WO2019230345A1

WO2019230345A1 - Photosensitive transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, and touch panel manufacturing method

Info

Publication number: WO2019230345A1
Application number: PCT/JP2019/018816
Authority: WO
Inventors: 藤本　進二; 漢那　慎一; 壮二石坂; 一真両角; 克己篠田; 知樹松田
Original assignee: 富士フイルム株式会社
Priority date: 2018-05-29
Filing date: 2019-05-10
Publication date: 2019-12-05
Also published as: JPWO2019230345A1; JP7102517B2; TW202005805A; CN112204468A

Abstract

Provided are: a photosensitive transfer material; and a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method which use the photosensitive transfer material. The photosensitive transfer material has a temporary support, an intermediate layer, and a photosensitive resin layer that includes a polymer having a structural unit which has an acid group protected with an acid-decomposable group, and a photoacid generator, wherein the polymer contained in the photosensitive resin layer is an acrylic resin having an acid value of 10 mgKOH/g or less, the intermediate layer contains a water-soluble or alkali-soluble acrylic resin, and the intermediate layer and the photosensitive resin layer are in contact with each other.

Description

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

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

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

As a conventional photosensitive transfer material, those described in Patent Document 1 or 2 are known.
Patent Document 1 includes a support, a thermoplastic resin layer, and a photosensitive resin composition layer in this order, and the photosensitive resin composition layer is protected by (A) an acid group with an acid-decomposable group. A photosensitive transfer material comprising a polymer component containing a polymer having a structural unit (a1) having a group formed and (B) a photoacid generator is disclosed.
Patent Document 2 includes a temporary support, a polymer containing a structural unit represented by the following general formula A and a structural unit having an acid group, and having a glass transition temperature of 90 ° C. or lower, and a photoacid. A photosensitive transfer material having a positive photosensitive resin layer containing a generator is disclosed.

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

Patent Document 1: Japanese Patent Laid-Open No. 2014-85643 Patent Document 2: Japanese Patent Laid-Open No. 2017-156735

The problem to be solved by one embodiment of the present invention is to provide a photosensitive transfer material that is excellent in storage stability and adhesion between the intermediate layer and the photosensitive resin layer.
Another problem to be solved by another embodiment of the present invention is to provide a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method using the photosensitive transfer material. .

Means for solving the above problems include the following aspects.
<1> A polymer having a temporary support, an intermediate layer, and a photosensitive resin layer, wherein the photosensitive resin layer has a structural unit having an acid group protected by an acid-decomposable group, and light The polymer that contains an acid generator and is contained in the photosensitive resin layer is an acrylic resin having an acid value of 10 mgKOH / g or less, the intermediate layer contains a water-soluble or alkali-soluble acrylic resin, A photosensitive transfer material in contact with the photosensitive resin layer.
<2> The photosensitive transfer material according to <1>, wherein an acid value of the acrylic resin contained in the photosensitive resin layer is 0 mgKOH / g to 3 mgKOH / g.
<3> The photosensitive transfer material according to <1> or <2>, wherein the acrylic resin contained in the photosensitive resin layer further includes a structural unit having a group that is pKaH3 or more.
<4> The photosensitive transfer material according to any one of <1> to <3>, wherein the water-soluble or alkali-soluble acrylic resin in the intermediate layer is a water-soluble acrylic resin.
<5> The water-soluble acrylic resin according to <4>, wherein the water-soluble acrylic resin has an acid group or a basic group, and the neutralization rate of the acid group or the basic group is 90 mol% or more. The photosensitive transfer material as described.
<6> The photosensitive transfer material according to any one of <1> to <3>, wherein the water-soluble or alkali-soluble acrylic resin in the intermediate layer is an alkali-soluble acrylic resin.
<7> The photosensitive transfer material according to <6>, wherein the acid value of the alkali-soluble acrylic resin is 30 mgKOH / g to 150 mgKOH / g.
<8> The photosensitive transfer material according to any one of <1> to <7>, wherein an average film thickness of the intermediate layer is 3 μm or less.
<9> The photosensitive transfer material according to any one of <1> to <8>, wherein the water-soluble or alkali-soluble acrylic resin in the intermediate layer contains a resin having a hydroxy group.
<10> The intermediate layer includes at least one water-soluble resin selected from the group consisting of a phenol resin, a modified cellulose resin, and a polyvinyl alcohol resin on the side opposite to the side in contact with the photosensitive resin layer. The photosensitive transfer material according to any one of <1> to <9>, further comprising a water-soluble resin layer.
<11> The photosensitive transfer material according to any one of <1> to <10>, wherein the structural unit having an acid group protected with an acid-decomposable group is a structural unit represented by the following formula A: .

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

<12> The step of bringing the outermost layer on the photosensitive resin layer side of the photosensitive transfer material according to any one of <1> to <11> into contact with a substrate and bonding the photosensitive resin layer to the pattern A method for producing a resin pattern, comprising: an exposing step; and a step of developing the exposed photosensitive resin layer to form a pattern in this order.
<13> The step of bringing the outermost layer on the photosensitive resin layer side of the photosensitive transfer material according to any one of <1> to <11> into contact with a substrate having a conductive layer, and bonding the photosensitive layer A step of pattern exposing the photosensitive resin layer, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching the conductive layer in the region where the pattern is not disposed. A method of manufacturing circuit wiring including the same.
<14> The method for producing circuit wiring according to <13>, wherein the conductive layer is a layer containing copper.
<15> The step of bringing the outermost layer on the photosensitive resin layer side of the photosensitive transfer material according to any one of <1> to <11> into contact with a substrate having a conductive layer, and bonding the photosensitive layer A step of pattern exposing the photosensitive resin layer, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching the conductive layer in the region where the pattern is not disposed. A method for manufacturing a touch panel.

According to one embodiment of the present invention, it is possible to provide a photosensitive transfer material that is excellent in storage stability and adhesion between the intermediate layer and the photosensitive resin layer.
In addition, according to another embodiment of the present invention, a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method using the photosensitive transfer material can be provided.

It is the schematic which shows an example of the laminated constitution of the photosensitive transfer material which concerns on this indication. FIG. 6 is a schematic diagram showing a pattern A. FIG. 6 is a schematic diagram showing a pattern B.

Hereinafter, the contents of the present disclosure will be described. In addition, although it demonstrates referring an accompanying drawing, a code | symbol may be abbreviate | omitted.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, “(meth) acryl” represents both and / or acryl and methacryl, and “(meth) acrylate” represents both and / or acrylate and methacrylate.
Further, in the present specification, the amount of each component in the composition is the sum of the plurality of corresponding substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.
In this specification, 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 groups (atomic groups) in this specification, 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 addition, the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
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 addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) unless otherwise specified. The molecular weight was detected by a gel permeation chromatography (GPC) analyzer using a THF (tetrahydrofuran) solvent and a differential refractometer, and converted using polystyrene as a standard substance.

(Photosensitive transfer material)
A photosensitive transfer material according to the present disclosure includes a temporary support, an intermediate layer, and a photosensitive resin layer, and the photosensitive resin layer includes a structural unit having an acid group protected by an acid-decomposable group. An acrylic resin that contains a polymer (hereinafter also referred to as “acid-decomposable resin”) and a photoacid generator, and the polymer contained in the photosensitive resin layer has an acid value of 10 mgKOH / g or less. The intermediate layer contains a water-soluble or alkali-soluble acrylic resin, and the intermediate layer and the photosensitive resin layer are in contact with each other.
In addition, the photosensitive transfer material which concerns on this indication is excellent in the adhesiveness of an intermediate | middle layer and the photosensitive resin layer.
The photosensitive transfer material according to the present disclosure preferably includes a temporary support, an intermediate layer, and a photosensitive resin layer in this order.

When the conventional photosensitive transfer material is stored for a long time, the line width of the resin pattern formed by exposing the photosensitive resin layer may fluctuate, and the storage stability is not sufficient.
In response to the above-mentioned storage stability problem, the present inventors have found that storage stability can be improved by making the polymer contained in the photosensitive resin layer an acrylic resin having an acid value of 10 mgKOH / g or less. It was.
However, in the photosensitive transfer material having a photosensitive resin layer containing an acrylic resin having an acid value of 10 mgKOH / g or less and an intermediate layer containing polyvinyl alcohol (PVA) described in Patent Document 1, etc., the intermediate layer The present inventors have found that the adhesion between the resin and the photosensitive resin layer deteriorates.
On the other hand, as a result of intensive studies, the present inventors can improve the adhesion between the intermediate layer and the photosensitive resin layer while maintaining the storage stability by using the photosensitive transfer material having the above-described configuration. I found.

Although the detailed expression mechanism of the above effect is unknown, it is considered as follows.
First, the mechanism with improved storage stability will be described. When the photosensitive transfer material is stored for a long period of time, if the acrylic resin contained in the photosensitive resin layer has an acid value greater than 10 mgKOH / g, the photosensitive resin layer absorbs moisture in the air. It is presumed that the storage stability deteriorated because the acid derived from the water absorbed and the acid group of the polymer contained in the photosensitive resin layer decomposes the acid-decomposable group of the polymer. .
On the other hand, by setting the acrylic resin contained in the photosensitive resin layer to 10 mgKOH / g or less, it becomes a low-acid-value and hydrophobic photosensitive resin layer, and acid and water contributing to decomposition are reduced. As a result of suppressing the reaction that decomposes the functional group, it is considered that the storage stability can be improved.
In addition, by using an intermediate layer containing a water-soluble or alkali-soluble acrylic resin, the polarities of the acrylic resin and the polymer contained in the photosensitive resin layer become close to each other, and the mutual interaction is improved. It is considered that the adhesiveness with the photosensitive resin layer is improved.

Hereinafter, the photosensitive transfer material according to the present disclosure will be described in detail.

FIG. 1 schematically illustrates an example of a layer configuration of a photosensitive transfer material according to the present disclosure. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 10, an intermediate layer 12, a photosensitive resin layer 14, and a cover film 16 are laminated in this order.
The acid value of the acrylic resin contained in the photosensitive resin layer 14 is 10 mgKOH / g or less, and the intermediate layer 12 contains a water-soluble or alkali-soluble acrylic resin.
Hereinafter, constituent materials and the like of the photosensitive transfer material according to the present disclosure will be described.

<Temporary support>
The temporary support is a support that supports the intermediate layer and the photosensitive resin layer and is peelable from the intermediate layer.
The temporary support used in the present disclosure preferably has light transmittance from the viewpoint that the photosensitive resin layer can be exposed through the temporary support when the photosensitive resin layer is subjected to pattern exposure.
In the present disclosure, having light transmittance means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is exposure. From the viewpoint of improving sensitivity, 60% or more is preferable, and 70% or more is more preferable. Examples of the method for measuring the transmittance include a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the 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. Among these, a biaxially stretched polyethylene terephthalate film is particularly preferable.

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

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.

<Intermediate layer>
The photosensitive transfer material according to the present disclosure has an intermediate layer containing a water-soluble or alkali-soluble acrylic resin.

-Water-soluble or alkali-soluble acrylic resin-
The intermediate layer includes a water-soluble or alkali-soluble acrylic resin.
In the present disclosure, “water-soluble” means that the solubility in water at pH 7.0 is 0.1% by mass or more at 22 ° C., and “alkali-soluble” means sodium carbonate at 22 ° C. It means that the solubility in a 1% by mass aqueous solution is 0.1% by mass or more.
The “water-soluble or alkali-soluble” may be either water-soluble or alkali-soluble, or water-soluble and alkali-soluble.
The water-soluble or alkali-soluble acrylic resin is preferably a water-soluble acrylic resin that exhibits at least water solubility from the viewpoint of storage stability.
The water-soluble or alkali-soluble acrylic resin is preferably an alkali-soluble acrylic resin from the viewpoint of adhesion.

The water-soluble or alkali-soluble acrylic resin preferably has a hydrophilic group, and more preferably has a structural unit having a hydrophilic group, from the viewpoint of water-solubility and alkali-solubility.
Preferred examples of the hydrophilic group include an acid group, a hydroxy group, a polyalkyleneoxy group, an amide group, and a basic group.
The water-soluble or alkali-soluble acrylic resin is an acid group or a basic compound from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer (hereinafter also simply referred to as “adhesion”) and water-solubility or alkali-solubility. It is preferable to include a resin having a group or a hydroxy group, and it is more preferable to include a resin having an acid group or a basic group.
The water-soluble or alkali-soluble acrylic resin is at least one selected from the group consisting of an acid group, a hydroxy group, an amide group, a basic group, and a polyalkyleneoxy group from the viewpoint of adhesion and storage stability. It is preferable to include a resin having a group, more preferably including a resin having at least one group selected from the group consisting of an acid group, a hydroxy group and a basic group, and including a resin having a hydroxy group. Particularly preferred.

As the acid group, from the viewpoint of adhesion, a carboxy group, a sulfonic acid group, a phosphoric acid group, or a phosphonic acid group is preferable, and a carboxy group or a sulfonic acid group is more preferable.
The acid group is preferably neutralized with a known basic compound from the viewpoint of water solubility and storage stability. Water solubility and acid value can be adjusted by neutralization.
The basic compound used for neutralization is preferably sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, primary to tertiary amine or ammonium hydroxide from the viewpoint of storage stability. More preferred is sodium hydroxide or potassium hydroxide.
When the water-soluble or alkali-soluble acrylic resin is a water-soluble acrylic resin having an acidic group and exhibiting at least water solubility, the neutralization rate of the acid group is 70 from the viewpoint of water solubility and storage stability. It is preferably at least mol%, more preferably at least 80 mol%, particularly preferably at least 90 mol%. In addition, the upper limit of a preferable neutralization rate is 100 mol%.
Preferred examples of the polyalkyleneoxy group include a polyethyleneoxy group, a polypropyleneoxy group, and a poly (ethyleneoxy / propyleneoxy) group.

The basic group as the group possessed by the water-soluble or alkali-soluble acrylic resin is preferably a basic group having a nitrogen atom, more preferably an amino group or a heteroaromatic group, from the viewpoint of storage stability. It is done.
The basic group is preferably neutralized with a known acidic compound. Water solubility and alkali solubility can be adjusted by neutralization.
As an acidic compound used for neutralization, from the viewpoint of storage stability, carboxylic acid, sulfonic acid, hydrogen halide, boronic acid, hexafluorophosphoric acid, nitric acid, sulfuric acid, perchloric acid, phosphoric acid, or phosphonic acid It is preferable that it is carboxylic acid or sulfonic acid.
When the water-soluble or alkali-soluble acrylic resin is a water-soluble acrylic resin having a basic group and at least water-soluble, the neutralization rate of the basic group is from the viewpoint of water solubility and alkali solubility, It is preferably 70 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more. In addition, the upper limit of a preferable neutralization rate is 100 mol%.

The neutralization rate of the acid group or basic group in the resin in the present disclosure is represented by the following formula.
Neutralization rate (mol%) = 100 × mole equivalent of neutralized acid group or basic group in resin / mole equivalent of total acid group or basic group in resin In the present disclosure, neutralization rate of acid group in resin The measuring method is shown below.
Measures infrared absorption spectrum of resin, corresponds to acid group and neutralized acid group, or peak corresponding to acid group (eg C = O stretching vibration of carboxy group) and neutralized acid group The area ratio to the peak (for example, the symmetrical stretching vibration of the carboxylate group) is determined, and the neutralization rate (mol%) is calculated.
The measurement method of the neutralization rate of the basic group in the resin also measures the neutralization rate of the acid group except that the peak to be compared is changed to the peak of the basic group and the peak of the neutralized basic group The method is the same as the method.

From the viewpoint of storage stability, the acid value of the water-soluble or alkali-soluble resin is preferably 0 mgKOH / g to 200 mgKOH / g, more preferably 0 mgKOH / g to 150 mgKOH / g, and 0 mgKOH / g to More preferably, it is 100 mgKOH / g.
When the water-soluble or alkali-soluble acrylic resin is a water-soluble acrylic resin, the acid value of the water-soluble alkali-soluble resin is preferably 0 mgKOH / g to 50 mgKOH / g from the viewpoint of storage stability. 0 mg KOH / g to 20 mg KOH / g, more preferably 0 mg KOH / g to 10 mg KOH / g.
When the water-soluble or alkali-soluble acrylic resin is an alkali-soluble acrylic resin (preferably an alkali-soluble resin not having water solubility), the acid value of the alkali-soluble resin is from 30 mgKOH / g to from the viewpoint of storage stability. It is preferably 200 mgKOH / g, more preferably 30 mgKOH / g to 150 mgKOH / g, and still more preferably 30 mgKOH / g to 100 mgKOH / g. When the acid value is 200 mgKOH / g or less, unnecessary decomposition of the acid-decomposable resin in the photosensitive resin layer can be suppressed. Moreover, mixing with the photosensitive resin layer and an intermediate | middle layer can be suppressed as an acid value is 30 mgKOH / g or more.
In addition, the acid value of the said water-soluble or alkali-soluble acrylic resin shall be measured with the acid value measuring method mentioned later.

The acrylic resin in the present disclosure may be a resin containing 50% by mass or more of a structural unit derived from a compound selected from the group consisting of a (meth) acrylate compound, a (meth) acrylamide compound, and (meth) acrylic acid, It is preferably a resin containing 70% by mass or more of the structural unit derived from the compound, more preferably a resin containing 80% by mass or more of the structural unit derived from the compound, and 90% by mass or more of the structural unit derived from the compound. It is especially preferable that it is resin to contain.
As a method for introducing a hydrophilic group into the water-soluble or alkali-soluble acrylic resin, a method of homopolymerizing or copolymerizing a (meth) acrylate compound or (meth) acrylic acid having a hydrophilic group, and an acrylic resin And a method of introducing a hydrophilic group by performing a polymer reaction.

When the water-soluble or alkali-soluble acrylic resin has at least an acid group or an acid group salt, the water-soluble or alkali-soluble acrylic resin has an acid group or an acid group salt from the viewpoint of adhesion (meth). It is preferably a copolymer of an acrylate compound or a copolymer of (meth) acrylic acid, and more preferably a copolymer of (meth) acrylic acid.
When the water-soluble or alkali-soluble acrylic resin has a hydroxy group, the water-soluble or alkali-soluble acrylic resin is a homopolymer or copolymer of a (meth) acrylate compound having a hydroxy group from the viewpoint of adhesion. It is preferably a coalescence.
Although there is no restriction | limiting in particular as said (meth) acrylate compound which has the said hydroxyl group, A hydroxyalkyl (meth) acrylate compound is mentioned preferably and a hydroxyethyl (meth) acrylate is mentioned more preferably.

From the viewpoint of adhesion, the water-soluble or alkali-soluble acrylic resin preferably has an ethylenically unsaturated group, and more preferably has a structural unit having an ethylenically unsaturated group.
Examples of the ethylenically unsaturated group include a (meth) acryl group, an allyl group, a vinyl group, and a styryl group (aromatic vinyl group). Among these, a (meth) acryloxy group or an allyl group is preferable, and an allyl group is more preferable.

The water-soluble or alkali-soluble acrylic resin has a weight average molecular weight of 1,000 or more from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in the developer after exposure, and transferability. It is preferably 2,000 to 100,000, more preferably 10,000 to 50,000.

The said intermediate | middle layer may contain the said water-soluble or alkali-soluble acrylic resin individually by 1 type, or may contain 2 or more types.
The content of the water-soluble or alkali-soluble acrylic resin in the intermediate layer is from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in a developer after exposure, and transferability. It is preferably 10% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 100% by mass or less, and further preferably 40% by mass or more and 100% by mass or less, based on the total mass of the intermediate layer. It is particularly preferably 60% by mass or more and 100% by mass or less.

-Resins other than the above water-soluble or alkali-soluble acrylic resins-
The intermediate layer may contain a resin other than the water-soluble or alkali-soluble acrylic resin, and from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability, the water-soluble or alkali-soluble acrylic resin. It is preferable to contain other water-soluble or alkali-soluble resins.

Examples of the resin other than the water-soluble or alkali-soluble acrylic resin include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p (May be either-or m- / p-mixed) Phenol resins such as mixed formaldehyde resins or novolac resins, pyrogallol acetone resins, polyhydroxystyrene resins, modified cellulose resins, starches, glycogens, chitins, agaroses, Carrageenans, pullulans, gum arabic, soya gum, polyamide resins, epoxy resins, polyacetal resins, acrylic resins other than the above water-soluble or alkali-soluble acrylic resins, polystyrene resins, polyurethane Tan resins, polyvinyl alcohol resins, polyvinyl formal, polyamide resin, polyester resin, polyethyleneimine, polyallylamine, polyalkylene glycol, and the like.

Among these, as the water-soluble or alkali-soluble resin other than the water-soluble or alkali-soluble acrylic resin, from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability, a phenol resin, a modified cellulose resin, and It is preferably at least one resin selected from the group consisting of polyvinyl alcohol resins, and more 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, hydroxypropylmethylcellulose phthalate and the like.
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.

The weight average molecular weight of the resin other than the water-soluble or alkali-soluble acrylic resin is 1 from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in the developer after exposure, and transferability. Of 2,000 to 100,000, preferably 2,000 to 100,000, more preferably 10,000 to 50,000.

The intermediate layer may contain one kind of resin other than the water-soluble or alkali-soluble acrylic resin alone, or may contain two or more kinds.
The content of the resin other than the water-soluble or alkali-soluble acrylic resin in the intermediate layer is such that the adhesion between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in the developer after exposure, and transferability. From the viewpoint, it is preferably 0% by mass to 90% by mass, more preferably 0% by mass to 80% by mass, and more preferably 5% by mass to 60% by mass with respect to the total mass of the intermediate layer. It is particularly preferred.

-particle-
The intermediate layer may contain particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer.
From the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, the particles are preferably metal oxide particles or organic particles, and an oxidation of an element selected from the group consisting of Si, Ti, and Zr. More preferably, it is a physical particle or an organic particle.
Note that the metal of the metal oxide particles in the present disclosure includes metalloids such as B, Si, Ge, As, Sb, and Te.
As the metal oxide particles, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B Oxide particles containing atoms such as Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc. are preferred, silica, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide, or Antimony / tin oxide is more preferable, silica, titanium oxide, titanium composite oxide, or zirconium oxide is further preferable, and silica, titanium oxide, or zirconium oxide is particularly preferable.
As the organic particles, organic resin particles are preferably exemplified.
Examples of the organic resin particles include homopolymers and copolymers of acrylic acid monomers such as acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester, and cellulose polymers such as nitrocellulose, methylcellulose, ethylcellulose, and cellulose acetate. , Polyethylene, polypropylene, polystyrene, vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, polyvinyl pyrrolidone, polyvinyl butyral, vinyl polymers such as polyvinyl alcohol, and copolymers of vinyl compounds, polyesters, polyurethanes, polyamides Condensation polymers such as butadiene-styrene copolymers, rubber-based thermoplastic polymers such as butadiene-styrene copolymers, polymers obtained by polymerizing and crosslinking photopolymerizable or thermopolymerizable compounds such as epoxy compounds, Min compounds and the like.
Among these, acrylic resin particles are preferable as the organic particles, and polymethyl methacrylate particles are more preferable.
Moreover, the surface of these particles can be treated with an organic material or an inorganic material in order to impart dispersion stability. The particles are preferably particles having a hydrophilic surface. For example, the surface of particles having a hydrophobic surface may be subjected to a hydrophilic treatment.

The arithmetic average particle diameter of the particles is preferably 400 nm or less, more preferably 250 nm or less, and further preferably 150 nm or less, from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer. A thickness of 10 nm to 200 nm is particularly preferable.
The method for measuring the arithmetic average particle diameter of particles in the present disclosure refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the maximum diameter is taken as the diameter.

The volume fraction of the particles in the intermediate layer (volume ratio of particles in the intermediate layer) is 5% to 90% with respect to the total volume of the intermediate layer from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer. It is preferably 10% to 80%, more preferably 15% to 70%, and particularly preferably 20% to 60%.

-Dye-
From the viewpoint of easy confirmation of the exposure pattern, the intermediate layer contains a dye having a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development of 450 nm or more, and the maximum absorption wavelength being changed by an acid, base or radical. Is preferred.
“The maximum absorption wavelength is changed by an acid, base or radical” when the dye is in a state where the dye in a colored state is decolored by an acid, base or radical, and the dye in a decolored state is colored by an acid, base or radical It may refer to any of the embodiments in which the dye in a colored state changes to a colored state in another hue.
Specifically, the dye may be a compound that changes color from a decolored state upon exposure or a compound that changes color from a developed state upon exposure. In this case, the dye may be changed in coloration or decoloration by introducing an acid, base or radical into the composition by exposure, and the properties in the system (by introducing the acid, base or radical) For example, it may be a dye whose coloring or decoloring state changes as the pH changes. Further, it may be a dye whose color development or decoloring state is changed by direct application of acid, base or radical as a stimulus without exposure.
Among them, the dye may be a compound that develops color by exposure or a compound that erases by exposure, but from the viewpoint of visibility, it is preferably a compound that can be erased by exposure. More preferably, it is a latent dye that is decolored by an acid generated from the acid, that is, a pH sensitive dye that is decolored by changing the pH due to the generation of an acid.

Confirmation of the pH-sensitive dye can be performed by the following method.
0.1 g of the dye is dissolved in 100 mL of a mixed solution of ethanol and water (ethanol / water = 1/2 [mass ratio]), and 0.1 mol / L (1N) aqueous hydrochloric acid solution is added to adjust to pH = 1. Titrate with 0.01 mol / L (0.01 N) aqueous sodium hydroxide to confirm the color change and the pH at which the color change appears. The pH is a value measured at 25 ° C. using a pH meter (model number: HM-31, manufactured by Toa DKK Co., Ltd.).

The dye has a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development of 450 nm or more, and from the viewpoint of visibility, is preferably 550 nm or more, more preferably 550 nm to 700 nm, and more preferably 550 nm to 650 nm. More preferably it is.
Further, the dye may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development, or may have two or more. When the dye has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm at the time of color development, among the maximum absorption wavelengths at the time of at least one two or more color development, the maximum absorption wavelength at the time of color development with the highest absorbance is 450 nm. That is all you need.

The measurement method of the maximum absorption wavelength in the present disclosure is to measure a transmission spectrum in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) at 25 ° C. in an air atmosphere. The wavelength at which the light intensity is minimized (maximum absorption wavelength) is measured.

Examples of the dye that develops or decolors upon exposure include leuco compounds.
Examples of the dye that can be erased by exposure include leuco compounds, diphenylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, anthraquinone dyes, and the like.
Among these, as the pigment, a leuco compound is preferable from the viewpoint of visibility.
Examples of the leuco compound include triarylmethane-based (for example, triphenylmethane-based), spiropyran-based, fluoran-based, diphenylmethane-based, rhodamine lactam-based, indolylphthalide-based, leucooramine-based leuco compounds. Among them, a leuco compound (triarylmethane dye) having a triarylmethane skeleton is preferable, and a triphenylmethane dye is more preferable.
In addition, from the viewpoint of visibility, the leuco compound preferably has a lactone ring, sultin ring, or sultone ring, and the lactone ring, sultin ring, or sultone ring is preferably opened or closed, and has a sultone ring. And it is more preferable that it is a leuco compound in which a sultone ring is closed and decolored.

The dye is preferably a water-soluble compound for the purpose of preventing defects due to precipitation of the dye in the aqueous resist stripping solution.
Water-soluble means that the amount of the dye dissolved in 100 parts by mass of water at 25 ° C. is 0.1 parts by mass or more (preferably 1 part by mass or more, more preferably 5 parts by mass or more).

Among the above, the dye is preferably a compound represented by the following formula PI from the viewpoint of visibility.

In formula PI, Ar ^1p and Ar ^2p each independently represent an aromatic group, and R ^1p to R ^4p each independently represent a hydrogen atom or a monovalent substituent.

The aromatic group in Ar ^1p and Ar ^2p may be an aryl group, a heteroaryl group, or a monocyclic aromatic group, which is a condensed ring in which two or more rings are condensed. May be.
Ar ^1p and Ar ^2p may combine to form a ring.
The aromatic group in Ar ^1p and Ar ^2p may have a substituent.
Examples of the substituent include a hydroxyl group, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylarylamino group, a diarylamino group, a dialkylamino group, an alkylarylamino group, A diarylamino group is preferred. The halogen atom is preferably a bromine atom or an iodine atom, and more preferably a bromine atom. In addition, each of the alkyl groups is preferably independently an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.
These substituents may be further substituted with a substituent.
The total carbon number of Ar ^1p and Ar ^2p is each independently preferably 4 to 50, more preferably 6 to 40, and still more preferably 10 to 30 from the viewpoints of sensitivity and visibility. .
R ^1p to R ^4p each independently include a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylarylamino group, a diarylamino group, and the like. Of these, a hydrogen atom is preferable.

As preferred specific examples of the dye, compounds PI-1 to PI-3 are described below, but it is needless to say that the dye in the present disclosure is not limited thereto.

The dye may be used alone or in combination of two or more.
The content of the pigment in the intermediate layer is preferably 0.01% by mass to 10% by mass and preferably 0.1% by mass to 8% by mass with respect to the total mass of the intermediate layer from the viewpoint of visibility. More preferably, it is more preferably 0.5% by mass to 5% by mass, and particularly preferably 1.0% by mass to 3.0% by mass.

-Other additives-
The intermediate layer in the present disclosure may contain a known additive as necessary in addition to the above components.
As other additives, other additives used in the photosensitive resin layer described later are preferably exemplified.
The intermediate layer may contain a colorant.

-Average thickness of intermediate layer-
The average film thickness of the intermediate layer is preferably 0.05 μm to 10 μm, more preferably 0.05 μm to 5 μm, more preferably 0.05 μm from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability. Is more preferably 3 μm, and particularly preferably 0.05 μm to 1 μm.
The average film thickness of the intermediate layer is preferably 3 μm or less from the viewpoint of storage stability.
There is no restriction | limiting in particular in the measuring method of the average film thickness of each layer in this indication, A well-known method can be used. The average value is preferably measured and calculated at 10 points or more.
Specific examples include surface shape measurement and cross-sectional optical microscope or electron microscope observation. 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.

-Formation method of intermediate layer-
The method for forming the intermediate layer is not particularly limited, but each component and a solvent (preferably an aqueous solvent) are mixed at a predetermined ratio and in an arbitrary method, and stirred to dissolve to form the intermediate layer. An intermediate layer forming composition can be prepared. For example, it is possible to prepare a composition by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent. The composition prepared as described above can be used after being filtered using a filter having a pore diameter of 5 μm.
Examples of the aqueous solvent include water and water-soluble solvents such as alcohols.

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 particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
In addition, after forming other layers (for example, a thermoplastic resin layer or the like) described later on the temporary support, an intermediate layer can be applied.

<Water-soluble resin layer>
The photosensitive transfer material according to the present disclosure is water-soluble on the side of the intermediate layer opposite to the side where the photosensitive resin layer is in contact from the viewpoint of post-exposure stability (PED (post exposure delay)). It is preferable to further have a water-soluble resin layer containing a resin, on the side opposite to the side where the photosensitive resin layer is in contact with the intermediate layer, from the group consisting of a phenol resin, a modified cellulose resin, and a polyvinyl alcohol resin. It is more preferable to further have a water-soluble resin layer containing at least one selected water-soluble resin.

The water-soluble resin layer contains a water-soluble resin.
As the water-soluble resin used in the water-soluble resin layer, the water-soluble acrylic resin used in the above-described intermediate layer or the same water-soluble resin as the water-soluble acrylic resin other than the water-soluble acrylic resin can be used. It is the same.
The water-soluble resin layer may contain one type of water-soluble resin, or may contain two or more types.
The content of the water-soluble resin is preferably 50% by mass to 100% by mass with respect to the total mass of the water-soluble resin layer, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer, and preferably 65% by mass to It is more preferably 99% by mass, and particularly preferably 80% by mass to 98% by mass.

The water-soluble resin layer may contain particles.
The particles used for the water-soluble resin layer can be the same as the particles used for the intermediate layer described above, and the preferred embodiments are also the same.
The water-soluble resin layer may contain one kind of particles or two or more kinds.
The content of the particles is preferably 5% by mass or less and more preferably 3% by mass or less with respect to the total mass of the water-soluble resin layer from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer. It is preferably 1% by mass or less.

The water-soluble resin layer may contain other compounds other than those described above.
There is no restriction | limiting in particular in the other compound used for a water-soluble resin layer, The thing similar to the other compound used for the intermediate | middle layer mentioned above can be used, A preferable aspect is also the same.

The average thickness of the water-soluble resin layer is preferably from 0.3 μm to 10 μm, more preferably from 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 3 μm to 2.5 μm.
Moreover, it is preferable that the average thickness of the water-soluble resin layer is thicker than the average thickness of the intermediate layer from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation.
Furthermore, when the photosensitive transfer material according to the present disclosure has both an intermediate layer and a water-soluble resin layer, the total average thickness of the intermediate layer and the water-soluble resin layer is a viewpoint of storage stability and pattern formability. Therefore, 0.3 μm to 10 μm is preferable, 0.3 μm to 5 μm is more preferable, and 0.3 μm to 2.5 μm is particularly preferable.

<< Method for forming water-soluble resin layer >>
There is no restriction | limiting in particular in the formation method of a water-soluble resin layer, A well-known method can be used.
Moreover, when forming a water-soluble resin layer, as a method of forming the said water-soluble resin layer and the said intermediate | middle layer, a sequential coating method or a multilayer coating method can be used suitably.
Even when it is formed by a sequential coating method, the binder component of the water-soluble resin layer and the intermediate layer is a water-soluble resin, so the composition for forming a water-soluble resin layer is applied onto a temporary support and dried. A water-soluble resin layer is formed, and when the intermediate layer forming composition is applied on the formed water-soluble resin layer, a part of the water-soluble resin layer is dissolved and mixed with the intermediate layer forming composition. For example, some of the particles in the intermediate layer forming composition move to the water-soluble resin layer.
Even when a composition for forming a water-soluble resin layer that does not contain particles is used, the water-soluble resin layer may be a layer that contains particles.
When the water-soluble resin layer and the intermediate layer are formed by a multilayer coating method, the mixing is considered to be more remarkable.
From the viewpoint of the liquid stability of the water-soluble resin layer forming composition, the water-soluble resin layer forming composition used for forming the water-soluble resin layer may or may not contain particles. It is preferable that no particles are contained.

Further, the water-soluble resin layer forming composition can be prepared in the same manner as the above-described intermediate layer forming composition. A water-soluble resin layer can be suitably formed by adding a water-soluble solvent to each component, adjusting the viscosity, and applying and drying.

<Photosensitive resin layer>
The photosensitive transfer material according to the present disclosure includes a temporary support, an intermediate layer, and a photosensitive resin layer, and preferably includes the temporary support, the intermediate layer, and the photosensitive resin layer in this order.
The photosensitive resin layer includes a polymer having a structural unit having an acid group protected with an acid-decomposable group, and a photoacid generator, and the polymer contained in the photosensitive resin layer has an acid value. Is an acrylic resin of 10 mg KOH / g or less.
The photosensitive resin layer is a positive photosensitive resin layer, and is preferably a chemically amplified positive photosensitive resin layer.
Photo acid generators such as onium salts and oxime sulfonate compounds described below are protected acids in a binder having an acid group in which the acid generated in response to actinic radiation (active light) is acid-decomposable and protected. Since it acts as a catalyst for the deprotection of the group, the acid generated by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, for example, the power of 10 As a result of so-called chemical amplification, high sensitivity is obtained.
On the other hand, when a quinonediazide compound (NQD) is used as a photoacid generator sensitive to actinic radiation, a carboxy group is generated by a sequential photochemical reaction, but its quantum yield is always 1 or less. Not applicable.

<< A polymer having a structural unit having an acid group protected by acid-decomposability >>
The photosensitive resin layer includes a polymer (also referred to as “specific polymer”) having a structural unit (also referred to as “structural unit A”) having an acid-decomposable and protected acid group.
In addition to the polymer having the structural unit A, the photosensitive resin layer may contain other polymers described later.
The specific polymer is an acrylic resin.

The acid value of the specific polymer in the present disclosure is 10 mgKOH / g or less, and from the viewpoint of storage stability, it is preferably 0 mgKOH / g or more and 8 mgKOH / g or less, and 0 mgKOH / g or more and 5 mgKOH / g or less. Is more preferably 0 mgKOH / g or more and 3 mgKOH / g or less, particularly preferably 0 mgKOH / g or more and 1 mgKOH / g or less, and most preferably 0 mgKOH / g.
In this specification, an acid value means the value measured according to the method as described in JIS K0070 (1992).
In particular, in the case of a photosensitive resin layer containing a hydrophobic acrylic resin having an acid value of 3 mgKOH / g or less, from the viewpoint of storage stability, as the water-soluble or alkali-soluble acrylic resin contained in the intermediate layer, the acid value Preferably contains 30 mg KOH / g or more.

The I / O value of the specific polymer is preferably 1.00 or less, more preferably 0.80 or less, and 0.65 or less from the viewpoint of storage stability and pattern shape. It is particularly preferred. Further, the lower limit value of the I / O value of the specific polymer is preferably 0.30 or more, more preferably 0.40 or more, from the viewpoint of storage stability and pattern shape. Is more preferably 50 or more, and particularly preferably 0.56 or more.
The I / O value in the present disclosure is an I / O value obtained by dividing the inorganic value I based on the organic conceptual diagram by the organic value O.
Regarding the above I / O values, organic conceptual diagram (Yoshio Koda, Sankyo Publishing (1984)); No. 10, 719-725 (1957); Fragrance Journal, No. 34, 97-111 (1979); Fragrance Journal, No. 50, 79-82 (1981); There is a detailed explanation. The concept of the I / O value is that the properties of a compound are divided into an organic group that represents covalent bonding and an inorganic group that represents ionic bonding, and all the organic compounds are orthogonal coordinates named organic axes and inorganic axes. Each of the above points is shown.

In the specific polymer, the structural unit A having an acid-decomposable protected acid group in the specific polymer undergoes a deprotection reaction to be an acid group by the action of a catalytic amount of an acidic substance generated by exposure. This acid group enables a curing reaction.
Hereinafter, preferred embodiments of the structural unit A will be described.

The photosensitive resin layer may further contain a polymer other than the polymer having a structural unit having an acid group protected with an acid-decomposable group.
Moreover, it is preferable that all the polymers contained in the said polymer component are polymers which have at least the structural unit which has the acid group mentioned later, respectively.
The photosensitive resin layer may further contain a polymer other than these. Unless otherwise specified, the polymer component in the present disclosure means a material including other polymers added as necessary. In addition, even if it is a high molecular compound, the compound applicable to the crosslinking agent and dispersing agent mentioned later shall not be contained in the said polymer component.

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

The photosensitive resin layer is a polymer having a structural unit represented by the following formula A as the structural unit A as the specific polymer from the viewpoint of suppressing deformation of the pattern shape, solubility in a developer, and transferability. As the specific polymer, it is more preferable to include a specific polymer having a structural unit represented by the following formula A as the structural unit A and having a glass transition temperature of 90 ° C. or lower.
The specific polymer contained in the photosensitive resin layer may be one type or two or more types.

-Constituent units having acid groups protected with acid-decomposable groups-
The polymer A includes at least a structural unit having an acid group protected with an acid-decomposable group.
By including the polymer A having the structural unit having an acid group protected with an acid-decomposable group, the photosensitive resin layer can be an extremely sensitive chemically amplified positive photosensitive resin layer.
As the “acid group protected with an acid-decomposable group” in the present disclosure, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited. Specific examples of the acid group preferably include a carboxy group and a phenolic hydroxyl group. The acid group protected with an acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an ester group, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester protected with a group represented by the formula A). An acetal functional group such as a group) or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group). Can do.
Among these, the acid-decomposable group is preferably a group having a structure protected in the form of an acetal from the viewpoint of sensitivity and resolution.

The structural unit having an acid group protected with an acid-decomposable group is preferably a structural unit represented by the following formula A from the viewpoint of sensitivity and resolution.

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

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

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

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

Preferable specific examples of the structural unit represented by the formula A having a carboxy group protected with an acid-decomposable group include the following structural units. R ³⁴ represents a hydrogen atom or a methyl group.

The structural unit having an acid group protected with 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.

In Formula A3, R ^B1 and R ^B2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ^B1 and R ^B2 is an alkyl group or an aryl group, and R ^B3 is an alkyl group or Represents an aryl group, 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, and 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, when R ^B1 or R ^B2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ^B1 or R ^B2 is an aryl group, a phenyl group is preferable. R ^B1 and R ^B2 are each independently preferably 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, and more preferably an alkyl group having 1 to 6 carbon atoms.
In addition, the alkyl group and aryl group in R ^B1 to R ^B3 may have a substituent.
In Formula A3, R ^B1 or R ^B2 and R ^B3 may be linked to form a cyclic ether, and R ^B1 or R ^B2 and R ^B3 are preferably linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In Formula A3, X ^B represents a single bond or a divalent linking group, and represents a single bond or an alkylene group, —C (═O) O—, —C (═O) NR ^N —, —O—, or a combination thereof. Are preferable, and a single bond is more preferable. The alkylene group may be linear, branched or cyclic, and may have a substituent. The alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. When X ^B contains —C (═O) O—, 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. R ^N represents an alkyl group or a hydrogen atom, preferably an alkyl group or a hydrogen atom having 1 to 4 carbon atoms, more preferably a hydrogen atom.
In Formula A3, the group containing R ^B1 to R ^B3 and X ^B are preferably bonded to each other at the para position.
In Formula A3, R ^B12 represents a substituent, and is preferably an alkyl group or a halogen atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
In the formula A3, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In formula A3, R ^B4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of lowering the Tg of the polymer.
More specifically, with respect to the total content of the structural unit having an acid group protected by the acid-decomposable group contained in the polymer, the structural unit in which R ^B4 in formula A3 is a hydrogen atom is 20% by mass or more. It is preferable that
In the structural unit having an acid group protected with an acid-decomposable group, the content (content ratio: mass ratio) of the structural unit in which R ^B4 in formula A3 is a hydrogen atom is ¹³ C-nuclear magnetic resonance. It can be confirmed by the intensity ratio of the peak intensity calculated from the spectrum (NMR) measurement by a conventional method.

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 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^B12 represents a substituent, and n is 0 Represents an integer of ~ 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, and is preferably an alkyl group or a halogen atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
In the 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 A4 represented by the formula A4 include the following structural units. R ^B4 represents a hydrogen atom or a methyl group.

The structural unit having an acid group protected by the acid-decomposable group contained in the polymer A may be one type or two or more types.
The content of the structural unit having an acid group protected by the acid-decomposable group in the polymer A is preferably 10% by mass or more with respect to the total mass of the polymer A, and is preferably 10% by mass to 90% by mass. %, More preferably 20% by mass to 70% by mass.
The content (content ratio: mass ratio) of the structural unit having an acid group protected by the acid-decomposable group in the polymer A is confirmed by the intensity ratio of the peak intensity calculated by ¹³ C-NMR measurement by a conventional method. can do.
Moreover, after decomposing all the polymer components into structural units (monomer units), the content ratio of the structural unit having an acid group protected by the acid-decomposable group in the polymer component is the total content of the polymer components. The mass is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 80% by mass, and particularly preferably 20% by mass to 70% by mass.

From the viewpoints of developability and resolution, the polymer A is a structural unit other than a structural unit having an acid group protected with an acid-decomposable group (for example, a structural unit having a pKaH group of 3 or more, an acid group, And other structural units).

-Structural unit having an acid group-
The said specific polymer may further have the structural unit which has an acid group in the range whose acid value is 10 mgKOH / g or less.
The structural unit having an acid group is a structural unit having a protective group, for example, an acid group that is not protected by an acid-decomposable group, that is, an acid group that has no protective group. By including a polymer having a structural unit having an acid group in the polymer component, the sensitivity at the time of pattern formation becomes good, and it becomes easier to dissolve in an alkaline developer in the development process after pattern exposure, thereby shortening the development time. Can be planned.
The acid group in this specification means a proton dissociable group having a pKa of 12 or less. The acid group is usually incorporated into the polymer as a structural unit having an acid group using a monomer capable of forming an acid group. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. The pKa of the acid group is preferably −5 or more.

Having at least a constituent unit having an acid group not protected by an acid-decomposable group in any of the polymers in the polymer component, and setting the glass transition temperature of the polymer component to 90 ° C. or less, The positive type photosensitive resin layer to be contained has better resolution and sensitivity at the time of pattern formation while maintaining transferability and peelability from the temporary support at good levels.

Examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonylimide group. Among these, at least one acid group selected from the group consisting of a carboxy group and a phenolic hydroxyl group is preferable.
The introduction of the structural unit having an acid group into the polymer can be carried out by copolymerizing a monomer having an acid group.
The structural unit having an acid group is more preferably a structural unit derived from styrene or a structural unit obtained by substituting an acid group for a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid. preferable.

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

The structural unit having an acid group contained in the specific polymer may be only one type or two or more types.
When the specific polymer has a structural unit having an acid group, the structural unit having an acid group is preferably contained in an amount of 0.1% by mass to 20% by mass with respect to the total mass of the specific polymer. More preferably, it is contained in an amount of ˜10% by mass, and more preferably 0.1% by mass to 5% by mass. When it is in the above range, the pattern formability becomes better.
The content (content ratio: mass ratio) of the structural unit having an acid group in the polymer can be confirmed by the intensity ratio of peak intensity calculated by ¹³ C-NMR measurement by a conventional method.

-Structural unit in which pKaH has 3 or more groups-
The specific polymer preferably further includes a structural unit having a pKaH group of 3 or more from the viewpoint of storage stability.
PKaH in the present disclosure is a pKa of a conjugate acid, and a group having a pKaH of 3 or more represents a group having a pKa of a conjugate acid of the group of 3 or more. For example, the value of pKaH of —NH ₂ is the value of pKa of —NH ₃ ⁺ .
Further, in the present disclosure, it 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, from the viewpoints of resolution and retention time-dependent suppression. The group is more preferably 5 or more and 15 or less, and particularly preferably a group having a pKaH of 6 or more and 10 or less.

The group having a 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, an aromatic amino group, or a nitrogen-containing complex. It is more preferably an aromatic ring group, further preferably an aliphatic amino group or a nitrogen-containing heteroaromatic ring group, and particularly preferably an aliphatic amino group.
The aliphatic amino group may be any of a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoints of resolution and retention time dependence suppression, It is preferably a secondary amino group or a tertiary amino group.
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 a pyridine ring. Is particularly preferred.
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-penta Examples include an alkyl-4-piperidyl group and a 2,2,6,6-tetraalkyl-4-piperidyl group.

The structural unit having a pKaH group of 3 or more is preferably a structural unit represented by the following formula I or formula II from the viewpoint of resolution and retention time-dependent inhibition properties, and represented by the following formula I: More preferably, it is a structural unit.

In Formulas I and II, 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) —. Represents O—, and R ₂ may have a single bond or at least one group 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 of 1 to 10, wherein R ₃ and R ₄ are each independently a hydrogen atom, or an ether bond, a thioether bond, a hydroxy group, a formyl group, an acetoxy group, a cyano group A linear group having 1 to 20 carbon atoms which may have at least one group selected from the group consisting of a group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond, and an aromatic group Represents a branched or cyclic alkyl group, R ₂ and R ₃ , R ₂ and R ₄ , or R ₃ and R ₄ may be bonded to each other to form a ring, and Q ₁ is a nitrogen atom Represents an aromatic group having nitrogen or a nitrogen-containing heteroaromatic group.

Z in Formula I is a single bond, an arylene group, —C (═O) —NH— or —C (═O) —O— from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. It is preferably an arylene group or —C (═O) —O—, more preferably —C (═O) —NH— or —C (═O) —O—.
Z in Formula II is preferably a single bond, an arylene group, or —C (═O) —O—, and is a single bond, from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. Is more preferable.
R ₂ in Formula I 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, and 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 preferably a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms.
R ₂ in Formula II is preferably a single bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis.

R ₃ and R ₄ in Formula I are each independently a hydrogen atom or a carbon number of 1 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 of ˜20, more preferably a hydrogen atom or a linear, branched or cyclic alkyl group of 1 to 20 carbon atoms.
Further, in the formula I, from the viewpoints of resolution and retention time dependence suppression, an embodiment in which R ₂ , R ₃ and R ₄ in the formula I are combined to form a nitrogen-containing aliphatic ring is preferable, An embodiment in which a piperidine ring is formed is more preferable.
Q ₁ in Formula II is preferably a nitrogen-containing heteroaromatic group from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis, and is pyridyl, methylpyridyl, imidazolyl, methylimidazolyl Group or a triazolyl group is more preferable, a pyridyl group is more preferable, and a 4-pyridyl group is particularly preferable.

Specific examples of the monomer that forms a structural unit having a pKaH group of 3 or more include the following monomers.
1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2- (dimethylamino) ethyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2,2 methacrylate , 6,6-tetramethyl-4-piperidyl, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, acrylic acid 2- (diethylamino) ethyl, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate, N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino acrylate) ) Propyl, 2-morpholinoethyl methacrylate, 2-morpholinoethyl acrylate, allylamine, 4 Aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allyl imidazole.

The structural unit having a pKaH group of 3 or more includes an amino group or a nitrogen-containing heterocycle described in paragraph 0140 of JP-A-2015-187634 or paragraphs 0068 to 0070 of JP-A-2011-39266. Also included are monomers having groups.

The pKaH contained in the specific polymer may have only one type of structural unit having 3 or more groups, or two or more types of structural units.
The content of the structural unit having the pKaH group of 3 or more in the specific polymer is 0.01% by mass or more and 30% by mass with respect to the total mass of the polymer from the viewpoint of resolution and storage stability. Is preferably 0.05% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, and further preferably 0.4% by mass or more and 4% by mass or less. It is particularly preferable that the ratio be 0.6 mass% or more and 2 mass% or less.
The content (content ratio: mass ratio) of the structural unit having a pKaH group of 3 or more in the polymer A 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 specific polymer has other constituents other than the constituent unit having an acid group protected with an acid-decomposable group, a constituent unit having an acid group, and a constituent unit having a pKaH of 3 or more. The unit may be included in a range not impairing the effect of the photosensitive transfer material according to the present disclosure.
There is no restriction | limiting in particular as a monomer which forms other structural units, For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid Diester, bicyclounsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, group having aliphatic cyclic skeleton, other Mention may be made of unsaturated compounds.
Various characteristics of the polymer can be adjusted by adjusting at least one of the type and content using other structural units. In particular, the Tg of the polymer component can be easily adjusted to 90 ° C. or lower by appropriately using other structural units.
The polymer may contain only 1 type of other structural units, and may contain 2 or more types.

Other structural units are specifically 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 the like. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be given.

As other structural units, structural units having an aromatic ring or structural units having an aliphatic cyclic skeleton are preferable from the viewpoint of improving the electrical properties of the obtained transfer material. Specific examples of monomers that form these structural units include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, And benzyl (meth) acrylate etc. are mentioned. Especially, the structural unit derived from a cyclohexyl (meth) acrylate is mentioned preferably.

In addition, as a monomer that forms other structural unit, 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. Among these, at least one monomer selected from the group consisting of methyl (meth) acrylate and ethyl (meth) acrylate is particularly preferable.

The content of other structural units is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less with respect to the total mass of the polymer. The lower limit may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more. Within the above range, the resolution and adhesion are further improved.

-Glass transition temperature of specific polymer: Tg-
The glass transition temperature (Tg) of the specific polymer in the present disclosure is preferably 90 ° C. or lower. When the Tg is 90 ° C. or lower, the photosensitive resin layer has high adhesion and is excellent in transferability.
The Tg is more preferably 60 ° C. or less, and further preferably 40 ° C. or less.
The lower limit of Tg is not particularly limited, but is preferably −20 ° C. or higher, and more preferably −10 ° C. or higher. When the Tg of the specific polymer 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.
Furthermore, the glass transition temperature (Tg) of the entire polymer component in the present disclosure is preferably 90 ° C. or lower, more preferably 60 ° C. or lower, and 40 ° C. or lower from the viewpoint of transferability. Is more preferable.

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

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

-Molecular weight of polymer: Mw-
The molecular weight of the specific polymer is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. When the weight average molecular weight of the specific polymer is 60,000 or less, the melt viscosity of the photosensitive resin layer is suppressed to be low, and the bonding at a low temperature (for example, 130 ° C. or less) is realized when bonding to the substrate. Can do.
Further, the weight average molecular weight of the specific polymer is preferably 2,000 to 60,000, and more preferably 3,000 to 50,000.
In addition, the weight average molecular weight and number average molecular weight of the polymer can be measured by GPC (gel permeation chromatography), and various commercially available apparatuses can be used as the measuring apparatus, and the contents of the apparatus, and Measurement 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 Corporation) was used as a measuring device, and TSKgel (registered trademark) Super HZM-M (4 .6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ4000 (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ2000 (4.6 mm ID) × 15 cm, manufactured by Tosoh Corp.), each connected in series, and THF (tetrahydrofuran) can be used as an eluent.
Measurement conditions are 0.2% by mass, flow rate is 0.35 ml / min, sample injection amount is 10 μl, 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 produced by using two or more of any of the seven samples of “A-2500” and “A-1000”.

The ratio (dispersion degree) between the number average molecular weight and the weight average molecular weight of the specific polymer is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

-Manufacturing method of specific polymer-
The production method (synthesis method) of the specific polymer is not particularly limited. For example, a polymerizable monomer for forming the structural unit A1 represented by the formula A and a structural unit B having an acid group are formed. It is possible to synthesize by polymerizing using a polymerization initiator in an organic solvent containing a polymerizable monomer for the purpose, and further, if necessary, a polymerizable monomer for forming other structural unit C. it can. It can also be synthesized by so-called polymer reaction.

In the present disclosure, the photosensitive resin layer is 50% by mass to 99.9% by mass of the polymer component with respect to the total solid content of the photosensitive resin layer, from the viewpoint of developing good adhesion to the substrate. Preferably, it is contained in a proportion of 70% by mass to 98% by mass.
In addition, the photosensitive resin layer has a specific polymer content of 50% by mass to 99.9% by mass with respect to the total solid content of the photosensitive resin layer, from the viewpoint of developing good adhesion to the substrate. It is preferably contained in a proportion, more preferably in a proportion of 70% by mass to 98% by mass.

<< other polymers >>
In addition to the specific polymer, the photosensitive resin layer is a polymer having no structural unit having an acid group protected with an acid-decomposable group within a range not impairing the effect of the photosensitive transfer material according to the present disclosure ( It may be referred to as “other polymer”). When the photosensitive resin layer contains another polymer, the blending amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less in the total polymer component, More preferably, it is 20 mass% or less.

In addition to the specific polymer, the photosensitive resin layer may contain only one type of other polymer, or may contain two or more types.
As other polymers, for example, polyhydroxystyrene can be used and are commercially available, such as 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.), and Joncryl 690, Joncryl 6 Joncryl 67, Joncryl 586 (manufactured by BASF) or the like can also be used.

<< Photoacid generator >>
The photosensitive resin layer contains a photoacid generator.
The photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiation with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
The photoacid generator used in the present disclosure is preferably a compound that generates an acid in response to an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, 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 be used as a sensitizer as long as 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 used in the present disclosure 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 pKa of 2 or less. A photoacid generator that generates an acid is particularly preferable. The lower limit of pKa is not particularly defined, but is preferably −10.0 or more, for example.

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

Examples of nonionic photoacid generators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, the photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP 2011-212494A.

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

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

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

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

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

A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
The content of the photoacid generator in the photosensitive resin layer is preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of sensitivity and resolution. More preferably, the content is 5% by mass to 5% by mass.

<< benzotriazole compound >>
The photosensitive resin layer preferably contains a benzotriazole compound from the viewpoint of pattern shape and linearity of circuit wiring formed by etching.
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, 2-ethyl-2H-benzotriazo And the like.

Also, the benzotriazole compound is preferably a compound represented by the following formula (1) from the viewpoint of pattern shape and linearity of circuit wiring formed by etching.

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), 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. , -ZY group and the like.

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 a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, an octyl group, a decyl group, and a dodecyl group. Etc.

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 the 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 2 to 8 carbon atoms, and particularly preferably a carbon number. 2 to 4 acyl groups. Examples of the acyl group having 1 to 12 carbon atoms include acetyl group, propionyl group, butanoyl group, benzoyl group and the like.

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. Octyl group, decyl group and the like.

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, decyl group and the like.

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. It is 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, decyl group and the like.

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. Group, alkoxyacyl group and the like.

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 methoxy group, ethoxy group, butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group and the like.

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), dodecyl An oxyacyl group (namely, dodecyloxycarbonyl group) etc. are 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 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 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; More 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 may be substituted with a carboxy group. An alkylene group having 1 or 2 carbon atoms, and Y is each 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, carboxy 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 0.01% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of transferability, pattern shape, and linearity of circuit wiring formed by etching. It is preferably 0.05% by mass to 10% by mass, more preferably 0.05% by mass to 2% by mass, and even more preferably 0.05% by mass to 1% by mass. Is particularly preferred.

<< basic compound >>
The photosensitive resin layer may further contain a basic compound.
The molecular weight of the basic compound in the present disclosure is less than 2,000, and preferably less than 1,000.
Moreover, the basic compound in this indication shall be compounds other than the said benzotriazole compound.
As the basic compound, any basic compound used in a chemically amplified positive resist can be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include compounds described in JP-A-2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.

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

The said basic compound may be used individually by 1 type, or may use 2 or more types together.
The content of the basic compound is preferably 0.001% by mass to 5% by mass, and preferably 0.005% by mass to 3% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of storage stability. % Is more preferable.

<< Other additives >>
The said photosensitive resin layer in this indication can contain a well-known additive as needed besides the said component.

-Surfactant-
The photosensitive resin layer preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic (nonionic), or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . 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), MegaFuck (manufactured by DIC Corporation), and 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.).
Further, as a surfactant, it contains a structural unit A and a structural unit B represented by the following formula I-1, and is a weight average in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferable example is a copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less.

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

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

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

Moreover, as the surfactant, a polymer containing a structural unit having a fluorine atom (hereinafter also referred to as polymer F) is preferably used from the viewpoint of the coated surface and the dimple suppression of the resulting resin pattern. Can do.
In addition, the fluorine atom content in the polymer F is 20% by mass or more and 50% by mass or less with respect to the total mass of the polymer F from the viewpoint of the coated surface and the dimple suppression of the resulting resin pattern. It is preferable that it is 20 mass% or more and 45 mass% or less, and it is especially preferable that it is 20 mass% or more and 40 mass% or less.
The fluorine atom content in the polymer F in the present disclosure is the mass-based fluorine atom content with respect to the entire polymer F. The chemical structure analysis or elemental analysis of the polymer F is performed (in the polymer F It can be calculated from (total mass of fluorine atoms) / (total mass of polymer F).

The I / O value of the polymer F is not particularly limited. However, when the I / O value of the polymer F is less than 0.45, the polymer F has an acid group or a basic group described later. It is preferable that the structural unit which has is included.
The I / O value in the present disclosure is an I / O value obtained by dividing the inorganic value I based on the organic conceptual diagram by the organic value O.
Regarding the above I / O values, organic conceptual diagram (Yoshio Koda, Sankyo Publishing (1984)); No. 10, 719-725 (1957); Fragrance Journal, No. 34, 97-111 (1979); Fragrance Journal, No. 50, 79-82 (1981); There is a detailed explanation. The concept of the I / O value is that the properties of a compound are divided into an organic group that represents covalent bonding and an inorganic group that represents ionic bonding, and all the organic compounds are orthogonal coordinates named organic axes and inorganic axes. Each of the above points is shown.

The I / O value of the polymer F is preferably 0.20 or more, more preferably 0.30 or more, and more preferably 0.30 or more from the viewpoint of suppressing the occurrence of dimples in the resulting pattern. More preferably, it is 50 or less.
In addition, the polymer F preferably includes a structural unit having an acid group or a basic group from the viewpoint of suppressing generation of dimples in a pattern to be obtained and a planar shape.

The glass transition temperature (Tg) of the polymer F is preferably 90 ° C. or less, more preferably 50 ° C. or less, from the viewpoints of pattern formability, transferability, and surface shape of the resulting pattern. The temperature is more preferably −30 ° C. or more and 50 ° C. or less, and particularly preferably −10 ° C. or more and 20 ° C. or less. Moreover, when using a cover film as it is the said range, the adhesion defect of a cover film or the peeling defect at the time of peeling a cover film is suppressed.

The weight average molecular weight (Mw) of the polymer F is preferably 2,000 or more, more preferably 2,000 to 100,000, and still more preferably 2,000 to 20,000.
The ratio (Mw / Mn, degree of dispersion) of the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer F is preferably 1.0 to 5.0, more preferably 1.05 to 3.5. .

[Structural unit having fluorine atom]
The polymer F includes a structural unit having a fluorine atom.
The number of fluorine atoms in the structural unit having fluorine atoms is not particularly limited, but is preferably 5 or more and 50 or less, more preferably 7 or more and 30 or less, from the viewpoint of the surface state during coating. More preferably, it is 7 or more and 20 or less.

The structural unit having a fluorine atom preferably has a fluorine atom as a perfluoroalkyl group or a perfluoroaryl group, more preferably as a perfluoroalkyl group, from the viewpoint of planarity at the time of coating. In other words, the structural unit having a fluorine atom preferably has a perfluoroalkyl group or a perfluoroaryl group, and more preferably has a perfluoroalkyl group, from the viewpoint of planarity at the time of coating.
The number of carbon atoms of the perfluoroalkyl group is preferably 4 or more and 30 or less, more preferably 6 or more and 24 or less, and particularly preferably 9 or more and 15 or less, from the viewpoint of the surface state during coating. .

The structural unit having a fluorine atom is preferably a structural unit represented by the following formula F-1 from the viewpoint of planarity during coating.

In Formula F-1, R ^f1 represents a hydrogen atom or a methyl group, X ^f1 represents a single bond, —COO—, —OCO—, or an arylene group, and L ^f1 represents a single bond, an alkylene group, Alternatively, it represents a group in which two or more groups selected from the group consisting of an alkylene group, —COO—, —OCO—, and an arylene group are bonded, and Rf represents a perfluoroalkyl group.

X ^f1 in formula F-1 is preferably a single bond or —COO—, more preferably —COO—, from the viewpoints of availability and synthesis suitability.
L ^f1 in Formula F-1 is an alkylene group or a group in which two or more groups selected from the group consisting of —COO—, —OCO—, and an arylene group are bonded from the viewpoint of availability and synthesis suitability. An alkylene group or a group formed by bonding two or more groups selected from the group consisting of —COO— and —OCO— is more preferable, and an alkylene group is particularly preferable.
The alkylene group may be linear, branched, or have a ring structure. The alkylene group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably a methylene group or an ethylene group.
Rf in Formula F-1 is preferably a perfluoroalkyl group having 4 to 30 carbon atoms, more preferably a perfluoroalkyl group having 4 to 24 carbon atoms, from the viewpoint of the surface state during coating. A perfluoroalkyl group having 9 to 15 carbon atoms is particularly preferred.
The perfluoroalkyl group may be linear, branched, or have a ring structure, but it is possible to suppress dimple generation in the pattern obtained and to obtain a planar view at the time of coating. Therefore, a linear or branched perfluoroalkyl group is preferable, and a linear perfluoroalkyl group is more preferable.

The polymer F may have the structural unit which has a fluorine atom individually by 1 type, or may have 2 or more types.
The structural unit having a fluorine atom is preferably a structural unit different from the structural unit having an acid group or basic group and the structural unit having a hydrophilic group, which will be described later. Moreover, it is preferable that the structural unit which has an acid group or a basic group, and the structural unit which has a hydrophilic group do not have a fluorine atom.
The polymer F preferably contains 20% by mass or more and 99% by mass or less, and 30% by mass or more and 99% by mass or less of a structural unit having a fluorine atom with respect to the total mass of the polymer F, from the viewpoint of planarity at the time of coating. More preferably, it is more preferably 30% by mass or more and 95% by mass or less, and particularly preferably 35% by mass or more and 70% by mass or less.
The content (content ratio: mass ratio) of the structural unit having a fluorine atom in the polymer F can be confirmed by the intensity ratio of the peak intensity calculated by ¹³ C-NMR measurement or ¹⁹ F-NMR measurement by a conventional method. it can.

[Structural unit having acid group or basic group]
The polymer F preferably contains a structural unit having an acid group or a basic group from the viewpoint of suppressing the occurrence of dimples in the resulting pattern, and the I / O value of the polymer F is less than 0.45. In this case, it is more preferable to include a structural unit having an acid group or a basic group.

The pKa of the acid group in the structural unit having an acid group in the polymer F is preferably 10 or less, more preferably 6 or less, from the viewpoint of improving sensitivity. The pKa of the acid group is preferably −5 or more.
Examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonylimide group. Among these, at least one acid group selected from the group consisting of a carboxy group and a phenolic hydroxyl group is preferable.
The introduction of the structural unit having an acid group into the polymer can be carried out by copolymerizing a monomer having an acid group.
The structural unit having an acid group is more preferably a structural unit derived from styrene or a structural unit obtained by substituting an acid group for a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid. preferable.

The structural unit having an acid group is preferably a structural unit having a carboxy group or a structural unit having a phenolic hydroxyl group, from the viewpoint of pattern formation and suppression of the occurrence of dimples in the resulting pattern, and has a carboxy group. A structural unit is more preferable.
The monomer having an acid group that can form a structural unit having an acid group is not limited to the examples described above.

The structural unit having an acid group contained in the polymer F may be only one type or two or more types.
The polymer F contains 0.1% by mass to 20% by mass of a structural unit having an acid group with respect to the total mass of the polymer F, from the viewpoints of pattern formability and suppression of occurrence of dimples in the resulting pattern. The content is preferably 0.5% by mass to 15% by mass, more preferably 1% by mass to 10% by mass.
The content (content ratio: mass ratio) of the structural unit having an acid group in the polymer F can be confirmed by the intensity ratio of the peak intensity calculated by ¹³ C-NMR measurement by a conventional method.

The basic group is preferably a group having a nitrogen atom from the viewpoint of pattern formation and suppression of dimple formation in the resulting pattern, and is preferably an aliphatic amino group, an aromatic amino group, or a nitrogen-containing complex. It is more preferably an aromatic ring group, further preferably an aliphatic amino group or a nitrogen-containing heteroaromatic ring group, and particularly preferably an aliphatic amino group.
The aliphatic amino group may be a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoint of suppressing the occurrence of dimples in the pattern obtained and a planar shape, It is preferably a secondary amino group or a tertiary amino group, more preferably a tertiary amino group.
The tertiary amino group is preferably a dialkylamino group or an N-alkylmorpholino group.
The structural unit having a basic group is preferably a structural unit derived from a (meth) acrylate compound.

The structural unit having a basic group contained in the polymer F may be only one type or two or more types.
From the viewpoint of pattern formation and suppression of dimple formation in the resulting pattern, the polymer F contains 0.1% by mass to 50% by mass of a structural unit having a basic group with respect to the total mass of the polymer F. It is preferably contained, more preferably 1% by mass to 40% by mass, and even more preferably 5% by mass to 30% by mass.
The content (content ratio: mass ratio) of the structural unit having a basic group in the polymer F can be confirmed by the intensity ratio of peak intensity calculated by ¹³ C-NMR measurement by a conventional method.

The structural unit having an acid group or basic group is preferably a structural unit represented by the following formula F-2 from the viewpoint of suppressing the occurrence of dimples in the resulting pattern.

In Formula F-2, R ^f2 represents a hydrogen atom or a methyl group, X ^f2 represents a single bond, —COO—, —OCO—, or an arylene group, and L ^f2 represents a single bond, an alkylene group, Alternatively, it represents a group in which two or more groups selected from the group consisting of an alkylene group, —COO—, —OCO— and an arylene group are bonded, and R ^p represents an acid group or a basic group.

X ^f2 in Formula F-2 is preferably a single bond or —COO— from the viewpoints of availability and synthesis suitability.
L ^f2 in Formula F-2 is a single bond, an alkylene group, or two or more groups selected from the group consisting of an alkylene group, —COO—, and —OCO— bonded from the viewpoint of availability and synthesis suitability. It is preferably a group, more preferably a single bond or an alkylene group.
The alkylene group may be linear, branched, or have a ring structure. The alkylene group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably an ethylene group or a propylene group.
R ^p in Formula F-2 is preferably a carboxy group or a group having a nitrogen atom from the viewpoint of suppressing the occurrence of dimples in the resulting pattern, and a group having a carboxy group or a tertiary amino group Of these, a carboxy group, a dialkylamino group, or an N-alkylmorpholino group is particularly preferable.

Moreover, the structural unit which has the said acid group or basic group may further have the hydrophilic group mentioned later other than an acid group and a basic group.
Furthermore, the structural unit having an acid group or a basic group is a structural unit different from the structural unit having a hydrophilic group described later.

[Structural unit having hydrophilic group]
The polymer F preferably contains a structural unit having a hydrophilic group, and more preferably contains a structural unit having a hydrophilic group in the side chain, from the viewpoint of suppressing the occurrence of dimples in the resulting pattern.
In the present disclosure, “main chain” represents a relatively long bond chain in the molecule of the polymer compound constituting the resin, and “side chain” represents a carbon chain branched from the main chain. .
Hydrophilic groups include hydroxy group, ether bond, thioether bond, carbonyl group, amide structure, lactone structure, ester bond, thioester bond, urea bond, thiourea bond from the viewpoint of suppressing dimple generation in the resulting pattern and planarity. And at least one structure selected from the group consisting of a urethane bond and a cyano group is preferred, a hydroxy group, an ether bond, a thioether bond, a carbonyl group, an amide structure, a lactone structure, a thioester bond, a urea bond, a thiourea bond, and a urethane More preferable is at least one structure selected from the group consisting of a bond and a cyano group, and at least selected from the group consisting of a hydroxy group, an ether bond, an amide structure, a lactone structure, a urea bond, a urethane bond, and a cyano group. One kind of structure The preferred, hydroxy group, and particularly preferably a chain ether structure or a cyclic ether group.
In other words, the polymer F has a hydroxy group, an ether bond, a thioether bond, a carbonyl group, an amide structure, a lactone structure, an ester bond, and a thioester bond from the viewpoint of suppressing the occurrence of dimples in the pattern obtained and the surface state during coating. A structural unit having at least one structure selected from the group consisting of a urea bond, a thiourea bond, a urethane bond, and a cyano group, a hydroxy group, an ether bond, a thioether bond, a carbonyl group, an amide structure, At least one structure selected from the group consisting of a lactone structure, a thioester bond, a urea bond, a thiourea bond, a urethane bond, and a cyano group is more preferable, and a hydroxy group, an ether bond, an amide structure, a lactone structure, a urea bond, and a urethane Bond and cyano More preferably comprising a structural unit having at least one structure selected from the group consisting of, and particularly preferably contains a structural unit having a hydroxy group or a cyclic ether group.
The cyclic ether group is preferably a group having a 4-membered to 6-membered cyclic ether ring, more preferably a group having a 5-membered or 6-membered cyclic ether ring. Particularly preferred is a group having a cyclic ether ring.
Among them, the cyclic ether group is preferably a tetrahydrofuranyl group or a tetrahydropyranyl group, and more preferably a tetrahydrofuranyl group.
The carbonyl group and the ether bond mean a carbonyl group and an ether bond that do not form an ester bond.

The structural unit having hydrophilicity is preferably a structural unit represented by the following formula F-3, from the viewpoint of suppressing the generation of dimples in the pattern obtained and the surface state during coating.

In Formula F-3, R ^f3 represents a hydrogen atom or a methyl group, X ^f3 represents a single bond, —COO—, —OCO—, —CONR ^a —, or an arylene group, and L ^f3 represents a single bond Represents a bond, an alkylene group, or a group in which two or more groups selected from the group consisting of an alkylene group, —COO—, —OCO—, —O— and an arylene group are bonded, and R ^aq represents a hydrophilic group. R ^a represents ^a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

X ^f3 in formula F-3 is preferably —COO— or —CONR _a —, more preferably —COO—, from the viewpoint of availability and synthesis suitability.
L ^f3 in Formula F-3 is an alkylene group, or a group selected from the group consisting of —COO—, —OCO—, —O—, and an arylene group, from the viewpoint of availability and surface suitability for synthesis. An alkylene group or a group selected from the group consisting of —COO— and —OCO— is more preferable, and an alkylene group is particularly preferable.
The alkylene group may be linear, branched, or have a ring structure. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably a methylene group or an ethylene group.
R ^aq in Formula F-3 is a hydroxy group, an ether bond, a thioether bond, a carbonyl group, an amide structure, a lactone structure, an ester bond, a thioester bond, or a urea bond, from the viewpoint of suppressing the dimple generation in the resulting pattern. , At least one structure selected from the group consisting of a thiourea bond, a urethane bond, and a cyano group is preferable, and is preferably a hydroxy group, a cyclic ether group, a polyalkyleneoxy group, an alkyleneoxy group, or a cyano group, More preferably, it is a hydroxy group, an alkyleneoxy group or a cyclic ether group.

The polymer F may have the structural unit which has a hydrophilic group individually by 1 type, or may have 2 or more types.
When the polymer F includes a structural unit having a hydrophilic group, the polymer F is hydrophilic from the viewpoints of pattern formability, transferability, generation of dimples in the resulting pattern, and surface conditions during coating. The structural unit having a functional group is preferably contained in an amount of more than 0% by mass and 70% by mass or less, more preferably 5% by mass to 70% by mass, more preferably 10% by mass to 65%, based on the total mass of the polymer F. More preferably, it is contained in an amount of 20% by mass or less, and particularly preferably 20% by mass or more and 60% by mass or less.
The content (content ratio: mass ratio) of the structural unit having a hydrophilic group in the polymer F can be confirmed by the intensity ratio of peak intensity calculated from ¹³ C-NMR measurement by a conventional method.

[Structural unit having an acid group protected with an acid-decomposable group]
The polymer F preferably includes a structural unit having an acid group protected with an acid-decomposable group, from the viewpoint of suppressing the occurrence of dimples in the pattern to be obtained and the surface state during coating.
As the structural unit having an acid group protected with an acid-decomposable group, those similar to the structural unit having an acid group protected with an acid-decomposable group in the specific polymer can be applied.
70 mass% or less is preferable with respect to the total mass of the polymer F, and, as for content of the structural unit which has the acid group protected by the acid-decomposable group in the said polymer F, 50 mass% or less is more preferable, 50 A mass% or less is more preferable. The lower limit may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more. Within the above range, the resolution and adhesion are further improved.
The content (content ratio: mass ratio) of other structural units in the polymer F can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR measurement.

[Other structural units]
The polymer F has the above-described constitutional unit having a fluorine atom, a constitutional unit having an acid group or a basic group, a constitutional unit having a hydrophilic group, and an acid group protected by an acid-decomposable group. Other structural units other than the unit may be included within a range that does not impair the effects of the photosensitive transfer material according to the present disclosure.
There is no restriction | limiting in particular as a monomer which forms other structural units, For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid Examples include diesters, bicyclounsaturated compounds, unsaturated aromatic compounds, conjugated diene compounds, and other unsaturated compounds.
Various characteristics of the polymer can be adjusted by adjusting at least one of the type and content using other structural units. In particular, the Tg of the polymer can be easily adjusted by appropriately using other structural units.

Other structural units are specifically styrene, methyl styrene, α-methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, methyl (meth) acrylate, Examples include structural units formed by polymerizing ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, and the like. it can. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be given.

Further, as a monomer that forms other structural unit, for example, (meth) acrylic acid alkyl ester is preferable from the viewpoint of suppressing the occurrence of dimples in the resulting pattern. 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.

The said polymer F may contain only 1 type of other structural units, and may contain 2 or more types.
70 mass% or less is preferable with respect to the total mass of the polymer F, as for content of the other structural unit in the said polymer F, 60 mass% or less is more preferable, and 50 mass% or less is still more preferable. The lower limit may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more. Within the above range, the resolution and adhesion are further improved.
The content (content ratio: mass ratio) of other structural units in the polymer F can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR measurement.

From the viewpoint of transferability and pattern formability, the other structural unit in the polymer F is preferably a structural unit having a carboxylic acid ester structure, and more preferably a structural unit derived from an alkyl (meth) acrylate. preferable.
Further, from the viewpoint of transferability and pattern formability, the other structural unit in the polymer F is preferably a structural unit represented by the following formula F-4.

In Formula F-4, R ^f4 represents a hydrogen atom or a methyl group, X ^f4 represents a single bond, —COO—, —OCO—, or an arylene group, and L ^f4 represents a single bond, an alkylene group, Or a group in which two or more groups selected from the group consisting of an alkylene group, —COO—, —OCO—, and an arylene group are bonded, and R ^al represents a linear, branched, or cyclic alkyl group, or an aryl group Represents.

X ^f4 in formula F-4 is preferably a single bond or —COO—, more preferably —COO—, from the viewpoints of availability and synthesis suitability.
L ^f4 in Formula F-4 is preferably a single bond from the viewpoints of availability and synthesis suitability.
R ^al in formula F-4 is preferably a linear, branched or cyclic alkyl group, more preferably a linear or cyclic alkyl group, from the viewpoint of transferability and pattern formation.
In addition, the carbon number of R ^al in Formula F-4 is preferably 1 to 30, more preferably 8 to 20, and more preferably 10 to 20 from the viewpoint of transferability and pattern formability. Particularly preferred.
Specific examples of R ^al in Formula F-4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl, cyclohexyl group, 2-ethylhexyl group, n from the viewpoint of transferability and pattern formation. -Octyl group, n-decyl group, n-dodecyl group, dicyclopentanyl group and benzyl group are preferred, and cyclohexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group More preferred are a group and a dicyclopentanyl group, and particularly preferred are an n-dodecyl group and a dicyclopentanyl group.

The said polymer F may contain only 1 type of other structural units, and may contain 2 or more types.
In the case where the polymer F contains the structural unit represented by the formula F-4, the structural unit represented by the formula F-4 is all of the polymer F from the viewpoint of transferability and pattern formation. 1% to 70% by mass, preferably 10% to 60% by mass, more preferably 20% to 50% by mass, and more preferably 25% to 50% by mass with respect to the mass. It is particularly preferred.

The polymer F only needs to contain a structural unit having a fluorine atom. However, from the viewpoint of transferability, pattern formation, and dimple generation suppression and planarity in the resulting pattern, the structural unit having a fluorine atom. It is preferable to include a structural unit having a hydrophilic group, and it is more preferable to include a structural unit having a fluorine atom, a structural unit having a hydrophilic group, and a structural unit having an acid group or a basic group.
In addition, as the form contained in the polymer F, from the viewpoint of transferability, pattern formation, and dimple generation suppression and planarity in the resulting pattern, the structural unit represented by the formula F-1, and A form including the structural unit represented by F-3, the structural unit represented by Formula F-1, the structural unit represented by F-3, and Formula F-2 or Formula F- The form containing the structural unit represented by 4 is mentioned.
Further, the polymer F is preferably a polymer represented by the following formula F-5 from the viewpoints of transferability, pattern formation, and suppression of dimple generation in the pattern to be obtained and a planar shape.

In Formula F-5, R ^f1 to R ^f4 each independently represents a hydrogen atom or a methyl group, and X ^f1 to X ^f4 each independently represents a single bond, —COO—, —OCO—, or an arylene group. L ^f1 to L ^f4 each independently represents a single bond, an alkylene group, or a group in which two or more groups selected from the group consisting of an alkylene group, —COO—, —OCO—, and an arylene group are bonded. , Rf represents a perfluoroalkyl group, R ^p represents an acid group or a basic group, R ^aq represents a hydrophilic group, R ^al represents a linear, branched or cyclic alkyl group, or aryl R1 to r4 represent the mass ratio of each structural unit, the sum of r1 + r2 + r3 + r4 is 100, r1 represents 30 to 99, r2 to r4 each independently represents 0 to 70, r2 to r4 out of r4 One even without is greater than or equal to 1.

R ^f1 to R ^f4 , X ^f1 to X ^f4 , L ^f1 to L ^f4 , Rf, R ^p , R ^aq , and R ^al in the above formula F-5 are the same as R in the above formulas F-1 to F-4. ^f1 to R ^f4 , X ^f1 to X ^f4 , L ^f1 to L ^f4 , Rf, R ^p , R ^aq , and R ^al are synonymous with each other, and preferred embodiments are also the same.
r1 is preferably from 30 to 95, more preferably from 35 to 70, from the viewpoint of planarity.
r2 is preferably from 0 to 50, more preferably from 0 to 40, and even more preferably from 0 to 30 from the viewpoints of pattern formability and suppression of dimple generation in the resulting pattern. In the case where the polymer F includes a structural unit having an acid group or a basic group, r2 is 1 to 50 from the viewpoints of pattern formation, suppression of dimple generation in the resulting pattern, and planar shape. It is preferably 5 to 40, more preferably 10 to 30.
r3 is preferably 0 to 70, more preferably 0 to 60, from the viewpoint of suppressing the occurrence of dimples in the resulting pattern. In the case where the polymer F includes a structural unit having a hydrophilic group, r3 is 5 to 70 from the viewpoints of transferability, pattern formation, and dimple generation suppression and planarity in the resulting pattern. It is preferably 10 to 65, more preferably 20 to 60.
r4 is preferably from 0 to 60, more preferably from 0 to 50, from the viewpoints of transferability and pattern formability. In the case where the polymer F contains the structural unit represented by the formula F-4, r4 is 1 to 70 from the viewpoints of pattern formability, suppression of dimple generation in the obtained pattern, and planarity. It is preferably 10 to 60, more preferably 20 to 50, and particularly preferably 25 to 50.

When r2 is 0, it is preferable that r1 is 30 to 95, r3 is 5 to 70, and r4 is 0 to 65 from the viewpoint of planarity.
Further, when r2 is 1 to 70, it is preferable that r1 is 30 to 99, r3 is 0 to 69, and r4 is 0 to 69 from the viewpoint of planarity.

[Production Method of Polymer F]
The production method (synthesis method) of the polymer F is not particularly limited. For example, a polymerizable monomer for forming a structural unit having a fluorine atom, and, if necessary, an acid group or a basic group. Polymerization using a polymerization initiator in an organic solvent containing a polymerizable monomer for forming a structural unit having a polymerizable monomer and a polymerizable monomer for forming a structural unit having a hydrophilic group Can be synthesized. It can also be synthesized from other polymers by so-called polymer reaction.

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

Surfactant may be used individually by 1 type and may use 2 or more types together.
The addition amount of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and 0.01% by mass with respect to the total mass of the photosensitive resin layer. More preferably, the content is from 3% to 3% by mass.

-Polymerization inhibitor-
The photosensitive resin layer may contain at least one polymerization inhibitor.
As the polymerization inhibitor, for example, a thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 can be used.
Of these, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.

When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and 0.01% by mass with respect to the total mass of the photosensitive resin layer. % To 1% by mass is more preferable, and 0.01% to 0.8% by mass is even more preferable.

-solvent-
The photosensitive resin layer may contain a solvent.
In addition, the photosensitive resin composition for forming the photosensitive resin layer is a photosensitive resin composition containing a solvent by adjusting the viscosity of the photosensitive resin composition once by adding a solvent in order to easily form the photosensitive resin layer. The photosensitive resin layer can be suitably formed by applying and drying the photosensitive resin composition.
As the solvent used in the present disclosure, a known solvent can be used. Solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers And diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, 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, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, -Solvents such as nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate or propylene carbonate can also be added.
Only 1 type may be used for a solvent and 2 or more types may be used for it.
The solvent which can be used for this indication may be used individually by 1 type, and it is more preferable to use 2 types together. When two or more solvents are used, for example, 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 Use in combination with the other is preferred.

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

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

-Plasticizer-
The photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity.
The plasticizer preferably has a weight average molecular weight smaller than that of the polymer represented by a1 or a2.
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 still more preferably 800 or more and less than 4,000 from the viewpoint of imparting plasticity.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the specific polymer and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

In the above formula, R represents an alkyl 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 a compound having an alkyleneoxy group having the above structure (referred to as “compound X”) is a chemically amplified positive photosensitive material obtained by mixing compound X, a specific polymer, and a photoacid generator. When plasticity does not improve compared with the chemically amplified positive photosensitive resin composition formed without containing compound X, the resin composition does not fall under the plasticizer in the present disclosure. For example, the optionally added surfactant is generally not used in an amount that brings plasticity to the photosensitive resin composition, and thus does not correspond to the plasticizer in the present specification.

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

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. preferable.
The said photosensitive resin layer may contain only 1 type of plasticizers, and may contain 2 or more types.

-Sensitizer-
The photosensitive resin layer can further contain a sensitizer.
The sensitizer absorbs actinic rays and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid.
Exposure sensitivity can be improved by containing a sensitizer.

As the sensitizer, a compound selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a base styryl derivative, and a distyrylbenzene derivative is preferable, and an anthracene derivative is more preferable.
Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 1,10-dibromoanthracene, 2-ethylanthracene, or 9,10-dimethoxyanthracene is preferred.

Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/092731.

The content of the sensitizer is preferably 0% by mass to 10% by mass and more preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer.

-Heterocyclic compounds-
The photosensitive resin layer in the present disclosure can include a heterocyclic compound.
There is no restriction | limiting in particular in the heterocyclic compound in this indication. For example, the following compounds having an epoxy group or oxetanyl group in the molecule, alkoxymethyl group-containing heterocyclic compounds, other cyclic ethers, oxygen-containing monomers such as cyclic esters (lactones), silicon, sulfur, phosphorus, etc. Heterocyclic monomers having the following d electrons can be added.

The addition amount of the heterocyclic compound in the photosensitive resin layer is preferably 0.01% by mass to 50% by mass with respect to the total mass of the photosensitive resin layer when the heterocyclic compound is added. The content is more preferably 0.1% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. It is preferable in the said range from a viewpoint of adhesiveness and etching tolerance. Only 1 type may be used for a heterocyclic compound and it can also use 2 or more types together.

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

A compound having an epoxy group in the molecule can be obtained as a commercial product. For example, JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like, commercially available products described in paragraph 0189 of JP2011-221494A, and the like can be mentioned.
Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD- 1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX- 411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212 , EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX -121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (manufactured by Nagase Chemtech), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolide GT400, Cellbiners B0134, B0177 (manufactured by Daicel Corporation), and the like.
The compound which has an epoxy group in a molecule | numerator may be used individually by 1 type, and may use 2 or more types together.

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

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

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

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

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

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

<< Average film thickness of photosensitive resin layer >>
The average film thickness of the photosensitive resin layer is preferably 1.0 μm or more, more preferably 2.0 μm or more, and still more preferably 5.0 μm or more, from the viewpoint of transferability (laminate). The average film thickness of the photosensitive resin layer is preferably 20 μm or less, more preferably 15 μm or less, from the viewpoint of production suitability.

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

The photosensitive transfer material according to the present disclosure having the photosensitive resin layer on the temporary support can be obtained by applying the photosensitive resin composition onto the intermediate layer and drying it.
The coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
In addition, the photosensitive resin layer can also be applied after forming other layers described later on the intermediate layer.

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

-Thermoplastic resin layer, cover film, etc.-
The photosensitive transfer material according to the present disclosure preferably further includes a thermoplastic resin layer between the temporary support and the intermediate layer from the viewpoint of transferability.
The photosensitive transfer material according to the present disclosure may have a cover film for the purpose of protecting the photosensitive resin layer.
Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP 2014-85643 A, and preferred embodiments of the other layers are described in paragraphs 0194 to 0196 of JP 2014-85643 A, respectively. The contents of this publication are incorporated herein.
Especially, it is preferable that a thermoplastic resin layer contains the at least 1 sort (s) of thermoplastic resin chosen from the group which consists of an acrylic resin and a styrene / acryl copolymer from a transferable viewpoint.

When the photosensitive transfer material according to the present disclosure has other layers such as a thermoplastic resin layer, the photosensitive transfer material is prepared according to the method for preparing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138. can do.
For example, when preparing a photosensitive transfer material according to the present disclosure having a thermoplastic resin layer, a solution (for thermoplastic resin layer) in which a thermoplastic organic polymer and an additive are dissolved on a temporary support. A coating solution prepared by adding a resin and an additive to a solvent that does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer after applying the coating liquid) and drying to provide a thermoplastic resin layer (intermediate) The layer composition) is applied and dried to laminate the intermediate layer. A photosensitive transfer material according to the present disclosure is obtained by further 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 be suitably produced.

-Contrast enhancement layer-
The photosensitive transfer material according to the present disclosure can have a contrast enhancement layer in addition to the photosensitive resin layer.
A contrast enhancement layer (CEL) is a material (photo-decoloring) that has a large absorption with respect to an exposure wavelength before exposure, but gradually decreases with exposure, that is, has a higher light transmittance. It is a layer containing a coloring pigment component). Known photodecolorable dye components include diazonium salts, stilbazolium salts, arylnitroso salts, and the like. A phenolic resin or the like is used as the film forming component.
In addition, as contrast enhancement layers, paragraphs 0004 to 0051 of JP-A-6-97065, paragraphs 0012 to 0055 of JP-A-6-332167, photopolymer handbook, photopolymer social gathering, industrial research group ( 1989), photopolymer technology, Yamaoka, edited by Nagamatsu, Nikkan Kogyo Shimbun (1988) can be used.

(Resin pattern manufacturing method and circuit wiring manufacturing method)
The method for producing a resin pattern according to the present disclosure is not particularly limited as long as it is a method for producing a resin pattern using the photosensitive transfer material according to the present disclosure, but the photosensitive resin in the photosensitive transfer material according to the present disclosure. A step of bringing the outermost layer on the layer side into contact with the substrate, a step of pattern-exposing the photosensitive resin layer, and a step of developing the exposed photosensitive resin layer to form a pattern in this order. It is preferable to include a step of peeling the temporary support after the step of bonding to the substrate and before the step of forming the pattern.
The circuit wiring manufacturing method according to the present disclosure is not particularly limited as long as it is a circuit wiring manufacturing method using the photosensitive transfer material according to the present disclosure. A step of bringing the outermost layer on the side of the photosensitive resin layer into contact with a substrate having a conductive layer and bonding, a step of pattern exposing the photosensitive resin layer, and developing the exposed photosensitive resin layer to form a pattern And a step of etching the conductive layer in a region where the pattern is not disposed, in this order, after the step of bonding to the substrate and before the step of forming the pattern, the temporary support It is preferable to include a step of peeling the body.
The substrate preferably has a conductive layer, and more preferably has a conductive layer on the surface.

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

<Lamination process>
In the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure, the outermost layer on the photosensitive resin layer side in the photosensitive transfer material according to the present disclosure has a substrate, preferably a conductive layer. It is preferable to include the process (bonding process) which contacts and bonds to a board | substrate.
In the bonding step, for example, in the case of a photosensitive transfer material having a temporary support, an intermediate layer, and a photosensitive resin layer (which may further have a cover film), the outermost layer on the transfer side Is a photosensitive resin layer, but another layer may be further formed on the photosensitive resin layer, and the outermost layer may be another layer.
In the bonding step, it is preferable that the outermost layer on the photosensitive resin layer side of the photosensitive transfer material is brought into contact with a substrate having a conductive layer on the surface for bonding.
Moreover, in the said bonding process, it is preferable to crimp | bond so that the said conductive layer and the outermost layer by the side of the said photosensitive resin layer may contact. In the above embodiment, the patterned photosensitive resin layer after exposure and development can be suitably used as an etching resist when the conductive layer is etched.
There is no restriction | limiting in particular as a method of crimping | bonding the said board | substrate and the said photosensitive transfer material, A well-known transfer method and a lamination method can be used.
Specifically, for example, it is preferable that the photosensitive resin layer side of the photosensitive transfer material is overlaid on a substrate, and pressure is applied with a roll or the like, or pressure and heating are performed. For laminating, a known laminator such as a laminator, a vacuum laminator, or an auto-cut laminator that can further increase productivity can be used.
There are no particular limitations on the pressure and temperature of the bonding in the bonding step, and it depends on the surface material of the substrates to be bonded, for example, the material of the conductive layer, the material of the photosensitive resin layer, the conveyance speed, and the pressure bonding machine used. Can be set as appropriate. Moreover, what is necessary is just to crimp | bond, after removing a cover film from the photosensitive resin layer, when having a cover film on the photosensitive resin layer of a photosensitive transfer material.
When the base material is a resin film, a roll-to-roll pressure bonding may be performed.

The substrate used in the present disclosure is preferably a substrate having a conductive layer on the surface of a base material. A wiring is formed by patterning the conductive layer. In the present disclosure, a film substrate such as polyethylene terephthalate is preferably provided with a plurality of conductive layers such as metal oxide and metal.
Moreover, it is preferable that the said conductive layer is a layer containing copper from a viewpoint which exhibits the effect in this indication more.

The substrate is preferably a substrate in which a plurality of conductive layers are stacked on a support.
As for the board | substrate with which the some electroconductive layer was laminated | stacked on the support body, it is preferable that a support body 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 support is particularly preferably a sheet-shaped resin composition.
The support is preferably transparent.
The refractive index of the support is preferably 1.50 to 1.52.
The support may be composed of a light-transmitting substrate such as a glass substrate, and tempered glass represented by Corning's gorilla glass can be used. In addition, as the above-described transparent substrate, materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
When a film substrate is used as the substrate, it is more preferable to use a substrate that is not optically distorted and a substrate having high transparency. Specific examples of the material include polyethylene terephthalate (PET), Examples thereof include polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

Examples of the conductive layer include any conductive layer used for general 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 resin pattern manufacturing method according to the present disclosure or 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 for a visual recognition part used in a capacitive touch panel or a wiring for a peripheral extraction part.

<Exposure process>
It is preferable that the manufacturing method of the resin pattern which concerns on this indication, or the manufacturing method of the circuit wiring which concerns on this indication includes the process (exposure process) of carrying out pattern exposure of the said photosensitive resin layer after the said bonding process.
In the exposure step, it is preferable that the photosensitive resin layer is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce an acid group, for example, a carboxy group or a phenolic hydroxyl group.
In the present disclosure, the detailed arrangement and specific size of the pattern are not particularly limited. Since it is desired to improve the display quality of a display device (for example, a touch panel) including an input device having a circuit board manufactured in the present disclosure 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.
The exposure in the exposure step may be exposure through a mask or digital exposure using a laser or the like, but is preferably exposure through an exposure mask.
The method for producing a resin pattern according to the present disclosure or the method for producing a circuit wiring according to the present disclosure includes a step of bringing the photosensitive transfer material and an exposure mask into contact between the bonding step and the exposure step. It is preferable to contain. It is excellent in the resolution of the pattern obtained as it is the said aspect.

Visible light, ultraviolet light, and an electron beam are mentioned as actinic light, However, Visible light or ultraviolet light is preferable and an ultraviolet-ray is especially preferable.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator, etc. can be used. Actinic rays having a wavelength of 300 nm to 450 nm, such as h-ray (405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
Exposure dose, depending on the photosensitive resin layer to be used may be appropriately ^selected, but is preferably from 5mJ / cm 2 ~ 200mJ / cm 2, more preferably 10mJ / cm 2 ~ 100mJ / 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. The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.

<Development process>
The resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure includes a step of developing the exposed photosensitive resin layer and forming a pattern after the exposing step (developing step). It is preferable to contain.
When the photosensitive transfer material has an intermediate layer, the exposed intermediate layer is also removed together with the exposed photosensitive resin layer in the development step.
Furthermore, in the development step, the intermediate layer in the unexposed area may also be removed in a form of being dissolved or dispersed in the developer.
Development of the exposed photosensitive resin layer in the development step 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. The developer is preferably an alkaline aqueous solution, and more preferably, for example, an alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L. The developer may further contain an organic solvent miscible with water, a surfactant, and the like. Examples of the developer suitably used in the present disclosure include the developer described in Paragraph 0194 of International Publication No. 2015/092731.

The development method is not particularly limited, and any of paddle development, shower development, shower and spin development, dip development, and the like may be used. Here, the shower development will be described. The exposed portion can be removed by spraying a developer onto the 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.
Moreover, the effect which suppresses the deformation | transformation of the pattern shape in this indication is more exhibited in the aspect with long time from exposure to image development. Although development may be performed immediately after exposure, in a mode in which development is performed after the time from exposure to development is preferably 0.5 hours or more, more preferably 1 hour or more, and further preferably 6 hours or more after exposure. The effect of suppressing the deformation of the pattern shape in the present disclosure is further exhibited.
In addition, a method for manufacturing a resin pattern according to the present disclosure or a method for manufacturing a circuit wiring according to the present disclosure includes a step of washing with water after development, a step of drying a substrate having the obtained pattern, and the like. These steps may be included.

Furthermore, you may have the post-baking process which heat-processes the pattern 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, it is more preferable to perform in an environment of 111.46 kPa or less, and it is particularly preferable to perform in an environment of 101.3 kPa or less.
The post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.
The post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
The post-bake may be performed in an air environment or a nitrogen substitution environment.

The transport speed of the support in each step of the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure is not particularly limited. It is preferably from min to 10 m / min, and more preferably from 2.0 m / min to 8.0 m / min except during exposure.

<Peeling process>
The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure peels off the temporary support after the step of bonding to the substrate and before the step of forming the pattern. It is preferable to include a step (peeling step).
Since the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure uses the photosensitive transfer material, at any timing after the photosensitive transfer material is bonded and before development. Even if the support is peeled off, the adhesiveness with the photosensitive resin layer is excellent, so that the cause of defects such as partial peeling is suppressed, and the pattern can be formed satisfactorily.
Moreover, the manufacturing method of the resin pattern according to the present disclosure or the manufacturing method of the circuit wiring according to the present disclosure includes the step of bonding to the substrate and the photosensitive resin layer from the viewpoint of pattern formability and resolution. It is more preferable that a step of peeling the temporary support is included before the pattern exposure step. Furthermore, when the pattern exposure is performed by bringing the mask into contact with the above aspect, the photosensitive resin layer and the mask are not in direct contact with each other.
There is no restriction | limiting in particular in the method of peeling the temporary support body in the said peeling process, What is necessary is just to peel by a well-known method.

<Etching process>
The circuit wiring manufacturing method according to the present disclosure preferably includes a step (etching step) of etching the conductive layer in a region where the pattern is not disposed.
In the etching step, the pattern formed from the photosensitive resin layer in the developing step is used as an etching resist, and the conductive layer is etched.
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 etchants include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, or aqueous solutions of acidic components such as phosphoric acid alone, acidic components and ferric chloride, ammonium fluoride, or permanganese A mixed aqueous solution of a salt such as potassium acid is exemplified. As the acidic component, a component obtained by combining a plurality of acidic components may be used.
Alkali type etching solutions include sodium hydroxide, potassium hydroxide, ammonia, organic amine, or an aqueous solution of an alkaline component alone such as a salt of an organic amine such as tetramethylammonium hydroxide, an alkaline component and potassium permanganate. A mixed aqueous solution of a salt such as 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. In the present disclosure, the pattern used as an etching mask (etching pattern) preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, the pattern is prevented from peeling off during the etching process, and a portion where the pattern does not exist is selectively etched.

After the etching process, in order to prevent contamination of the process line, a process of cleaning the etched substrate (cleaning process) and a process of drying the etched substrate (drying process) are performed as necessary. Also good. As for the cleaning step, for example, the substrate may be cleaned with pure water at room temperature (10 ° C. to 35 ° C.) for 10 seconds to 300 seconds. Regarding the drying step, for example, air blow may be used, and the air blow pressure (about 0.1 kg / cm ² to about 5 kg / cm ² ) may be appropriately adjusted for drying.

<Etching resist stripping process>
It is preferable that the manufacturing method of the circuit wiring which concerns on this indication includes the process (etching resist peeling process) which peels the said photosensitive resin layer using peeling liquid after the said etching process.
After the etching process is finished, the patterned photosensitive resin layer remains. If the photosensitive resin layer is unnecessary, all the remaining photosensitive resin layers may be removed.
As a method of peeling using a peeling solution, for example, a substrate having the above-mentioned photosensitive resin layer or the like in the peeling solution preferably stirred at 30 to 80 ° C., more preferably 50 to 80 ° C. for 5 minutes. Examples include a method of immersing for ˜30 minutes.
As the stripping solution, for example, an inorganic alkali component such as sodium hydroxide or potassium hydroxide, or an organic alkali component such as a tertiary amine or quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or And a stripping solution dissolved in 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.

Moreover, the manufacturing method of the circuit wiring which concerns on this indication may repeat an exposure process, a image development process, and an etching process twice or more as needed.
As examples of the exposure step, the development step, and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present disclosure.

The resin pattern manufacturing method according to the present disclosure or 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.

<Step of reducing visible light reflectance>
The circuit wiring manufacturing method according to the present disclosure may include a process of reducing the visible light reflectance of the surface of the conductive layer, for example, part or all of the surface of the conductive layer on the substrate. .
Examples of the treatment for reducing the visible light reflectance include an oxidation treatment. For example, the visible light reflectance can be reduced by blackening by oxidizing copper to copper oxide.
Regarding preferred embodiments of the processing 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.

<Process for forming an insulating film on the etched substrate and process for forming a new conductive layer on the insulating film>
A method of manufacturing a circuit wiring according to the present disclosure includes a step of forming an insulating film on the substrate, for example, a formed wiring (etched conductive layer), and a step of forming a new conductive layer on the insulating film. It is also preferable to contain.
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 method of manufacturing a circuit wiring according to the present disclosure, the new conductive layer may be etched by forming an etching resist by a method similar to the above, or may be separately etched by a known method. .
The substrate having the circuit wiring obtained by the circuit wiring manufacturing method according to the present disclosure may have only one layer of wiring on the substrate, or may have two or more layers of wiring.

Further, in the method for manufacturing circuit wiring according to the present disclosure, the substrate may have a plurality of conductive layers on both surfaces, and the circuit may be sequentially or simultaneously formed on the conductive layers formed on both surfaces of the substrate. preferable. With such a configuration, a wiring in which a first conductive pattern (first wiring) is formed on one surface of the substrate and a second conductive pattern (second wiring) is formed on the other surface, preferably a touch panel wiring. Can be formed.

(Circuit wiring and substrate having circuit wiring)
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 board | substrate which has the circuit wiring which concerns on this indication is a board | substrate which has the circuit wiring manufactured by the manufacturing method of the circuit wiring which concerns on this indication.
Although the use of the board | substrate which has the circuit wiring which concerns on this indication is not limited, For example, it is preferable that it is a circuit wiring board for touchscreens.

(Input device and display device)
An input device is an example of a device provided with circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure.
The input device according to the present disclosure may be an input device having at least circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure, and is preferably a capacitive touch panel.
The display device according to the present disclosure preferably includes the input device according to the present disclosure. The display device according to the present disclosure is preferably an organic EL display device and an image display device such as a liquid crystal display device.

(Touch panel and touch panel display device)
The touch panel according to the present disclosure is a touch panel having at least circuit wiring manufactured by the circuit wiring manufacturing method 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.
Further, the touch panel manufacturing method according to the present disclosure is not particularly limited as long as it is a touch panel manufacturing method using the photosensitive transfer material according to the present disclosure, but the photosensitive resin of the photosensitive transfer material according to the present disclosure. A step of bringing the outermost layer on the layer side into contact with a substrate having a conductive layer, a step of pattern-exposing the photosensitive resin layer, and a step of developing the exposed photosensitive resin layer to form a pattern And a step of etching the conductive layer in the region where the pattern is not disposed are preferably included in this order.
The detection method in the touch panel according to the present disclosure and the touch panel display device according to the present disclosure may be any known method such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among these, the electrostatic capacity method is preferable.

As the touch panel type, 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, JP 2013-168125 A). 19 of the gazette, those described in FIGS. 1 and 5 of JP 2012-89102 A, OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP No. 2013-54727 shown in FIG. 2), other configurations (for example, those shown in FIG. 6 of JP2013-164671A), various out-cell types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.).

As the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, “latest touch panel technology” (issued July 6, 2009, published by Techno Times Co., Ltd.), supervised by Yuji Mitani, “touch panel technology and development” ( The configurations disclosed in FPD International 2009 Forum T-11 lecture textbook, Cypress Semiconductor Corporation application note AN2292, etc. can be applied.

Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the embodiment of the present invention. Therefore, the scope of the embodiment of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

In the following synthesis examples, the following abbreviations represent the following compounds, respectively.
ATHF: 2-tetrahydrofuranyl acrylate (synthetic product)
AA: Acrylic acid (Fuji Film Wako Pure Chemical Industries, Ltd.)
EA: ethyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
MAA: Methacrylic acid (Fuji Film Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (Fuji Film Wako Pure Chemical Industries, Ltd.)
HEMA: 2-hydroxyethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
CHA: cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
PMPMA: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (pKaH = 10, manufactured by Tokyo Chemical Industry Co., Ltd.)
TMCAC: Methacrylcholine chloride (manufactured by Tokyo Chemical Industry Co., Ltd.)
SMP: 3-sulfopropyl potassium methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
DMAPS: [2- (methacryloyloxy) ethyl] dimethyl (3-sulfopropyl) ammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)
MFG: 1-methoxy-2-propanol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)

<Synthesis Example of Intermediate Layer Forming Polymer P-2>
MFG (75.0 parts by mass) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere.
MAA (4.0 parts by mass), HEMA (50.0 parts by mass), MMA (46.0 parts by mass), V-601 (2.5 parts by mass), MFG (75.0 parts by mass) Was dropped into a three-necked flask solution maintained at 90 ° C. ± 2 ° C. over 2 hours.
After completion of dropping, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain an intermediate layer-forming polymer P-2 (solid content concentration 40.0%).

<Synthesis Example of Intermediate Layer Forming Polymers P-3 to P-6>
The monomer type and the like were changed as shown in Table 1 below, and the other conditions were synthesized in the same manner as for the intermediate layer forming polymer 1. The solid content concentration of the polymer was 40% by mass.

<Synthesis Example of Intermediate Layer Forming Polymer P-7>
MFG (67.5 parts by mass) and water (7.5 parts by mass) were placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere.
SMP (15.0 parts by mass), HEMA (50.0 parts by mass), MMA (35.0 parts by mass), V-601 (2.5 parts by mass), MFG (67.5 parts by mass), water (7 0.5 parts by mass) was added dropwise to the three-necked flask solution maintained at 90 ° C. ± 2 ° C. over 2 hours.
After completion of the dropwise addition, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain an intermediate layer forming polymer P-7 (solid content concentration 40.0%).

<Synthesis Example of Intermediate Layer Forming Polymers P-8 and P-9>
The monomer type and the like were changed as shown in Table 1 below, and the other conditions were synthesized in the same manner as the intermediate layer forming polymer P-7. The solid content concentration of the polymer was 40% by mass.

In addition, the numerical value of each monomer column of Table 1 represents the quantity of the structural unit formed from each monomer in the obtained polymer, The unit is the mass%.
Further, the intermediate layer forming polymers P-7 to P-9 are acrylic resins having a neutralization rate of acid groups or basic groups of 100 mol%.

<Preparation of intermediate layer forming composition or water-soluble resin layer forming composition>
It melt-mixed by the prescription shown in following Table 2 or Table 3, and filtered with the filter made from a polytetrafluoroethylene with the hole diameter of 0.2 micrometer, and obtained each intermediate | middle layer formation composition or the composition for water-soluble resin layer formation, respectively. .
The abbreviations listed in Table 2 or Table 3 are as follows.
Resin A: Methacrylic acid / Allyl methacrylate copolymer resin (Mw: 25,000, composition ratio: 40/60)
Resin B: Nissan HPC-SSL (manufactured by Nippon Soda Co., Ltd.)
E-11: Megafuck F-444 (manufactured by DIC Corporation)
F-1: Bromophenol blue (colorant (pigment), manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., maximum absorption wavelength: 606 nm)
MEK: Methyl ethyl ketone (Fuji Film Wako Pure Chemical Industries, Ltd.)

The unit of the amount of each component in Table 2 or Table 3 is part by mass. Moreover, NaOH (1N) in Table 2 or Table 3 is a 1 mol / L sodium hydroxide aqueous solution.

<Preparation of photosensitive resin composition>
<< Synthesis of ATHF >>
Acrylic acid (72.1 parts, 1.0 molar equivalent) and hexane (72.1 parts) were added to a three-necked flask and cooled to 20 ° C. After adding camphorsulfonic acid (0.007 parts, 0.03 mmol equivalent) and 2-dihydrofuran (77.9 parts, 1.0 molar equivalent) dropwise, the mixture was stirred at 20 ° C. ± 2 ° C. for 1.5 hours. The temperature was raised to 35 ° C. and stirred for 2 hours. After spreading Kyoward 200 (filter material, aluminum hydroxide powder, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (filter material, hydrotalcite powder, manufactured by Kyowa Chemical Industry Co., Ltd.) in order in Nutsche, The filtrate was obtained by filtering the reaction solution. Hydroquinone monomethyl ether (MEHQ, 0.0012 parts) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ° C., whereby 140.8 parts of tetrahydrofuran-2-yl acrylate (ATHF) was obtained as a colorless oil. Obtained (yield 99.0%).

<< Synthesis Example of Polymer A-1 >>
PGMEA (75.0 parts) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. A solution in which ATHF (30.0 parts), MMA (40.0 parts), ethyl acrylate (EA, 30.0 parts), V-601 (4.0 parts), and PGMEA (75.0 parts) were added. The solution was dropped into a three-necked flask solution maintained at 90 ° C. ± 2 ° C. 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 Example of Polymers A-2 to A-7 >>
The monomer type was changed as shown in Table 4 below, and the other conditions were synthesized in the same manner as for Polymer A-1. The solid content concentrations of the polymers A-2 to A-7 were each 40% by mass.
In addition, the unit of the quantity of the monomer of Table 4 is the mass%.

The weight average molecular weights of the polymers A-1 to A-7 were 20,000, respectively.

<< Photoacid generator >>
B-1: Compound having the structure shown below (Compound described in paragraph 0227 of JP 2013-47765 A, synthesized according to the method described in paragraph 0227)

<< Surfactant >>
E-1: Compound having the structure shown below

E-2: Compound with the structure shown below

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

<< benzotriazole compound >>
C-1: 1,2,3-benzotriazole (the following compound)

<< Preparation of photosensitive resin compositions 1 to 7 >>
A polymer, a photoacid generator, a basic compound, a benzotriazole compound, and a surfactant were dissolved and mixed in PGMEA so that the solid content ratio was 10% by mass so that the solid content ratio shown in Table 5 was obtained. Then, the mixture was filtered through a polytetrafluoroethylene filter having a pore diameter of 0.2 μm to obtain photosensitive resin compositions 1 to 7, respectively.

In addition, the unit of the quantity of each component in Table 5 is part by mass.

Example 1
<Production of photosensitive transfer material>
Using a slit-like nozzle on a 30 μm thick polyethylene terephthalate film (hereinafter also referred to as PET (A)) as a temporary support so that the composition for forming an intermediate layer has the structure shown in Table 6 below. It apply | coated so that application | coating width | variety might be set to 1.0 m, and it passed through the 80 degreeC drying zone over 40 second, and formed the intermediate | middle layer. Thereafter, the photosensitive resin composition is applied onto the intermediate layer using a slit-like nozzle so that the coating width is 1.0 m, and passed through an 80 ° C. drying zone for 40 seconds to obtain a photosensitive resin. A layer was formed. A polyethylene film (trade name, OSM-N, manufactured by Tredegar Co., Ltd.) was pressed as a cover film on the photosensitive resin layer to prepare a photosensitive transfer material 1, and the photosensitive transfer material 1 was wound into a roll form.

(Examples 2 to 17)
Before using the composition shown in Table 6 or Table 7 and forming the intermediate layer, the water-soluble resin layer is formed in the average film thickness described in Table 6 or Table 7 in the same manner as the intermediate layer in Example 1. Then, photosensitive transfer materials 2 to 17 were used in the same manner as in Example 1 except that the compositions shown in Table 6 or 7 below were used and the intermediate layer was formed to have an average film thickness shown in Table 6 or Table 7. Were prepared respectively.

(Comparative Examples 1 to 3)
Photosensitive transfer materials C1 to C3 were prepared in the same manner as in Example 1 except that the compositions shown in Table 6 below were used.

Using the obtained photosensitive transfer materials 1 to 17 and C1 to C3, the following evaluations were performed.

<Performance evaluation>
A PET substrate with a copper layer, in which copper was formed into a film with a thickness of 200 nm by a vacuum deposition method on a polyethylene terephthalate (PET) film having a thickness of 100 μm, was used.

-Evaluation of adhesion between intermediate layer and photosensitive resin layer-
The protective film was peeled from the photosensitive transfer material of Example 1, and the photosensitive transfer material obtained on the copper layer in the above-mentioned PET substrate with a copper layer was subjected to conditions of 100 ° C., 4 m / min, linear pressure 0.6 MPa. Then, the temporary support was peeled off to produce a laminate in which a positive photosensitive layer was laminated on the copper layer.
Printac C (manufactured by Nitto Denko Corporation) was applied on the laminate, and cut out to 4.5 cm × 9 cm so that the width of the tape and the support was matched. This was peeled 180 ° at a peeling speed of 100 mm / min using an A & D Tensilon universal testing machine, and the adhesion between the intermediate layer and the photosensitive resin layer was measured.
The adhesion at that time was evaluated according to the following evaluation criteria. A larger value is preferable, and 5 to 3 is a practical range.
〔Evaluation criteria〕
5: Measurement upper limit (22 gf / cm (0.22 N / cm)) or more 4: 5.0 gf / cm (0.098 N / cm) or more and less than 22.0 gf / cm 3: 2.0 gf / cm (0.049 N / cm) or more and less than 5.0 gf / cm 2: less than 2.0 gf / cm 1: Evaluation not possible because the intermediate layer was also peeled off when the support was peeled

-Evaluation of storage stability-
After unwinding the produced photosensitive transfer material, it was laminated on the PET substrate with a copper layer under the lamination conditions of a roll temperature of 120 ° C., a linear pressure of 1.0 MPa, and a linear velocity of 0.5 m / min. After peeling with a super high pressure mercury lamp through a line-and-space pattern mask (Duty ratio 1: 1) having a line width of 10 μm without peeling off the temporary support, and after leaving in an environment of 23 ° C. and 55% RH for 3 hours. The support was peeled off and developed. Development was performed by shower development for 30 seconds using a 1.0% aqueous sodium carbonate solution at 25 ° C.
When a 10 μm line and space pattern was formed by the above method, the residue in the space portion was observed with a scanning electron microscope (SEM), and the exposure amount at which the resist line width was exactly 10 μm was determined.
The produced photosensitive transfer material was allowed to stand in an environment of 40 ° C. and 55% RH for 7 days, and then laminated on a PET substrate with a copper layer under the same conditions as described above. Without exposing the temporary support, the film was exposed through a line-and-space pattern mask (duty ratio 1: 1) having a line width of 10 μm after exposure to obtain a resist line width of just 10 μm, and the temperature was 23 ° C. After leaving for 3 hours in an environment of 55% RH, the temporary support was peeled off and developed. Development was performed by shower development for 30 seconds using a 1.0% aqueous sodium carbonate solution at 25 ° C.
The line width of the obtained line and space pattern was observed with a scanning electron microscope (SEM), the line width was measured at a total of 50 points for 5 lines, and the fluctuation of the line width from 10 μm was obtained. The average value was calculated, and the average value was evaluated according to the following criteria. The smaller the average value of the line width variation from 10 μm, the better the storage stability, and the average value of the line width variation from 10 μm is preferably less than 1.5 μm.
5: Less than 0.5 μm 4: 0.5 μm or more and less than 1.0 μm 3: 1.0 μm or more and less than 1.5 μm 2: 1.5 μm or more and less than 3 μm 1: 3 μm or more

-Evaluation of retention stability (PED) after exposure-
Post-exposure delay stability (PED) after exposure was evaluated as follows.
After unwinding the produced photosensitive transfer material, it was laminated on the PET substrate with a copper layer under the lamination conditions of a roll temperature of 120 ° C., a linear pressure of 1.0 MPa, and a linear velocity of 0.5 m / min. 3 hours or 24 hours in an environment of 23 ° C. and 55% RH after exposure with an ultra high pressure mercury lamp through a line and space pattern mask (duty ratio 1: 1) having a line width of 6 μm without peeling off the temporary support. After leaving with time, the temporary support was peeled off and developed. Development was performed by shower development for 30 seconds using a 1.0% aqueous sodium carbonate solution at 25 ° C.
The line width of the obtained line and space pattern was observed with a scanning electron microscope (SEM), and the line width was measured at a total of 50 points for five lines.
The amount of change in the line width of the resin pattern formed in the post-exposure holding time of 24 hours relative to the line width of the resin pattern formed in the post-exposure holding time of 3 hours was evaluated.
3: Line width variation is less than 1.0 μm 2: Line width variation is 1.0 μm or more and less than 2.0 μm 1: Line width variation is 2.0 μm or more

From Table 6 and Table 7, it can be seen that the photosensitive transfer materials of the examples are superior in storage stability and adhesion between the intermediate layer and the photosensitive resin layer as compared with the photosensitive transfer materials of the comparative examples.

(Example 101)
Indium tin oxide (ITO) was deposited as a second conductive layer on a 100 μm thick PET substrate by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer to a thickness of 200 nm by vacuum evaporation. To form a circuit forming substrate.
The photosensitive transfer material produced in Example 1 was laminated on the copper layer (linear pressure 0.8 MPa, linear velocity 3.0 m / min, roll temperature 90 ° C.). Contact pattern exposure was performed using a photomask provided with a pattern (hereinafter also referred to as “pattern A”) shown in FIG. 2 having a configuration in which conductive layer pads are connected in one direction without peeling off the temporary support.
In the pattern A shown in FIG. 2, 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 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 copper (solid line portion SL) and ITO (gray portion G) were both drawn with the pattern A was obtained.

Next, pattern alignment was performed using a photomask provided with openings of a pattern shown in FIG. 3 (hereinafter also referred to as “pattern B”) in the aligned state, and development and washing were performed.
In the pattern B shown in FIG. 3, 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 (10% by mass sodium hydroxide aqueous solution) 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 2 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 openings of pattern B in the aligned state, and after the PET (A) was peeled off, 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 2 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.
Next, the photosensitive transfer material obtained in Example 2 was bonded onto the remaining resist (roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min). In this state, pattern exposure was performed using a photomask provided with openings of pattern B in the aligned state, and the temporary support of the photosensitive transfer material was peeled off, followed by development and washing with water. 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 having a conductive pattern. .
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. 2018-102135 filed on May 29, 2018 and the disclosure of Japanese Patent Application No. 2019-057799 filed on March 26, 2019 are entirely Which is incorporated herein by reference.
All documents, patent applications, and technical standards described in this specification are the same as if each document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. Which is incorporated herein by reference.

10: Temporary support, 12: Intermediate layer, 14: Photosensitive resin layer, 16: Cover film, 100: Photosensitive transfer material, SL: Solid line part, G: Gray part, DL: Dotted line part

Claims

Having a temporary support, an intermediate layer, and a photosensitive resin layer;
The photosensitive resin layer includes a polymer having a structural unit having an acid group protected with an acid-decomposable group, and a photoacid generator,
The polymer contained in the photosensitive resin layer is an acrylic resin having an acid value of 10 mgKOH / g or less,
The intermediate layer includes a water-soluble or alkali-soluble acrylic resin,
A photosensitive transfer material in which the intermediate layer and the photosensitive resin layer are in contact with each other.
The photosensitive transfer material according to claim 1, wherein an acid value of the acrylic resin contained in the photosensitive resin layer is 0 mgKOH / g to 3 mgKOH / g.
The photosensitive transfer material according to claim 1 or 2, wherein the acrylic resin contained in the photosensitive resin layer further includes a structural unit having a group of pKaH3 or more.
The photosensitive transfer material according to any one of claims 1 to 3, wherein the water-soluble or alkali-soluble acrylic resin in the intermediate layer is a water-soluble acrylic resin.
The photosensitive resin according to claim 4, wherein the water-soluble acrylic resin is a water-soluble acrylic resin having an acid group or a basic group, and a neutralization rate of the acid group or the basic group is 90 mol% or more. Transfer material.
The photosensitive transfer material according to any one of claims 1 to 3, wherein the water-soluble or alkali-soluble acrylic resin in the intermediate layer is an alkali-soluble acrylic resin.
The photosensitive transfer material according to claim 6, wherein the acid value of the alkali-soluble acrylic resin is from 30 mgKOH / g to 150 mgKOH / g.
The photosensitive transfer material according to any one of claims 1 to 7, wherein an average film thickness of the intermediate layer is 3 µm or less.
The photosensitive transfer material according to any one of claims 1 to 8, wherein the water-soluble or alkali-soluble acrylic resin in the intermediate layer contains a resin having a hydroxy group.
A water-soluble resin comprising at least one water-soluble resin selected from the group consisting of a phenol resin, a modified cellulose resin, and a polyvinyl alcohol resin on the side opposite to the side where the photosensitive resin layer is in contact with the intermediate layer The photosensitive transfer material according to any one of claims 1 to 9, further comprising a layer.
11. The photosensitive transfer material according to claim 1, wherein the structural unit having an acid group protected with an acid-decomposable group is a structural unit represented by the following formula A.

In formula A, R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or Represents an aryl group, and R 31 or R 32 and R 33 may combine to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or a divalent linking group. Represents.
A step of bringing the outermost layer on the photosensitive resin layer side of the photosensitive transfer material according to any one of claims 1 to 11 into contact with a substrate and bonding the substrate;
Pattern exposing the photosensitive resin layer;
And developing the exposed photosensitive resin layer to form a pattern, in this order.
A step of bringing the outermost layer on the photosensitive resin layer side of the photosensitive transfer material according to any one of claims 1 to 11 into contact with a substrate having a conductive layer;
Pattern exposing the photosensitive resin layer;
Developing the exposed photosensitive resin layer to form a pattern;
And a step of etching the conductive layer in a region where the pattern is not disposed, in this order.
The method for manufacturing circuit wiring according to claim 13, wherein the conductive layer is a layer containing copper.
A step of bringing the outermost layer on the photosensitive resin layer side of the photosensitive transfer material according to any one of claims 1 to 11 into contact with a substrate having a conductive layer;
Pattern exposing the photosensitive resin layer;
Developing the exposed photosensitive resin layer to form a pattern;
And a step of etching the conductive layer in a region where the pattern is not disposed, in this order.