WO2019021622A1

WO2019021622A1 - Photosensitive resin composition, photosensitive transfer material, circuit wiring production method, and touch panel production method

Info

Publication number: WO2019021622A1
Application number: PCT/JP2018/020842
Authority: WO
Inventors: 山田　悟; 後藤　英範
Original assignee: 富士フイルム株式会社
Priority date: 2017-07-28
Filing date: 2018-05-30
Publication date: 2019-01-31
Also published as: JP6808045B2; CN110998441A; JPWO2019021622A1; TW201910916A

Abstract

Provided is a photosensitive resin composition that comprises: a polymer containing a structural unit having a group obtained by protecting a carboxylic acid group by an acid-decomposable group; a photoacid generator; and a latent pigment which is a compound that has formed therein a conjugate acid having a pKa of less than 4.5 or no conjugate acid, the latent pigment having a local maximum absorption wavelength of 500 nm or higher in a wavelength range of 400-780 nm at color development. Also provided are a photosensitive transfer material, a circuit wiring production method, and a touch panel production method that use the abovementioned photosensitive resin composition.

Description

Photosensitive resin composition, photosensitive transfer material, method of manufacturing circuit wiring, and method of manufacturing touch panel

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

In a display device (organic electroluminescence (EL) display device, liquid crystal display device, etc.) provided with a touch panel such as a capacitance type input device, an electrode pattern corresponding to a sensor of a visible portion, wiring of peripheral wiring portion and extraction wiring portion And the like are provided inside the touch panel.
In general, for forming a patterned layer, a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material since the number of steps for obtaining a required pattern shape is small. On the other hand, a method of developing after exposure through a mask having a desired pattern is widely used.

Further, as conventional photosensitive resin compositions, those described in JP-A-2008-64908, JP-A-2004-54106, JP-A-2009-3000, or JP-A-2002-341544. It has been known.

Problem to be solved by one embodiment of the present invention is to provide a photosensitive resin composition which is excellent in sensitivity and excellent in visibility of an exposed area and an unexposed area.
In addition, another problem to be solved by another embodiment of the present invention is to provide a photosensitive transfer material using the above photosensitive resin composition, a method of producing a circuit wiring, or a method of producing a touch panel. .

Means for solving the above problems include the following aspects.
<1> A polymer containing a structural unit having a carboxylic acid group protected by an acid-degradable group, a photoacid generator, and a compound having a pKa of less than 4.5 of a conjugated acid or which does not form a conjugated acid 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 at the time of color development.
The photosensitive resin composition as described in said <1> whose said maximal absorption wavelength in <2> said latent pigment is 550 nm or more.
<3> The photosensitive resin composition according to <1> or <2>, wherein the latent dye is a latent dye that develops a color by an acid generated from the photoacid generator.
<4> The photosensitivity 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.
The photosensitive resin composition as described in said <4> whose acid generated from <5> said photo-acid generator is a sulfonic acid represented by following formula S1 or Formula S2.

In 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 0-5.

<6> The photosensitive resin composition according to any one of the above <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 the above <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 the above <1> to <7>, which further contains a basic compound.
The photosensitive resin composition as described in any one of said <1>-<8> which further contains a <9> solvent.
<10> The photosensitive resin composition according to any one of the above <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 one Represents a valent organic group.

The photosensitive resin composition as described in said <10> whose XC in <11> said Formula I is ^C.
<12> The structural unit having a group in which the above carboxylic acid group is protected by an acid decomposable group is a structural unit represented by the following formula II described in any one of the above <1> to <11> Photosensitive 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 R ¹ or R ² and R ³ may combine 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.

The photosensitive transfer which has a <13> temporary support body and a photosensitive resin layer, and the said photosensitive resin layer contains the photosensitive resin composition as described in any one of said <1>-<12>. material.
The process of making the said photosensitive resin layer of the photosensitive transfer material as described in said <13> contact with the said substrate with respect to a <14> board | substrate, and bonding together, The said photosensitive of the said photosensitive transfer material after the process of bonding together The step of exposing the conductive resin layer to a pattern, the step of developing the photosensitive resin layer after the exposing step to form a pattern, and the step of etching the substrate in the area where the pattern is not disposed Method of manufacturing circuit wiring, including in order.
The process which makes the said photosensitive resin layer of photosensitive transfer material as described in said <13> contact the said board | substrate, and it bonds together with respect to a <15> board | substrate, The said sensitivity of the said photosensitive transfer material after the process of bonding The step of exposing the conductive resin layer to a pattern, the step of developing the photosensitive resin layer after the exposing step to form a pattern, and the step of etching the substrate in the area where the pattern is not disposed A method of manufacturing a touch panel, including in order.

According to one embodiment of the present invention, it is possible to provide a photosensitive resin composition which is excellent in sensitivity and excellent in visibility of an exposed area and an unexposed area.
In addition, according to another embodiment of the present invention, it is possible to provide a photosensitive transfer material using the photosensitive resin composition, a method of producing a circuit wiring, or a method of producing a touch panel.

FIG. 2 is a schematic view showing an example of a layer configuration of a photosensitive transfer material according to the present disclosure. It is the schematic which shows an example of the manufacturing method of the circuit wiring for touch panels using the photosensitive transfer material which concerns on this indication. FIG. 6 is a schematic view showing a pattern A. FIG. 7 is a schematic view showing a pattern B.

The contents of the present disclosure will be described below. Although the description will be made with reference to the attached drawings, the reference numerals may be omitted.
Further, in the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
Moreover, in this specification, "(meth) acryl" represents both or any of acrylic and methacryl, and "(meth) acrylate" represents both or any of acrylate and a methacrylate.
Furthermore, in the present specification, the amount of each component in the composition is the total of a plurality of corresponding substances present in the composition unless a plurality of substances corresponding to each component are present in the composition. Means quantity.
In the present specification, the term "process" is included in the term if the intended purpose of the process is achieved, even if it can not be clearly distinguished from other processes, as well as independent processes.
In the notation of groups (atomic groups) in the present specification, notations not describing substitution and non-substitution include those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Moreover, the chemical structural formula in this specification may be described by the simplified structural formula which abbreviate | omitted the hydrogen atom.
In the present disclosure, “mass%” and “weight%” are synonymous, and “mass part” and “part by weight” are synonymous.
Also, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
Moreover, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all are trade names manufactured by Tosoh Corporation) unless otherwise noted. It is a molecular weight which is detected using a solvent THF (tetrahydrofuran) and a differential refractometer by a gel permeation chromatography (GPC) analyzer and a polystyrene as a standard substance.

(Photosensitive resin composition)
The photosensitive resin composition according to the present disclosure has a polymer having a structural unit having a carboxylic acid group protected by an acid-degradable group, a photoacid generator, and a conjugated acid pKa of less than 4.5 Or a latent dye which is a compound which does not form a conjugate acid and whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at color development is 500 nm or more.

The photosensitive resin composition used for the resist layer of the dry film resist is required to have visibility of the exposed portion from the viewpoint of confirmation of the exposed portion.
As a general color-developing agent, an acid-colored leuco dye such as CVL (Crystal Violet lactone) is known. The CVL has three dimethylamino groups in the molecule and is highly basic. Therefore, although color development is possible, in a positive resist using a photoacid generator, the acid necessary for the decomposition of the acid-degradable group is neutralized, so that patterning is difficult or the sensitivity is low. The inventors have found that there is a problem of becoming lower.
In addition, in order to lower the basicity of leuco dye and improve the sensitivity, it is conceivable to exclude the amino group from the leuco dye, whereby the maximum absorption wavelength of the color former is shifted to the short wavelength side, and the visibility of the exposed portion The present inventors have found that there is a problem that is not sufficient.

With respect to these problems, the inventors of the present invention conducted intensive studies, and as a result, by using the photosensitive resin composition having the above-described configuration, a photosensitive resin which is excellent in sensitivity and excellent in visibility of exposed portions and unexposed portions. It has been found that a composition is obtained.
Although the mechanism of expression of the above-mentioned effect is unknown, the sensitivity is sufficiently obtained by using the latent dye which is a compound having a pKa of less than 4.5 of the conjugate acid or which does not form the conjugate acid. Of the light absorption dye and the unexposed area is excellent because the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development is 500 nm or more, and the carboxylic acid group is protected by an acid degradable group. The present inventors estimate that the sensitivity and the visibility can be compatible by containing a polymer containing a structural unit having

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

<A latent dye whose compound has a pKa of less than 4.5 or does not form a conjugate acid and whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at color development is 500 nm or more>
The photosensitive resin composition according to the present disclosure is a compound in which the pKa of a conjugate acid is less than 4.5 or does not form a conjugate acid, and the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at color development is 500 nm or more. It contains a dye (hereinafter also referred to as "specific latent dye").
The specific latent dye may be a compound that develops color upon exposure or a compound that loses color upon exposure, but from the viewpoint of sensitivity and visibility, a compound that develops color upon exposure is preferable, and photoacid It is more preferable that it is a latent dye that develops color by an acid generated from a generator.

The specific latent dye is a compound having a conjugated acid pKa (also referred to as “pKaH”) of less than 4.5 or not forming a conjugated acid.
The pKa of the conjugate acid of the compound in the present invention is the pKa (negative common logarithm of the acid dissociation constant) of the chemical species (conjugate acid) obtained by binding H ⁺ to the compound.
In addition, a compound in which H ⁺ is dissociated is more stable than a chemical species (conjugate acid) obtained by binding H ⁺ to the specific latent dye that the specific latent dye is a compound that does not form a conjugate acid. Say that.
The pKa (pKaH) of compounds and the like in the present disclosure shall be calculated using ACD / pka DB ver 8.07 of Advanced Chemistry Development ACD / Labs software Ver 8.0 for Microsoft windows.
The pKaH of the specific latent dye is preferably -30 or more, more preferably -10 or more.

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 color development, preferably 550 nm or more from the viewpoint of visibility, more preferably 550 nm to 700 nm, 550 nm More preferably, it is at least 650 nm.
In addition, the specific latent dye may have only one maximum absorption wavelength, or may have two or more. When the specific latent dye has two or more maximum absorption wavelengths, the maximum absorption wavelength at which the absorbance is the highest among the two or more maximum absorption wavelengths may be 500 nm or more.
The method of measuring the maximum absorption wavelength in the present disclosure is to measure the transmission spectrum in the range of 400 nm to 780 nm using a spectrophotometer: UV 3100 (manufactured by Shimadzu Corporation) at 25 ° C. under the atmosphere atmosphere. The wavelength at which the light intensity is minimized (maximum absorption wavelength) is measured.

Specific latent dyes that develop color upon exposure include, for example, leuco compounds.
Further, specific latent dyes which are decolorized by exposure to light include, for example, triphenylmethane dyes, diphenylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, anthraquinone dyes and the like. .
Among them, as the specific latent dye, a leuco compound is preferable from the viewpoint of sensitivity and visibility.
Examples of leuco compounds include leuco compounds such as triphenylmethanes, spiropyrans, fluorans, diphenylmethanes, rhodamine lactams, indolylphthalides, and leucoauramines.
Further, from the viewpoint of sensitivity and visibility, the leuco compound is preferably one in which a lactone ring, sultin ring or sultone ring is ring-opened, and more preferably a leuco compound in which a lactone ring is ring-opened to develop color.

The specific latent dye is preferably a compound represented by the following formula I from the viewpoint of sensitivity and visibility.

The aromatic group in Ar ^1C and Ar ^2C may be an aryl group or a heteroaryl group, and even if it is a monocyclic aromatic group, it is a condensed ring in which two or more rings are condensed. May be
Further, Ar ^1C and Ar ^2C may be combined to form a ring, and from the viewpoint of sensitivity and visibility, Ar ^1C and Ar ^2C are preferably combined 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, a diarylamino group and the like, and a dialkylamino group, an alkylarylamino group and a diarylamino group Is preferred. The alkyl group in the dialkylamino group and the alkylarylamino group is preferably independently 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 in Ar ^1C and Ar ^2C is independently preferably 4 to 50, more preferably 6 to 40, and still more preferably 10 to 30 from the viewpoint of sensitivity and visibility. .

From the viewpoint of sensitivity and visibility, X ^C is preferably C or S = O, and more preferably C.
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.
In addition, the carbon number of each of R ^1C to R ^4C is preferably independently 0 to 20, and more preferably 0 to 10.
R ^1C to R ^4C are preferably each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group or an aryl It is more preferably a group, particularly preferably a hydrogen atom.

Although compounds C-1 to C-9 are described below as preferable specific examples of the specific latent dyes, it goes without saying that the specific latent dyes in the present disclosure are not limited thereto.

The specific latent dyes 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 visibility. Is preferably 0.1% by mass to 8% by mass, more preferably 0.5% by mass to 5% by mass, and 1.0% by mass to 3.0% by mass. Is particularly preferred.
In the present invention, “solid content” in the photosensitive resin composition means a component excluding the volatile component of the solvent.

<A polymer containing a structural unit having a group in which a carboxylic acid group is protected by an acid-degradable group>
The photosensitive resin composition according to the present disclosure includes a polymer (also referred to as a “specific polymer”) containing a structural unit (also referred to as “structural unit A”) having a group in which a carboxylic acid group is protected with an acid-degradable group. Say).
Moreover, in addition to the polymer which has the structural unit A, the photosensitive resin composition which concerns on this indication may contain the other polymer. In the present disclosure, the polymer having the structural unit A and the other polymers are collectively referred to as a “polymer component”.
In the specific polymer, the structural unit A having an acid-degradable protected carboxylic acid group 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.
The preferable aspect of the structural unit A is demonstrated below.

The photosensitive resin composition may further contain a polymer other than the polymer having a structural unit having an acid-degradable protected acid group.
Moreover, it is preferable that all the polymers contained in the said polymer component are polymers which have a structural unit which has the carboxylic acid group mentioned later at least, respectively.
Moreover, the said photosensitive resin composition may further contain polymers other than these. The above-mentioned polymer component in the present disclosure is intended to mean one including other polymers added as needed, unless otherwise stated. In addition, even if it is a high molecular compound, the compound applicable to the plasticizer, the heterocyclic compound, and surfactant which are mentioned later shall not be contained in the said polymer component.

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

The photosensitive resin composition has a weight having a structural unit A1 represented by the following formula II as the structural unit A as a polymer component from the viewpoint of pattern formability, solubility in a developer and transferability. Preferably, the polymer component contains a specific polymer having a constituent unit A1 represented by the following formula II as the constituent unit A and having a glass transition temperature of 90 ° C. or less, as the 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 later as a polymer component and having a glass transition temperature of 90 ° C. or less More preferably,
The specific polymer contained in the photosensitive resin composition may be only one type, or two or more types.

<< Constituent 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 by an acid-degradable group. When the polymer component contains a polymer having the structural unit A, it is possible to obtain a highly sensitive chemically amplified positive type photosensitive resin layer.
As the “group in which the carboxylic acid group is protected with an acid-degradable group” in the present disclosure, those known as an acid-degradable group can be used without particular limitation. As the acid-degradable group, a group which is relatively easy to be decomposed by acid (for example, an acetal-based functional group such as an ester group protected by a group represented by formula II described later, tetrahydropyranyl ester group, or tetrahydrofuranyl ester group) Groups or groups which are relatively difficult to be decomposed by acids (eg, tertiary alkyl groups such as tert-butyl ester group, tertiary alkyl carbonate groups such as tert-butyl carbonate group) can be used.
Among these, as the above-mentioned acid-decomposable group, a group having a structure protected in the form of acetal is preferable.

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

In the 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.
In addition, 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 are 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 preferred. 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 is excellent, and is superior to the resolution.

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, it is preferable that the structural unit whose R ⁴ in Formula II is a hydrogen atom is 20% by mass or more with respect to the total amount of the structural unit A1 contained in the specific polymer.
In addition, content (content ratio: mass ratio) of the structural unit whose R ⁴ in Formula II is a hydrogen atom in the structural unit A1 is calculated by ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement according to a conventional method. It can confirm by intensity ratio of peak intensity.

Among the structural units A1 represented by the formula II, structural units represented by the following formula A2 are more preferable from the viewpoint of further enhancing the sensitivity at the time of pattern formation.

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

The following structural unit can be illustrated as a preferable specific example of structural unit A1 which has a group with which the carboxylic acid group was protected by the acid-degradable group represented by Formula II. R ³⁴ represents a hydrogen atom or a methyl group.

The constituent 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 20% by mass or more, more preferably 20% by mass to 90% by mass, and more preferably 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 the intensity ratio of peak intensities calculated from ¹³ C-NMR measurement by a conventional method.
Further, the ratio of the structural unit A is preferably 5% by mass to 80% by mass with respect to the total mass of the polymer component after all the polymer components are decomposed into constituent units (monomer units). It is more preferably 10% by mass to 80% by mass, still more preferably 10% by mass to 40% by mass, and particularly preferably 10% by mass to 30% by mass.

<< Constituent Unit B >>
The specific polymer preferably contains a structural unit B having a carboxylic acid group.
The structural unit B is a structural unit including a protective group, for example, a carboxylic acid group not protected with an acid-degradable group, that is, a carboxylic acid group having no protective group. When the specific polymer contains the structural unit B, the sensitivity at the time of pattern formation becomes good, and it becomes easily soluble in an alkaline developer in the development step after pattern exposure, and the development time can be shortened.

The introduction of a structural unit having a carboxylic acid group into a specific polymer can be carried out 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 obtained by substituting a carboxylic acid group for a structural unit derived from a vinyl compound, or derived from (meth) acrylic acid It is more preferable that it is a structural unit.

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

<< Other composition unit >>
The specific polymer does not impair the effects of the photosensitive transfer material according to the present disclosure other structural units (hereinafter, may be referred to as structural unit C) other than the structural unit A and the structural unit B described above. You may include in the range.
There is no restriction | limiting in particular as a monomer which forms the structural unit C, For example, Styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester , Bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, group having aliphatic cyclic skeleton, other unsaturated Saturated compounds can be mentioned.
Various properties of the specific polymer can be adjusted by adjusting at least one of the type and the content using the structural unit C. 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 contain only one type of the structural unit C, or may contain two or more types.

Specifically, structural unit C is styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, (meth) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) Examples thereof include structural units formed by polymerizing benzyl acrylate, isobornyl (meth) acrylate, acrylonitrile, or ethylene glycol monoacetoacetate mono (meth) acrylate. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 can be mentioned.

Further, 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 properties of the transfer material to be obtained. Specifically as a monomer which forms these structural units, styrene, tert- butoxystyrene, methylstyrene, alpha-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, And benzyl (meth) acrylate and the like. Among them, as the structural unit C, structural units derived from cyclohexyl (meth) acrylate are preferably mentioned.

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

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

The specific polymer also includes a constituent unit having an ester of an acid group in the above-mentioned constituent unit B as the constituent unit C, and a viewpoint of optimizing the solubility in a developer and physical properties of the photosensitive resin layer described later. It is preferable from
Among them, the specific polymer preferably contains, as the structural unit B, a structural unit having a carboxylic acid group, and further preferably contains a structural unit C containing a carboxylic acid ester group as a copolymerization component, for example, (meth) acrylic acid More preferred is a polymer containing the structural unit B derived from and a structural unit (c) derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate.
Hereinafter, although the preferable example of the specific polymer in this indication is given, this indication is not limited to the following illustrations. In addition, the ratio of the structural unit in the following exemplary compounds and the weight average molecular weight are suitably selected in order to obtain preferable physical properties.

<< Glass transition temperature of polymer: Tg >>
It is preferable that the glass transition temperature (Tg) of the specific polymer in this indication is 90 degrees C or less. When the Tg is 90 ° C. or less, the photosensitive resin layer formed of the photosensitive resin composition has high adhesion and is more excellent in transferability.
The Tg is more preferably 60 ° C. or less, still more preferably 40 ° C. or less.
Further, the lower limit value of the above Tg is not particularly limited, but is preferably −20 ° C. or more, more preferably −10 ° C. or more. 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, the decrease in peelability at the time of peeling the cover film is suppressed.
Furthermore, the glass transition temperature (Tg) of the entire polymer component in the present disclosure is preferably 90 ° C. or less, more preferably 60 ° C. or less, and 40 ° C. or less 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 in accordance with the method described in JIS K 7121 (1987) or JIS K 6240 (2011). The glass transition temperature in the present specification uses an extrapolated glass transition start temperature (hereinafter sometimes referred to as Tig).
The method of measuring the glass transition temperature will be described more specifically.
When the glass transition temperature is determined, the temperature is kept at about 50 ° C. lower than the expected polymer Tg until the device is stabilized, and then the heating rate: 20 ° C./min, and the temperature is about 30 Heat to a high temperature and draw a DTA curve or a DSC curve.
Extrapolation glass transition start temperature (Tig), that is, the glass transition temperature Tg in the present specification, is a straight line extending the baseline on the low temperature side in the DTA curve or DSC curve to the high temperature side, and the step change portion of the glass transition It is determined as the temperature at the point of intersection with the tangent drawn at the point where the slope of the curve is at a maximum.

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

<< molecular weight of polymer: Mw >>
The molecular weight of the specific polymer is preferably 60,000 or less in terms of weight average molecular weight in terms of polystyrene. 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 described later is suppressed low, and when bonding to the substrate, the temperature is low (for example, 130 ° C. or less). Bonding can be realized.
In addition, the weight average molecular weight of the specific polymer is preferably 2,000 to 60,000, more preferably 3,000 to 50,000, and still more preferably 10,000 to 30,000. preferable.
In addition, the weight average molecular weight of a polymer can be measured by GPC (gel permeation chromatography), and various commercially available apparatuses can be used as a measuring apparatus, and the contents of the apparatus and the measuring technique It is known to those skilled in the art.
The measurement of the weight average molecular weight by gel permeation chromatography (GPC) is carried out using HLC (registered trademark)-8220 GPC (manufactured by Tosoh Corp.) as a measuring device, and TSKgel (registered trademark) Super HZM-M (4) as a column. .6 mm ID x 15 cm, Tosoh Corp. product, Super HZ 4000 (4.6 mm ID x 15 cm, Tosoh Corp. product), Super HZ 3000 (4.6 mm ID x 15 cm, Tosoh Corp. product), Super HZ 2000 (4.6 mm ID) It is possible to use THF (tetrahydrofuran) as an eluent using one obtained by connecting in series each one x 15 cm, manufactured by Tosoh Corp., in series.
In addition, as measurement conditions, the sample concentration is 0.2% by mass, the flow rate is 0.35 ml / min, the sample injection amount is 10 μl, and the measurement temperature is 40 ° C., using a differential refractive index (RI) detector be able to.
The standard curve is the "standard sample TSK standard, polystyrene" manufactured by Tosoh Corp .: "F-40", "F-20", "F-4", "F-1", "A-5000", " It can be prepared using any of the seven samples of A-2500 "and" A-1000 ".

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

<< Method of producing specific polymer >>
The method for producing the specific polymer (synthetic method) is not particularly limited, but one example is a polymerizable monomer for forming the structural unit A1 represented by the formula II, a structural unit B having a carboxylic acid group Synthesis by polymerization using a polymerization initiator in a solvent containing a polymerizable monomer for forming, and, if necessary, a polymerizable monomer for forming another constitutional unit C it can. Moreover, it can also be synthesized by so-called polymer reaction.

The photosensitive resin composition according to the present disclosure contains the specific polymer in a proportion 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 include 70% by mass to 98% by mass.
In addition, the photosensitive resin composition according to the present disclosure has a ratio of 50% by mass to 99.9% by mass of the above polymer component with respect to the total solid content of the photosensitive resin composition from the viewpoint of sensitivity and resolution. It is preferable to contain at a ratio of 70% by mass to 98% by mass.

<< Other polymer >>
The above-mentioned photosensitive resin composition contains, as a polymer component, a polymer not containing the structural unit A (“the other polymer in a range not impairing the effect of the photosensitive resin composition according to the present disclosure in addition to the specific polymer May be further included). When the said photosensitive resin composition contains another polymer, it is preferable that the compounding quantity of another polymer is 50 mass% or less in all the polymer components, and it is more preferable that it is 30 mass% or less More preferably, it is 20% by mass or less.

The photosensitive resin composition may contain only one type of other polymer in addition to the specific polymer, or may contain two or more types.
As other polymers, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (all, manufactured by Sartmar) , ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (all manufactured by Toagosei Co., Ltd.), and Joncryl 690, Joncryl 678 , Joncryl 67, and Joncryl 586 (above, manufactured by BASF Corp.) can also be used.

<Photo acid generator>
The photosensitive resin composition according to the present disclosure contains a photoacid generator.
The photoacid generator used in the present disclosure is a compound capable of generating an acid upon irradiation with radiation such as ultraviolet light, far ultraviolet light, X-ray, and charged particle beam.
The photoacid generator used in the present disclosure is preferably a compound that responds to actinic light having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, and generates an acid, but its chemical structure is not limited. In addition, a photoacid generator which does not directly react to actinic light having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that responds to actinic light having a wavelength of 300 nm or more to generate an acid It can be preferably used in combination.
The pKa of the acid generated from the 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 visibility. The following is more preferable, and -1.0 or less is particularly preferable. The lower limit of the pKa of the acid generated from the photoacid generator is not particularly limited, but is preferably, for example, -10.0 or more, and from the viewpoint of sensitivity and visibility, it is more preferably -4.0 or more Preferably, it is -3.5 or more, more preferably -3.0 or more.

The acid generated from the 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 visibility, and is sulfonic acid. The sulfonic acid is more preferably a sulfonic acid represented by the following formula S1 or S2.

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

As a photo-acid generator, an ionic photo-acid generator and a nonionic photo-acid generator can be mentioned.
Further, the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later from the viewpoint of sensitivity and resolution, and an oxime sulfonate compound More preferably,

Examples of nonionic photoacid generators include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds. Among these, the photoacid generator is preferably an oxime sulfonate compound in terms of sensitivity, resolution, and adhesion. These photoacid generators can be used singly or in combination of two or more. As specific examples of trichloromethyl-s-triazines and diazomethane derivatives, compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 can be exemplified.

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

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

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

Moreover, as a compound having an oxime sulfonate structure represented by the formula (B1), an oxime sulfonate compound described in paragraphs 0078 to 0111 of JP-A 2014-85643, or a paragraph 0080 of JP-A 2015-151347 And compounds described in ~ 0081.

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

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

A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
From the viewpoint of sensitivity and resolution, the content of the photoacid generator in the photosensitive resin composition is 0.1% by mass to 10% by mass with respect to the total solid content of the photosensitive resin composition. Preferably, 0.5% by mass to 5% by mass is more preferable.

<Basic compound>
The photosensitive resin composition according to the present disclosure preferably further contains a basic compound.
As the basic compound, any one of basic compounds used in a chemical amplification resist can be selected and used. For example, aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids can be mentioned. 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, as aliphatic amines, for example, trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of aromatic amines 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, nicotinic acid amide, 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- Diazabishi (B) [5.3.0] -7-undecene and the like.
Examples of quaternary ammonium hydroxides include tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetra-n-butyl ammonium hydroxide, and tetra-n-hexyl ammonium hydroxide.
Examples of quaternary ammonium salts of carboxylic acids include tetramethyl ammonium acetate, tetramethyl ammonium benzoate, tetra-n-butyl ammonium acetate, and tetra-n-butyl ammonium benzoate.

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

<Solvent>
The photosensitive resin composition according to the present disclosure preferably further contains a solvent.
Moreover, in order to form easily the photosensitive resin layer mentioned later, the said photosensitive resin composition is made to contain a solvent once, the viscosity of the photosensitive resin composition is adjusted, and the photosensitive resin composition containing a solvent is apply | coated. And it can dry and can form a photosensitive resin layer suitably.
A well-known solvent can be used as a solvent used for this indication. As a solvent, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol mono alkyl ether acetates, propylene glycol mono alkyl ethers, propylene glycol dialkyl ethers, propylene glycol mono alkyl ether acetates, diethylene glycol dialkyl ethers And diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Further, specific examples of the solvent also include the solvents described in paragraphs [0174] to [0178] of JP-A-2011-221494, the contents of which are incorporated in the present specification.

In addition to the solvents described above, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1 if necessary. Solvents such as nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate or propylene carbonate can also be added.
The solvent may be used alone or in combination of two or more.
The solvents that can be used in the present disclosure may be used alone or in combination of two. When two or more solvents are used, for example, combined use of propylene glycol monoalkyl ether acetates and dialkyl ethers, combined use of diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetate Preferably used in combination with a class.

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 solvents 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.), Propylene glycol methyl-n-propyl ether (boiling point 131 ° C.) can be exemplified.
As solvents having a boiling point of 160 ° C. or higher, 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.

When the photosensitive resin composition is applied, the content of the solvent is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, it is 900 parts by mass.
The content of the solvent in the photosensitive resin layer described later is preferably 2% by mass or less, more preferably 1% 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 can contain known additives, as necessary, in addition to the above-described components such as the specific latent dye, the specific polymer, and the photoacid generator.

-Plasticizer-
The photosensitive resin composition according to the present disclosure may contain a plasticizer for the purpose of improving the plasticity.
It is preferable that the said plasticizer has a smaller weight average molecular weight than a 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 still more preferably 800 or more and less than 4,000 from the viewpoint of imparting plasticity.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the specific polymer to exhibit 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 formulae, R is an alkyl group having 2 to 8 carbon atoms, n is an integer of 1 to 50, and * represents a bonding site to another atom.

In addition, for example, even a compound having an alkyleneoxy group of the above structure (referred to as “compound X”), a chemical obtained by mixing the compound X, a specific latent dye, a specific polymer, and a photoacid generator When the amplification positive photosensitive resin composition does not improve the plasticity 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, surfactants that are optionally added do not fall under the plasticizers herein because they are not generally used in amounts that provide plasticity to the photosensitive resin composition.

As said plasticizer, although the compound which has the following structure is mentioned, for example, it is not limited to these.

The content of the plasticizer is 1% by mass to 50% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of the adhesion of the photosensitive resin layer formed of the photosensitive resin composition. Is preferable, and 2% by mass to 20% by mass is more preferable.
The photosensitive resin composition may contain only one type of plasticizer, or may contain two or more types.

-Sensitizer-
The photosensitive resin composition according to the present disclosure can further include a sensitizer.
The sensitizer absorbs an actinic ray to be in an electronically excited state. The sensitizer in the electronically excited state comes into contact with the photoacid generator to produce actions such as electron transfer, energy transfer and heat generation. Thus, the photoacid generator chemically changes and decomposes to generate an acid.
Exposure sensitivity can be improved by containing a sensitizer.

As the sensitizer, compounds selected from the group consisting of anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, base styryl derivatives, and distyryl benzene derivatives are preferable, and anthracene derivatives are more preferable.
As the anthracene derivative, 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 paragraph 0139 to paragraph 0141 of WO 2015/093271.

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

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

When the heterocyclic compound is added, the content of the heterocyclic compound in the photosensitive resin composition is 0.01% by mass to 50% by mass with respect to 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. It is preferable in the viewpoint of adhesiveness and etching tolerance as it is the said range. The heterocyclic compound may be used alone or in combination of two or more.

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

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 JER 828, JER 1007, JER 157 S70 (manufactured by Mitsubishi Chemical Corporation), JER 157 S 65 (manufactured by Mitsubishi Chemical Holdings), and the like can be mentioned.
Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- 1000, EPPN-501, EPPN-502 (above, made by ADEKA Co., Ltd.), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX- 411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212 , EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX -121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (manufactured by Nagase Chemtech Inc.), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Celoxide 2021 P, 2081, 2000, 3000, EHPE 3150, Epolide GT 400, Celliners B 0134, B 0177 (manufactured by Daicel Co., Ltd.) and the like.
The compound which has an epoxy group in a molecule may be used individually by 1 type, and may use 2 or more types together.

Among the compounds having an epoxy group in the molecule, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac 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, PNOX Co., Ltd. can be used.

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

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 viewpoint 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. As an alkoxysilane compound, a trialkoxysilane compound is mentioned preferably.
As the alkoxysilane compound, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropyl alkyldialkoxysilane, γ-methacryloxypropyl Trialkoxysilane, γ-methacryloxypropyl alkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane It can be mentioned. Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used singly or in combination of two or more.
The content of the alkoxysilane compound is preferably 0.1% by mass to 30% by mass, and more preferably 0.5% by mass to 20% by mass with respect to 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), or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. . In addition, KP (made by Shin-Etsu Chemical Co., Ltd.), Polyflow (made by Kyoeisha Chemical Co., Ltd.), F-top (made by JEMCO), Megafac (made by DIC), Florard (Sumitomo 3M) under the following trade names. Each series may be mentioned, such as (manufactured by Co., Ltd.), Asahi Guard, Surfron (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (manufactured by Toray Dow Corning).
Moreover, the weight average as polystyrene conversion measured by the gel permeation chromatography at the time of using tetrahydrofuran (THF) as a solvent, containing the structural unit A and the structural unit B represented by following formula I-1 as surfactant is used A copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferred example.

In formula (I-1), each of R ⁴⁰¹ and R ⁴⁰³ independently represents a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or carbon L represents an alkyl group having 3 to 6 carbon atoms, p and q each represent a polymerization percentage, and p represents a numerical value of 10% to 80% by mass. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18 and s represents an integer of 1 to 10, and * represents a binding site to 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 in view of compatibility and wettability to the coated surface, an alkyl group having 1 to 3 carbon atoms is preferable, and the carbon number is 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 1,500 or more and 5,000 or less.

In addition, surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraph 0060 to paragraph 0071 of JP2009-237362A can also be used.

The surfactant may be used alone or in combination of two or more.
The addition amount of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, with respect to the total solid content of the photosensitive resin composition. It is more preferable that the content be from 01% by mass to 3% by mass.

-Other ingredients-
The photosensitive resin composition according to the present disclosure includes metal oxide particles, an antioxidant, a dispersant, an acid multiplication agent, a development accelerator, a conductive fiber, a colorant, a thermal radical polymerization initiator, a thermal acid generator, Further known additives such as UV absorbers, thickeners and organic or inorganic suspending agents can be added.
Preferred embodiments of the other components are described in paragraphs [0165] to [0184] of JP-A-2014-85643, the contents of which are incorporated herein.

(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 by an acid-degradable group. Polymers, photoacid generators, and compounds that do not have a pKa of less than 4.5 or conjugate acids, and have a maximum absorption wavelength of 500 nm or more in the wavelength range of 400 nm to 780 nm during color development It is preferable that it contains a dye, has a temporary support, and a photosensitive resin layer, and the photosensitive resin layer contains the photosensitive resin composition according to the present disclosure.

FIG. 1 schematically shows an example of the layer configuration of a photosensitive transfer material according to the present disclosure. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 10, an intermediate layer 12, a photosensitive resin layer 14, and a cover film 16 are laminated in this order.
The photosensitive resin layer 14 is a polymer having a structural unit having a carboxylic acid group protected by an acid-degradable group, a photoacid generator, and a conjugated acid having a pKa of less than 4.5 or a conjugated acid. It is a compound which is not formed, and contains a latent dye having a maximum absorption wavelength of 500 nm or more in the wavelength range of 400 nm to 780 nm in color development.
Hereinafter, constituent materials and the like of the photosensitive transfer material according to the present disclosure will be described. In the present specification, the above configuration in the present disclosure may be referred to as follows.
The polymer which has a structural unit which has an acidic radical protected by an acid degradable group may be called a "specific polymer."
The said photosensitive resin layer is a positive photosensitive resin layer, and may be called 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 can be peeled off.
The temporary support used in the present disclosure preferably has light transmittance from the viewpoint of being able to expose the photosensitive resin layer through the temporary support when the photosensitive resin layer is subjected to pattern exposure.
Having light transmission means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is a viewpoint of improving exposure sensitivity. Therefore, 60% or more is preferable, and 70% or more is more preferable. As a measuring method of the transmittance | permeability, the method of measuring using Otsuka Electronics Co., Ltd. product MCPD Series is mentioned.
As a temporary support body, a glass substrate, a resin film, paper etc. are mentioned, A resin film is especially preferable from a viewpoint of intensity | strength, flexibility, etc. As a resin film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film etc. are mentioned. Among them, biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the temporary support is not particularly limited, and 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 handleability, versatility and the like.
The thickness of the temporary support is selected according to the material from the viewpoint of strength as a support, flexibility required for bonding to a circuit wiring formation substrate, light transmittance required in the first exposure step, etc. do it.

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

<Photosensitive resin layer>
A photosensitive transfer material according to the present disclosure has a photosensitive resin layer, and the photosensitive resin layer contains a structural unit having a group in which a carboxylic acid group is protected with an acid-degradable group, a photoacid It contains a generator and a latent dye having a pKa of less than 4.5 of a conjugate acid or a compound which does not form a conjugate acid and having a maximum absorption wavelength of 500 nm or more in a wavelength range of 400 nm to 780 nm at color development.
The photosensitive resin layer is preferably a layer formed of the photosensitive resin composition according to the present disclosure.
Moreover, it is preferable that the said photosensitive resin layer contains the photosensitive resin composition which concerns on this indication.
In addition, the photosensitive resin layer in the present disclosure is a positive photosensitive resin layer, and is preferably a chemically amplified positive photosensitive resin layer.
The photo acid generators such as onium salts and oxime sulfonate compounds described later are prepared by using an acid generated in response to actinic radiation (active light) as a catalyst for the deprotection of the protected acid group in the specific polymer. Since the acid generated by the action of one photon contributes to a large number of deprotection reactions, the quantum yield is greater than 1, for example, a large value such as a power of 10, so-called chemical amplification High sensitivity is obtained as a result of
On the other hand, when a quinonediazide compound is used as a photoacid generator sensitive to actinic radiation, a carboxy group is produced by successive photochemical reactions, but its quantum yield is necessarily 1 or less and does not fall under the chemical amplification type.

A polymer containing a structural unit having a group in which the carboxylic acid group in the photosensitive resin layer is protected by an acid-degradable group, a photoacid generator, and a pKa of a conjugate acid of less than 4.5 or a conjugate acid The latent dyes having a maximum absorption wavelength of 500 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development are each a group in which the carboxylic acid group in the photosensitive resin composition is protected with an acid degradable group. A polymer having a structural unit, a photoacid generator, and a compound having a pKa of less than 4.5 of a conjugated acid or not forming a conjugated acid, and a maximum absorption wavelength of 500 nm in a wavelength range of 400 nm to 780 nm at color development It is synonymous with the latent dye which is the above, and its preferable aspect is also the same.
Moreover, the said photosensitive resin layer can preferably contain each component in the said photosensitive resin composition other than the said solvent.
Furthermore, in the photosensitive resin layer, the preferable content of each component with respect to the total mass of the photosensitive resin layer is a preferable content of each component with respect to the total solid content of the photosensitive resin composition in the photosensitive resin composition. Similar to the amount.

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

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

A photosensitive transfer material according to the present disclosure having a photosensitive resin layer on a temporary support can be obtained by applying the photosensitive resin composition to the temporary support and drying.
The coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, or ink jet coating.
In addition, a photosensitive resin layer can also be apply | coated on the laminated body of the temporary support body which has the below-mentioned other layer on a temporary support body, and another layer.

<Other layers>
The photosensitive transfer material according to the present disclosure may have a layer (hereinafter, may be referred to as "other layer") other than the photosensitive resin layer. 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 can have a contrast enhancement layer in addition to the photosensitive resin layer.
A material with a contrast enhancement layer (Contrast Enhancement Layer; CEL) that absorbs significantly to the exposure wavelength before exposure but gradually decreases as it is exposed, that is, the light transmittance increases (photo-decoloring (Referred to as a sex pigment component). As the photobleachable dye component, diazonium salts, stilbazolium salts, aryl nitroso salts and the like are known. A phenolic resin etc. are used as a film formation component.
In addition, as a contrast enhancement layer, paragraphs 0004 to 0051 of JP-A-6-97065, paragraphs 0012 to 0055 of JP-A-6-332167, a photopolymer handbook, a photopolymer conference, an industry survey 1989), Photopolymer Technology, Yamaoka, Nagamatsu ed., Nikkan Kogyo Shimbun Co., Ltd. (1988) can be used.

<Middle class>
An intermediate layer can be provided on the photosensitive resin layer for the purpose of applying a plurality of layers and for the purpose of preventing the mixing of the components during storage after application.
As the intermediate layer, the intermediate layers described in paragraphs 0084 to 0087 of JP-A-2005-259138 can be used. As the intermediate layer, those which are dispersed or dissolved in water or an aqueous alkali solution are preferable.
Materials used for the intermediate layer include, for example, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers of these. Resin is mentioned. 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 can also have, for example, a temporary support, a thermoplastic resin layer, and a photosensitive resin layer in this order. Furthermore, you may have a cover film in order to protect the photosensitive resin layer.
Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP-A-2014-85643, and preferred embodiments of the other layers are described in paragraphs 0194 to 0-196 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 produced according to the method for producing a photosensitive transfer material described in paragraph 0094 to paragraph 0098 of JP-A-2006-259138. can do.
For example, when preparing a photosensitive transfer material according to the present disclosure having a thermoplastic resin layer and an intermediate layer, a solution obtained by dissolving a thermoplastic organic polymer and an additive on a temporary support (thermoplastic Coating solution for resin layer) is applied and dried to form a thermoplastic resin layer, and then a resin and an additive are added to a solvent which does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer. The solution (coating solution for intermediate layer) is applied and dried to laminate the intermediate layer. Furthermore, according to the present disclosure, the photosensitive resin composition according to the present disclosure prepared using a solvent that does not dissolve the intermediate layer is applied onto the formed intermediate layer, and the photosensitive resin composition is laminated to form a photosensitive resin layer. A photosensitive transfer material can be suitably produced.

(Method of manufacturing circuit wiring)
A first embodiment of a method of manufacturing a circuit wiring using a photosensitive transfer material according to the present disclosure will be described.
The first embodiment of the method of manufacturing circuit wiring
A step of bringing the photosensitive resin layer of the photosensitive transfer material according to the present disclosure into contact with the substrate and bonding the substrate to the substrate (bonding step);
Exposing the photosensitive resin layer of the photosensitive transfer material after the attaching step to a pattern (exposure step);
Developing the photosensitive resin layer after the exposing step to form a pattern (developing step);
Etching the substrate in the region where the pattern is not disposed (etching step) in this order.
The substrate in the first embodiment of the method for producing a circuit wiring may be a substrate provided with a layer such as a desired conductive layer on a substrate such as glass, silicon, or film.
According to the first embodiment of the method of manufacturing a circuit wiring, a fine pattern can be formed on the substrate surface.

The second embodiment of the method of manufacturing circuit wiring is:
A substrate, and a plurality of conductive layers including a first conductive layer and a second conductive layer which are different in constituent material from each other, and the outermost surface layer on the surface of the substrate in order from the surface of the substrate Bonding the photosensitive resin layer of the photosensitive transfer material according to the present disclosure to the first conductive layer in contact with the substrate on which the first conductive layer and the second conductive layer are laminated. Process,
A first exposure step of subjecting the photosensitive resin layer to pattern exposure through the temporary support of the photosensitive transfer material after the laminating step;
A first development step of developing the photosensitive resin layer after the first exposure step to form a first pattern after peeling off the temporary support from the photosensitive resin layer after the first exposure step;
A first etching step of etching at least the first conductive layer and the second conductive layer among the plurality of conductive layers in a region where the first pattern is not disposed;
A second exposure step of exposing the first pattern after the first etching step to a pattern different from the first pattern;
A second developing step of developing the first pattern after the second exposure step to form a second pattern;
And a second etching step of etching at least the first conductive layer among the plurality of conductive layers in the region where the second pattern is not disposed. The second embodiment can be referred to WO 2006/190405, the contents of which are incorporated herein.

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

<Lamination process>
An example of the bonding step is schematically shown in FIG. 2 (a).
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 which are different in constituent material from each other are provided. The photosensitive transfer material according to the present disclosure described above with respect to the substrate (substrate for circuit wiring formation) 20 on which the first conductive layer 24 and the second conductive layer 26 as the outermost surface layer are stacked in order from the surface of The positive photosensitive resin layer 14 of 100 is brought into contact with the first conductive layer 24 and attached. In addition, bonding of such a substrate for circuit wiring formation and photosensitive transfer material may be called "transfer" or "lamination."

As shown in FIG. 1, when the cover film 16 is provided on the positive photosensitive resin layer 14 of the photosensitive transfer material 100, 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 attached.
Bonding (transfer) of the photosensitive transfer material onto the first conductive layer is performed by overlapping the positive photosensitive resin layer side of the photosensitive transfer material on the first conductive layer and applying pressure and heat with a roll or the like. Preferably to be performed. For lamination, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further enhancing productivity can be used.
When the base material of the circuit wiring formation substrate is a resin film, bonding by roll-to-roll can also be performed.

〔Base material〕
The substrate in which a plurality of conductive layers are laminated on a substrate is preferably a glass substrate or a film substrate, and more preferably a film substrate. When the circuit wiring manufacturing method according to the present disclosure is a circuit wiring for a touch panel, it is particularly preferable that the base material is a sheet-like resin composition.
Moreover, it is preferable that a base material is transparent.
The refractive index of the substrate is preferably 1.50 to 1.52.
The substrate may be made of a translucent substrate such as a glass substrate, and for example, tempered glass represented by Gorilla glass of Corning Co., Ltd. can be used. Further, as the above-mentioned transparent base material, materials used in JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be preferably used.
In the case of using a film substrate as the substrate, it is more preferable to use a substrate having no optical distortion and a substrate having high transparency, and for a specific material, 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 substrate include any conductive layer used for general circuit wiring or touch panel wiring.
Examples of the material of the conductive layer include metals and metal oxides.
As the metal oxide, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), may be mentioned SiO ₂ and the like. Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo and the like.

In the method of manufacturing a circuit wiring according to the present disclosure, at least one of the plurality of conductive layers preferably includes a metal oxide.
As a conductive layer, it is preferable that it is an electrode pattern corresponded to the sensor of the visual recognition part used for an electrostatic capacitance type touch panel, or wiring of a periphery extraction part.

[Substrate for forming circuit wiring]
It is a substrate which has a conductive layer on the surface of a substrate. The conductive layer is patterned to form a circuit wiring. In this example, it is preferable that a plurality of conductive layers such as metal oxides and metals be provided on a film substrate such as PET.

<Exposing step (first exposing step)>
In the first embodiment, the exposure step is performed, and in the second embodiment, the first exposure step is performed. An example of the exposure process (first exposure process) is schematically shown in FIG.
In the exposure step (first exposure step), the positive photosensitive resin layer 14 is pattern-exposed through 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 then the mask 30 is formed. And exposure to ultraviolet light from above the mask.
In the present disclosure, the detailed arrangement and specific size of the pattern are not particularly limited. Since it is desirable to improve the display quality of a display device (for example, a touch panel) provided with an input device having a circuit wiring manufactured by the method of manufacturing a circuit wiring according to the present disclosure and to minimize the area occupied by the extraction wiring It is preferable that at least a part (particularly, the electrode pattern of the touch panel and the part of the lead-out wiring) be a thin line of 100 μm or less, and more preferably 70 μm or less.
Here, as a light source used for exposure, it can be appropriately selected and used as long as it can emit light (for example, 365 nm, 405 nm, etc.) in a wavelength range in which the exposed portion of the photosensitive transfer material can dissolve in the developer. . Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp and the like can be mentioned.
The exposure dose is preferably about 5 mJ / cm ² to 200 mJ / cm ² , and more preferably about 10 mJ / cm ² to 100 mJ / cm ² .
Further, it is also preferable to carry out heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. By means of a process called so-called PEB (Post Exposure Bake), it is possible to reduce roughness of the pattern edge due to standing waves generated in the photosensitive resin layer at the time of exposure.

In addition, even if pattern exposure is performed after peeling a temporary support from a photosensitive resin layer, before peeling a temporary support, it exposes through a temporary support, and peels a temporary support after that. It is also good. In order to prevent the contamination of the mask due to the contact between the photosensitive resin layer and the mask, and to avoid the influence on the exposure by the foreign matter attached to the mask, it is preferable to perform the exposure without peeling off the temporary support. The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.

<Development Process (First Development Process)>
In the first embodiment, the developing step is performed, and in the second embodiment, the first developing step is performed. An example of the developing step (first developing step) is schematically shown in FIG. 2 (c).
In the developing step (first developing step), after the temporary support 12 is peeled off from the positive photosensitive resin layer 14 after the exposing step (first exposing step), the positive photosensitive after the exposing step (first exposing step) The conductive resin layer 14 is developed to form a first pattern 14A.

The developing step (first developing step) is a step of forming a pattern (first pattern) by developing the positive photosensitive resin layer which has been subjected to the pattern exposure.
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, and for example, a known developer such as a developer described in JP-A-5-72724 may be used. it can. The developing solution is preferably a developing solution in which the exposed part of the positive photosensitive resin layer has a dissolution type developing behavior. For example, a developing solution of an aqueous alkali solution system containing a compound of pKa = 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is preferable. The developer may further contain an organic solvent miscible with water, a surfactant, and the like. As a developing solution preferably used in the present disclosure, for example, a developing solution described in paragraph 0194 of WO 2015/093271 can be mentioned.

The developing method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, dip development and the like. Here, in the shower development, the exposed portion can be removed by spraying the developing solution onto the positive photosensitive resin layer after exposure by a shower. In addition, after development, it is preferable to remove a development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The temperature of the developing solution is preferably 20.degree. C. to 40.degree.

Furthermore, you may have the post-baking process which heat-processes the pattern containing the positive type photosensitive resin layer obtained by developing.
Post-baking heating is preferably performed under an environment of 8.1 kPa to 121.6 kPa, and more preferably performed under an environment of 506.6 kPa or more. On the other hand, it is more preferable to carry out under an environment of 1114.6 kPa or less, and it is particularly preferable to carry out under an environment of 101.3 kPa or less.
The post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.
The post-baking time is preferably 1 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 of manufacturing a circuit wiring according to the present disclosure may have other steps such as a post-exposure step.

<Etching Process (First Etching Process)>
In the first embodiment, the etching step is performed, and in the second embodiment, the first etching step is performed. 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 among the plurality of conductive layers in the region where the first pattern 14A is not disposed are etched. By the etching, the first conductive layer 24A and the second conductive layer 26A having the same pattern are formed.

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

For example, as a method of etching, a commonly performed wet etching method in which the substrate is immersed in an etching solution can be mentioned. The etching solution used for wet etching may be appropriately selected from acid type or alkaline type etching solution in accordance with the object of etching.
Examples of the acid type etching solution include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid and phosphoric acid alone, and mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride, potassium permanganate and the like. Be done. An acidic component may use the component which combined the several acidic component.
As an alkaline type etching solution, an aqueous solution of an alkali component alone such as sodium hydroxide, potassium hydroxide, ammonia, organic amine, salt of organic amine such as tetramethyl ammonium hydroxide, alkali component and potassium permanganate etc. A mixed aqueous solution of salts and the like are exemplified. 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 less. The first pattern used as the etching mask (etching pattern) in the present disclosure preferably exhibits particularly excellent resistance to an acidic and alkaline etching solution in a temperature range of 45 ° C. or less. Therefore, peeling of the positive photosensitive resin layer during the etching process is prevented, and the portion where the positive photosensitive resin layer is not present is selectively etched.

After the etching process, a cleaning process and a drying process may be performed as needed in order to prevent contamination of the process line. The cleaning process is performed by, for example, cleaning the substrate with pure water at normal temperature for 10 seconds to 300 seconds, and the drying process is performed using an air blow, for example, using an air blow pressure (about 0.1 kg / cm ² to 5 kg / cm ² ). Is 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, a portion corresponding to a portion to be removed of at least the first conductive layer in the second developing step described later is exposed to the first pattern remaining on the first conductive layer.
The pattern exposure in the second exposure step can apply the same method as the pattern exposure in the first exposure step except that a mask 40 having a different pattern from that of the mask 30 used in the first exposure step is used.

<Second developing step>
In the second embodiment, the second development 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.
By the development, a portion of the first pattern exposed in the second exposure step is removed.
In the second development step, the same method as the development in the first development step can be applied.

<Second etching step>
In the second embodiment, 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 disposed is etched.

For the etching in the second etching step, the same method as the etching in the first etching step can be applied except that an etching solution corresponding to the conductive layer to be removed by etching is selected.
In the second etching step, depending on the desired pattern, it is preferable to selectively etch less conductive layers than in the first etching step. For example, as shown in FIG. 2, the first conductive layer is etched by performing etching using an etching solution that selectively etches only the first conductive layer 24B in the region where the positive photosensitive resin layer is not disposed. The pattern of the second conductive layer can be different from that of the second conductive layer.
After the completion of the second etching process, a circuit wiring including the

conductive layers

24B and 26A of at least two types of patterns is formed.

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

Although there is no restriction | limiting in particular as a method to remove the positive type photosensitive resin layer which remains, The method to remove by chemical processing can be mentioned.
As a method of removing the positive photosensitive resin layer, for example, a substrate having a positive photosensitive resin layer or the like is preferably added to the stripping solution under agitation at preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. A method of immersion for 1 minute to 30 minutes may be mentioned.

As the peeling 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, And dimethylsulfoxide, N-methyl pyrrolidone or a mixture thereof. A peeling solution may be used to peel off by a spray method, a shower method, a paddle method or the like.

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

<Step of sticking protective film>
In the second embodiment, even after the first etching step and before the second exposure step, the method further includes the step of sticking a light transmitting protective film (not shown) on the first pattern. Good.
In this case, it is preferable that in the second exposure step, the first pattern is pattern-exposed through the protective film, and after the second exposure step, the second development step is performed after the protective film is peeled off from the first pattern.

<Step of reducing visible light reflectance>
The method of manufacturing a circuit wiring according to the present disclosure can include the step of reducing the visible light reflectance of part or all of the plurality of conductive layers on the substrate.
An oxidation process etc. can be mentioned as a process which reduces the visible light reflectance. For example, the visible light reflectance can be reduced by oxidizing copper to copper oxide and blackening the copper.
About the preferable aspect of the process to which the visible light reflectance is reduced, Paragraph 0017-Paragraph 0025 of Unexamined-Japanese-Patent No. 2014-150118, and Paragraph 0041, Paragraph 0042, Paragraph 0048 and Paragraph 0058 of Unexamined-Japanese-Patent No. 2013-206315. The contents of this publication are incorporated herein by reference.

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

Further, in the description with reference to FIG. 2, the case of forming the circuit wiring having two different patterns on the circuit wiring formation substrate provided with 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, and a combination of the exposure step, the development step, and the etching step described above is used using the circuit wiring formation substrate in which three or more conductive layers are stacked. By carrying out three or more times, three or more conductive layers can be formed in different circuit wiring patterns.

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

(Circuit wiring and circuit board)
The circuit wiring according to the present disclosure is a circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure.
A circuit board according to the present disclosure is a substrate having a circuit interconnect manufactured by the method of manufacturing a circuit interconnect according to the present disclosure.
Although the use of the circuit board which concerns on this indication is not limited, For example, it is preferable that it is a circuit board for touch panels.

(Input device and display device)
As an apparatus provided with the circuit wiring manufactured by the manufacturing method of the circuit wiring which concerns on this indication, an input device is mentioned.
The input device in the present disclosure is preferably a capacitive touch panel.
The display device in the present disclosure preferably includes the input device in the present disclosure.
Further, the display device in the present disclosure is preferably an image display device such as an organic EL display device and a liquid crystal display device.

(Touch panel, and touch panel display device and manufacturing method thereof)
The touch panel according to the present disclosure is a touch panel having at least the circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure. In addition, the touch panel according to the present disclosure preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
The touch panel display device according to the present disclosure is a touch panel display device having at least a circuit wiring manufactured by the method of manufacturing a circuit wiring according to the present disclosure, and is preferably a touch panel display device having a touch panel according to the present disclosure.
It is preferable that the manufacturing method of the touch panel or touch-panel display apparatus which concerns on this indication includes the manufacturing method of the circuit wiring which concerns on this indication.
In the method of manufacturing a touch panel or a touch panel display device according to the present disclosure, the step of bonding the photosensitive resin layer of the photosensitive transfer material obtained by the method of manufacturing a photosensitive transfer material in contact with the substrate A step of pattern exposing the photosensitive resin layer of the photosensitive transfer material after the step, a step of developing the photosensitive resin layer after the step of exposing to form a pattern, and a region where the pattern is not disposed And the step of etching the substrate in the following order: The details of each step are the same as the details of each step in the method of manufacturing a circuit wiring described above, 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 methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among them, the capacitance method is preferable.
As a touch panel type, a so-called in-cell type (for example, those shown in FIGS. 5, 6, 7 and 8 of JP-A-2012-517051), a so-called on-cell type (for example, JP-A 2013-168125) 19 described in Japanese Patent Application Laid-Open No. 2012-89102, and those described in FIG. 1 and FIG. 5 of Japanese Patent Application Laid-Open No. 2012-89102, OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (e.g. 2 of 2013-54727, other configurations (for example, the one described in FIG. 6 of JP-A-2013-164871), various out-cell types (so-called GG, G1 · G2, GFF, GF2, GF1, G1F etc. can be mentioned.
As the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, “latest touch panel technology” (issued on July 6, 2009, Techno Times Inc.), supervised by Yuji Mitani, “touch panel technology and development”, CMC Publishing (2004, 12), FPD International 2009 Forum T-11 lecture textbook, Cypress
The configuration disclosed in Semiconductor Corporation Application Note AN2292 and the like can be applied.

Hereinafter, the embodiments of the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment 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. Accordingly, the scope of the embodiments of the present invention is not limited to the specific examples shown below. In addition, unless there is particular notice, "part" and "%" are mass references. The “maximum absorption wavelength” in the present example is the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development.

<Method of calculating pKa and pKaH>
The pKa of the compound and the pKa (pKaH) of the conjugate acid of the compound were calculated using ACD / Labs software Ver 8.0 for Microsoft windows manufactured by Advanced Chemistry Development, ACD / pka DB ver 8.07.

[Polymer]
In the following examples, the following abbreviations respectively represent the following compounds:
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 (made 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.)
EHMA: 2-ethylhexyl acrylate (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-methyl propionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

<Synthesis of ATHF>
Acrylic acid (72.1 parts, 1.0 molar equivalent) and hexane (72.1 parts) were added to a three-necked flask and cooled to 20 ° C. After dropwise addition of camphorsulfonic acid (0.00070 parts by mass, 0.003 mmol equivalent), 2-dihydrofuran (70.1 parts by mass, 1.0 molar equivalent)), 1.5 hours at 20 ° C. ± 2 ° C. After stirring, the temperature was raised to 35 ° C. and stirred for 2 hours. The reaction liquid is filtered after laying in order of KNU ward 200 (aluminum hydroxide adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) and KYOWARD 1000 (hydrotalcite-based adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) in Nutsche. The filtrate was obtained by doing. After adding hydroquinone monomethyl ether (MEHQ, 0.0012 parts) to the obtained filtrate, the solution is concentrated under reduced pressure at 40 ° C. to obtain 140.8 parts of tetrahydrofuran-2-yl acrylate as a colorless oil. Obtained (yield 99.0%).

<Synthesis of MATHF>
In a three-necked flask, methacrylic acid (86.1 parts, 1.0 molar equivalent) and hexane (86.1 parts) were added and cooled to 20 ° C. After dropwise addition of camphorsulfonic acid (0.00070 parts by mass, 0.003 mmol equivalent), 2-dihydrofuran (70.1 parts by mass, 1.0 molar equivalent)), 1.5 hours at 20 ° C. ± 2 ° C. After stirring, the temperature was raised to 35 ° C. and stirred for 2 hours. After laying in the order of Kyo Ward 200 and Kyo Ward 1000 in Nutsche, the filtrate was obtained by filtering the reaction liquid. MEHQ (0.0012 parts) was added to the obtained filtrate, and the solution was concentrated under reduced pressure at 40 ° C. to obtain 156.2 parts of tetrahydrofuran-2-yl methacrylate (MATHF) as a colorless oil (collection 98.0%).

Synthesis Example of Polymer A1
In a three-necked flask, n-propyl acetate (150.0 parts by mass) was placed, 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 A solution obtained by mixing 1 part by mass) was dropped into a three-necked flask maintained at a temperature range of 90 ° C. ± 2 ° C. over 2 hours. After completion of the dropwise addition, by stirring for 2 hours within a temperature range of 90 ° C. ± 2 ° C., a polymer A1 (solid content concentration 40.0 mass%) was obtained.

Synthesis Example of Polymers A-2 to A-9
The types of monomers and the like were changed as shown in Table 1 below, and other conditions were synthesized in the same manner as in the polymer A-1. The solid content concentration of the polymer was 40% by mass.

Synthesis Example of Polymer A-10
A polymer synthesized by the same method as the acid-degradable polymer compound PS-2 described in JP-A-2008-64908 has a polymer A-10 (having a group in which the carboxylic acid group is protected by the acid-degradable group) It was set as the polymer which does not contain a unit.

[Photo acid generator]
B-1: Compound of the structure shown below (synthesized according to the method described in paragraph 0227 of JP-A-2013-47765)

B-2: BASF Irgacure PAG-103, the following compounds

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

B-4: WPAG-281 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)

B-5: Compound having the following structure (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 C-2 described above, manufactured by Chameleon, maximum absorption wavelength: 533 nm, pKaH: no conjugated acid is formed C-3: the same compound as C-3 described above, manufactured by Yamamoto Kasei Co., Ltd. Maximum absorption wavelength: 531 nm, pKaH: not forming conjugated 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 C-5 described above, manufactured by Fukui Yamada Chemical Industry Co., Ltd., maximum absorption wavelengths: 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'-1: The following compound, Fukui Yamada Chemical Industries, Ltd. make, maximum absorption wavelength: 598 nm, pKaH: 4.73
C'-2: The following compound, Hodogaya Chemical Industry Co., Ltd. product, maximum absorption wavelength: 444 nm, pKaH: 1.86

[Basic compound]
D-1: Compound of 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: 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 22 and Comparative Examples 1 to 4)
Preparation of Photosensitive Transfer Material
In Examples 1 to 22 and Comparative Examples 1 to 4, the polymer component, the photoacid generator, the basic compound, the surfactant, and the other components were made to have acetic acid so as to obtain the solid content ratio shown in Table 2 below. Dissolve and mix n-propyl / methyl ethyl ketone = 70/30 (volume%) to a solid content concentration of 14% by mass, filter with a polytetrafluoroethylene filter with a pore size of 0.2 μm, obtain a photosensitive resin composition Obtained.
This photosensitive resin composition was dried on a 16 μm thick polyethylene terephthalate film (hereinafter, also referred to as “PET (A)”) to be a temporary support by using a slit nozzle and having a dry film thickness of 3.0 μm. It applied so that it might become. Then, it was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polypropylene film (Alfane PK-002, manufactured by Oji F-TEX Co., Ltd.) was press-bonded as a cover film to prepare a photosensitive transfer material.

[Performance evaluation]
A copper layer-coated PET substrate was used in which a copper layer was produced by sputtering at a thickness of 200 nm on a polyethylene terephthalate (PET) film having a thickness of 100 μm.

<Sensitivity evaluation>
The prepared photosensitive transfer material was subjected to a linear pressure of 0.8 MPa, a linear velocity of 3.0 m / min. The laminate was laminated on a PET substrate with a copper layer under the following lamination conditions. The area where the photosensitive resin layer is in close contact with the copper layer without bubbles or floats is confirmed by visual evaluation at a roll temperature of 90 ° C., and when the above area is less than 95%, the above area is 95% or more The roll temperature was raised until it became and the sample was produced.
After exposing the photosensitive resin layer with an ultra-high pressure mercury lamp through a line-and-space pattern mask (Duty ratio 1: 1) with a line width of 3 μm to 20 μm without peeling off the temporary support, the temporary support is allowed to stand for 1 hour. It peeled and developed. The development was carried out for 30 seconds by shower development using a 1.0% aqueous sodium carbonate solution at 28 ° C. 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 exposure amount at which the residue could not be confirmed was determined in the observation by SEM. An exposure dose of 200 mJ / cm ² or less is a practical level. The smaller the exposure amount, the better the exposure sensitivity.
-Evaluation criteria-
A: 80mJ / cm ² or less B: 80mJ / cm ² beyond 100 mJ / cm ² or less C: exceed 100mJ / cm ^² 200mJ / cm ² or less D: exceed 200mJ / cm ^² 300mJ / cm ² or less E: 300 mJ / more than cm ²

<Visibility evaluation>
The prepared photosensitive transfer material was subjected to a linear pressure of 0.8 MPa, a linear velocity of 3.0 m / min. The laminate was laminated on a PET substrate with a copper layer under the following lamination conditions. The area where the photosensitive resin layer is in close contact with the copper layer without bubbles or floats is confirmed by visual evaluation at a roll temperature of 90 ° C., and when the above area is less than 95%, the above area is 95% or more The roll temperature was raised until it became and the sample was produced. A part of the temporary support was light-shielded without peeling, and after exposing the photosensitive resin layer with an extra-high pressure mercury lamp, it was left for 4 hours. The amount of exposure used was the amount of exposure obtained by the above sensitivity evaluation.
An optical lens with a magnification of 4 was attached to the tip of a black and white CCD (Charge Coupled Device) camera, and the reflected light intensity of the exposed area and the reflected light intensity of the unexposed area were measured.
Reflected light intensity ratio = (reflected light intensity of exposed area) / (reflected light intensity of unexposed area)
The smaller the value of the reflected light intensity ratio, the better the performance, and the practical level is A to C in the following evaluation criteria.

-Measurement condition-
Reading camera pixel count: 5 million pixels (2,432 × 2, 050)
Reading camera spectral sensitivity: 400 nm = x 0.6, 500 nm = x 1.0, 600 nm = x 0.84, 700 nm = x 0.55
Light source: D65 light source (International Lighting Commission (CIE) standard light source D65) passed through Fujifilm Corporation Sharp Cut Filter SC-42

-Evaluation criteria-
A: Reflected light intensity ratio is less than 0.45 B: Reflected light intensity ratio is 0.45 or more and less than 0.65 C: Reflected light intensity ratio is 0.65 or more and less than 0.78 D: Reflected light intensity ratio is 0. 78 or more and less than 0.90 E: reflected light intensity ratio is 0.90 or more

<Linearity evaluation>
The prepared photosensitive transfer material was subjected to a linear pressure of 0.8 MPa, a linear velocity of 3.0 m / min. The laminate was laminated on a PET substrate with a copper layer under the following lamination conditions. The area where the photosensitive resin layer is in close contact with the copper layer without bubbles or floats is confirmed by visual evaluation at a roll temperature of 90 ° C., and when the above area is less than 95%, the above area is 95% or more The roll temperature was raised until it became and the sample was produced.
Without peeling off the temporary support, the photosensitive resin layer was exposed with an exposure amount obtained by sensitivity evaluation with an ultra-high pressure mercury lamp through a line and space pattern (Duty ratio 1: 1) mask with 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 carried out for 30 seconds by shower development using a 1.0% aqueous sodium carbonate solution at 28 ° C. With the line and space pattern thus obtained, 50 points of the line width are measured for the range of 40 μm of the longitudinal edge of the pattern in which the line width falls within 7 ± 0.5 μm, and the standard deviation of the measurement variation is determined , 3σ was calculated. This was measured at n = 5 and the average value (LWR, line width roughness) was determined. The smaller the value, the better the performance, and the practical level is AC.
-Evaluation criteria-
A: LWR less than 200 nm B: LWR less than 200 nm and less than 240 nm C: LWR less than 240 nm and less than 290 nm D: LWR less than 290 nm and less than 340 nm E: LWR less than 340 nm

The evaluation results are summarized in Table 2.

In addition, the unit of the quantity of each component of Table 2 is a mass part.
Further, in Comparative Example 4, since no sensitivity was obtained, a clean pattern could not be formed and the linearity was "E".
As shown in Table 2, the photosensitive resin composition according to the present disclosure was able to achieve both sensitivity and visibility at a high level.
Also, as shown in Table 2, the photosensitive transfer material according to the present disclosure was capable of transfer to a copper layer.

(Example 101)
Indium tin oxide (ITO) is deposited by sputtering as a conductive layer of the second layer on a 100 μm-thick PET substrate by sputtering to a thickness of 150 nm, and copper is vacuum deposited thereon as a conductive layer of the first layer. A film was formed at a thickness of 200 nm to form a circuit formation substrate.
The photosensitive transfer material 1 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 contact pattern was exposed using a photomask provided with a pattern (hereinafter also referred to as “pattern A”) shown in FIG. 3 having a configuration in which conductive layer pads are connected in one direction without peeling off the temporary support. .
In the pattern A shown in FIG. 3, the solid line portion SL and the gray portion G are light shielding portions, and the dotted line portion DL virtually illustrates the alignment alignment frame.
Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Next, the copper layer is etched using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO layer is etched using an ITO etching liquid (ITO-02 manufactured by Kanto Chemical Co., Ltd.) The board | substrate with which copper (solid line part SL) and ITO (gray part G) were both drawn by the pattern A was obtained.

Next, pattern alignment was performed using a photomask provided with an opening of a pattern (hereinafter, also referred to as “pattern B”) shown in FIG. 4 in a state where alignment is aligned, and development and washing were performed.
In the pattern B shown in FIG. 4, the gray portion G is a light shielding portion, and the dotted line portion DL virtually illustrates the alignment alignment frame.
Thereafter, the copper layer was etched using Cu-02, and the remaining photosensitive resin layer was peeled using a peeling solution (10 mass% aqueous sodium hydroxide solution) to obtain a circuit wiring board.
Thus, a circuit wiring board was obtained. When observed with a microscope, there was no peeling or chipping, and it was a beautiful pattern.

(Example 102)
ITO is deposited as a conductive layer of the second layer by sputtering to a thickness of 150 nm on a 100 μm-thick PET substrate, and copper is deposited thereon by a vacuum evaporation method to a thickness of 200 nm as a conductive layer of the first layer. The film was formed as a circuit formation substrate.
The photosensitive transfer material 1 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 pattern-exposed using a photomask provided with a pattern A shown in FIG. 3 having a configuration in which conductive layer pads are connected in one direction without peeling off the temporary support. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Next, the copper layer is etched using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), and then the ITO layer is etched using an ITO etching liquid (ITO-02 manufactured by Kanto Chemical Co., Ltd.) The board | substrate with which copper (solid line part SL) and ITO (gray part G) were both drawn by the pattern A was obtained.
Then, PET (A) was laminated as a protective layer on the remaining resist. In this state, pattern alignment was performed using a photomask provided with the opening of pattern B shown in FIG. 4 in a state of alignment, and after PET (A) was peeled off, development and water washing were performed.
Thereafter, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Ltd.) to obtain a circuit wiring board.
When observed with a microscope, there was no peeling or chipping, and it was a beautiful pattern.

12 temporary support 14 photosensitive resin layer 14A first pattern 14B second pattern 16 cover film 20 substrate for circuit formation 22 base material 24 first conductive layer 24A first conductive layer (after first etching process)
24B first conductive layer (after second etching step)
26 second conductive layer 26A second conductive layer (after the first etching step and the second etching step)
30 mask 40 mask 100 photosensitive transfer material SL solid line portion G gray portion DL dotted portion

Claims

A polymer containing a structural unit having a carboxylic acid group protected by an acid degradable group,
Photo acid generator, and
A photosensitive resin composition comprising: a latent dye having a pKa of less than 4.5 of a conjugated acid or a compound which does not form a conjugated acid and having a maximum absorption wavelength of 500 nm or more in a wavelength range of 400 nm to 780 nm at color development.
The photosensitive resin composition according to claim 1, wherein the maximum absorption wavelength of the latent dye is 550 nm or more.
The photosensitive resin composition according to claim 1 or 2, wherein the latent dye is a latent dye that develops a color by an acid generated from the photoacid generator.
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 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 0-5.
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 pKa of the acid generated from the photoacid generator is 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 one 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 constituent unit having a group in which the carboxylic acid group is protected by an acid-degradable group is a constituent unit represented by the following formula II object.

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 R 1 or R 2 and R 3 may combine 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,
And a photosensitive resin layer,
A photosensitive transfer material, wherein the photosensitive resin layer comprises the photosensitive resin composition according to any one of claims 1 to 12.
A step of bringing the photosensitive resin layer of the photosensitive transfer material according to claim 13 into contact with the substrate and bonding the substrate to the substrate;
Pattern exposing the photosensitive resin layer of the photosensitive transfer material after the laminating step;
Developing the photosensitive resin layer after the exposing step to form a pattern;
And E. etching the substrate in the area where the pattern is not arranged.
A step of bringing the photosensitive resin layer of the photosensitive transfer material according to claim 13 into contact with the substrate and bonding the substrate to the substrate;
Pattern exposing the photosensitive resin layer of the photosensitive transfer material after the laminating step;
Developing the photosensitive resin layer after the exposing step to form a pattern;
And etching the substrate in the area where the pattern is not arranged.