin layer.

The intermediate layer preferably contains a binder.
The binder is preferably a water-soluble or alkali-soluble binder, more preferably a water-soluble or alkali-soluble polymer. In the present disclosure, “water-soluble” means that the solubility in water at pH 7.0 at 25 ° C. is 0.1% by mass or more. In the present disclosure, “alkali-soluble” means that the solubility in an aqueous alkali solution having a pH of 8.5 or higher at 25 ° C. is 0.1% by mass or higher. In addition, the above “water-soluble or alkali-soluble” may be either water-soluble or alkali-soluble, or may be water-soluble and alkali-soluble.

Examples of the binder include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, or m- / p-mixed). Any may be used) novolak resin such as mixed formaldehyde resin, pyrogallol acetone resin, polyhydroxystyrene resin, modified cellulose resin, acrylic resin having a hydroxy group (for example, hydroxyalkyl (meth) acrylate homopolymer or copolymer), Starches, glycogens, chitins, agaroses, carrageenans, pullulans, gum arabic, soya gum, polyamide resin, epoxy resin, polyacetal resin, acrylic resin, polystyrene resin, polyester Urethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyethyleneimine, polyallylamine, and polyalkylene glycols.

Among the above, the binder is at least one selected from the group consisting of a novolak resin, a modified cellulose resin, and an acrylic resin having a hydroxy group, from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability. The resin is preferably at least one resin selected from the group consisting of a modified cellulose resin and an acrylic resin having a hydroxy group, and particularly preferably a modified cellulose resin.
The modified cellulose resin is preferably hydroxyalkylated cellulose from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation.
Preferred examples of the hydroxyalkylated cellulose include hydroxymethylcellulose, hydroxyethylcellulose, polyhydroxyethylated cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, glyoxalized hydroxypropylmethylcellulose, and hydroxypropylmethylcellulose phthalate.
Among these, from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability, it is preferably at least one resin selected from the group consisting of hydroxypropylcellulose and hydroxypropylmethylcellulose, and is hydroxypropylmethylcellulose. It is more preferable.
In addition, the binder is preferably at least one resin selected from the group consisting of polyvinyl alcohol and polyvinyl formal from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, and is polyvinyl alcohol. Is more preferable.

The weight average molecular weight of the binder is preferably 1,000 or more, more preferably from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in the developer after exposure, and transferability. Is from 2,000 to 100,000, particularly preferably from 10,000 to 50,000.

In the present disclosure, the binder contained in the intermediate layer may be used alone or in combination of two or more.

The content of the binder in the intermediate layer is based on the adhesiveness between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in the developer after exposure, and transferability, with respect to the total mass of the intermediate layer, It is preferably 10% by mass to 100% by mass, more preferably 20% by mass to 100% by mass, still more preferably 40% by mass to 100% by mass, and particularly preferably 65% by mass to 85% by mass. .

The intermediate layer preferably contains particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer.
The particles are preferably metal oxide particles or organic particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, and at least one selected from the group consisting of Si, Ti and Zr. More preferred are metal oxide particles containing elements or organic particles.
Note that the metal of the metal oxide particles in the present disclosure includes semimetals such as B, Si, Ge, As, Sb, and Te.

The intermediate layer may have two or more layers. When the intermediate layer has two or more layers, each layer preferably contains a water-soluble or alkali-soluble binder. In addition, when the intermediate layer has two or more layers, the particles may be contained in a plurality of layers, but from the viewpoint of adhesion between the intermediate layer and the photosensitive layer, the particles are contained in the layer in contact with the photosensitive layer. It is preferable.

The average film thickness of the intermediate layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation. Particularly preferred is 0.3 μm to 2 μm.
The measuring method of the average film thickness of an intermediate | middle layer is not restrict | limited, A well-known method can be used. The average film thickness of the intermediate layer is preferably calculated by measuring 10 points of the intermediate layer. Specific examples include surface shape measurement, cross-sectional optical microscope or electron microscope observation, and the like. In addition, Bruker's Dektak series can be suitably used for surface shape measurement. Moreover, a scanning electron microscope (SEM) can be used suitably for cross-sectional observation.
Moreover, it is preferable that the thickness of the said intermediate | middle layer is thinner than the thickness of the said photosensitive resin layer.

The method for forming the intermediate layer is not limited, and the intermediate layer can be easily formed on the temporary support by applying the intermediate layer-forming composition to the temporary support and drying it. The coating method is not limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.

The method for preparing the intermediate layer forming composition is not limited, and for example, the above-mentioned resin and solvent can be mixed at a predetermined ratio by an arbitrary method, and can be prepared by stirring and dissolving. For example, an intermediate layer-forming composition can be prepared by preparing a solution in which each of the above resins is previously dissolved in a solvent, and then mixing the obtained solution at a predetermined ratio. The intermediate layer-forming composition prepared as described above can be used after being filtered using a filter having a pore diameter of 5 μm. As the solvent used in the method for forming the intermediate layer, an aqueous solvent is preferable. Examples of the aqueous solvent include water and alcohols.

[Other layers]
The photosensitive transfer material of the present disclosure may have layers other than those described above (hereinafter, may be referred to as “other layers”).

Other layers include, for example, a cover film, a thermoplastic resin layer, and a contrast enhancement layer.

When the photosensitive transfer material of the present disclosure has other layers, the photosensitive transfer material should be produced according to the method for producing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138. Can do.
For example, when producing a photosensitive transfer material having a thermoplastic resin layer, a solution (thermoplastic resin layer coating solution) in which a thermoplastic organic polymer and an additive are dissolved on a temporary support is used. After applying and drying to provide a thermoplastic resin layer, a prepared liquid (composition for intermediate layer) was prepared by adding a resin and additives to a solvent that does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer And the intermediate layer is laminated. A photosensitive transfer material is suitably produced by applying a photosensitive resin composition prepared using a solvent that does not dissolve the intermediate layer on the formed intermediate layer, and drying and laminating the photosensitive resin layer. can do.

[Cover film]
The photosensitive transfer material of the present disclosure can have a cover film from the viewpoint of protecting the photosensitive resin layer.
Examples of the cover film include a resin film and paper, 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. The resin film is preferably a polyethylene terephthalate film, more preferably a biaxially stretched polyethylene terephthalate film.
The thickness of the cover film is not limited and is preferably 1 μm to 2,000 μm.

[Thermoplastic resin layer]
The photosensitive transfer material of the present disclosure can have a thermoplastic resin layer between the temporary support and the intermediate layer from the viewpoint of transferability.
Preferred embodiments of the thermoplastic resin layer are described in JP-A-2014-85643, paragraphs 0189 to 0193, and the contents of this publication are incorporated herein.
From the viewpoint of transferability, it is preferable that the thermoplastic resin layer contains at least one thermoplastic resin selected from the group consisting of acrylic resins and styrene / acrylic copolymers.

[Contrast enhancement layer]
The photosensitive transfer material according to the present disclosure can have a contrast enhancement layer.
The contrast enhancement layer (Contrast Enhancement Layer: CEL) has a large absorption with respect to the exposure wavelength before the exposure, but the absorption gradually decreases with the exposure, that is, a material (hereinafter referred to as “light transmittance”). This layer is sometimes referred to as a “photo-decolorable dye component”. Examples of the photodecolorable dye component include diazonium salts, stilbazolium salts, and arylnitroso salts. For example, a phenolic resin 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 social gathering, industrial research group ( 1989), Photopolymer Technology, Yamaoka, edited by Nagamatsu, Nikkan Kogyo Shimbun (1988).

<Circuit wiring manufacturing method>
A first embodiment of a circuit wiring manufacturing method using the photosensitive transfer material according to the present disclosure will be described.
The first embodiment of the method for producing circuit wiring includes a step of bonding the outermost layer on the photosensitive resin layer side of the temporary support of the photosensitive transfer material according to the present disclosure to the substrate (bonding step), A step of exposing the photosensitive resin layer of the photosensitive transfer material after the bonding step (exposure step), and a step of developing an exposed portion after the pattern exposure step to form a pattern (development step) And a step of etching the substrate in a region where the pattern is not disposed (etching step).
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 includes a base material and a plurality of conductive layers including a first conductive layer and a second conductive layer having different constituent materials from each other, on the surface of the base material. The photosensitive transfer material according to the present disclosure is exposed to a temporary support on a substrate on which the first conductive layer and the second conductive layer, which are the outermost surface layers, are laminated in order from the surface of the base material. A step of bonding the outermost layer on the side of the photosensitive resin layer to the first conductive layer (bonding step), and the photosensitive resin via the temporary support of the photosensitive transfer material after the bonding step A first exposure step for pattern exposure of the layer, and after peeling the temporary support from the photosensitive resin layer after the first exposure step, the exposed portion after the first exposure step is developed to form a first pattern The first developing step and the region where the first pattern is not disposed. A first etching step for etching at least the first conductive layer and the second conductive layer among the plurality of conductive layers, and a pattern different from the first pattern in the first pattern after the first etching step. A second exposure step of performing pattern exposure in the second step, a second development step of developing the first pattern after the second exposure step to form a second pattern, and the plurality of regions in a region where the second pattern is not disposed. A second etching step of etching at least the first conductive layer among the conductive layers in this order. As the second embodiment, International Publication No. 2006/190405 can be referred to, the contents of which are incorporated herein.

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

[Lamination process]
An example of the bonding process is schematically shown in FIG.
For example, as shown in FIG. 2A, first, in the bonding step, the substrate 22 and a plurality of conductive layers including the first conductive layer 24 and the second conductive layer 26 having different constituent materials are included. On the surface of the material 22 with respect to the substrate (circuit wiring forming substrate) 20 in which the first conductive layer 24 and the second conductive layer 26 which are the outermost surface layers are laminated in order from the surface of the base material 22, In the photosensitive transfer material 100 according to the present disclosure described above, the photosensitive resin layer 12 that is the outermost layer on the photosensitive resin layer side of the temporary support 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”.
In FIG. 2A, the outermost layer of the photosensitive transfer material 100 on the photosensitive resin layer side of the temporary support is a photosensitive resin layer, but other layers are formed on the photosensitive resin layer, and the outermost layer is formed. May be other layers.

As shown in FIG. 1, when the cover film 16 is provided on the photosensitive resin layer 12 of the photosensitive transfer material 100A, the cover film 16 is removed from the photosensitive transfer material 100A (photosensitive resin layer 12), and then the photosensitive film is formed. The photosensitive resin layer 12 of the conductive transfer material 100A is brought into contact with the first conductive layer 24 and bonded.

The bonding (transfer) of the photosensitive transfer material onto the first conductive layer is performed by stacking the 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. Are preferred. For laminating, for example, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of improving 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 according to the present disclosure 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 1.50 to 1.52.
The base material may be composed of a light-transmitting base material such as a glass base material, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. Further, as the above-mentioned transparent base material, 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). ), Polyethylene naphthalate, polycarbonate, triacetylcellulose, and cycloolefin polymers.

[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 according to the present disclosure, it is preferable that at least one of the plurality of conductive layers includes a metal oxide.
The conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition part used in a capacitive touch panel or a wiring of a peripheral extraction part.

[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, it is preferable that a film substrate such as PET is provided with a plurality of conductive layers such as metal oxide and metal.

[Exposure process (first exposure process)]
The exposure process is performed in the first embodiment, and the first exposure process is performed in the second embodiment. An example of the exposure process (first exposure process) is schematically shown in FIG.
For example, as shown in FIG. 2B, in the exposure step (first exposure step), the photosensitive resin layer 12 is subjected to pattern exposure via the temporary support 10 and the intermediate layer 14 of the photosensitive transfer material after the bonding step. .

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 can be suitably used in the present embodiment.

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 part of the lead-out wiring) 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, and a metal halide lamp are mentioned.
The exposure dose is preferably 5 mJ / cm ² to 200 mJ / cm ² , and more preferably 10 mJ / cm ² to 100 mJ / cm ² .
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.

In addition, even if pattern exposure performs after peeling a temporary support body from the photosensitive resin layer, before peeling a temporary support body, it exposes through a temporary support body, and peels a temporary support body after that. Also good. In order to prevent mask contamination due to the contact between the photosensitive resin layer and the mask and to avoid the influence on the exposure caused by 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.

[Development process (first development process)]
In the first embodiment, the developing step is performed, and in the second embodiment, the first developing step is performed. An example of the development process (first development process) is schematically shown in FIG.
For example, as shown in FIG. 2C, in the development step (first development step), the temporary support 10 (and the intermediate layer 14) is peeled from the photosensitive resin layer 12 after the exposure step (first exposure step). The photosensitive resin layer 12 after the exposure step (first exposure step) is developed to form the first pattern 12A.

The development step (first development step) is a step of forming a pattern (first pattern) by developing the pattern-exposed photosensitive resin layer.
Development of the pattern-exposed photosensitive resin layer can be performed using a developer.
The developer is not particularly limited as long as the exposed portion of the photosensitive resin layer can be removed. For example, a known developer such as the developer described in JP-A-5-72724 can be used. The developer is preferably a developer in which the exposed portion of the photosensitive resin layer exhibits a dissolution type development behavior. For example, an alkaline aqueous 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 and a surfactant. Examples of the developer suitably used in the present embodiment include the developer described in paragraph 0194 of International Publication No. 2015/092731.

The development method is not particularly limited and may be any of paddle development, shower development, shower and spin development, dip development, and the like. Here, the shower development will be described. The exposed portion can be removed by spraying the developer onto the exposed photosensitive resin layer by shower. 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 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 50.66 kPa or more. On the other hand, the post-bake heating is more preferably performed under an environment of 114.6 kPa or less, and particularly preferably performed under 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-baking time is preferably 1 to 30 minutes, more preferably 2 to 10 minutes, and particularly preferably 2 to 4 minutes.
The post-bake may be performed in an air environment or a nitrogen substitution environment.

Other steps such as a post-exposure step may be included.

[Etching step (first etching step)]
The etching process is performed in the first embodiment, and the first etching process is performed in the second embodiment. An example of the etching process (first etching process) is schematically shown in FIG.
For example, as shown in FIG. 2D, in the etching step (first etching step), at least the first conductive layer 24 and the second conductive layer 26 among the plurality of conductive layers in the region where the first pattern 12A is not disposed are formed. Etching process. By etching, a first conductive layer 24A and a second conductive layer 26A having the same pattern as the first pattern 12A are formed.

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

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.
Acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, mixed aqueous solutions of acidic components and salts such as ferric chloride, ammonium fluoride, and potassium permanganate. Is exemplified. 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 with a 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 photosensitive resin layer is prevented from being peeled off during the etching process, and a portion where the 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. The cleaning process is performed by cleaning the substrate with pure water for 10 seconds to 300 seconds at room temperature, for example, and the drying process is performed using an air blow, for example, with an air blow pressure (preferably 0.1 kg / cm ² to 5 kg / cm ^2). The degree of drying may be appropriately adjusted.

[Second exposure step]
In the second embodiment, the second exposure process is performed. An example of the second exposure step is schematically shown in FIG.
For example, as shown in FIG. 2E, after the first etching step, the first pattern 12A 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.
The pattern exposure in the second exposure process is different from the mask used in the first exposure process (for example, the mask 30 as shown in FIG. 2B) (for example, as shown in FIG. 2E). The same method as the pattern exposure in the first exposure step can be applied except that the mask 40) is used.

[Second development step]
In the second embodiment, the second development step is performed. An example of the second developing process is schematically shown in FIG.
For example, as shown in FIG. 2F, in the second development step, the first pattern 12A after the second exposure step is developed to form the second pattern 12B.
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.

[Second etching step]
In the second embodiment, the second exposure process is performed. An example of the second etching step is schematically shown in FIG.
For example, as shown in FIG. 2G, in the second etching step, at least the first conductive layer 24A is etched among the plurality of conductive layers in the region where the second pattern 12B is not disposed.

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 removed by etching using an etchant that selectively etches only the first conductive layer 24 </ b> A in a region where the photosensitive resin layer is not disposed. The pattern can be different from the pattern of the 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.

[Photosensitive resin layer removal step]
An example of the photosensitive resin layer removing step is schematically shown in FIG.
After the second etching step, the second pattern 12B remains on a part of the first conductive layer 24B. If the photosensitive resin layer is unnecessary, the second pattern 12B of all remaining photosensitive resin layers may be removed.

Although there is no restriction | limiting in particular as a method of removing the remaining photosensitive resin layer, The method of removing by chemical processing can be mentioned.
As a method for removing the photosensitive resin layer, the substrate having the photosensitive resin layer and the like is immersed in a stripping solution that is preferably stirred at 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 1 minute to 30 minutes. The method of doing is mentioned.

Examples of the stripping solution include inorganic alkali components such as sodium hydroxide and potassium hydroxide, or organic alkali components such as primary amine, secondary amine, tertiary amine, and quaternary ammonium salt. , A stripping solution dissolved in dimethyl sulfoxide, N-methylpyrrolidone or a mixed solution thereof. 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 according to the present disclosure may include other optional steps. For example, although the following processes are mentioned, it is not limited to these processes.

[Process of attaching protective film]
The second embodiment may further include a step of attaching a light-transmitting protective film (not shown) on the first pattern after the first etching step and before the second exposure step. Good.
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 which concerns on this indication can include the process of reducing the visible light reflectance of some or all of the some conductive layers on a base material.
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.
Regarding preferred embodiments of the treatment for reducing the visible light reflectance, paragraphs 0017 to 0025 of JP2014-150118A, and paragraphs 0041, 0042, 0048 and 0058 of JP2013-206315A are described. 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 disclosure 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, the above-described second electrode pattern 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.

Further, in the description with reference to FIG. 2, the case where the circuit wiring having two different patterns is formed on the circuit wiring forming substrate including the 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.

Moreover, although not shown in FIG. 2, the manufacturing method of the circuit wiring which concerns on this indication WHEREIN: The base material has a some conductive layer in both surfaces, respectively, and the conductive layer formed in 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 and circuit board>
The circuit wiring according to the present disclosure is a circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure.
The circuit board according to the present disclosure is a substrate having circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure.
Although the use of the circuit board concerning this indication is not limited, for example, it is preferred that it is a circuit board for touch panels.

<Input device and display device>
An input device is mentioned as an apparatus provided with the circuit wiring manufactured by the manufacturing method of the circuit wiring concerning this indication.
The input device in the present embodiment is preferably a capacitive touch panel.
The display device in the present embodiment preferably includes the input device in the present embodiment. The display device in the present embodiment is preferably an image display device such as an organic EL display device and a liquid crystal display device.

<Touch panel, touch panel display device and manufacturing method thereof>
The touch panel according to the present disclosure is a touch panel having at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure. In addition, the touch panel according to the present disclosure preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
The touch panel display device according to the present disclosure is a touch panel display device having at least circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure, and is preferably a touch panel display device including the touch panel according to the present disclosure.
The method for manufacturing a touch panel or a touch panel display device according to the present disclosure preferably includes a method for manufacturing a circuit wiring according to the present disclosure.
The method for manufacturing a touch panel or a touch panel display device according to the present disclosure includes a step of bonding the outermost layer on the photosensitive resin layer side of the temporary support of the photosensitive transfer material obtained by the method for manufacturing a photosensitive transfer material, and the above A pattern exposure step of the photosensitive layer of the photosensitive transfer material after the bonding step, a step of developing the photosensitive layer after the pattern exposure step to form a pattern, and the pattern is not disposed It is preferable to include a process of etching the substrate in the region in this order. The details of each process are synonymous with the details of each process in the above-described circuit wiring manufacturing method, and the preferred embodiments are also the same.
As a detection method in the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among these, the electrostatic capacity method is preferable.
As the touch panel type, for example, a so-called in-cell type (for example, those described in FIGS. 5, 6, 7 and 8 of JP-T-2012-517051), a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2013-517051). No. 168125 in FIG. 19, JP 2012-89102 A in FIGS. 1 and 5), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP-A-2013-54727 shown in FIG. 2), other configurations (for example, those shown in FIG. 6 of JP-A-2013-164871), and various out-cell types (so-called GG, G1, G2) , GFF, GF2, GF1, G1F, etc.).
As the touch panel of this embodiment and the touch panel display device of this embodiment, “latest touch panel technology” (July 6, 2009, issued by Techno Times Co., Ltd.), supervised by Yuji Mitani, “Touch Panel Technology and Development”, The configurations disclosed in CM Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. can be applied.

Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.

The following abbreviations represent the following compounds, respectively.
“ATHF”: 2-tetrahydrofuranyl acrylate (synthetic product) (monomer forming the structural unit represented by the formula (A1))
“MATHF”: 2-tetrahydrofuranyl methacrylate (synthetic product) (monomer forming the structural unit represented by the formula (A1))
“TBMA”: tert-butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
“TBS”: 4-tert-butoxystyrene (manufactured by Tokyo Chemical Industry Co., Ltd.)
“AA”: acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
“CHA”: cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
“DMAEMA”: 2- (dimethylamino) ethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
“EA”: ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
“MEMA”: 2-morpholinoethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
“MMA”: Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
“MS”: 4-methoxystyrene (manufactured by Tokyo Chemical Industry Co., Ltd.)
“PGMEA”: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK)
“PMPMA”: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
“V-601”: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

<Synthesis of 2-tetrahydrofuranyl acrylate>
Acrylic acid (72.1 g, 1.0 mol) and hexane (72.1 g) were added to a three-necked flask and cooled to 20 ° C. To the resulting solution, camphorsulfonic acid (7.0 mg, 0.03 mmol) and 2-dihydrofuran (77.9 g, 1.0 mol) were added dropwise and stirred at 20 ° C. ± 2 ° C. for 1.5 hours, It heated up to 35 degreeC and stirred for 2 hours. Kyoward 200 (aluminum hydroxide adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) and then Kyoward 1000 (hydrotalcite-based adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) were spread over Nutsche, and then the reaction solution was Filtered. Hydroquinone monomethyl ether (1.2 mg) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ° C. to obtain 2-tetrahydrofuranyl acrylate (140.8 g) as a colorless oil (yield: 99. 0%).

<Synthesis of 2-tetrahydrofuranyl methacrylate>
Methacrylic acid (86.1 g, 1.0 mol) and hexane (86.1 g) were added to a three-necked flask and cooled to 20 ° C. To the obtained solution, camphorsulfonic acid (7.0 mg, 0.03 mmol) and 2-dihydrofuran (70.1 g, 1.0 mol) were added dropwise and stirred at 20 ° C. ± 2 ° C. for 1.5 hours, It heated up to 35 degreeC and stirred for 2 hours. After Kyoward 200 and Kyoward 1000 were spread over Nutsche in this order, the reaction solution was filtered. Hydroquinone monomethyl ether (1.2 mg) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ° C. to obtain 2-tetrahydrofuranyl methacrylate (156.2 g) as a colorless oil (yield 98.98). 0%).

<Synthesis of Polymer A-1>
PGMEA (75.0 g) was added to the three-necked flask, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. To a solution in a three-necked flask maintained at 90 ° C. ± 2 ° C., ATHF (25.0 g), CHA (60.0 g), EA (10.0 g), AA (5.0 g), V-601 (4. 1 g) and a solution containing PGMEA (75.0 g) were added dropwise over 2 hours. After completion of the dropping, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain a polymer A-1 (solid content concentration 40.0%).

<Synthesis of Polymers A-2 to A-11>
Polymer A-2 to Polymer A-11 were synthesized by the same procedure as for Polymer A-1, except that the monomer type and the like were changed as shown in Table 1. The solid content concentration of each polymer is 40% by mass.

<Example 1>
[Preparation of photosensitive resin composition 1]
Photosensitive resin composition 1 was prepared according to the following formulation.
Polymer (A-1): 93.9 parts Photoacid generator (B-1): 2.0 parts Surfactant (C-1): 0.1 part Amine compound (D-2): 0.3 Part Benzotriazole compound (E-1): 0.2 part PGMEA: 900 parts

[Production of photosensitive transfer material]
The photosensitive resin composition 1 was applied on a polyethylene terephthalate film (thickness 25 μm), which is a temporary support, using a slit nozzle so that the dry film thickness was 3.0 μm. After drying in a convection oven at 100 ° C. for 2 minutes, a polyethylene film (Tradegar, OSM-N) was pressure-bonded as a cover film to produce the photosensitive transfer material of Example 1.

<Comparative Examples 1 and 3>
Photosensitive transfer of Comparative Examples 1 and 3 in the same procedure as in Example 1 except that the photosensitive resin compositions 1a and 3a were used in which the components of the photosensitive resin composition 1 were changed according to the description in Table 2. Each material was made.

<Example 2>
[Preparation of photosensitive resin composition 2]
Photosensitive resin composition 2 was prepared according to the following formulation.
Polymer (A-1): 93.9 parts Photoacid generator (B-1): 2.0 parts Surfactant (C-1): 0.1 part Amine compound (D-1): 0.3 Part Benzotriazole compound (E-1): 0.2 part PGMEA: 900 parts

[Preparation of composition 1 for intermediate layer]
The intermediate layer composition 1 was prepared according to the following formulation.
Distilled water: 13.4 parts Methanol: 75.6 parts Hydroxypropyl methylcellulose (trade name: TC-5, manufactured by Shin-Etsu Chemical Co., Ltd.): 4.1 parts

[Production of photosensitive transfer material]
The intermediate layer composition 1 is slit coated on a polyethylene terephthalate film (thickness 25 μm) as a temporary support so that the dry film thickness becomes 2.0 μm, and then dried in a convection oven at 100 ° C. for 2 minutes. did. Next, the photosensitive resin composition 2 was applied on the intermediate layer using a slit-like nozzle so that the dry film thickness was 3.0 μm. After drying in a convection oven at 100 ° C. for 2 minutes, a photosensitive transfer material of Example 2 was produced by pressure-bonding a polyethylene film (OSM-N, manufactured by Tredegar) as a cover film.

<Examples 3 to 6>
The photosensitive transfer compositions of Examples 3 to 6 were prepared in the same manner as in Example 2 except that the photosensitive resin compositions 3 to 6 were used in which the components of the photosensitive resin composition 2 were changed according to the description in Table 2. Each material was made.

<Example 7>
The same procedure as in Example 2 except that the photosensitive resin composition 2 was changed to the following photosensitive resin composition 7 and the intermediate layer composition 1 was changed to the following intermediate layer composition 2. Thus, a photosensitive transfer material of Example 7 was produced.

[Preparation of photosensitive resin composition 7]
The photosensitive resin composition 7 was prepared by preparing with the following prescription and filtering with a filter made of polytetrafluoroethylene having a pore diameter of 0.2 μm.
Polymer (A-4): 93.9 parts Photoacid generator (B-1): 2.0 parts Surfactant (C-2): 0.1 part Benzotriazole compound (E-1): 0. 2 parts PGMEA: 900 parts

[Preparation of intermediate layer composition 2]
An intermediate layer composition 2 was prepared according to the following formulation.
Distilled water: 13.4 parts Methanol: 75.6 parts Hydroxymethylcellulose (trade name: HPC-SSL, manufactured by Nippon Soda Co., Ltd.): 4.1 parts Snowtex O (manufactured by Nissan Chemical Industries, Ltd.): 68. 5 copies

<Examples 8 to 15 and Comparative Examples 2 and 4 to 10>
Each component of the photosensitive resin composition 7 was changed in accordance with the description in Table 2, except that the photosensitive resin compositions 8 to 15 and the photosensitive resin compositions 2a and 4a to 10a were used. The photosensitive transfer materials of Examples 8 to 15 and Comparative Examples 2 and 4 to 10 were prepared by the above procedure.

<Example 16>
A photosensitive transfer material of Example 16 was produced in the same manner as in Example 7 except that the amount of the benzotriazole compound used was changed to 1.0 part.

<Example 17>
A photosensitive transfer material of Example 17 was produced in the same manner as in Example 7, except that the amount of the benzotriazole compound used was changed to 2.0 parts.

<Example 18>
[Preparation of composition 3 for intermediate layer]
An intermediate layer composition 3 was prepared according to the following formulation.
Distilled water: 13.4 parts Methanol: 75.6 parts Hydroxymethylcellulose (trade name: HPC-SSL, manufactured by Nippon Soda Co., Ltd.): 4.1 parts Snowtex XL (manufactured by Nissan Chemical Industries, Ltd.): 68. 5 copies

[Production of photosensitive transfer material]
The intermediate layer composition 1 is slit coated on a polyethylene terephthalate film (thickness 25 μm) as a temporary support so that the dry film thickness becomes 2.0 μm, and then dried in a convection oven at 100 ° C. for 2 minutes. did. Next, the intermediate layer forming composition 3 was slit coated so as to have a dry film thickness of 2.0 μm, and then dried in a convection oven at 100 ° C. for 2 minutes. Next, the photosensitive resin composition 7 was applied onto the intermediate layer using a slit nozzle so that the dry film thickness was 3.0 μm. After drying in a convection oven at 100 ° C. for 2 minutes, a photosensitive transfer material of Example 18 was produced by pressure-bonding a polyethylene film (Tradegar, OSM-N) as a cover film.

<Evaluation>
Using the photosensitive transfer materials of Examples 1 to 18 and Comparative Examples 1 to 10, transferability, shape reproducibility, wettability, and linearity were evaluated. Table 2 summarizes the results of the evaluation.
In the following evaluation, a PET substrate having a copper layer with a thickness of 500 nm formed by sputtering on a polyethylene terephthalate (PET) film having a thickness of 188 μm (hereinafter referred to as “PET substrate with a copper layer”). It was used.

[Transferability]
The photosensitive transfer material was cut into a 50 cm square to obtain a sample piece. Next, after the cover film was peeled off, the roll temperature was 90 ° C., the linear pressure was 0.6 MPa, and the linear velocity (laminate velocity) was 3.6 m / min. Under the laminating conditions, the photosensitive transfer material was bonded to the surface of the copper layer of the PET substrate with a copper layer to obtain a laminate. The adhesion part of the photosensitive resin layer on the surface of the copper layer is visually discriminated, and the adhesion part of the photosensitive resin layer on the surface of the copper layer is marked with an oily magic on the temporary support, and the entire PET substrate is photographed. did. From the obtained image, the adhesion area of the photosensitive resin layer on the surface of the copper layer and the area of the entire sample piece were calculated using image analysis software (ImageJ (manufactured by National Institute of Health, USA)). And area ratio was calculated | required from the following formula and evaluated according to the following evaluation criteria.
Area ratio (%) = (Attached area of photosensitive resin layer / Area of entire sample piece) × 100
5: 95% or more 4: 90% or more and less than 95% 3: 85% or more and less than 90% 2: 80% or more and less than 85% 1: less than 80%

[Shape reproducibility]
After peeling off the cover film, the laminate was prepared by laminating the photosensitive transfer material on the surface of the copper layer of the PET substrate with the copper layer under the laminating conditions of a linear pressure of 0.6 MPa and a linear velocity (laminate velocity) of 3.6 m / min. did. When the transferability was 4 or less at a roll temperature of 90 ° C., the roll temperature was raised until the transferability was 5, and a laminate was produced. Thereafter, the laminate was pressurized with an autoclave. The pressing condition is 50 MPa, 3 hours, and 0.6 MPa. Without peeling off the temporary support, the laminated body was exposed with an ultra-high pressure mercury lamp through a line and space pattern (duty ratio 1: 1) mask with a line width of 10 μm, and then left for 5 hours to peel off the temporary support. Developed. In the exposure, an exposure amount at which the ratio of the line width to the space width was 1: 1 was determined, and the laminate was exposed with the exposure amount. In the development, a 1.0% sodium carbonate aqueous solution at 28 ° C. was used, and shower development was performed for 40 seconds. By the above procedure, a sample having a resin pattern with a line and space of 10 μm was produced. The form of the resin pattern of the obtained sample was observed by SEM (scanning electron microscope, magnification 20000 times), and shape reproducibility was evaluated using the following criteria as an index. Two or more are practical levels.
3: A resin pattern with a good hem was obtained.
2: A slightly skirted resin pattern was obtained.
1: A resin pattern with a long skirt was obtained, or the resin pattern was connected without resolution because the skirt was long.

[Wettability]
The sample prepared in the evaluation of the shape reproducibility was immersed in a copper etching solution (Cu-02: manufactured by Kanto Chemical Co., Ltd.) at 25 ° C. for 5 minutes. The etching state of the copper layer was visually confirmed, and the wettability was evaluated using the following criteria as an index. 3 is a practical level.
3: The copper layer has been etched normally.
2: There is an area with poor wettability, and only a part of the copper layer can be etched.
1: Wetting is poor and the copper layer cannot be etched.

[Linearity]
The sample prepared in the evaluation of the shape reproducibility was etched at 23 ° C. for 30 seconds using a copper etching solution (Cu-02: manufactured by Kanto Chemical Co., Ltd.), and then the resist was peeled off using PGMEA. A copper wiring having a conductive pattern with a line and space of 10 μm was formed. The copper wiring LWR (Line Width Roughness, 3σ of a value obtained by measuring the width of the copper wiring at 250 points) was obtained, and the linearity was evaluated using the following criteria as an index. Three or more are practical levels.
5: LWR is less than 160 nm.
4: LWR is 160 nm or more and less than 200 nm.
3: LWR is 200 nm or more and less than 250 nm.
2: LWR is 250 nm or more and less than 300 nm.
1: LWR was 300 nm or more, or a conductive pattern could not be formed.

<Photo acid generator>
B-1: A compound having the structure shown below was synthesized according to the method described in paragraph 0204 of JP2013-047765A.

B-2: Compound having the following structure (PAG-103, manufactured by BASF)

<Surfactant>
C-1: Compound having the following structure

C-2: Megafuck F552 (manufactured by DIC)

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

D-2: Trioctylamine

<Benzotriazole compound>
E-1: Compound having the structure shown below (1,2,3-benzotriazole)

E-2: Compound having the structure shown below (1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole)

E-3: Compound having the structure shown below (5-carboxybenzotriazole)

E-4: Compound having the structure shown below (1- (hydroxymethyl) -1H-benzotriazole)

E-5: Compound having the structure shown below (1-acetyl-1H-benzotriazole)

E-6: Compound having the structure shown below (1-aminobenzotriazole)

<Comparative compound>
E-7: A compound having the structure shown below.

E-8: A compound having the structure shown below.

E-9: A compound having the structure shown below.

E-10: Compound having the structure shown below.

E-11: A compound having the structure shown below.

E-12: A compound having the structure shown below.

In Table 2, the numerical value described in the column of [benzotriazole] / [polymer] is a value calculated based on the solid content mass of the polymer.

From Table 2, each photosensitive transfer material of Comparative Examples 1, 2, and 4 to 9 not using a benzotriazole compound as an additive, and a structural unit having a group in which an acid group is protected by an acid-decomposable group are included. However, the photosensitive transfer materials of Examples 1 to 18 are excellent in shape reproducibility and linearity as compared with the photosensitive transfer materials of Comparative Examples 3 and 10 using a polymer having a glass transition temperature exceeding 90 ° C. all right. Table 2 also shows that the photosensitive transfer materials of Examples 1 to 18 are excellent in transferability and wettability.

<Example 101>
On the 100 μm-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer at a thickness of 200 nm by vacuum evaporation. Thus, a substrate for forming a conductive pattern was obtained.
The photosensitive transfer material obtained in Example 1 was bonded to a substrate on a copper layer (roll temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.) To obtain a laminate. The laminate is contacted using a photomask provided with a pattern shown in FIG. 3 (hereinafter also referred to as “pattern A”) having a configuration in which conductive layer pads are connected in one direction without peeling off the temporary support. The pattern was exposed.
In the pattern A shown in FIG. 3, the solid line portion SL and the gray portion G are light shielding portions, and the dotted line portion DL virtually shows an alignment alignment frame.
Thereafter, the temporary support was peeled off, developed and washed with water to obtain a resin pattern drawn with pattern A. Next, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), A substrate on which both copper and ITO were drawn in pattern A was obtained.
Next, pattern alignment was performed using a photomask provided with openings of the pattern shown in FIG. 4 (hereinafter also referred to as “pattern B”) in the aligned state, and development and washing were performed.
In the pattern B shown in FIG. 4, the gray portion G is a light shielding portion, and the dotted line portion DL is a virtual alignment alignment frame.
Thereafter, the copper layer 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., Inc.) to obtain a circuit wiring board.
When the obtained circuit wiring board was observed with a microscope, it was a clean pattern with no peeling or chipping.

<Example 102>
On the 100 μm-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer at a thickness of 200 nm by vacuum evaporation. Thus, a substrate for forming a conductive pattern was obtained.
The photosensitive transfer material obtained in Example 1 was bonded to a substrate on a copper layer (roll temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.) To obtain a laminate. The laminate was subjected to pattern exposure 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. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a resin pattern drawn with pattern A. Next, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), A substrate on which both copper and ITO were drawn in pattern A was obtained.
Subsequently, PET (A) was bonded as a protective layer on the remaining resist. In this state, pattern exposure was performed using a photomask provided with an opening of pattern B in the aligned state, and after developing PET (A), development and washing were performed. Thereafter, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was stripped using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
When the obtained circuit wiring board was observed with a microscope, it was a clean pattern with no peeling or chipping.

<Example 103>
On the 100 μm-thick cycloolefin polymer (COP) substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by a thickness of 200 nm by vacuum evaporation. To form a substrate for forming a conductive pattern.
The photosensitive transfer material obtained in Example 1 was bonded to a substrate on a copper layer (roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.) To obtain a laminate. The laminate was subjected to pattern exposure 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. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a resin pattern drawn with pattern A. Next, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), and a peeling solution. By peeling using (KP-301, manufactured by Kanto Chemical Co., Inc.), a substrate on which both copper and ITO were drawn with the pattern A was obtained.
Subsequently, COP (A) was bonded as a protective layer on the remaining resist. In this state, pattern exposure was performed using a photomask provided with an opening of pattern B in the aligned state, and after developing COP (A), development and washing were performed. Thereafter, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was stripped using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
When the obtained circuit wiring board was observed with a microscope, it was a clean pattern with no peeling or chipping.

The disclosure of Japanese Patent Application No. 2018-098328 filed on May 22, 2018 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, It is incorporated herein by reference.

Claims

A temporary support;
A photosensitive resin layer containing a polymer having a structural unit having an acid group protected by an acid-decomposable group and having a glass transition temperature of 90 ° C. or less, a photoacid generator, and a benzotriazole compound; ,
A photosensitive transfer material.
The photosensitive transfer material according to claim 1, wherein the benzotriazole compound is a compound represented by the following formula (1).

In formula (1), P represents a hydrogen atom or a substituent, Q represents a substituent, n represents an integer of 0 to 4, and when n is 2 or more, a plurality of Q are the same But it can be different. However, a benzotriazole compound having at least one functional group selected from the group consisting of a sulfonic acid group, a thiol group, and a thioether group is excluded.
In the formula (1), P represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, a carboxy group, an alkylamino group, a dialkylamino group, or —Z—. The photosensitive transfer material according to claim 2, wherein the photosensitive transfer material is a Y group, Z represents an alkylene group, and Y represents a hydroxy group, a carboxy group, an alkylamino group, or a dialkylamino group.
In the formula (1), Q is a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an amino group, a —ZY group, an alkoxy group, a carboxy group, or an alkoxyacyl group. 4. The photosensitive transfer material according to claim 2, wherein Z represents an alkylene group, and Y represents a hydroxy group, a carboxy group, an alkylamino group, or a dialkylamino group.
In the formula (1), P is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, an amino group, or a -ZY group, and Z is , Represents an alkylene group having 1 or 2 carbon atoms which may be substituted with a carboxy group, Y represents a hydroxy group, a carboxy group, or a dialkylamino group having 1 to 10 carbon atoms in each alkyl group; Q is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, an amino group, an alkoxy group having 1 to 6 carbon atoms, a carboxy group, or 1 carbon atom. The photosensitive transfer material according to claim 2, which is an alkoxyacyl group of 1 to 6, wherein n is 0 or 1.
In the formula (1), P represents a hydrogen atom or a —Z—Y group, Z represents an alkylene group having 1 or 2 carbon atoms which may be substituted with a carboxy group, and Y represents Each alkyl group represents a dialkylamino group having 1 to 10 carbon atoms, Q is an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and n is 0 or 1 The photosensitive transfer material according to claim 5.
The photosensitive transfer material according to claim 1, wherein the content of the benzotriazole compound is 0.01% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer. .
The photosensitive transfer material according to any one of claims 1 to 7, wherein a mass ratio of the content of the benzotriazole compound to the content of the polymer is 0.001 to 0.1.
The photosensitive transfer material according to any one of claims 1 to 8, wherein a mass ratio of the content of the benzotriazole compound to the content of the photoacid generator is 0.01 to 5.
The content of the structural unit having a group in which an acid group in the polymer is protected by an acid-decomposable group is 20% by mass to 50% by mass with respect to the total mass of the polymer. 10. The photosensitive transfer material according to any one of 9 above.
The photosensitive transfer according to any one of claims 1 to 10, wherein the structural unit having a group in which the acid group is protected with an acid-decomposable group is a structural unit represented by the following formula (A1). material.

In formula (A1), R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least one of R 31 and R 32 is an alkyl group or an aryl group. , R 33 represents an alkyl group or an aryl group, R 31 or R 32 and R 33 may be linked to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, X 0 represents a single bond or a linking group.
The photosensitive transfer material according to any one of claims 1 to 11, wherein the photosensitive resin layer further contains an amine compound other than the benzotriazole compound.
The photosensitive transfer material according to any one of claims 1 to 12, wherein the polymer further comprises a structural unit having a pKaH group of 3 or more.
The photosensitive transfer material according to any one of claims 1 to 13, further comprising an intermediate layer between the temporary support and the photosensitive resin layer.
A step of bonding the outermost layer on the photosensitive resin layer side of the temporary support of the photosensitive transfer material according to any one of claims 1 to 14 to a substrate;
Pattern exposure of the photosensitive resin layer of the photosensitive transfer material after the bonding step;
Developing the photosensitive resin layer after the pattern exposing step to form a pattern; and
Etching the substrate in a region where the pattern is not disposed,
Circuit wiring manufacturing method.
The circuit wiring manufacturing method according to claim 15, wherein the substrate is a substrate containing copper.
A step of bonding the outermost layer on the photosensitive resin layer side of the temporary support of the photosensitive transfer material according to any one of claims 1 to 14 to a substrate;
Pattern exposure of the photosensitive resin layer of the photosensitive transfer material after the bonding step;
Developing the photosensitive resin layer after the pattern exposing step to form a pattern; and
Etching the substrate in a region where the pattern is not disposed,
A method for manufacturing a touch panel.