JPWO2019022089A1 - Photosensitive resin composition, photosensitive transfer material, method for manufacturing circuit wiring, and method for manufacturing touch panel - Google Patents

Abstract

Carboxylic acid group is a polymer containing a structural unit having a group protected in the form of an acetal, at least one photoacid generator selected from the group consisting of oxime compounds and onium salt compounds, and A photosensitive resin composition containing a latent dye having a maximum absorption wavelength of 500 nm or more in a wavelength range of 400 nm to 780 nm, a photosensitive transfer material containing the photosensitive resin composition, and a circuit wiring using the photosensitive transfer material And a touch panel manufacturing method.

Description

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

In a display device having a touch panel such as a capacitive input device (such as an organic electroluminescence (EL) display device and a liquid crystal display device), an electrode pattern corresponding to a sensor of a visual recognition portion, wiring of a peripheral wiring portion, and wiring of a lead-out wiring portion. Such a conductive layer pattern is provided inside the touch panel.
In general, the formation of a patterned layer requires a small number of steps to obtain a required pattern shape. Therefore, a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material. In contrast, a method of developing after exposing through a mask having a desired pattern is widely used.

  Further, as conventional photosensitive resin compositions, those described in Patent Documents 1 to 4 are known.

Patent Document 1: Japanese Patent Application Laid-Open No. 2008-64908 Patent Document 2: Japanese Patent Application Laid-Open No. 2004-54106 Patent Document 3: Japanese Patent Application Laid-Open No. 2009-3000 Patent Document 4: Japanese Patent Application Laid-Open No. 2002-341544

The problem to be solved by one embodiment of the present invention is to provide a photosensitive resin composition having excellent sensitivity, excellent recognizability of an exposed portion and an unexposed portion, and suppressing corrosion of a substrate.
A problem to be solved by another embodiment of the present invention is to provide a photosensitive transfer material, a method for manufacturing circuit wiring, or a method for manufacturing a touch panel using the photosensitive resin composition. .

Means for solving the above problems include the following aspects.
<1> at least one photoacid generator selected from the group consisting of a polymer containing a structural unit having a group in which a carboxylic acid group is protected in the form of an acetal, an oxime compound and an onium salt compound; and A photosensitive resin composition containing a latent dye having a maximum absorption wavelength of 500 nm or more in a wavelength range of 400 nm to 780 nm during color formation.
<2> The photosensitive resin composition according to <1>, wherein the latent dye is a latent dye that develops color upon exposure.
<3> The photosensitive resin composition according to <1> or <2>, wherein the latent dye is a latent dye that develops a color with an intermediate radical or an acid generated from the photoacid generator.
<4> The photosensitive material according to any one of <1> to <3>, wherein the acid generated from the photoacid generator is at least one acid selected from the group consisting of phosphoric acid and sulfonic acid. Resin composition.
<5> The photosensitive resin composition according to <4>, wherein the acid generated from the photoacid generator is a sulfonic acid represented by the following formula S1 or S2.

In the formulas S1 and S2, R ^S represents an alkyl group, L ^S represents an alkylene group having 2 or more carbon atoms, ns represents 0 or 1, provided that R ^S is an alkyl group having a halogen atom. in some cases an n is 1, X ^S are each independently, represent an alkyl group, an aryl group, an alkoxy group or an aryloxy group, ms represents an integer of 0 to 5.
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the pKa of the acid generated from the photoacid generator is -4.0 or more.
<7> The photosensitive resin composition according to any one of <1> to <6>, wherein the pKa of the acid generated from the photoacid generator is 4.0 or less.
<8> The photosensitive resin composition according to any one of <1> to <7>, further including a basic compound.
<9> The photosensitive resin composition according to any one of <1> to <8>, further including a solvent.
<10> The photosensitive resin composition according to any one of <1> to <9>, wherein the latent dye is a compound represented by the following formula I.

In Formula I, Ar ^1C and Ar ^2C each independently represent an aromatic group, X ^C represents C, S or S ＝ O, and R ^{1C to} R ^4C each independently represent a hydrogen atom, a halogen atom or Represents a valent organic group.
<11> The photosensitive resin composition according to <10>, wherein X ^C in Formula I is ^C.
<12> The photosensitive material according to any one of <1> to <11>, wherein the structural unit having a group in which the carboxylic acid group is protected in the form of an acetal is a structural unit represented by the following formula II. Resin composition.

In Formula II, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group Or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.
<13> A photosensitive transfer including a temporary support and a photosensitive resin layer, wherein the photosensitive resin layer includes the photosensitive resin composition according to any one of <1> to <12>. material.
<14> a step of bringing the photosensitive resin layer of the photosensitive transfer material according to <13> into contact with the substrate and bonding the photosensitive resin layer to the substrate, and the step of bonding the photosensitive transfer material after the bonding step Pattern-exposing the conductive resin layer, developing the photosensitive resin layer after the exposing step to form a pattern, and etching the substrate in a region where the pattern is not arranged, A method of manufacturing a circuit wiring including the order.
<15> A step of bringing the photosensitive resin layer of the photosensitive transfer material according to <13> into contact with the substrate and bonding the photosensitive resin layer to the substrate, and the step of bonding the photosensitive transfer material after the bonding step. Pattern-exposing the conductive resin layer, developing the photosensitive resin layer after the exposing step to form a pattern, and etching the substrate in a region where the pattern is not arranged, A method for manufacturing a touch panel, which includes:

According to one embodiment of the present invention, it is possible to provide a photosensitive resin composition which is excellent in sensitivity, excellent in recognizability of an exposed portion and an unexposed portion, and suppresses corrosion of a substrate.
Further, according to another embodiment of the present invention, it is possible to provide a method for manufacturing a photosensitive transfer material, a circuit wiring, or a touch panel using the photosensitive resin composition.

1 is a schematic diagram illustrating an example of a layer configuration of a photosensitive transfer material according to the present disclosure. 1 is a schematic diagram illustrating an example of a method for manufacturing a circuit wiring for a touch panel using a photosensitive transfer material according to the present disclosure. FIG. 3 is a schematic diagram showing a pattern A. FIG. 4 is a schematic view 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.
Further, in this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
Further, in the present specification, “(meth) acryl” represents both or one of acryl and methacryl, and “(meth) acrylate” represents both or one of acrylate and methacrylate.
Furthermore, in the present specification, the amount of each component in the composition is the total of the plurality of corresponding substances present in the composition unless a plurality of substances corresponding to each component are present in the composition unless otherwise specified. Means the quantity.
In this specification, the term “step” is included in the term as well as an independent step, even if it cannot be clearly distinguished from other steps as long as the intended purpose of the step is achieved.
In the notation of a group (atomic group) in the present specification, the notation not indicating substituted or unsubstituted includes not only a group having no substituent but also a group having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Further, the chemical structural formula in this specification may be described by a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, “% by mass” and “% by weight” have the same meaning, and “parts by mass” and “parts by weight” have the same meaning.
Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In addition, columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) are used for the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure, unless otherwise specified. The molecular weight was determined using a gel permeation chromatography (GPC) analyzer and using a solvent THF (tetrahydrofuran) and a differential refractometer, and converted using polystyrene as a standard substance.

(Photosensitive resin composition)
The photosensitive resin composition according to the present disclosure is a polymer containing a structural unit having a group in which a carboxylic acid group is protected in the form of an acetal, at least one selected from the group consisting of an oxime compound and an onium salt compound. It contains a photoacid generator and a latent dye having a maximum absorption wavelength of 500 nm or more in a wavelength range of 400 nm to 780 nm at the time of coloring.

Use of a positive photosensitive resin composition as a photosensitive resin composition used for a resist layer of a dry film resist has been studied.
In addition, in order to confirm the exposed portion, it has been studied to improve the recognizability of the exposed portion and the unexposed portion by adding a latent dye that develops or decolors by exposure to the photosensitive resin composition. I have.
Here, various materials are known as a latent dye, a polymer, and a photoacid generator used in a positive photosensitive resin composition, but the present inventors have found that depending on the combination of these materials, It has been found that the sensitivity to exposure may not be sufficient, or that the acid generated by the photoacid generator may corrode the substrate (particularly, the metal layer contained in the substrate).

In response to these problems, the present inventors have conducted intensive studies and found that, by using the photosensitive resin composition having the above structure, the sensitivity is excellent, the recognizability of exposed portions and unexposed portions is excellent, and It has been found that a photosensitive resin composition that suppresses corrosion of the substrate can be obtained.
The mechanism of manifestation of the above detailed effects is unknown, and it is considered that the above effects are obtained by all elements working in concert, for example, by combining a specific polymer and a specific photoacid generator. It is considered that the sensitivity can be sufficiently obtained by using.
In addition, it is considered that the recognizability of the exposed part and the unexposed part is excellent because the latent dye has a maximum absorption wavelength of 500 nm or more in the wavelength range of 400 nm to 780 nm at the time of coloring.
Further, it is considered that the corrosion of the substrate is suppressed when the photoacid generator is at least one selected from the group consisting of an oxime compound and an onium salt compound.

  Hereinafter, the photosensitive resin composition according to the present disclosure will be described in detail.

<Potential dye having a maximum absorption wavelength of 500 nm or more in a wavelength range of 400 nm to 780 nm>
The photosensitive resin composition according to the present disclosure contains a latent dye having a maximum absorption wavelength of 500 nm or more in a wavelength range of 400 nm to 780 nm at the time of color development (hereinafter, also referred to as “specific latent dye”).
The specific latent dye may be a compound that develops color by exposure or a compound that decolorizes by exposure, but from the viewpoint of sensitivity and recognition, it is preferably a compound that develops color by exposure, and It is more preferable that the latent dye is a latent dye that is colored by an intermediate radical or an acid generated from the acid generator.

The specific latent dye preferably has a pKa of the conjugate acid (also referred to as “pKaH”) of less than 4.5 or a compound that does not form a conjugate acid.
The pKa of the conjugate acid of the specific latent dye is the pKa (negative common logarithm of the acid dissociation constant) of a chemical species (conjugate acid) obtained by bonding H ⁺ to the specific latent dye.
A compound in which the specific latent dye does not form a conjugate acid is defined as a compound in which H ⁺ is more dissociated than a chemical species (conjugate acid) obtained by bonding H ⁺ to the specific latent dye. It means that.
The pKa (pKaH) of compounds and the like in the present disclosure is calculated using ACD / pka DB ver 8.07 of ACD / Labs software Ver 8.0 for Microsoft windows manufactured by Advanced Chemistry Development.

The specific latent dye has a maximum absorption wavelength of 500 nm or more in the wavelength range of 400 nm to 780 nm at the time of coloring, and is preferably 550 nm or more, more preferably 550 nm to 700 nm, and more preferably 550 nm from the viewpoint of recognition. More preferably, it is at least 650 nm.
Further, the specific latent dye may have only one maximum absorption wavelength, or may have two or more absorption wavelengths. When the specific latent dye has two or more maximum absorption wavelengths, it is sufficient that at least one maximum absorption wavelength is 500 nm or more.
The method for measuring the maximum absorption wavelength in the present disclosure is to measure a transmission spectrum in a range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) at 25 ° C. in an atmosphere of the air. The wavelength at which the light intensity is minimal (maximum absorption wavelength) shall be measured.

Specific latent dyes that develop color upon exposure include, for example, leuco compounds.
Examples of the specific latent dye that is decolored by exposure include, for example, triphenylmethane dye, diphenylmethane dye, oxazine dye, xanthene dye, iminonaphthoquinone dye, azomethine dye, and anthraquinone dye. .
Among them, a leuco compound is preferable as the specific latent dye from the viewpoints of sensitivity and recognition.
Examples of the leuco compound include leuco compounds such as triphenylmethane, spiropyran, fluoran, diphenylmethane, rhodamine lactam, indolylphthalide, and leuco auramine.
As the leuco compound, from the viewpoints of sensitivity and recognition, a compound in which a lactone ring, a sultone ring, and a sultone ring are opened is preferable, and a leuco compound in which a lactone ring is opened to form a color is more preferable.

  In addition, the specific latent dye is preferably a compound represented by the following formula I from the viewpoint of sensitivity and recognition.

In Formula I, Ar ^1C and Ar ^2C each independently represent an aromatic group, X ^C represents C, S or S ＝ O, and R ^{1C to} R ^4C each independently represent a hydrogen atom, a halogen atom or Represents a valent organic group.

The aromatic group in Ar ^1C and Ar ^2C may be an aryl group or a heteroaryl group, or a monocyclic aromatic group or a condensed ring in which two or more rings are condensed. You may.
Ar ^1C and Ar ^2C may combine to form a ring, and from the viewpoint of sensitivity and recognizability, it is preferable that Ar ^1C and Ar ^2C combine to form a xanthene ring.
The aromatic group in Ar ^1C and Ar ^2C may have a substituent.
Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylarylamino group, and a diarylamino group. It is preferable that The alkyl groups in the dialkylamino group and the alkylarylamino group are each independently preferably an alkyl group having 2 to 20 carbon atoms, and more preferably an alkyl group having 2 to 10 carbon atoms. In addition, at least one of the two alkyl groups in the dialkylamino group is preferably an alkyl group having 3 to 20 carbon atoms, and more preferably an alkyl group having 3 to 10 carbon atoms.
These substituents may be further substituted by a substituent.
The total number of carbon atoms of Ar ^1C and Ar ^2C is independently preferably from 4 to 50, more preferably from 6 to 40, further preferably from 10 to 30, from the viewpoint of sensitivity and recognizability. .

X ^C is preferably C or S ＝ O, and more preferably C, from the viewpoints of sensitivity and recognizability.
The monovalent organic group in R ^{1C to} R ^4C is preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylarylamino group, or a diarylamino group.
Further, the carbon number of R ^{1C to} R ^4C is preferably each independently 0 to 20, more preferably 0 to 10.
R ^{1C to} R ^4C are each independently preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and are preferably a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group, or an aryl group. It is more preferably a group, and particularly preferably a hydrogen atom.

  Compounds C-1 to C-9 are described below as preferred specific examples of the specific latent dye, but it goes without saying that the specific latent dye in the present disclosure is not limited thereto.

Examples of the compound that is decolorized by the exposure include oxidatively decolorizable compounds, and include formazan dyes, cyanine dyes, ferroessen dyes, rhodamine dyes, quinodimethane dyes, methine dyes, anthraquinone dyes, indigoid dyes, and thiane dyes. , Azane dyes, azine dyes, oxazine dyes and the like can be used.
The specific latent pigment may be used alone or in combination of two or more.
The content of the specific latent dye in the photosensitive resin composition according to the present disclosure is 0.01% by mass to 10% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of sensitivity and recognizability. It is preferable that it is 0.1 mass%-8 mass%, it is still more preferred that it is 0.5 mass%-5 mass%, and that it is 1.0 mass%-3.0 mass%. Is particularly preferred.
In the present disclosure, “solid content” in the photosensitive resin composition means a component excluding a volatile component of a solvent.

<Polymer containing a structural unit having a carboxylic acid group protected in the form of an acetal>
The photosensitive resin composition according to the present disclosure includes a polymer containing a structural unit having a group in which a carboxylic acid group is protected in the form of an acetal (also referred to as “structural unit A”) (also referred to as “specific polymer”). .).
In addition, the photosensitive resin composition according to the present disclosure may include another polymer in addition to the polymer having the structural unit A. In the present disclosure, the polymer having the structural unit A and another polymer are collectively referred to as a “polymer component”.
In the specific polymer, the structural unit A having a carboxylic acid group protected in the form of an acetal in the specific polymer undergoes a deprotection reaction to become a carboxylic 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 composition may further contain a polymer other than the polymer having a structural unit having an acid group protected by acid decomposition.
Further, it is preferable that all the polymers contained in the above-mentioned polymer components are polymers having at least a structural unit having a carboxylic acid group described later.
Further, the photosensitive resin composition may further contain a polymer other than these. Unless otherwise stated, the polymer component in the present disclosure means a polymer including other polymers added as needed. Compounds corresponding to a plasticizer, a heterocyclic compound, and a surfactant, which will be described later, are not included in the polymer component, even if they are high molecular compounds.

  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 the structural unit 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.

From the viewpoints of pattern formability, solubility in a developer, and transferability, the photosensitive resin composition includes a polymer component having the structural unit A1 represented by the following formula II as the structural unit A as a polymer component. It is preferable to include a specific polymer having a structural unit A1 represented by the following formula II as the structural unit A, and having a glass transition temperature of 90 ° C. or lower, as a polymer component. As a polymer component, a specific polymer having a structural unit A1 represented by the following formula II as the structural unit A and a structural unit B having a carboxylic acid group described below, and having a glass transition temperature of 90 ° C. or lower. More preferably,
The specific polymer contained in the photosensitive resin composition may be only one kind or two or more kinds.

<< structural unit A >>
The polymer component includes a polymer having at least a structural unit A having a group in which a carboxylic acid group is protected in the form of an acetal. When the polymer component contains a polymer having the structural unit A, a chemically amplified positive photosensitive resin layer having extremely high sensitivity can be obtained.

  The structural unit A having a group in which the carboxylic acid group is protected in the form of an acetal is preferably a structural unit A1 represented by the following formula II from the viewpoint of sensitivity and resolution.

In Formula II, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group Or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.

In Formula II, when R ¹ or R ² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ or R ² is an aryl group, a phenyl group is preferred. Each of R ¹ and R ² is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In Formula II, R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Further, the alkyl group and the aryl group in R ^{1 to} R ³ may have a substituent.
In Formula II, R ¹ or R ² and R ³ may be linked to form a cyclic ether, and it is preferable that R ¹ or R ² and R ³ be linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In Formula II, X represents a single bond or an arylene group, and a single bond is preferable. The arylene group may have a substituent.
When the specific polymer contains the structural unit A1 represented by the formula II, the sensitivity at the time of pattern formation and the resolution are excellent.

In Formula II, R ⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of lowering the Tg of the specific polymer.
More specifically, the amount of the structural unit in which R ⁴ in Formula II is a hydrogen atom is preferably 20% by mass or more based on the total amount of the structural unit A1 contained in the specific polymer.
In addition, the content (content ratio: mass ratio) of the constituent unit in which R ⁴ in Formula II is a hydrogen atom in the constituent unit A1 is calculated from a ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement by an ordinary method. It can be confirmed by the intensity ratio of the peak intensities.

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

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

Preferred specific examples of the structural unit A1 having a group in which the carboxylic acid group represented by the formula II is protected in the form of an acetal include the following structural units. ^{Incidentally, R 34} represents a hydrogen atom or a methyl group.

The structural unit A contained in the specific polymer may be one type or two or more types.
The content of the structural unit A in the specific polymer is preferably at least 20% by mass, more preferably from 20% by mass to 90% by mass, and more preferably from 30% by mass to the total mass of the specific polymer. More preferably, it is 70% by mass.
The content (content ratio: mass ratio) of the structural unit A in the specific polymer can be confirmed by an intensity ratio of peak intensities calculated from a ¹³ C-NMR measurement by an ordinary method.
Further, after decomposing all polymer components into constituent units (monomer units), the ratio of constituent unit A is preferably 5% by mass to 80% by mass with respect to the total mass of the polymer components. It is more preferably from 10% by mass to 80% by mass, particularly preferably from 10% by mass to 40% by mass, most preferably from 10% by mass to 30% by mass.

<<< structural unit B >>>
The specific polymer preferably contains a structural unit B having a carboxylic acid group.
The structural unit B is a structural unit containing a protecting group, for example, a carboxylic acid group not protected by an acid-decomposable group, that is, a carboxylic acid group having no protecting group. When the specific polymer contains the structural unit B, the sensitivity at the time of pattern formation is improved, and the specific polymer is easily dissolved in an alkaline developer in a development step after pattern exposure, so that the development time can be reduced.

The introduction of the structural unit having a carboxylic acid group into the specific polymer can be performed by copolymerizing a monomer having a carboxylic acid group.
The structural unit containing a carboxylic acid group, which is the structural unit B, is a structural unit derived from styrene or a structural unit derived from a vinyl compound and substituted with a carboxylic acid group, or derived from (meth) acrylic acid. More preferably, the structural unit is

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

<< other structural units >>
The specific polymer does not impair the effects of the photosensitive transfer material according to the present disclosure by using other structural units (hereinafter, sometimes referred to as structural units C) other than the above-described structural units A and B. It may be included in the range.
The monomer forming the structural unit C is not particularly limited, and examples thereof include styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl (meth) acrylates, and diesters of unsaturated dicarboxylic acids. , Bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, groups having an aliphatic cyclic skeleton, other Saturated compounds can be mentioned.
By adjusting at least one of the type and the content using the structural unit C, various properties of the specific polymer can be adjusted. In particular, by appropriately using the structural unit C, the Tg of the specific polymer can be easily adjusted to 90 ° C. or less.
The specific polymer may include only one type of the structural unit C, or may include two or more types of the structural unit C.

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

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

  As the monomer forming the structural unit C, for example, (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Among them, alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

  The content of the structural unit C is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less based on the total mass of the specific polymer. The lower limit may be 0% by mass, but is preferably 1% by mass or more, more preferably 5% by mass or more. Within the above range, the resolution and the adhesion of the photosensitive resin layer formed of the photosensitive resin composition are further improved.

The specific polymer may contain, as the structural unit C, a structural unit having an ester of the acid group in the structural unit B, from the viewpoint of optimizing solubility in a developer and physical properties of a photosensitive resin layer described later. Is preferred.
Above all, the specific polymer preferably includes, as the structural unit B, a structural unit having a carboxylic acid group, and further includes a structural unit C having a carboxylic ester group as a copolymer component. A polymer containing a structural unit B derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate is more preferable.
Hereinafter, preferable examples of the specific polymer in the present disclosure will be described, but the present disclosure is not limited to the following examples. The ratio of the structural units and the weight average molecular weight in the following exemplified compounds are appropriately selected in order to obtain preferable physical properties.

<< glass transition temperature of polymer: Tg >>
The glass transition temperature (Tg) of the specific polymer in the present disclosure is preferably 90 ° C. or less. When the Tg is 90 ° C. or lower, the photosensitive resin layer formed from the photosensitive resin composition has high adhesion and is excellent in transferability.
The above Tg is more preferably 60 ° C or lower, further preferably 40 ° C or lower.
The lower limit of the Tg is not particularly limited, but is preferably -20 ° C or higher, 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.
Further, 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 more preferably 40 ° C or lower from the viewpoint of transferability. Is more preferred.

The glass transition temperature of the polymer can be measured using differential scanning calorimetry (DSC).
The specific measurement method was performed according to the method described in JIS K 7121 (1987) or JIS K 6240 (2011). As the glass transition temperature in this 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 the glass transition temperature is determined, the temperature is maintained at about 50 ° C. lower than the expected polymer Tg until the apparatus is stabilized, and then the heating rate is 20 ° C./min. Heat to ℃ higher temperature and draw DTA or DSC curve.
The extrapolated glass transition onset temperature (Tig), that is, the glass transition temperature Tg in the present specification, is defined as a straight line obtained by extending the low-temperature-side baseline in the DTA curve or the DSC curve to the high-temperature side, and a step change portion of the glass transition. Determined as the temperature at 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-mentioned preferable range, for example, the TOX formula is used as a guideline based on the Tg of the homopolymer of each structural unit of the target polymer and the mass ratio of each structural unit. It is possible to control the Tg of the specific polymer of interest.
Regarding the FOX formula, the Tg of the homopolymer of the first constitutional unit contained in the polymer is Tg1, the mass fraction of the copolymer of the first constitutional unit is W1, and the Tg of the homopolymer of the second constitutional unit is Tg1. Is defined as Tg2, and the mass fraction of the copolymer of the second constituent unit as W2, Tg0 (K) of the copolymer including the first constituent unit and the second constituent unit is as follows. It can be estimated according to the equation.
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)
By using the above-described FOX formula, the type and mass fraction of each structural unit contained in the copolymer can be adjusted to obtain a copolymer having a desired Tg.
Further, the Tg of the polymer can be adjusted 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 in the photosensitive transfer material to be described later is suppressed to be low, and when the resin is bonded to a substrate at a low temperature (for example, 130 ° C. or less). Bonding can be realized.
Further, the weight average molecular weight of the specific polymer is preferably from 2,000 to 60,000, more preferably from 3,000 to 50,000, and even more preferably from 10,000 to 30,000. preferable.
The weight average molecular weight of the polymer can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device. The contents of the device and the measuring technique are as follows. It is known to those skilled in the art.
The weight average molecular weight was measured by gel permeation chromatography (GPC) using HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) as a measuring device and TSKgel (registered trademark) Super HZM-M (4) as a column. Super HZ4000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ2000 (4.6 mm ID) × 15 cm, manufactured by Tosoh Corporation) connected in series, and THF (tetrahydrofuran) can be used as an eluent.
The measurement was performed using a differential refractive index (RI) detector at a sample concentration of 0.2% by mass, a flow rate of 0.35 ml / min, a sample injection amount of 10 μl, and a measurement temperature of 40 ° C. be able to.
The calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-5000”, A-2500 "and" A-1000 "can be produced using any one of the seven samples.

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

<< Production 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 II and the structural unit B having a carboxylic acid group may be used. It can be synthesized by polymerizing using a polymerization initiator in a solvent containing a polymerizable monomer for forming and, if necessary, a polymerizable monomer for forming other structural units C. it can. Further, it can be synthesized by a so-called polymer reaction.

The photosensitive resin composition according to the present disclosure contains the specific polymer at a ratio of 50% by mass to 99.9% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of sensitivity and resolution. Is preferable, and it is more preferable to contain it in a ratio of 70% by mass to 98% by mass.
Further, the photosensitive resin composition according to the present disclosure has a ratio of the polymer component of 50% by mass to 99.9% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of sensitivity and resolution. , And more preferably 70 to 98% by mass.

<< other polymer >>
The above-mentioned photosensitive resin composition includes, as a polymer component, a polymer containing no structural unit A ("other polymer") as long as the effect of the photosensitive resin composition according to the present disclosure is not impaired in addition to the specific polymer. May be referred to as "."). When the photosensitive resin composition contains another polymer, the amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, based on all polymer components. , 20% by mass or less.

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

<At least one photoacid generator selected from the group consisting of oxime compounds and onium salt compounds>
The photosensitive resin composition according to the present disclosure contains at least one photoacid generator selected from the group consisting of an oxime compound and an onium salt compound (also referred to as a “specific photoacid generator”).
The specific photoacid generator used in the present disclosure is a compound capable of generating an acid upon irradiation with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
The specific photoacid generator used in the present disclosure is preferably a compound that generates an acid in response to actinic rays having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but the chemical structure is not limited. In addition, the specific photoacid generator which is not directly sensitive to actinic light having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound which, when used in combination with a sensitizer, is sensitive to actinic light having a wavelength of 300 nm or more and generates an acid. Can be preferably used in combination with
The pKa of the acid generated from the specific photoacid generator used in the present disclosure is preferably 4.0 or less, more preferably 3.0 or less, from the viewpoint of sensitivity and recognizability. It is more preferably 0 or less, more preferably -1.0 or less. Although the lower limit of the pKa of the acid generated from the specific photoacid generator is not particularly defined, it is preferably, for example, -10.0 or more, and from the viewpoint of sensitivity and recognizability, it is -4.0 or more. More preferably, it is more preferably -3.5 or more, particularly preferably -3.0 or more.

  Further, the acid generated from the specific photoacid generator is preferably at least one acid selected from the group consisting of phosphoric acid and sulfonic acid from the viewpoint of sensitivity and recognizability, and more preferably sulfonic acid. More preferably, it is a sulfonic acid represented by the following formula S1 or S2.

In the formulas S1 and S2, R ^S represents an alkyl group, L ^S represents an alkylene group having 2 or more carbon atoms, ns represents 0 or 1, provided that R ^S is an alkyl group having a halogen atom. in some cases an n is 1, X ^S are each independently, represent an alkyl group, an aryl group, an alkoxy group or an aryloxy group, ms represents an integer of 0 to 5.

The alkyl group in ^RS may have a substituent.
Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, and an aryloxy group.
The number of carbon atoms of the alkyl group in R ^S is preferably 1 to 20, and more preferably 2 to 16.
L ^S is preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and particularly preferably an ethylene group.
X ^S is preferably each independently an alkyl group, more preferably an alkyl group having 1 to 20 carbon atoms, further preferably an alkyl group having 1 to 8 carbon atoms, and a methyl group. Is particularly preferred.
ms is preferably an integer of 0 to 3, more preferably 0 or 1, and particularly preferably 1.

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

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

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

Examples of the onium salt compound include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and triarylsulfonium salts and diaryliodonium salts are preferable.
As the onium salt compound, onium salt compounds described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.

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

<Basic compound>
The photosensitive resin composition according to the present disclosure preferably further contains a basic compound.
The basic compound can be arbitrarily selected from the basic compounds used in the chemically amplified resist. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include the compounds described in paragraphs 0204 to 0207 of JP-A-2011-221494, the contents of which are incorporated herein.

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

The above basic compounds may be used alone or in combination of two or more.
The content of the basic compound is preferably from 0.001% by mass to 5% by mass, and more preferably from 0.005% by mass to 3% by mass, based on the total solid content of the photosensitive resin composition. More preferred.

<Solvent>
It is preferable that the photosensitive resin composition according to the present disclosure further contains a solvent.
In addition, the above-mentioned photosensitive resin composition is used to adjust the viscosity of the photosensitive resin composition by once containing a solvent, and to coat the photosensitive resin composition containing the solvent, in order to easily form a photosensitive resin layer described later. Then, by drying, the photosensitive resin layer can be suitably formed.
Known solvents can be used as the solvent used in the present disclosure. Solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers , Diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Further, specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP-A-2011-221494, and the contents thereof are incorporated herein.

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

The solvent is preferably a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., a solvent having a boiling point of 160 ° C. or more, or a mixture thereof.
As the solvent having a boiling point of 130 ° C. or more and less than 160 ° C., propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), and Propylene glycol methyl-n-propyl ether (boiling point 131 ° C.) can be exemplified.
Examples of the solvent having a boiling point of 160 ° C. or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), dipropylene glycol methyl ether acetate (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol 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 when applying the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and more preferably 100 parts by mass, per 100 parts by mass of the total solids in the photosensitive resin composition. More preferably, it is 900 parts by mass.
In addition, the content of the solvent in the photosensitive resin layer described below is preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.5% by mass or less based on the total mass of the photosensitive resin layer. It is more preferable that the content is not more than mass%.

<Other additives>
The photosensitive resin composition according to the present disclosure may include known additives as necessary in addition to the above-described components such as a specific latent dye, a specific polymer, and a specific photoacid generator.

-Plasticizer-
The photosensitive resin composition according to the present disclosure may contain a plasticizer for the purpose of improving plasticity.
The plasticizer preferably has a smaller weight average molecular weight than the specific polymer.
The weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and even more preferably 800 or more and less than 4,000 from the viewpoint of imparting plasticity.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the 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 to another atom.

  In addition, for example, even with a compound having an alkyleneoxy group having the above structure (hereinafter referred to as “compound X”), a compound X, a specific latent dye, a specific polymer, and a specific photoacid generator are obtained by mixing. When the plasticity of the chemically amplified positive photosensitive resin composition does not improve as compared with the chemically amplified positive photosensitive resin composition formed without containing the compound X, it does not correspond to the plasticizer in the present disclosure. For example, an optional surfactant is not generally used in an amount that brings plasticity to the photosensitive resin composition, and thus does not fall under the plasticizer in the present specification.

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

The content of the plasticizer is 1% by mass to 50% by mass based on the total solid content of the photosensitive resin composition from the viewpoint of the adhesion of the photosensitive resin layer formed by the photosensitive resin composition. It is preferable that it is 2 mass%-20 mass%.
The photosensitive resin composition may include only one type of plasticizer, or may include two or more types of plasticizers.

-Sensitizer-
The photosensitive resin composition according to the present disclosure can further include a sensitizer.
The sensitizer absorbs actinic rays and enters an electronically excited state. The sensitizer in the electronically excited state comes into contact with the specific photoacid generator, and causes actions such as electron transfer, energy transfer, and heat generation. This causes the specific photoacid generator to undergo a chemical change and decompose to generate an acid.
Exposure sensitivity can be improved by including a sensitizer.

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

  Examples of the sensitizer include the compounds described in paragraphs 0139 to 0141 of WO2015 / 093271.

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

-Heterocyclic compound-
The photosensitive resin composition according to the present disclosure can include a heterocyclic compound.
There is no particular limitation on the heterocyclic compound in the present disclosure. For example, compounds having an epoxy group or oxetanyl group in the molecule described below, heterocyclic compounds containing an alkoxymethyl group, oxygen-containing monomers such as various cyclic ethers and cyclic esters (lactones), and nitrogen-containing monomers such as cyclic amines and oxazolines Further, a heterocyclic monomer having a d-electron such as silicon, sulfur or phosphorus may be added.

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

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

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

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

  Specific examples of the compound having an oxetanyl group in the molecule include Alonoxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, and PNOX (these are Toagosei Co., Ltd.) (Manufactured by K.K.).

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

  In the photosensitive resin composition according to the present disclosure, it is preferable that the heterocyclic compound is a compound having an epoxy group from the viewpoints of etching resistance and line width stability of the obtained pattern.

-Alkoxysilane compound-
The photosensitive resin composition according to the present disclosure may contain an alkoxysilane compound. Preferred examples of the alkoxysilane compound include trialkoxysilane compounds.
Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriakoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxy Propyl trialkoxysilane, γ-methacryloxypropylalkyl dialkoxysilane, γ-chloropropyl trialkoxysilane, γ-mercaptopropyl trialkoxysilane, β- (3,4-epoxycyclohexyl) ethyl trialkoxysilane, vinyl trialkoxysilane Is mentioned. Of these, γ-glycidoxypropyl trialkoxysilane and γ-methacryloxypropyl trialkoxysilane are more preferable, γ-glycidoxypropyl trialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used alone or in combination of two or more.
The content of the alkoxysilane compound is preferably from 0.1% by mass to 30% by mass, more preferably from 0.5% by mass to 20% by mass, based on the total solid content of the photosensitive resin composition. .

-Surfactant-
The photosensitive resin composition according to the present disclosure preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic (nonionic) and amphoteric surfactants can be used, and a preferred surfactant is a nonionic surfactant.
Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based, and fluorine-based surfactants. . In the following trade names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by JEMCO), Megafac (manufactured by DIC Corporation), Florard (manufactured by Sumitomo 3M) Series, such as Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (manufactured by Dow Corning Toray).
In addition, the composition contains a structural unit A and a structural unit B represented by the following formula I-1 as a surfactant, and has a weight average in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.

In Formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or a carbon atom. L represents an alkyl group having a number of 1 to 4; L represents an alkylene group having a carbon number of 3 to 6; And q represents a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 or more and 18 or less, s represents an integer of 1 or more and 10 or less, and * represents a bonding site with another structure. Represent.

L is preferably a branched alkylene group represented by the following formula (I-2). R ⁴⁰⁵ in the 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 view of compatibility and wettability to a surface to be coated. Two or three alkyl groups are more preferred. The sum of p and q (p + 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.

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

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

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

(Photosensitive transfer material)
The photosensitive transfer material according to the present disclosure has a temporary support and a photosensitive resin layer, and the photosensitive resin layer contains a structural unit having a group in which a carboxylic acid group is protected in the form of an acetal. Contains at least one photoacid generator selected from the group consisting of a polymer, an oxime compound and an onium salt compound, and a latent dye having a maximum absorption wavelength of 500 nm or more in a wavelength range of 400 nm to 780 nm upon coloring. Preferably, the photosensitive resin layer includes a temporary support and a photosensitive resin layer, and the photosensitive resin layer preferably includes the photosensitive resin composition according to the present disclosure.

FIG. 1 schematically illustrates an example of a layer configuration of the photosensitive transfer material according to the present disclosure. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 10, an intermediate layer 12, a photosensitive resin layer 14, and a cover film 16 are laminated in this order.
The photosensitive resin layer 14 is at least one selected from the group consisting of a polymer containing a structural unit having a group in which a carboxylic acid group is protected in the form of an acetal, an oxime compound, and an onium salt compound. And a latent dye having a maximum absorption wavelength of 500 nm or more in a wavelength range of 400 nm to 780 nm at the time of color development.
Hereinafter, constituent materials and the like of the photosensitive transfer material according to the present disclosure will be described. The above configuration in the present disclosure may be referred to as follows in this specification.
A polymer having a constituent unit in which a carboxylic acid group is protected in the form of an acetal may be referred to as a “specific polymer”.
The photosensitive resin layer is a positive photosensitive resin layer, and may be referred to as a “positive photosensitive resin layer”.

<Temporary support>
The photosensitive transfer material according to the present disclosure has a temporary support.
The temporary support is a support that supports the photosensitive resin layer and is peelable.
The temporary support used in the present disclosure preferably has light transmissivity 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.
Having the light transmittance means that the transmittance of the main wavelength of the light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of the light used for pattern exposure is determined from the viewpoint of improving the exposure sensitivity. Therefore, it is preferably at least 60%, more preferably at least 70%. As a method of measuring the transmittance, there is a method of measuring by using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
Examples of the temporary support include a glass substrate, a resin film, and paper, and a resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, 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 in view of the strength as the support, the flexibility required for bonding with the circuit wiring forming substrate, the light transmittance required in the first exposure step, and the like. do it.

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

<Photosensitive resin layer>
The photosensitive transfer material according to the present disclosure has a photosensitive resin layer, the photosensitive resin layer is a polymer containing a structural unit having a group in which a carboxylic acid group is protected in the form of an acetal, an oxime compound, and It contains at least one photoacid generator selected from the group consisting of onium salt compounds, and a latent dye having a maximum absorption wavelength of 500 nm or more in a wavelength range of 400 nm to 780 nm at the time of coloring.
The photosensitive resin layer is preferably a layer formed from the photosensitive resin composition according to the present disclosure.
Further, the photosensitive resin layer preferably contains the photosensitive resin composition according to the present disclosure.
Further, the photosensitive resin layer in the present disclosure is a positive photosensitive resin layer, and is a chemically amplified positive photosensitive resin layer.
The photoacid generator, which is at least one selected from the group consisting of an oxime compound and an onium salt compound, is characterized in that an acid generated in response to actinic radiation (actinic ray) is a protected acid in the specific polymer. Since it acts as a catalyst for the deprotection of the group, the acid generated by the action of one photon contributes to a number of deprotection reactions, and the quantum yield exceeds one, for example, as a power of ten. And a high sensitivity is obtained as a result of so-called chemical amplification.
On the other hand, when a quinonediazide compound is used as a photoacid generator sensitive to actinic radiation, a carboxy group is generated by a sequential photochemical reaction, but the quantum yield is always 1 or less, and does not correspond to a chemically amplified type.

A photoacid generator that is at least one selected from the group consisting of a polymer containing a structural unit having a group in which a carboxylic acid group in the photosensitive resin layer is protected in the form of an acetal, an oxime compound, and an onium salt compound; , And a latent dye having a maximum absorption wavelength of 500 nm or more in a wavelength range of 400 nm to 780 nm at the time of color development is a structural unit having a group in which the carboxylic acid group in the photosensitive resin composition is protected in the form of an acetal. At least one photoacid generator selected from the group consisting of a polymer, an oxime compound and an onium salt compound, and a latent dye having a maximum absorption wavelength of 500 nm or more in a wavelength range of 400 nm to 780 nm upon coloring. And the preferred embodiment is also the same.
Further, the photosensitive resin layer can preferably contain each component in the photosensitive resin composition other than the solvent.
Furthermore, in the photosensitive resin layer, the preferred content of each component with respect to the total mass of the photosensitive resin layer is the preferred content of each component with respect to the total solid content of the photosensitive resin composition in the photosensitive resin composition. Same as quantity.

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

-Method of forming photosensitive resin layer-
The components and the solvent can be mixed at a predetermined ratio and in an arbitrary method, and stirred and dissolved to prepare a photosensitive resin composition for forming a photosensitive resin layer. For example, a composition can be prepared by preparing a solution in which each component is previously dissolved in a solvent, and then mixing the obtained solution at a predetermined ratio. The composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

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

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

<Contrast enhancement layer>
The photosensitive transfer material according to the present disclosure may have a contrast enhancement layer in addition to the photosensitive resin layer.
A contrast enhancement layer (CEL) has a large absorption at an exposure wavelength before exposure, but the absorption gradually decreases with exposure, that is, a material having a high light transmittance (light decoloring). (Referred to as a colorant component). As the photobleachable dye component, diazonium salts, stilbazolium salts, arylnitroso salts and the like are known. A phenolic resin or the like is used as a film forming component.
Other examples of the contrast enhancement layer include paragraphs 0004 to 0051 of JP-A-6-97065, paragraphs 0012 to 0055 of JP-A-6-332167, a photopolymer handbook, edited by a photopolymer social gathering, an industrial research committee ( 1989), Photopolymer Technology, edited by Yamaoka and Nagamatsu, Nikkan Kogyo Shimbun (1988).

<Intermediate layer>
On the photosensitive resin layer, an intermediate layer can be provided for the purpose of applying a plurality of layers and for preventing the components from being mixed during storage after the application.
As the intermediate layer, an intermediate layer described in paragraphs 0084 to 0087 of JP-A-2005-259138 can be used. The intermediate layer is preferably one that disperses or dissolves in water or an aqueous alkaline solution.
Examples of the material used for the intermediate layer include polyvinyl alcohol-based resins, polyvinyl pyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. Resins. Among them, particularly preferred is a combination of polyvinyl alcohol and polyvinyl pyrrolidone.

<Thermoplastic resin layer, cover film, etc.>
The photosensitive transfer material according to the present disclosure may have, for example, a temporary support, a thermoplastic resin layer, and a photosensitive resin layer in this order. Further, a cover film may be provided for the purpose of protecting the photosensitive resin layer.
For the preferred embodiment of the thermoplastic resin layer, paragraphs 0189 to 0193 of JP-A-2014-85643, and the preferred embodiments of the other layers are described in paragraphs 0194 to 0196 of JP-A-2014-85643, respectively. The contents of this publication are incorporated herein.

When the photosensitive transfer material according to the present disclosure has another layer such as a thermoplastic resin layer, it is manufactured according to the method for manufacturing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138. can do.
For example, when producing a photosensitive transfer material according to the present disclosure having a thermoplastic resin layer and an intermediate layer, a solution (thermoplastic) in which a thermoplastic organic polymer and an additive are dissolved on a temporary support is prepared. Coating solution for resin layer), dried to form a thermoplastic resin layer, and then prepared by adding a resin and additives to a solvent that does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer. The liquid (coating liquid for the intermediate layer) is applied and dried to laminate the intermediate layer. On the formed intermediate layer, further, by applying the photosensitive resin composition according to the present disclosure prepared using a solvent that does not dissolve the intermediate layer, and drying and laminating the photosensitive resin layer according to the present disclosure. A photosensitive transfer material can be suitably manufactured.

(Method of manufacturing circuit wiring)
A first embodiment of a method for manufacturing a circuit wiring using the photosensitive transfer material according to the present disclosure will be described.
A first embodiment of a method for manufacturing a circuit wiring includes:
A step of attaching the photosensitive resin layer of the photosensitive transfer material according to the present disclosure to the substrate by bringing the photosensitive resin layer into contact with the substrate (adhering step);
Pattern exposure of the photosensitive resin layer of the photosensitive transfer material after the bonding step (exposure step);
Developing the photosensitive resin layer after the exposing step to form a pattern (developing step);
A step of etching the substrate in an area where the pattern is not arranged (etching step).
The substrate in the first embodiment of the method for manufacturing circuit wiring may be a substrate in which a layer such as a desired conductive layer is provided on a base material such as glass, silicon, or a film.
According to the first embodiment of the method for manufacturing circuit wiring, a fine pattern can be formed on the substrate surface.

A second embodiment of the method for manufacturing a circuit wiring includes:
A base material, and a plurality of conductive layers including a first conductive layer and a second conductive layer whose constituent materials are different from each other; And bonding the photosensitive resin layer of the photosensitive transfer material according to the present disclosure in contact with the first conductive layer to a substrate on which the first conductive layer and the second conductive layer are laminated. Process and
A first exposure step of pattern-exposing the photosensitive resin layer through the temporary support of the photosensitive transfer material after the laminating step,
A first development step of removing the temporary support from the photosensitive resin layer after the first exposure step, and then developing the photosensitive resin layer after the first exposure step to form a first pattern;
A first etching step of etching at least the first conductive layer and the second conductive layer among the plurality of conductive layers in a region where the first pattern is not arranged;
A second exposure step of pattern-exposing the first pattern after the first etching step with a pattern different from the first pattern;
A second development step of developing the first pattern after the second exposure step to form a second pattern;
A second etching step of etching at least the first conductive layer out of the plurality of conductive layers in a region where the second pattern is not arranged. As the second embodiment, WO 2006/190405 can be referred to, and the contents thereof are incorporated herein.

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

<Lamination process>
An example of the bonding step is schematically shown in FIG.
First, in the bonding step, the base material 22 and a plurality of conductive layers including the first conductive layer 24 and the second conductive layer 26 having different constituent materials are provided. The substrate (circuit wiring forming substrate) 20 on which the first conductive layer 24 and the second conductive layer 26, which are the outermost layers, are laminated in order from the surface farther from the surface of the photosensitive transfer material according to the present disclosure described above. 100 positive-type photosensitive resin layers 14 are brought into contact with the first conductive layer 24 and bonded. Note that such bonding of the circuit wiring forming substrate and the photosensitive transfer material may be referred to as “transfer” or “laminate”.

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

〔Base material〕
The substrate in which a plurality of conductive layers are laminated on the substrate is preferably a glass substrate or a film substrate, and more preferably a film substrate. In the circuit wiring manufacturing method according to the present disclosure, when the circuit wiring is for a touch panel, it is particularly preferable that the substrate is a sheet-shaped resin composition.
Further, the substrate is preferably transparent.
The base material preferably has a refractive index of 1.50 to 1.52.
The base material may be composed of a light-transmitting base material such as a glass base material, and tempered glass represented by gorilla glass of Corning and the like can be used. Further, as the above-mentioned transparent substrate, the materials used in JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be preferably used.
When a film substrate is used as the substrate, it is more preferable to use a substrate having no optical distortion, and a substrate having high transparency, and specific materials include polyethylene terephthalate (PET), Examples include polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymers.

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

In the method for manufacturing a circuit wiring according to the present disclosure, it is preferable that at least one of the plurality of conductive layers contains a metal oxide.
The conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition unit used in a capacitance type touch panel or a wiring of a peripheral extraction unit.

(Circuit wiring formation substrate)
A substrate having a conductive layer on the surface of a substrate. Circuit wiring is obtained by patterning the conductive layer. In this example, it is preferable that a plurality of conductive layers such as a metal oxide and a metal are provided on a film base such as PET.

<Exposure step (first exposure step)>
The exposure step is performed in the first embodiment, and the first exposure step is performed in the second embodiment. An example of the exposure step (first exposure step) is schematically shown in FIG.
In the exposure step (first exposure step), the positive photosensitive resin layer 14 is subjected to pattern exposure via the temporary support 12 of the photosensitive transfer material after the bonding step.

  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.

For example, a mask 30 having a predetermined pattern is disposed above the photosensitive transfer material 100 disposed on the first conductive layer 24 (the side opposite to the side in contact with the first conductive layer 24), and thereafter, the mask 30 And a method of exposing to ultraviolet light from above the mask through the mask.
In the present disclosure, the detailed arrangement and specific size of the pattern are not particularly limited. In order to improve the display quality of a display device (for example, a touch panel) including an input device having circuit wirings manufactured by the method for manufacturing circuit wirings according to the present disclosure, and to reduce the area occupied by the extracted wirings as much as possible, At least a part (particularly, a part of the electrode pattern and the lead-out wiring of the touch panel) is preferably a fine line of 100 μm or less, more preferably 70 μm or less.
Here, a light source used for exposure can be appropriately selected and used as long as it can irradiate light (for example, 365 nm, 405 nm, or the like) in a wavelength range in which the exposed portion of the photosensitive transfer material can be dissolved in a developer. . Specifically, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp and the like can be mentioned.
Energy of exposure preferably ² ~200mJ / cm 2 of about ^{5 mJ} / cm, more preferably 10mJ ^/ cm ² ~100mJ ^/ cm 2 approximately.
It is also preferable to perform a heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. By a process called so-called PEB (Post Exposure Bake), it is possible to reduce the roughness of the pattern edge due to the standing wave generated in the photosensitive resin layer at the time of exposure.

  Incidentally, even if the pattern exposure is performed after peeling the temporary support from the photosensitive resin layer, before peeling the temporary support, exposure through the temporary support, and then peeling the temporary support Is also good. In order to prevent mask contamination due to the contact between the photosensitive resin layer and the mask and to avoid the influence of foreign matter adhering to the mask on the exposure, it is preferable to perform the exposure without removing the temporary support. The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.

<Developing step (first developing step)>
The developing step is performed in the first embodiment, and the first developing step is performed in the second embodiment. An example of the developing step (first developing step) is schematically shown in FIG.
In the developing step (first developing step), the temporary support 12 is separated from the positive photosensitive resin layer 14 after the exposing step (first exposing step), and then the positive photosensitive layer after the exposing step (first exposing step) is exposed. The first pattern 14A is formed by developing the conductive resin layer 14.

The developing step (first developing step) is a step of forming a pattern (first pattern) by developing the pattern-exposed positive photosensitive resin layer.
The development of the pattern-exposed positive photosensitive resin layer can be performed using a developer.
The developer is not particularly limited as long as the exposed portion of the positive photosensitive resin layer can be removed. For example, a known developer such as a developer described in JP-A-5-72724 may be used. it can. Incidentally, the developing solution is preferably a developing solution in which the exposed portion of the positive photosensitive resin layer exhibits a dissolving type developing behavior. For example, an alkaline aqueous solution-based developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is preferable. The developer may further contain an organic solvent having miscibility with water, a surfactant, and the like. As the developer suitably used in the present disclosure, for example, a developer described in paragraph 0194 of International Publication No. 2015/093271 is exemplified.

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

Further, a post-baking step of heating a pattern including the positive photosensitive resin layer obtained by development may be provided.
Post-baking is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably in an environment of 506.6 kPa or more. On the other hand, it is more preferable to perform in an environment of 114.6 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 from 80C to 250C, more preferably from 110C to 170C, and particularly preferably from 130C to 150C.
The post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
Post-baking may be performed in an air environment or in a nitrogen-substituted environment.

  The method for manufacturing a circuit wiring according to the present disclosure may include other steps such as a post-exposure step.

<Etching step (first etching step)>
The etching step is performed in the first embodiment, and the first etching step is performed in the second embodiment. An example of the etching step (first etching step) is schematically shown in FIG.
In the etching step (first etching step), at least the first conductive layer 24 and the second conductive layer 26 of the plurality of conductive layers in the region where the first pattern 14A is not arranged are etched. The first conductive layer 24A and the second conductive layer 26A having the same pattern are formed by the etching.

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

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

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

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

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

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

<Second developing step>
In the second embodiment, a second developing step is performed. An example of the second developing step is schematically shown in FIG.
In the second development step, the first pattern 14A after the second exposure step is developed to form a second pattern 14B.
The portion of the first pattern exposed in the second exposure step is removed by the development.
In the second development step, the same method as the development in the first development step can be applied.

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

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

<Positive photosensitive resin layer removal step>
An example of the positive photosensitive resin layer removing step is schematically shown in FIG.
After the end of the second etching step, the second pattern 14B remains on a part of the first conductive layer 24B. If the positive photosensitive resin layer is unnecessary, all the remaining positive photosensitive resin layers 14B may be removed.

The method of removing the remaining positive photosensitive resin layer is not particularly limited, and examples thereof include a method of removing by a chemical treatment.
As a method for removing the positive photosensitive resin layer, for example, a substrate having a positive photosensitive resin layer or the like in a stripping solution preferably stirred at 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. A method of immersing for 1 minute to 30 minutes is exemplified.

  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 primary amine, a secondary amine, a tertiary amine, or a quaternary ammonium salt is added to water , Dimethylsulfoxide, N-methylpyrrolidone, or a stripping solution dissolved in a mixed solution thereof. The peeling may be performed by a spraying method, a shower method, a paddle method, or the like using a peeling liquid.

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

<Process of attaching protective film>
In the second embodiment, after the first etching step and before the second exposure step, the method may further include a step of attaching a light-transmissive protective film (not shown) on the first pattern. Good.
In this case, in the second exposure step, it is preferable to perform pattern exposure of the first pattern through the protective film, and after the second exposure step, peel the protective film from the first pattern, and then perform the second development step.

<Step of lowering visible light reflectance>
The method for manufacturing a circuit wiring according to the present disclosure can include a step of performing a process of reducing visible light reflectance of a part or all of a plurality of conductive layers on a base material.
Oxidation treatment or the like can be given as a treatment for reducing the visible light reflectance. For example, visible light reflectance can be reduced by oxidizing copper to form copper oxide and blackening.
Regarding the preferred embodiment of the process of lowering the visible light reflectance, see paragraphs 0017 to 0025 of JP-A-2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of JP-A-2013-206315. And the contents of this publication are incorporated herein.

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

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

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

(Circuit wiring and circuit board)
The circuit wiring according to the present disclosure is a circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure.
A circuit board according to the present disclosure is a substrate having circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure.
Although the use of the circuit board according to the present disclosure is not limited, for example, it is preferably a circuit board for a touch panel.

(Input device and display device)
An input device is an example of a device including a circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure.
The input device according to the present disclosure is preferably a capacitive touch panel.
The display device according to the present disclosure preferably includes the input device according to the present disclosure.
Further, the display device according to the present disclosure is preferably an image display device such as an organic EL display device and a liquid crystal display device.

(Touch panel, touch panel display device, and manufacturing method thereof)
A touch panel according to the present disclosure is a touch panel having at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure. Further, the touch panel according to the present disclosure preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
A touch panel display device according to the present disclosure is a touch panel display device having at least circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure, and is preferably a touch panel display device including the touch panel according to the present disclosure.
The method for manufacturing a touch panel or a touch panel display device according to the present disclosure preferably includes the method for manufacturing circuit wiring according to the present disclosure.
The method for manufacturing a touch panel or a touch panel display device according to the present disclosure includes a step of bringing the photosensitive resin layer of the photosensitive transfer material obtained by the method for manufacturing a photosensitive transfer material into contact with the substrate and bonding the substrate, and the step of bonding. A step of pattern-exposing the photosensitive resin layer of the photosensitive transfer material after the step, a step of forming a pattern by developing the photosensitive resin layer after the step of exposing, and an area where the pattern is not arranged And the step of etching the substrate in the above. The details of each step are the same as the details of each step in the above-described circuit wiring manufacturing method, and the preferred embodiments are also the same.
As a detection method in the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, any known method such as a resistive method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among them, the capacitance type is preferable.
As the touch panel type, a so-called in-cell type (for example, the one described in JP-A-2012-517051 shown in FIGS. 5, 6, 7, and 8), a so-called on-cell type (for example, JP-A-2013-168125) Japanese Unexamined Patent Application Publication No. 19-89102, Japanese Unexamined Patent Application Publication No. 2012-89102 described in FIG. 1 and FIG. No. 2013-54727, FIG. 2), other configurations (for example, those described in FIG. 6 of JP-A-2013-164871), various out-cell types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.).
As a touch panel according to the present disclosure and a touch panel display device according to the present disclosure, “Latest Touch Panel Technology” (July 6, 2009, Techno Times Co., Ltd.), supervised by Yuji Mitani, “Technology and Development of Touch Panel”, CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress
Semiconductor Corporation The configuration disclosed in Application Note AN2292 or the like can be applied.

  Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed 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 described below. Unless otherwise specified, “parts” and “%” are based on mass. The “maximum absorption wavelength” in the present embodiment is a maximum absorption wavelength in a wavelength range of 400 nm to 780 nm at the time of coloring.

(Polymer)
In the following examples, the following abbreviations represent the following compounds, respectively.
ATHF: 2-tetrahydrofuranyl acrylate (synthetic product)
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
ATHP: Tetrahydro-2H-pyran-2-yl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
MATHP: tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
TBMA: t-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
AA: Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
MAA: methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
EA: Ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
MMA: Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
CHA: cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
CHMA: cyclohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
BMA: n-butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
PGMEA (propylene glycol monomethyl ether acetate): (manufactured by Showa Denko KK)
V-601: dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

<Synthesis of ATHF>
Acrylic acid (72.1 parts by mass, 1.0 molar equivalent) and hexane (72.1 parts by mass) were added to a three-neck flask and cooled to 20 ° C. After dropwise addition of camphorsulfonic acid (0.00070 parts by mass, 0.003 mmol equivalent) and 2-dihydrofuran (70.1 parts by mass, 1.0 mol equivalent), the mixture was stirred at 20 ° C. ± 2 ° C. for 1.5 hours. Then, the temperature was raised to 35 ° C., and the mixture was stirred for 2 hours. Kyoward 200 (aluminum hydroxide adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (hydrotalcite-based adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) are spread over Nutsche in this order, and then the reaction solution is filtered. Hydroquinone monomethyl ether (MEHQ, 0.0012 parts by mass) was added to the obtained filtrate, and the mixture was concentrated under reduced pressure at 40 ° C. to give tetrahydro-2H-furan-2-acrylate. 140.8 parts by mass of yl (ATHF) was obtained as a colorless oil (yield 99.0%).

<Synthesis of MATHF>
Methacrylic acid (86.1 parts, 1.0 molar equivalent) and hexane (86.1 parts) were added to a three-neck flask and cooled to 20 ° C. After dropwise addition of camphorsulfonic acid (0.00070 parts, 0.003 mmol equivalent) and 2-dihydrofuran (70.1 parts, 1.0 mol equivalent), the mixture was stirred at 20 ° C. ± 2 ° C. for 1.5 hours. , And the mixture was stirred for 2 hours. Kyoward 200 (aluminum hydroxide adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (hydrotalcite-based adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) are spread over Nutsche in this order, and then the reaction solution is filtered. After adding MEHQ (0.0012 parts) to the obtained filtrate, the mixture was concentrated under reduced pressure at 40 ° C. to obtain 156.2 parts of tetrahydrofuran-2-yl methacrylate (MATHF). Obtained as a colorless oil (yield 98.0%).

<Synthesis example of polymer A1>
N-Propyl acetate (150.0 parts by mass) was charged into a three-necked flask, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. ATHF (25.0 parts by mass), AA (3.7 parts by mass), EA (15.0 parts by mass), MMA (32.4 parts by mass), CHMA (23.9 parts by mass), V-601 (3 parts by mass) .1 parts by mass) was dropped into a three-neck flask solution maintained at a temperature of 90 ° C. ± 2 ° C. over 2 hours. After completion of the dropwise addition, the mixture was stirred for 2 hours in a temperature range of 90 ° C. ± 2 ° C. to obtain a polymer A1 (solid content concentration: 40.0% by mass).

<Synthesis example of polymers A2 to A8>
The type of the monomer was changed as shown in Table 2 below, and the other conditions were synthesized by the same method as that for the polymer A1. The solid content concentration of the polymer was 40% by mass.
In Table 1, "-" indicates that the corresponding monomer was not used. In Table 1, Mw was measured by the method described above.

<Synthesis example of polymer R1>
A polymer synthesized by the same method as the acid-decomposable polymer compound PS-2 described in JP-A-2008-64908 was converted to a polymer R1 (containing a structural unit having a group in which a carboxylic acid group was protected in the form of an acetal). Polymer).

<Synthesis example of polymer R2>
A polymer synthesized by the same method as the binder polymer A-2 described in JP-A-2009-3000 was used.
Polymer R2 (a polymer containing a structural unit having a group in which a carboxylic acid group was protected in the form of an acetal) was used.

(Photoacid generator)
B-1: Compound having the following structure (synthesized according to the method described in paragraph 0227 of JP-A-2013-47765).

  B-2: Irgacure PAG-103 manufactured by BASF, the following compound

  B-3: Compound having the structure shown below (synthesized according to the method described in paragraph 0210 of JP-A-2014-197155).

  B-4: NAI-105 (Midori Chemical Co., Ltd., imidosulfonate compound)

  B-5: Compound having the structure shown below (synthesized according to the method described in paragraph 0138 of JP-A-2015-151347).

(Latent dye)
C-1: The same compound as C-1 described above, manufactured by Fukui Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 576 nm, pKaH: -3.53.
C-2: the same compound as the above-mentioned C-2, manufactured by Chameleon, maximum absorption wavelength: 533 nm, pKaH: does not form a conjugate acid C-3: the same compound as the above-mentioned C-3, manufactured by Yamamoto Kasei Co., Ltd. , Maximum absorption wavelength: 531 nm, pKaH: does not form a conjugate acid C-4: the same compound as C-4 described above, manufactured by Fukui Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 460 nm and 595 nm, pKaH: 0.53
C-5: The same compound as the above C-5, manufactured by Fukui Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 470 nm and 672 nm, pKaH: 0.23
C-6: The same compound as C-6 described above, manufactured by Fukui Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 525 nm, pKaH: 0.27
C-7: The same compound as C-7 described above, manufactured by Fukui Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 507 nm
C-8: Same compound as C-8 described above, manufactured by Wako Pure Chemical Industries, Ltd., maximum absorption wavelength: 566 nm
C-9: The same compound as C-9 described above, manufactured by Yamada Chemical Industry Co., Ltd., maximum absorption wavelength: 591 nm

(Basic compound)
D-1: Compound having the structure shown below (CMTU)

D-2: 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-3: 1,5-diazabicyclo [4.3.0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.)

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

E-1: Megafac F-554 (fluorinated nonionic surfactant, manufactured by DIC Corporation)
E-2: Megafac F-552 (fluorinated nonionic surfactant, manufactured by DIC Corporation)
E-3: Megafac F-253 (fluorinated nonionic surfactant, manufactured by DIC Corporation)

(Examples 1 to 25 and Comparative Examples 1 to 3)
<Preparation of photosensitive transfer material>
In Examples 1 to 25 and Comparative Examples 1 to 3, a polymer component, a photoacid generator, a basic compound, a surfactant, and other components were added so that the solid content ratio shown in Table 2 below was obtained. Methyl ethyl ketone and n-propyl acetate are added and dissolved and mixed with methyl ethyl ketone / (other solvent) = 30/70 (mass%) so as to have a solid content concentration of 14 mass%, and polytetrafluoroethylene having a pore diameter of 0.2 μm The mixture was filtered through a filter made of a photosensitive resin composition.
This photosensitive resin composition was dried on a 16 μm-thick polyethylene terephthalate film (hereinafter referred to as “PET (A)”) serving as a temporary support with a dry film thickness of 3.0 μm using a slit nozzle. It applied so that it might become. Thereafter, the film was dried in a convection oven at 100 ° C. for 2 minutes, and finally, a 30 μ-thick polypropylene film (Alphan PK-002, manufactured by Oji F-tex) was pressed as a cover film to prepare a photosensitive transfer material.

[Performance evaluation]
A 200-nm-thick PET substrate provided with a copper layer by a sputtering method on a 100-μm-thick polyethylene terephthalate (PET) film was used.

<Lamination suitability evaluation>
The prepared photosensitive transfer material was cut into a 50 cm square, the cover film was peeled off, and the roll temperature was 90 ° C., the linear pressure was 0.8 MPa, and the linear velocity was 3.0 m / min. Was laminated on a PET substrate with a copper layer under the following lamination conditions. The area where the photosensitive resin layer was in contact with the copper layer without bubbles or floating was visually evaluated, and the ratio of the area in which the photosensitive resin layer was in contact with the copper layer was calculated based on the area where the photosensitive resin layer was in contact with the area of the cut transfer material (%). It can be said that the larger the area (%), the better the lamination suitability.
〔Evaluation criteria〕
Area (%) is 95% or more: 5
Area (%) is 90% or more and less than 95%: 4
Area (%) is 85% or more and less than 90%: 3
Area (%) is 80% or more and less than 85%: 2
Area (%) less than 80%: 1

<Sensitivity (exposure sensitivity) evaluation>
The prepared photosensitive transfer material was subjected to a linear pressure of 0.8 MPa and a linear velocity of 3.0 m / min. Was laminated on a PET substrate with a copper layer under the following lamination conditions. When the suitability for lamination at a roll temperature of 90 ° C. was 4 or less, a sample was prepared by increasing the temperature of the lami-roll until the suitability for lamination reached 5. Lamination suitability was evaluated by the method described above.
After exposing the photosensitive resin layer with an ultra-high pressure mercury lamp through a line and space pattern mask (duty ratio 1: 1) having a line width of 3 to 20 μm without peeling the temporary support, the temporary support is left It peeled and developed. The development was performed using a 1.0% aqueous solution of sodium carbonate at 28 ° C. for 30 seconds by shower development. When a 10 μm line-and-space pattern was formed by the above method, the residue in the space was observed and evaluated by a scanning electron microscope (SEM), and the amount of exposure at which the residue could not be confirmed by SEM was determined. An exposure amount of 200 mJ / cm ² or less is a practicable level. It can be said that the smaller the exposure amount, the better the exposure sensitivity. The evaluation results are shown in Table 2.
〔Evaluation criteria〕
80 mJ / cm ² or less: A
80mJ / cm ² to more than 100mJ / cm ² or less: B
More than 100 mJ / cm ² and 200 mJ / cm ² or less: C
More than 200 mJ / cm ² and 300 mJ / cm ² or less: D
Exceeds 300 mJ / cm ² : E

<Linearity evaluation>
The prepared photosensitive transfer material was subjected to a linear pressure of 0.8 MPa and a linear velocity of 3.0 m / min. Was laminated on a PET substrate with a copper layer under the following lamination conditions. In addition, when the evaluation result of the above-mentioned lamination suitability was 4 or less at a roll temperature of 90 ° C., a sample was prepared by increasing the temperature of the lami-roll until the evaluation result of the lamination suitability became 5 (the area (%) was 95% or more).
Without peeling off the temporary support, the photosensitive resin layer was exposed with an exposure amount determined by sensitivity evaluation through an ultrahigh pressure mercury lamp through a line and space pattern (duty ratio 1: 1) mask having a line width of 3 μm to 20 μm. After standing for 4 hours, the temporary support was peeled off and developed. The development was performed using a 1.0% aqueous solution of sodium carbonate at 28 ° C. for 30 seconds by shower development. In the line-and-space pattern thus obtained, the line width is measured at 50 points within a range of 40 μm in the longitudinal direction of the pattern whose line width falls within 7 ± 0.5 μm, and the standard deviation is obtained for the measurement variation. , 3σ was calculated. This was measured for n = 5, and the average value (LWR, line width roughness) was determined. The smaller the value, the better the performance, and it is practically preferable that the evaluation results are A to C. The evaluation results are shown in Table 2.
〔Evaluation criteria〕
LWR less than 200: A
LWR is 200 or more and less than 240: B
LWR is 240 or more and less than 290: C
LWR is 290 or more and less than 340: D
LWR is 340 or more: E

<Recognition evaluation>
The prepared photosensitive transfer material was subjected to a linear pressure of 0.8 MPa and a linear velocity of 3.0 m / min. Was laminated on a PET substrate with a copper layer under the following lamination conditions. If the evaluation result of the suitability for lamination is 4 or less at a roll temperature of 90 ° C., the roll temperature is increased until the evaluation result of the suitability for lamination becomes 5 (the area (%) is 95% or more) to prepare a sample. did. A part of the temporary support was shielded from light without being peeled off, and the photosensitive resin layer was exposed to light using an ultrahigh pressure mercury lamp, and then left for 4 hours. As the exposure amount, the exposure amount obtained in the above sensitivity evaluation was employed.
An optical lens having a magnification of 4 was attached to the tip of a monochrome CCD (Charge Coupled Device) camera, and the reflected light intensity of the exposed portion and the reflected light intensity of the unexposed portion were measured.
Reflected light intensity ratio = (reflected light intensity of exposed part) / (reflected light intensity of unexposed part)
The smaller the value of the reflected light intensity ratio is, the better the performance is, and it is practically preferable to be A to C in the following evaluation criteria. The evaluation results are shown in Table 2.

-Measurement conditions-
Number of read camera pixels: 5 million pixels (2,432 x 2,050)
Reading camera spectral sensitivity: 400 nm = x0.6, 500 nm = x1.0, 600 nm = x0.84, 700 nm = x0.55
Light source: D65 light source (International Commission on Illumination (CIE) standard light source D65) passed through a sharp cut filter SC-42 manufactured by FUJIFILM Corporation.

-Evaluation criteria-
A: The reflected light intensity ratio is less than 0.45. B: The reflected light intensity ratio is 0.45 or more and less than 0.65. C: The reflected light intensity ratio is 0.65 or more and less than 0.78. E: 78 or more and less than 0.90 E: Reflected light intensity ratio is 0.90 or more

<Evaluation of substrate corrosion>
Linear pressure 0.8 MPa, linear velocity 3.0 m / min. Was laminated on a PET substrate with a copper layer under the following lamination conditions. In addition, when the evaluation result of the above-mentioned lamination suitability was 4 or less at a roll temperature of 90 ° C., a sample was prepared by increasing the lami-roll temperature until the evaluation result of the lamination suitability became 5 (the area (%) was 95% or more). Without peeling off the temporary support, the entire surface of the photosensitive resin layer was exposed at an exposure amount of 500 mJ / cm ^{2 using} an ultrahigh pressure mercury lamp, and then left at 60 ° C. and 90% RH for 24 hours.
The temporary support was peeled off and developed. The development was performed using a 1.0% aqueous solution of sodium carbonate at 28 ° C. for 30 seconds by shower development. Subsequently, rinsing was performed with pure water for 20 seconds in a shower, and draining was performed with an air knife.
The surface of the copper layer after the development was visually observed and observed with a microscope (500 times), and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2.
〔Evaluation criteria〕
A: A state in which no defects such as pinholes due to corrosion are observed in the copper layer.
E: A state where corrosion is observed on the entire surface of the copper layer.

The unit of the amount of each component in Table 2 is parts by mass.
From the results described in Table 2, it can be seen that the photosensitive resin composition according to the present disclosure has excellent sensitivity, excellent recognition of exposed and unexposed portions, and suppresses corrosion of the substrate.
In addition, it can be seen that the photosensitive resin compositions according to the examples have excellent linearity of the obtained patterns.

(Example 101)
A plurality of particles of 3 μm in diameter (trade name: “SSX103” and a plurality of particles of 2 μm in diameter (trade name: “Zeonor ZF16”, manufactured by ZEON CORPORATION) having a thickness of 100 μm) Trade name: “SSX102”, manufactured by Sekisui Plastics Co., Ltd.), 0.05 part and 0 part for 100 parts of binder resin (trade name: “Unidick 17-824-9”, manufactured by DIC Corporation) The coating solution to which .02 parts was added was applied using a bar coater, dried in an oven at 80 ° C. for 1 minute, and irradiated with ultraviolet light (ultra high pressure mercury lamp) having an integrated light quantity of 500 mJ / cm ² , and 70 nm on both sides. A film having an anti-blocking layer was formed (hereinafter, referred to as a COP substrate), and a refractive index modifier (trade name: “OPSTAR K7415”) was applied to one surface of the COP substrate. SR Co., Ltd.) was applied with a bar coater, dried in an oven at 80 ° C. for 1 minute, and irradiated with ultraviolet rays (high-pressure mercury lamp) having an integrated light quantity of 300 mJ to obtain a layer having a thickness of 100 nm and a refractive index of 1.65. A refractive index adjusting layer was formed on the surface of the obtained refractive index adjusting layer of the COP base material, and a 23 nm-thick indium tin oxide layer (ITO) was used as a second conductive layer in a winding type sputtering apparatus. A 200 nm-thick copper film was formed thereon as a first conductive layer by a vacuum evaporation method to obtain a circuit-formed substrate.
The photosensitive transfer material obtained 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 shown in FIG. 3 (hereinafter, referred to as “pattern A”) having a configuration in which conductive layer pads were connected in one direction without removing the temporary support. .
In the pattern A shown in FIG. 3, a solid line portion SL and a gray portion G are light-shielding portions, and a dotted line portion DL is a virtual frame for alignment.
Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Then, the copper layer is etched using a copper etching solution (Kanto Chemical Co., Ltd. Cu-02), and then the ITO layer is etched using an ITO etching solution (Kanto Chemical Co., Ltd. ITO-02). A substrate on which both copper (solid line portion SL) and ITO (gray portion G) were drawn in pattern A was obtained.

Next, pattern exposure was performed using a photomask provided with openings of the pattern shown in FIG. 4 (hereinafter, also referred to as “pattern B”) in the aligned state, followed by development and washing with water.
In the pattern B shown in FIG. 4, the gray portion G is a light-shielding portion, and the dotted line portion DL is a virtual frame for alignment.
Thereafter, the copper layer is etched using Cu-02, and the remaining photosensitive resin layer is stripped using a stripping solution (dimethylsulfoxide: monoethanolamine = 7: 3 (mass ratio) solution) to remove the circuit wiring board. Obtained.
Thus, a circuit wiring board was obtained. Observation with a microscope revealed that there was no peeling or chipping and the pattern was clean.

(Example 102)
On a 100 μm-thick PET substrate, ITO is formed as a second conductive layer to a thickness of 150 nm by sputtering, and copper is formed thereon as a first conductive layer to a thickness of 200 nm by vacuum evaporation. The film was formed into a circuit forming substrate.
The photosensitive transfer material obtained in Example 1 was laminated on the copper layer (linear pressure: 0.8 MPa, linear velocity: 3.0 m / min, roll temperature: 90 ° C.).
The photosensitive resin layer was subjected to pattern exposure using a photomask provided with a pattern A shown in FIG. 3 having a configuration in which conductive layer pads were connected in one direction without peeling the temporary support. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Then, the copper layer is etched using a copper etching solution (Kanto Chemical Co., Ltd. Cu-02), and then the ITO layer is etched using an ITO etching solution (Kanto Chemical Co., Ltd. ITO-02). A substrate on which both copper (solid line portion SL) and ITO (gray portion G) were drawn in pattern A was obtained.
Next, PET (A) was laminated as a protective layer on the remaining resist. In this state, pattern exposure was performed using a photomask provided with an opening of pattern B shown in FIG. 4 in an aligned state, and PET (A) was peeled off, followed by development and washing with water.
Thereafter, the copper wiring is etched using Cu-02, and the remaining photosensitive resin layer is peeled off using a peeling solution (dimethylsulfoxide: monoethanolamine = 7: 3 (mass ratio) solution) to remove the circuit wiring board. Obtained.
Observation with a microscope revealed that there was no peeling or chipping and the pattern was clean.

The disclosure of Japanese Patent Application No. 2017-147151 filed on July 28, 2017 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards referred to in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

12 Temporary Support 14 Photosensitive Resin Layer 14A First Pattern 14B Second Pattern 16 Cover Film 20 Circuit Forming Substrate 22 Base 24 First Conductive Layer 24A First Conductive Layer (After First Etching Step)
24B first conductive layer (after second etching step)
26 second conductive layer 26A second conductive layer (after first etching step and second etching step)
30 mask 40 mask 100 photosensitive transfer material SL solid line part G gray part DL dotted line part

Claims (15)

A polymer containing a structural unit having a group in which a carboxylic acid group is protected in the form of an acetal,
At least one photoacid generator selected from the group consisting of an oxime compound and an onium salt compound, and
A photosensitive resin composition comprising a latent dye having a maximum absorption wavelength of 500 nm or more in a wavelength range of 400 nm to 780 nm during color formation.   The photosensitive resin composition according to claim 1, wherein the latent pigment is a latent pigment that develops color upon exposure.   3. The photosensitive resin composition according to claim 1, wherein the latent dye is a latent dye that is colored by an intermediate radical or an acid generated from the photoacid generator. 4.   The photosensitive resin composition according to any one of claims 1 to 3, wherein the acid generated from the photoacid generator is at least one acid selected from the group consisting of phosphoric acid and sulfonic acid. . The photosensitive resin composition according to claim 4, wherein the acid generated from the photoacid generator is a sulfonic acid represented by the following formula S1 or S2.

In the formulas S1 and S2, R ^S represents an alkyl group, L ^S represents an alkylene group having 2 or more carbon atoms, ns represents 0 or 1, provided that R ^S is an alkyl group having a halogen atom. in some cases an n is 1, X ^S are each independently, represent an alkyl group, an aryl group, an alkoxy group or an aryloxy group, ms represents an integer of 0 to 5.   The photosensitive resin composition according to any one of claims 1 to 5, wherein the pKa of the acid generated from the photoacid generator is -4.0 or more.   The photosensitive resin composition according to any one of claims 1 to 6, wherein the acid generated from the photoacid generator has a pKa of 4.0 or less.   The photosensitive resin composition according to any one of claims 1 to 7, further comprising a basic compound.   The photosensitive resin composition according to any one of claims 1 to 8, further comprising a solvent. The photosensitive resin composition according to any one of claims 1 to 9, wherein the latent dye is a compound represented by the following formula I.

In Formula I, Ar ^1C and Ar ^2C each independently represent an aromatic group, X ^C represents C, S or S ＝ O, and R ^{1C to} R ^4C each independently represent a hydrogen atom, a halogen atom or Represents a valent organic group. The photosensitive resin composition according to claim 10, wherein X ^C in the formula I is ^C. The photosensitive resin composition according to any one of claims 1 to 11, wherein the structural unit having a group in which the carboxylic acid group is protected in the form of an acetal is a structural unit represented by the following formula II. .

In Formula II, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group Or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. A temporary support,
Having a photosensitive resin layer,
A photosensitive transfer material, wherein the photosensitive resin layer contains the photosensitive resin composition according to any one of claims 1 to 12. For a substrate, a step of contacting and bonding the photosensitive resin layer of the photosensitive transfer material according to claim 13 to the substrate,
Pattern exposure of the photosensitive resin layer of the photosensitive transfer material after the bonding step,
Developing the photosensitive resin layer after the exposing step to form a pattern,
Etching a substrate in a region where the pattern is not arranged, in this order. For a substrate, a step of contacting and bonding the photosensitive resin layer of the photosensitive transfer material according to claim 13 to the substrate,
Pattern exposure of the photosensitive resin layer of the photosensitive transfer material after the bonding step,
Developing the photosensitive resin layer after the exposing step to form a pattern,
Etching a substrate in a region where the pattern is not disposed, in this order.