JP2019204070A - Photosensitive transfer material, manufacturing method for circuit wiring, and manufacturing method for touch panel - Google Patents

Abstract

To provide a photosensitive transfer material excellent in visibility of an exposed part and an unexposed part, a manufacturing method for the circuit wiring, and a manufacturing method for a touch panel.SOLUTION: A photosensitive transfer material has a temporary support body, an intermediate layer and a resist layer in the stated order. The intermediate layer contains a component (A) that is a pigment having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400-780 nm when color is produced, the maximum absorption wavelength varying depending on whether an acid, base or radical is involved. Also provided are a manufacturing method for circuit wiring, and a manufacturing method for a touch panel.SELECTED DRAWING: Figure 1

Description

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

In a display device (such as an organic electroluminescence (EL) display device and a liquid crystal display device) having a touch panel such as a capacitance-type input device, an electrode pattern corresponding to a sensor in a visual recognition portion, a wiring in a peripheral wiring portion, and a wiring in a take-out wiring portion A conductive layer pattern such as is provided inside the touch panel.
In general, the formation of a patterned layer requires a small number of steps for obtaining a required pattern shape, so that a resist layer provided on an arbitrary substrate using a photosensitive transfer material is desired. A method of developing after exposure through a mask having the following pattern is widely used.

  Further, as conventional resist layer compositions and photosensitive transfer materials, those described in Patent Documents 1 to 4 are known. Furthermore, a photosensitive transfer material having a support, a cushion layer containing a dye, and a photosensitive layer is disclosed (for example, Patent Document 5).

JP 2008-64908 A JP 2004-54106 A JP 2009-3000 A JP 2002-341544 A JP 2006-85116 A

A problem to be solved by an embodiment of the present disclosure is to provide a photosensitive transfer material that is excellent in visibility of an exposed portion and an unexposed portion.
Another problem to be solved by another embodiment of the present disclosure is to provide a method for manufacturing circuit wiring or a method for manufacturing a touch panel using the photosensitive transfer material.

Means for solving the above problems include the following aspects.
<1> A photosensitive transfer material having a temporary support, an intermediate layer, and a resist layer in this order, and the intermediate layer contains the following component (A).
Component (A): Dye whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or more, and whose maximum absorption wavelength changes due to acid, base or radical <2> The dye as component (A) is pH sensitive The photosensitive transfer material according to <1>, which is a dye.
<3> The photosensitive transfer material according to <1> or <2>, wherein the dye as the component (A) has a triarylmethane skeleton.
<4> The dye as the component (A) contains at least one selected from a dye represented by the following formula I, a ring-opened product of the dye represented by the following formula I, and a neutralized product of the ring-opened product < The photosensitive transfer material according to any one of 1> to <3>.

In formula I, Ar and Ar ′ each independently represent an aromatic group. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent.
<5> The photosensitive transfer material according to any one of <1> to <4>, wherein the resist layer contains the following components (B) and (C).
(B) Component: Polymer (C) component containing a structural unit having a group in which an acid group is protected with an acid-decomposable group: Photoacid generator

<6> The maximum absorption wavelength in a wavelength range of 400 nm to 780 nm at the time of coloring of the dye as the component (A) is changed by the acid released from the photoacid generator as the component (C) by exposure. Photosensitive transfer material.
<7> The photosensitivity according to <6>, wherein the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development of the dye as component (A) is shortened from the acid released from the (C) photoacid generator by exposure. Transfer material.
<8> The acid generated from the photoacid generator as the component (C) is phosphoric acid or sulfonic acid, and the pKa is 4 or less, and any one of <5> to <7> Photosensitive transfer material.

<9> The structural unit having a group in which the polymer as the component (B) has an acid group protected by an acid-decomposable group is a structural unit represented by the following formula II <5> to <8> The photosensitive transfer material as described in any one of.

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 Alternatively, it represents an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether. R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.
<10> The photosensitive transfer material according to any one of <1> to <9>, wherein the intermediate layer further contains the following component (G).
(G) Component: pH adjusting agent <11> The photosensitive transfer material according to <10>, wherein the pH adjusting agent is a quaternary ammonium salt.
<12> The photosensitive transfer material according to any one of <1> to <11>, wherein the resist layer further contains the following component (D).
Component (D): basic compound

<13> The step of bringing the resist layer of the photosensitive transfer material according to any one of <1> to <12> into contact with the substrate and bonding the substrate, and the photosensitive transfer material after the bonding step Circuit wiring including a step of pattern exposure of the resist layer, a step of developing the resist layer after the pattern exposure step to form a pattern, and a step of etching the substrate in a region where the pattern is not arranged Manufacturing method.

<14> The step of bringing the resist layer of the photosensitive transfer material according to any one of <1> to <12> into contact with the substrate and bonding the substrate, and the photosensitive transfer material after the bonding step A touch panel including, in this order, a step of pattern exposing a resist layer, a step of developing a resist layer after pattern exposure and forming a pattern, and a step of etching a substrate in a region where no pattern is arranged Production method.

According to an embodiment of the present disclosure, it is possible to provide a photosensitive transfer material that is excellent in visibility of an exposed portion and an unexposed portion.
In addition, according to another embodiment of the present disclosure, it is possible to provide a circuit wiring manufacturing method and a touch panel manufacturing method using the photosensitive transfer material.

It is the schematic which shows an example of the laminated constitution of the photosensitive transfer material which concerns on this indication. It is the schematic which shows an example of the manufacturing method of the circuit wiring for touchscreens using the photosensitive transfer material which concerns on this indication. FIG. 6 is a schematic diagram showing a pattern A. FIG. 6 is a schematic diagram showing a pattern B.

Hereinafter, the contents of the present disclosure will be described. In addition, although it demonstrates referring an accompanying drawing, a code | symbol may be abbreviate | omitted.
In the present disclosure, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. In a numerical range described in stages in the present disclosure, an upper limit value or a lower limit value described in a numerical range may be replaced with an upper limit value or a lower limit value in another numerical range. Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
In the present disclosure, “(meth) acryl” represents both and / or acryl and methacryl, and “(meth) acrylate” represents both and / or acrylate and methacrylate.
Furthermore, in the present disclosure, the amount of each component in the composition is the total amount of the plurality of corresponding substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.

In the present disclosure, the term “process” is included in the term as long as the intended purpose of the process is achieved, even when the process is not clearly distinguished from other processes.
In the notation of a group (atomic group) in the present disclosure, the notation that does not indicate substitution and non-substitution includes those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, the chemical structural formula in the present disclosure may be described as a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, “mass%” and “weight%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

  In the present disclosure, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are columns of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation). The molecular weight is detected by a gel permeation chromatography (GPC) analyzer used and detected by a solvent THF (tetrahydrofuran) and a differential refractometer and converted using polystyrene as a standard substance.

(Photosensitive transfer material)
The photosensitive transfer material according to the present disclosure has an intermediate layer and a resist layer in this order on a temporary support, and the intermediate layer has a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development as the component (A). It is a photosensitive transfer material that contains a dye that has a wavelength of 450 nm or more and whose maximum absorption wavelength is changed by acid, base, or radical.

  The photosensitive transfer material for dry film resist is required to have visibility of the exposed portion from the viewpoint of confirmation of the exposed portion. In order to impart visibility, it is known to introduce a color former into the resist layer, but there are concerns about various adverse effects. The present inventors have found that a photosensitive transfer material can be provided that does not have various adverse effects by introducing the color developing mechanism into the intermediate layer instead of the resist layer.

  As a result of intensive studies, the present inventors have found that a photosensitive transfer material having excellent visibility of exposed and unexposed areas can be obtained by using the photosensitive transfer material having the above-described configuration.

  The photosensitive transfer material of the present disclosure includes a material (for example, a photoacid generator described later) that promotes color development or decoloration of the dye as the component (A) by exposure. As a result, when the photosensitive transfer material is exposed, coloring or decoloring of the dye can be suppressed in the unexposed area, and coloring or decoloring of the dye can be generated only in the exposed area. As a result, it becomes easy to visually distinguish and distinguish between a portion where color development or decoloration has occurred and a portion where color development or decoloration has not occurred, and it is assumed that excellent visibility is obtained.

The photosensitive transfer material in the present disclosure may be a so-called negative photosensitive transfer material in which the removability in development is reduced by exposure, or the so-called positive photosensitivity in which the removability in development is increased by exposure. It may be a transfer material.
In the case of a positive photosensitive transfer material, the photosensitive transfer material is preferably a chemically amplified positive photosensitive transfer material.

The photosensitive transfer material according to the present disclosure can be an NQD-based photosensitive transfer material using NQD (naphthoquinone diazide).
As naphthoquinone diazide, for example, naphthoquinone diazide described in paragraph 0201 of JP-A No. 2004-126047 can be used.
Moreover, when making the photosensitive transfer material of this indication into a NQD type photosensitive transfer material, it is preferable that a novolak resin is included.
As the novolak resin, for example, the novolak resin described in paragraph 0201 of JP-A-2004-126047 can be used.
Hereinafter, the photosensitive transfer material according to the present disclosure will be described in detail.

[Middle layer]
The intermediate layer according to the present disclosure contains a dye (component (A)) having a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 nm to 780 nm at the time of color development, and having a maximum absorption wavelength changed by an acid, a base, or a radical. Moreover, it is preferable that the said intermediate | middle layer is a layer formed with the intermediate | middle layer composition which concerns on this indication. Furthermore, it is preferable that the said intermediate | middle layer contains the pigment | dye which concerns on this indication.
As the intermediate layer, the intermediate layer described in paragraphs 0084 to 0087 of JP-A-2005-259138 can be used. The intermediate layer is preferably one that is dispersed or dissolved in water or an aqueous alkali solution.

<Dye [(A) component]>
The intermediate layer of the photosensitive transfer material according to the present disclosure has a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development of 450 nm or more, and contains a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical.

“The maximum absorption wavelength is changed by an acid, base or radical” when the dye is in a state where the dye in a colored state is decolored by an acid, base or radical, and the dye in a decolored state is colored by an acid, base or radical It may refer to any of the embodiments in which the dye in a colored state changes to a colored state in another hue.
Specifically, the coloring matter may be a compound that changes color from a decolored state upon exposure, or a compound that changes color from a colored state upon exposure. In this case, it may be a dye whose color development or decoloring state is changed by introducing an acid, a base or a radical into the composition by exposure, and by introducing an acid, a base or a radical, the properties in the system ( For example, it may be a dye whose coloring or decoloring state changes as pH changes. Further, it may be a dye that changes its color development or decoloration state by being directly applied as a stimulus with acid, base or radical without exposure.
Among these, from the viewpoint of visibility, a compound that is decolored by exposure is preferable, and a latent dye that is decolored by an acid generated from a photoacid generator, that is, the pH is changed by the generation of an acid to be decolored. More preferably a pH sensitive dye.

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

Examples of the coloring mechanism of the dye in the present disclosure may include the following aspects.
A photoacid generator, a photobase generator or a photoradical generator is added to the intermediate layer, and after exposure, an acid-reactive dye or a base-reactive dye is generated by the acid, base or radical generated from the photoacid generator or the like after exposure. Alternatively, a radical reactive dye (for example, a water-soluble leuco dye) develops color.
In particular, in the case of a chemically amplified positive-type photosensitive transfer material, the following modes may be employed.
A photoacid generator described later is added to the resist layer, and after exposure, the photoacid generator contained in the resist layer moves to the intermediate layer to generate an acid. Then, an acid-reactive dye (for example, a water-soluble leuco dye) is colored by the generated acid.

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

  The maximum absorption wavelength is measured by measuring the transmission spectrum in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) at 25 ° C. in the atmosphere of air, and the light intensity. The wavelength at which is minimized (maximum absorption wavelength) shall be measured.

Examples of the dye that develops and decolors upon exposure include leuco compounds.
Examples of the dye that can be erased by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, anthraquinone dyes, and the like.
Among these, as the pigment, a leuco compound is preferable from the viewpoint of visibility.
Examples of the leuco compound include triarylmethane-based (for example, triphenylmethane-based), spiropyran-based, fluoran-based, diarylmethane-based, rhodamine lactam-based, indolylphthalide-based, and leucooramine-based leuco compounds. Among them, a leuco compound (triarylmethane dye) having a triarylmethane skeleton is preferable, and a triphenylmethane dye is more preferable.
In addition, the leuco compound preferably has a lactone ring, a sultin ring, or a sultone ring from the viewpoint of visibility. When the leuco compound has a lactone ring, a sultin ring, or a sultone ring, it reacts with an acid generated from, for example, a photoacid generator, changes to a ring-closed state and disappears, or enters a ring-opened state. It can change and color. A lactone ring, a sultin ring, or a sultone ring that is opened is preferable, and a leuco compound that has a sultone ring and that discolors when the sultone ring is closed is more preferable.

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

  Among the above, from the viewpoint of visibility, the dye is at least one selected from a dye represented by the following formula I, a ring-opened product of the dye represented by the following formula I, and a neutralized product of the ring-opened product. It is preferable to include.

In formula (I), Ar and Ar ′ each independently represents an aromatic group. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent.

The ring-closed body, ring-opened body, and neutralized body of the ring-opened body in the present disclosure will be described below using Compound A-1 described below as an example. The same applies to other compounds represented by formula (I).
The dye of the present disclosure exists in an equilibrium state of a ring-closed body, a ring-opened body, and a neutralized body of a ring-opened body in an intermediate layer, for example, as shown below. For example, if the pH in the intermediate layer is acidic, the abundance ratio of the ring-closed body increases, and the abundance ratio of the ring-opened body and the neutralized body of the ring-opening body relatively decreases. On the contrary, if the pH in the intermediate layer is alkaline, the abundance ratio of the ring-opened product and the neutralized product of the ring-opened product increases, and the abundance ratio of the ring-closed product relatively decreases.
Since the ring-closed body, ring-opened body, and neutralized body of the ring-opened body have different colors at the time of color development, for example, when the intermediate layer contains a photoacid generator, it is included in the exposed intermediate layer. As a result of the release of the acid from the photoacid generator, the pH of the exposed portion is reduced, and the color of the coloring dye changes.
On the other hand, there is no color change in the unexposed area. Thereby, good visibility of the exposed part and the unexposed part can be realized.

  In the above equilibrium state, in order to adjust the pH in the intermediate layer and adjust the abundance of the ring-closed body, ring-opened body and neutralized body of the ring-opened body, the component (G) that is a pH adjuster (such as NaOH) Is preferably used.

The aromatic group in Ar and Ar ′ in the formula (I) may be an aryl group or a heteroaryl group, and even if it is a monocyclic aromatic group, two or more rings are condensed. It may be a condensed ring.
Ar and Ar ′ in formula (I) may combine to form a ring. Furthermore, Ar and Ar ′ are preferably a 5-membered ring or a 6-membered ring.
The aromatic group in Ar and Ar ′ in formula (I) may have a substituent. Ar and Ar ′ may have a plurality of the above substituents.
Examples of the substituent include a hydroxy group, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylarylamino group, and a diarylamino group, and a hydroxy group, a halogen group, and a dialkylamino group. , Alkylarylamino group and diarylamino group are preferable.
The substituent can be bonded to at least one of the ortho position, the meta position, and the para position. Among them, it is preferable to bond to at least one of the ortho position and the para position, and it is more preferable to bond to at least the para position.
The halogen atom is preferably a bromo atom (bromine atom) and an iodine atom, and more preferably a bromo atom (bromine atom). Moreover, it is preferable that the said alkyl group is a C1-C20 alkyl group each independently, and it is more preferable that it is a C1-C10 alkyl group.
These substituents may be further substituted with a substituent. Among them, Ar and Ar ′ are preferably a phenyl group having a hydroxy group and a phenyl group substituted by a halogen atom.
The total carbon number of Ar and Ar ′ in formula (I) is preferably 4 to 50, more preferably 6 to 40, and more preferably 10 to 30 from the viewpoints of sensitivity and visibility. More preferably.

R ¹ , R ² , R ³ and R ^{4 in} formula (I) are each independently a hydrogen atom, hydroxy group, halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, dialkylamino group, alkylarylamino group And a diarylamino group. Of these, a hydrogen atom is preferable.

  As preferred specific examples of the dye, compounds A-1 to A-15 are described below, but it is needless to say that the dye in the present disclosure is not limited thereto.

The dye may be used alone or in combination of two or more.
The content of the dye in the photosensitive transfer material according to the present disclosure is preferably 0.01% by mass to 10% by mass with respect to the total solid content of the intermediate layer composition from the viewpoint of visibility. It is more preferably from 8% by mass to 8% by mass, still more preferably from 0.5% by mass to 5% by mass, and particularly preferably from 1.0% by mass to 3.0% by mass.
In the present disclosure, the “solid content” in the intermediate layer composition means a component excluding a volatile component (for example, a solvent).

Here, the content of the dye means the content of the dye when all of the dyes included in the intermediate layer composition are in a colored state. Below, the quantification method in case a pigment | dye is a pH sensitive pigment | dye is demonstrated.
Dissolve 0.001 g and 0.01 g of the dye contained in the intermediate layer composition in 100 mL of a mixed solution of ethanol and water (ethanol / water = 1/2 [mass ratio]), and add 0.1 mol / l (1 N). A hydrochloric acid aqueous solution is added to adjust to pH = 1, or a 0.01 mol / l (0.01N) aqueous sodium hydroxide solution is added to adjust to pH = 14, and all the dyes are brought into a colored state. Thereafter, the absorbance is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) at 25 ° C. in an air atmosphere to prepare a calibration curve.
Next, the absorbance is measured by adjusting to pH = 1 or pH = 14 in the same manner as described above except that 0.1 g of the dye is changed to 0.1 g of the intermediate layer composition. Then, the amount of the dye contained in the intermediate layer composition is calculated from the calibration curve prepared from the absorbance of the dye and the absorbance of the intermediate layer composition.

<Polymer>
The intermediate layer can include a polymer.
The polymer used for the intermediate layer is preferably a water-soluble resin. Examples of water-soluble resins include cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. These resins are mentioned. Of these, cellulose-based resins are preferable, and hydroxypropylcellulose and hydroxypropylmethylcellulose are more preferable.
The water solubility of the polymer in the present disclosure means that the amount of the polymer dissolved in 100 parts by mass of water at 25 ° C. is 0.1 parts by mass or more (preferably 1 part by mass or more, more preferably 5 parts by mass or more). It means that there is.

<Surfactant>
The intermediate layer preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic (nonionic), or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants are those described above.

<Inorganic filler>
The intermediate layer can contain an inorganic filler. The inorganic filler in the present disclosure is not particularly limited. Silica particles, aluminum oxide particles, zirconium oxide particles and the like can be mentioned, and silica particles are more preferable. From the viewpoint of transparency, particles having a small particle diameter are preferable, and those having an average particle diameter of 100 nm or less are more preferable. For example, if it is a commercial product, Snowtex (registered trademark) is preferably used.

<PH adjuster [(G) component]>
The intermediate layer can contain a pH adjusting agent. By including the pH adjusting agent, the coloring state or decoloring state of the dye in the composition can be more stably maintained, and the adhesion to the substrate is further improved.
There is no restriction | limiting in particular in the pH adjuster in this indication. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, organic amine, and organic ammonium salt. Sodium hydroxide is preferred from the viewpoint of water solubility. From the viewpoint of adhesion between the resist layer and the intermediate layer, an organic ammonium salt is preferable.
Examples of organic ammonium salts include primary ammonium salts, secondary ammonium salts, tertiary ammonium salts, and quaternary ammonium salts, with quaternary ammonium salts being preferred.
Examples of the quaternary ammonium salt include tetraalkylammonium hydroxide which may have a substituent. Specific examples include tetramethylammonium hydroxide, triethylmethylammonium hydroxide, tetraethylammonium hydroxide, tetra Examples thereof include propylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, hexadecyltrimethylammonium hydroxide, choline, benzyltrimethylammonium, benzyltriethylammonium, tris (2-hydroxyethyl) methylammonium hydroxide, and the like.
Among these, tetraalkylammonium hydroxide having an alkyl group having 1 to 30 carbon atoms (preferably 10 to 30 carbon atoms, more preferably 10 to 25 carbon atoms) is more preferable. In the case of having a substituent, examples of the substituent include an aryl group having 6 to 12 carbon atoms (for example, a phenyl group), a hydroxy group, and the like.

<Photo acid generator>
When the photosensitive transfer material in the present disclosure is a negative photosensitive transfer material, the intermediate layer can contain a photoacid generator. The photoacid generator is not particularly limited. They may be the same as the photoacid generator described below. The photoacid generator can be included in the intermediate layer composition and applied in advance. However, when the resist layer composition is applied, the photoacid generator diffuses and can be included in the intermediate layer.

<Photoradical generator>
When the photosensitive transfer material in the present disclosure is a negative photosensitive transfer material, the photosensitive transfer material can contain a photoradical generator.

Examples of the photo radical generator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), TAZ-110 (trade name: Midori) Manufactured by Chemical Co., Ltd.), benzophenone, TAZ-111 (trade name: manufactured by Midori Chemical Co., Ltd.), Irgacure OXE01, OXE02, OXE03 (manufactured by BASF), Omnirad 651 and 369 (product names: manufactured by IGM Resins BV) Examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
Moreover, the photoinitiator mentioned later can also be used as a photoradical generator.

<Photobase generator>
When the photosensitive transfer material in the present disclosure is a negative photosensitive transfer material, the photosensitive transfer material can contain a photobase generator.

Examples of photobase generators include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaamminecobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6 -Dimethyl-3, -Diacetyl-4- (2-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2,4-dinitrophenyl) -1,4-dihydropyridine, etc. Can do.
As examples of the thermal base generator, compounds described in International Publication No. 2015/199219 can be used.

-Average film thickness of intermediate layer-
The average film thickness of the intermediate layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and more preferably 0.3 μm to 2 μm from the viewpoints of adhesion between the intermediate layer and the resist layer and pattern formability. Is particularly preferred.
There is no restriction | limiting in particular in the measuring method of the average film thickness of each layer in this indication, A well-known method can be used. The average value is preferably measured and calculated at 10 points or more.
Specific examples include surface shape measurement and cross-sectional optical microscope or electron microscope observation. In addition, Bruker's Dektak series can be suitably used for surface shape measurement. Moreover, a scanning electron microscope (SEM) can be used suitably for cross-sectional observation.
Moreover, it is preferable that the thickness of the said intermediate | middle layer is thinner than the thickness of the said resist layer.

The intermediate layer can have two or more layers.
When the intermediate layer has two or more layers, the average film thickness of each layer is not particularly limited as long as it is within the above range. Of the two or more layers in the intermediate layer, the average of the layers closest to the resist layer The film thickness is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and particularly preferably 0.3 μm to 2.0 μm, from the viewpoints of adhesion between the intermediate layer and the resist layer and pattern formability. .

-Method for forming the intermediate layer-
An intermediate layer composition for forming an intermediate layer by mixing each component and a solvent in a predetermined ratio at an arbitrary method, and dissolving by stirring can be prepared. For example, it is possible to prepare a composition by preparing each solution of each component in advance in a solvent and then mixing the obtained solution at a predetermined ratio. The composition prepared as described above can be used after being filtered using a filter having a pore size of 3.0 μm.

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

[Resist layer]
The resist layer according to the present disclosure is a layer that has photosensitivity and can be patterned by developing with a developer after exposure. The resist layer preferably contains a polymer containing a structural unit having an acid group protected with an acid-decomposable group, and a photoacid generator. It is preferable that the said resist layer is a layer formed with the resist layer composition in this indication.
The resist layer in the present disclosure is preferably a chemically amplified positive resist layer from the viewpoint of high sensitivity.

<Polymer Containing Structural Unit Having Acid Group Protected with Acid-Decomposable Group [Component (B)]>
The resist layer composition according to the present disclosure includes a polymer (also referred to as “specific polymer”) containing a structural unit having an acid group protected with an acid-decomposable group (also referred to as “structural unit b”). Can be contained.
In addition to the polymer B having the structural unit b, the resist layer composition according to the present disclosure may contain another polymer. In the present disclosure, the polymer B having the structural unit b and the other polymer are collectively referred to as “polymer component”.
In the specific polymer, the structural unit b having an acid-decomposable and protected acid group in the specific polymer undergoes a deprotection reaction to be an acid group by the action of a catalytic amount of an acidic substance generated by exposure. This acid group enables dissolution by development.
Hereinafter, preferred embodiments of the structural unit b will be described.

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

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

The resist layer composition is a polymer having a structural unit b1 represented by the following formula II as the structural unit b as a polymer component from the viewpoint of pattern formability, solubility in a developer, and transferability. The polymer component preferably includes a specific polymer having the structural unit b1 represented by the following formula II as the structural unit b and having a glass transition temperature of 90 ° C. or less. As a coalescence component, a specific polymer having a structural unit b1 represented by the following formula II as the structural unit b and a structural unit bb having an acid group described later and having a glass transition temperature of 90 ° C. or lower is included. More preferably.
The specific polymer contained in the resist layer composition may be one type or two or more types.

<< constituent unit b >>
The polymer component includes a polymer having at least a structural unit b having an acid group protected with an acid-decomposable group. By including the polymer having the structural unit b in the polymer component, an extremely sensitive chemically amplified positive resist layer composition can be obtained.
The “acid group protected with an acid-decomposable group” in the present disclosure can be any known acid-decomposable group, and is not particularly limited. Examples of the acid-decomposable group include groups that are relatively easily decomposed by an acid (for example, an acetal functional group such as an ester group, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group protected with a group represented by the formula II described later). Group) or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).
Among these, the acid-decomposable group is preferably a group having a structure protected in the form of an acetal.

  The structural unit b having an acid group protected with an acid-decomposable group is preferably a structural unit b1 represented by the following formula II from the viewpoint of sensitivity and resolution.

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

In Formula II, when R ¹ or R ² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ or R ² is an aryl group, a phenyl group is preferred. R ¹ and R ² are each 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.
Moreover, the alkyl group and aryl group in R < ¹ > -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 R ¹ or R ² and R ³ are preferably linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In Formula II, X represents a single bond or an arylene group, and a single bond is preferable. The arylene group may have a substituent.
When the specific polymer includes the structural unit b1 represented by the formula II, the sensitivity at the time of pattern formation is excellent and the resolution is superior.

In Formula II, R ⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the specific polymer can be further lowered.
More specifically, the structural unit in which R ⁴ in Formula II is a hydrogen atom is preferably 20% by mass or more with respect to the total amount of the structural unit b1 contained in the specific polymer.
In addition, the content (content ratio: mass ratio) of the structural unit in which R ⁴ in Formula II in the structural unit b1 is a hydrogen atom is calculated by a conventional method from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity.

  Among the structural unit b1 represented by the formula II, the structural unit represented by the following formula b2 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.

In formula b2, R ³⁴ represents a hydrogen atom or a methyl group, and R ^{35 to} R ⁴¹ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula b2, R ³⁴ is preferably a hydrogen atom.
In formula b2, R ^{35 to} R ⁴¹ are preferably hydrogen atoms.

Preferable specific examples of the structural unit b1 having an acid group protected with an acid-decomposable group represented by the formula II include the following structural units. R ³⁴ represents a hydrogen atom or a methyl group.

<< Structural Unit b3 >>
The structural unit b is preferably a structural unit b3 represented by the following formula b3 from the viewpoint of suppressing deformation of the pattern shape.

In Formula b3, R ^B1 and R ^B2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ^B1 and R ^B2 is an alkyl group or an aryl group, and R ^B3 is an alkyl group or Represents an aryl group, R ^B1 or R ^B2 and R ^B3 may be linked to form a cyclic ether, R ^B4 represents a hydrogen atom or a methyl group, and X ^B represents a single bond or a divalent linking group; , R ^B12 represents a substituent, and n represents an integer of 0 to 4.

In Formula b3, when R ^B1 or R ^B2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ^B1 or R ^B2 is an aryl group, a phenyl group is preferable. R ^B1 and R ^B2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In Formula b3, R ^B3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Moreover, the alkyl group and aryl group in R ^{B1 to} R ^B3 may have a substituent.
In Formula b3, R ^B1 or R ^B2 and R ^B3 may be linked to form a cyclic ether, and R ^B1 or R ^B2 and R ^B3 are preferably linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In formula b3, X ^B represents a single bond or a divalent linking group, and represents a single bond or an alkylene group, —C (═O) O—, —C (═O) NR ^N —, —O—, or a combination thereof. Are preferable, and a single bond is more preferable. The alkylene group may be linear, branched or cyclic, and may have a substituent. 1-10 are preferable and, as for carbon number of an alkylene group, 1-4 are more preferable. If X ^B -C where (= O) containing O- a, -C (= O) and carbon atoms contained in the ^O-, embodiments the carbon atom ^{to which R B4} is bonded is directly bonded is preferable. When ^{containing, -C (= O) NR N} - - is ^{X B -C (= O) NR} N and carbon atoms contained in ^a mode in which the carbon atom ^{to which R B4} is bonded is directly bonded is preferable. R ^N represents an alkyl group or a hydrogen atom, preferably an alkyl group or a hydrogen atom having 1 to 4 carbon atoms, more preferably a hydrogen atom.
In formula b3, the group containing R ^{B1 to} R ^B3 and X ^B are preferably bonded to each other at the para position.
In Formula b3, R ^B12 represents a substituent, and is preferably an alkyl group or a halogen atom. 1-10 are preferable and, as for carbon number of an alkyl group, 1-4 are more preferable.
In formula b3, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In formula b3, R ^B4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of lowering the Tg of the specific polymer.
More specifically, the structural unit in which R ^B4 in formula b3 is a hydrogen atom is preferably 20% by mass or more with respect to the total content of structural unit b contained in the specific polymer.
In addition, the content (content ratio: mass ratio) of the structural unit in which R ^B4 in formula b3 is a hydrogen atom in the structural unit b is calculated from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement by a conventional method. It can be confirmed by the intensity ratio of the peak intensity.

  Among the structural units represented by the formula b3, the structural unit represented by the following formula b4 is more preferable from the viewpoint of suppressing deformation of the pattern shape.

In Formula b4, R ^B4 represents a hydrogen atom or a methyl group, R ^{B5 to} R ^B11 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^B12 represents a substituent, and n is 0 Represents an integer of ~ 4.
In formula b4, R ^B4 is preferably a hydrogen atom.
In formula b4, R ^{B5 to} R ^B11 are preferably hydrogen atoms.
In Formula b4, R ^B12 represents a substituent, and is preferably an alkyl group or a halogen atom. 1-10 are preferable and, as for carbon number of an alkyl group, 1-4 are more preferable.
In formula b4, n represents an integer of 0 to 4, 0 or 1 is preferable, and 0 is more preferable.

Preferable specific examples of the structural unit b4 represented by the formula b4 include the following structural units. R ^B4 represents a hydrogen atom or a methyl group.

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

<< Structural Unit bb >>
The specific polymer preferably includes a structural unit bb having an acid group.
The structural unit bb is a structural unit including a protecting group, for example, an acid group that is not protected by an acid-decomposable group, that is, an acid group that does not have a protecting group. When the specific polymer contains the structural unit bb, the sensitivity at the time of pattern formation becomes good, and it becomes easy to dissolve in an alkaline developer in the development step after pattern exposure, and the development time can be shortened.

Introduction of a structural unit having an acid group into a specific polymer can be carried out by copolymerizing a monomer having an acid group.
The structural unit containing an acid group, which is the structural unit bb, is a structural unit derived from styrene or a structural unit derived from a vinyl compound by an acid group, or a structure derived from (meth) acrylic acid. More preferably it is a unit.

The structural unit bb 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, and 0.5% by mass to 15% by mass of the structural unit having an acid group (the structural unit bb) with respect to the total mass of the specific polymer. It is more preferable to include 1% by mass to 10% by mass. When it is in the above range, the pattern formability becomes better.
Content (content ratio: mass ratio) of the structural unit b in a specific polymer can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from ¹³ C-NMR measurement.

<< Other structural units >>
The specific polymer does not impair the effects of the photosensitive transfer material according to an embodiment of the present invention, except for the structural unit b and the structural unit bb described above, other structural units (hereinafter sometimes referred to as the structural unit bbb). It may be included in the range.
The monomer for forming the structural unit bbb is not particularly limited, and examples thereof include styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, and unsaturated dicarboxylic acid diesters. , Bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, groups having an aliphatic cyclic skeleton, other Mention may be made of saturated compounds.
Various characteristics of the specific polymer can be adjusted by adjusting at least one of the kind and the content using the structural unit bbb. In particular, the Tg of the specific polymer can be easily adjusted to 90 ° C. or less by appropriately using the structural unit bbb.
The specific polymer may contain only one type of structural unit bbb or may contain two or more types.

  The structural unit bbb is specifically styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meth) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) Mention may be made of structural units formed by polymerizing benzyl acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, or the like. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

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

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

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

It is also preferable that the specific polymer includes, as the structural unit bbb, a structural unit having an acid group ester in the structural unit bb from the viewpoint of optimizing the solubility in the developer and the physical properties of the resist layer described later. .
Among them, the specific polymer preferably includes a structural unit having an acid group as the structural unit bb, and further includes a structural unit bbb including a carboxylic acid ester group as a copolymerization component, for example, derived from (meth) acrylic acid. The polymer containing the structural unit bb and the structural unit derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate is more preferable.
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 and the weight average molecular weight in the following exemplary compounds are appropriately selected to obtain preferable physical properties.

<< Glass Transition Temperature of Polymer: Tg >>
The glass transition temperature (Tg) of the specific polymer in the present disclosure is preferably 90 ° C. or less. When Tg is 90 ° C. or lower, the resist layer formed from the resist layer composition has high adhesion and is excellent in transferability.
The Tg is more preferably 60 ° C. or less, and further preferably 40 ° C. or less.
Moreover, there is no restriction | limiting in particular in the lower limit of said Tg, However, -20 degreeC or more is preferable and -10 degreeC or more is more preferable. When the Tg of the specific polymer is −20 ° C. or higher, good pattern formability is maintained. For example, when a cover film is used, a decrease in peelability when the cover film is peeled is suppressed.
Furthermore, the glass transition temperature (Tg) of the entire polymer component in the present disclosure is preferably 90 ° C. or lower, more preferably 60 ° C. or lower, and 40 ° C. or lower from the viewpoint of transferability. Is more preferable.

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

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

<< Molecular weight of polymer: Mw >>
The molecular weight of the specific polymer is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. When the weight average molecular weight of the specific polymer is 60,000 or less, the melt viscosity of the resist layer in the photosensitive transfer material described later is kept low, and bonding at a low temperature (for example, 130 ° C. or less) is performed when bonding to the substrate. Can be realized.
Further, the weight average molecular weight of the specific polymer is preferably 2,000 to 60,000, more preferably 3,000 to 50,000, and further preferably 10,000 to 30,000. preferable.
The weight average molecular weight of the polymer can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device. The content of the device and the measuring technique are the same. Known to those skilled in the art.
For the measurement of the weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) was used as a measuring device, and TSKgel (registered trademark) Super HZM-M (4) was used as a column. .6 mm ID × 15 cm, manufactured by Tosoh Corp.), Super HZ4000 (4.6 mm ID × 15 cm, manufactured by Tosoh Corp.), Super HZ3000 (4.6 mm ID × 15 cm, manufactured by Tosoh Corp.), Super HZ2000 (4.6 mm ID) × 15 cm, manufactured by Tosoh Corporation), one each connected in series, and THF (tetrahydrofuran) can be used as an eluent.
Measurement conditions are 0.2% by mass, flow rate is 0.35 ml / min, sample injection amount is 10 μl, measurement temperature is 40 ° C., and a differential refractive index (RI) detector is used. be able to.
The calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It can be produced using any one of 7 samples of “A-2500” and “A-1000”.

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

<< Method for Producing Specific Polymer >>
The production method (synthesis method) of the specific polymer is not particularly limited. For example, a polymerizable monomer for forming the structural unit b1 represented by the formula II and a structural unit bb having an acid group are formed. It can synthesize | combine by superposing | polymerizing using a polymerization initiator in the solvent containing the polymerizable monomer for forming, and also the polymerizable monomer for forming other structural unit bbb as needed. . It can also be synthesized by a so-called polymer reaction.

  The resist layer composition according to the present disclosure preferably includes the specific polymer in a proportion of 50% by mass to 99.9% by mass with respect to the total solid content of the resist layer composition from the viewpoint of sensitivity and resolution. More preferably, it is contained at a ratio of 70 mass% to 98 mass%.

<< other polymers >>
The resist layer composition includes, as a polymer component, a polymer that does not include the structural unit b (in addition to the specific polymer, in a range that does not impair the effect of the resist layer composition according to the present disclosure (“other polymer”). May be included). When the resist layer composition contains another polymer, the blending amount of the other polymer is preferably 50% by mass or less and more preferably 30% by mass or less in the total polymer components. More preferably, it is 20 mass% or less.

In addition to the specific polymer, the resist layer composition may contain only one type of other polymer, or may contain two or more types.
As other polymers, for example, polyhydroxystyrene can be used, which are commercially available, such as SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer). , ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), and Joncryl 690, Joncryl 6 Joncryl 67, Joncryl 586 (manufactured by BASF) or the like can also be used.

<Polymerizable compound>
When the photosensitive transfer material in the present disclosure is a negative photosensitive transfer material, the resist layer composition preferably contains a polymerizable compound.
As the polymerizable compound, an ethylenically unsaturated compound is preferable.
The ethylenically unsaturated compound is a component that contributes to the photosensitivity (that is, photocurability) of the photosensitive transfer material and the strength of the cured film.
An ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups.

The resist layer composition preferably includes a bifunctional or higher functional ethylenically unsaturated compound as the ethylenically unsaturated compound.
Here, the bifunctional or higher functional ethylenically unsaturated compound means a compound having two or more ethylenically unsaturated groups in one molecule.
As the ethylenically unsaturated group, a (meth) acryloyl group is more preferable.
As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

There is no restriction | limiting in particular as a bifunctional ethylenically unsaturated compound, It can select suitably from well-known compounds.
Examples of the bifunctional ethylenically unsaturated compound include tricyclodecane dimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,6-hexane. Examples include diol di (meth) acrylate.
More specifically, as the bifunctional ethylenically unsaturated compound, tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Co., Ltd.).
As the bifunctional ethylenically unsaturated compound, a bifunctional ethylenically unsaturated compound having a bisphenol structure is also preferably used.
Examples of the bifunctional ethylenically unsaturated compound having a bisphenol structure include the compounds described in paragraphs 0072 to 0080 of JP-A-2006-224162.
Specific examples include alkylene oxide-modified bisphenol A di (meth) acrylate, and 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane, 2,2-bis (4- (methacryloxyethoxy). Propoxy) phenyl) propane and the like are preferred.

The trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth). Examples include acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compounds having a glycerin tri (meth) acrylate skeleton.

  Here, “(tri / tetra / penta / hexa) (meth) acrylate” is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. "(Tri / tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

  As an ethylenically unsaturated compound, a caprolactone-modified compound of (meth) acrylate compound (Nippon Kayaku Co., Ltd. KAYARAD (registered trademark) DPCA-20, Shin-Nakamura Chemical Co., Ltd. A-9300-1CL, etc.), Alkylene oxide modified compound of (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd. Etc.), ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

Examples of the ethylenically unsaturated compound include urethane (meth) acrylate compounds (preferably trifunctional or higher functional urethane (meth) acrylate compounds).
Examples of the tri- or more functional urethane (meth) acrylate compound include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (Shin-Nakamura Chemical Industry ( Etc.).

Moreover, it is preferable that an ethylenically unsaturated compound contains the ethylenically unsaturated compound which has an acid group from a viewpoint of developability improvement.
Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxy group, and a carboxy group is preferable.
Examples of the ethylenically unsaturated compound having an acid group include, for example, a 3 to 4 functional ethylenically unsaturated compound having an acid group (one having a carboxy group introduced into a pentaerythritol tri and tetraacrylate (PETA) skeleton (acid value = 80 mg KOH / g to 120 mg KOH / g), 5 to 6 functional ethylenically unsaturated compounds having an acid group (dipentaerythritol penta and hexaacrylate (DPHA) skeleton with a carboxy group introduced therein (acid value = 25 mg KOH / g) ˜70 mg KOH / g)), and the like.
These trifunctional or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.

The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group and a carboxylic acid anhydride thereof.
The bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group is not particularly limited and can be appropriately selected from known compounds.
Examples of the bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), or Aronix M-510 (manufactured by Toagosei Co., Ltd.) can be preferably used.

  The ethylenically unsaturated compound having an acid group is also preferably a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942. The contents of this publication are incorporated into this disclosure.

The weight average molecular weight (Mw) of the polymerizable compound used in the present disclosure is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and 300 to 2,200. Particularly preferred.
Moreover, the ratio of the content of the polymerizable compound having a molecular weight of 300 or less among the polymerizable compounds used in the resist layer composition is based on all the ethylenically unsaturated compounds contained in the resist layer composition. 30 mass% or less is preferable, 25 mass% or less is more preferable, and 20 mass% or less is still more preferable.

A polymeric compound may be used individually by 1 type, or may use 2 or more types together.
The content of the polymerizable compound in the resist layer composition is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 70% by mass, and more preferably 20% by mass to the total mass of the resist layer composition. 60 mass% is still more preferable, and 20 mass%-50 mass% is especially preferable.

When the resist layer composition contains a bifunctional ethylenically unsaturated compound and a trifunctional or higher functional ethylenically unsaturated compound, the content of the bifunctional ethylenically unsaturated compound is determined by the resist layer composition. 10% by mass to 90% by mass is preferable, 20% by mass to 85% by mass is more preferable, and 30% by mass to 80% by mass is still more preferable with respect to all the ethylenically unsaturated compounds contained in.
In this case, the content of the trifunctional or higher functional ethylenically unsaturated compound is preferably 10% by mass to 90% by mass, and preferably 15% by mass with respect to all the ethylenically unsaturated compounds contained in the resist layer composition. -80 mass% is more preferable, and 20 mass% -70 mass% is still more preferable.
In this case, the content of the bifunctional or higher ethylenically unsaturated compound is 40% by mass or more and 100% with respect to the total content of the bifunctional ethylenically unsaturated compound and the trifunctional or higher ethylenically unsaturated compound. It is preferably less than mass%, more preferably 40 mass% to 90 mass%, further preferably 50 mass% to 80 mass%, and particularly preferably 50 mass% to 70 mass%. .

When the resist layer composition contains a bifunctional or higher functional ethylenically unsaturated compound, the resist layer composition may further contain a monofunctional ethylenically unsaturated compound.
Further, when the resist layer composition contains a bifunctional or higher functional ethylenically unsaturated compound, the bifunctional or higher functional ethylenically unsaturated compound is a main component in the ethylenically unsaturated compound contained in the resist layer composition. It is preferable that
Specifically, when the resist layer composition contains a bifunctional or higher functional ethylenically unsaturated compound, the content of the bifunctional or higher functional ethylenically unsaturated compound is the ethylene contained in the resist layer composition. 60 mass%-100 mass% are preferable with respect to the total content of an unsaturated compound, 80 mass%-100 mass% are more preferable, 90 mass%-100 mass% are especially preferable.

  When the resist layer composition contains an ethylenically unsaturated compound having an acid group (preferably a bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group or a carboxylic acid anhydride thereof), an acid group The content of the ethylenically unsaturated compound having 1 is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 20% by mass, and still more preferably 1% by mass to 10% by mass with respect to the resist layer composition. preferable.

<Binder polymer having acid group>
When the photosensitive transfer material in the present disclosure is a negative photosensitive transfer material, the resist layer composition preferably contains a binder polymer having an acid group.
As the binder polymer having an acid group, an alkali-soluble resin is preferable.
Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.
Of these, a carboxy group is preferred as the acid group.
The acid value of the binder polymer having an acid group is not particularly limited, but from the viewpoint of alkali developability, an acid-soluble resin having an acid value of 60 mgKOH / g or more is preferable, and a carboxy group having an acid value of 60 mgKOH / g or more. It is especially preferable that it is a containing acrylic resin.

The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more (hereinafter sometimes referred to as the specific polymer A) is not particularly limited as long as the above acid value is satisfied, and is appropriately selected from known resins. Can be used.
For example, among the polymers described in paragraph 0025 of JP2011-95716A, an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, paragraphs 0033 to 0052 of JP2010-237589A Carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in 1), Carboxy group having an acid value of 60 mgKOH / g or more among the binder polymers described in paragraphs 0053 to 0068 of JP-A-2006-224162 A containing acrylic resin or the like can be preferably used as the specific polymer A in the present disclosure.
Here, the (meth) acrylic resin refers to a resin including at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid ester.
30 mol% or more is preferable and, as for the total ratio of the structural unit derived from the (meth) acrylic acid in the (meth) acrylic resin and the structural unit derived from the (meth) acrylic acid ester, 50 mol% or more is more preferable.

A preferable range of the copolymerization ratio of the monomer having a carboxy group in the specific polymer A is 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and more preferably 100% by mass of the polymer. Preferably it exists in the range of 12 mass%-30 mass%.
The specific polymer A may have a reactive group, and means for introducing the reactive group into the specific polymer A include a hydroxyl group, a carboxy group, a primary, secondary amino group, an acetoacetyl group, and a sulfonic acid. Examples include a method of reacting an epoxy compound, a blocked isocyanate, an isocyanate, a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxylic anhydride, and the like.
As the specific polymer A, the following compound A is preferable. In addition, the content ratio of each structural unit shown below can be suitably changed according to the purpose.

The acid value of the binder polymer having an acid group used in the present disclosure is preferably 60 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 150 mgKOH / g, from the viewpoint of alkali developability. More preferably, it is 60 mgKOH / g-110 mgKOH / g.
In the present disclosure, the acid value means a value measured according to the method described in JIS K0070 (1992).

  The weight average molecular weight of the binder polymer having an acid group is preferably 1,000 or more, more preferably 10,000 or more, and still more preferably 20,000 to 100,000.

  In addition to the specific polymer A, the binder polymer having an acid group can be used by appropriately selecting any film-forming resin depending on the purpose. For example, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin and the like can be preferably exemplified.

The binder polymer having an acid group may be used alone or in combination of two or more.
The content of the binder polymer having an acid group in the resist layer composition is preferably 10% by mass or more and 90% by mass or less, and 20% by mass with respect to the total mass of the resist layer composition, from the viewpoint of photosensitivity. % To 80% by mass, more preferably 30% to 70% by mass.

<Photopolymerization initiator>
When the photosensitive transfer material in the present disclosure is a negative photosensitive transfer material, the resist layer composition preferably includes a photopolymerization initiator. The photopolymerization initiator receives actinic rays such as ultraviolet rays and visible rays, and initiates polymerization of the polymerizable compound (ethylenically unsaturated compound).
There is no restriction | limiting in particular as a photoinitiator, A well-known photoinitiator can be used.
Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as “oxime photopolymerization initiator”) and a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter referred to as “α- Also referred to as “aminoalkylphenone photopolymerization initiator”), photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as “α-hydroxyalkylphenone polymerization initiator”), acylphosphine oxide structure. Photopolymerization initiator (hereinafter, also referred to as “acylphosphine oxide photopolymerization initiator”), photopolymerization initiator having an N-phenylglycine structure (hereinafter referred to as “N-phenylglycine photopolymerization initiator”). Or the like)).

  The photopolymerization initiator is at least selected from the group consisting of an oxime photopolymerization initiator, an α-aminoalkylphenone photopolymerization initiator, an α-hydroxyalkylphenone photopolymerization initiator, and an N-phenylglycine photopolymerization initiator. 1 type is preferably included, and more preferably at least one selected from the group consisting of an oxime photopolymerization initiator, an α-aminoalkylphenone photopolymerization initiator, and an N-phenylglycine photopolymerization initiator. .

  Moreover, as a photoinitiator, it is also preferable to contain at least 1 sort (s) selected from the group which consists of a 2,4,5-triaryl imidazole dimer and its derivative (s). The 2,4,5-triarylimidazole dimer and its derivative may be a compound represented by the following formula PI.

In the formula PI, it is preferable that at least one of X ¹ and X ² is a chlorine atom. When Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have a substituent, the number of substituents is preferably 1 to 5, more preferably 1 to 3, and more preferably 1. Is more preferable. Moreover, when Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently have a substituent, the substitution position is not particularly limited, and is preferably the ortho position or the para position. p and q are each independently an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1.

  Examples of the compound represented by the formula PI include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer. , 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4 , 5-diphenylimidazole dimer. In addition, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same and give the target compound, or differently give an asymmetric compound.

  Moreover, as a photoinitiator, you may use the polymerization initiator described in Paragraphs 0031-0042 of Unexamined-Japanese-Patent No. 2011-95716, Paragraphs 0064-0081 of Unexamined-Japanese-Patent No. 2015-014783, for example.

  Commercially available photopolymerization initiators include 1- [4- (phenylthio)]-1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, BASF Corporation 1)-[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF) 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF), 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE 907, manufactured by BASF), 2-H Roxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one (trade name: IRGACURE 127, manufactured by BASF), 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: IRGACURE 369, manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: IRGACURE 1173) , Manufactured by BASF), 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE 651, manufactured by BASF) ), An oxime ester photopolymerization initiator (trade name: Lunar 6, D KSH Japan Co., Ltd.), 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole (2- (2-chlorophenyl) -4,5-diphenylimidazole (Product name: B-CIM, manufactured by Hampford) and the like.

A photoinitiator may be used individually by 1 type, or may use 2 or more types together.
Although there is no restriction | limiting in particular in content of the photoinitiator in the said resist layer composition, 0.1 mass% or more is preferable with respect to the total mass of the said resist layer composition, and 0.5 mass% or more is more preferable. 1.0 mass% or more is still more preferable.
Moreover, 10 mass% or less is preferable with respect to the total mass of a resist layer composition, and, as for content of a photoinitiator, 5 mass% or less is more preferable.

-Polymerization inhibitor-
When the photosensitive transfer material according to the present disclosure is a negative photosensitive transfer material, the resist layer composition may contain at least one polymerization inhibitor.
As the polymerization inhibitor, for example, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 can be used.
Among these, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.

  When the said resist layer composition contains a polymerization inhibitor, 0.01 mass%-3 mass% are preferable with respect to the total mass of the said resist layer composition, and content of a polymerization inhibitor is 0.01 mass. % To 1% by mass is more preferable, and 0.01% to 0.8% by mass is even more preferable.

<Photoacid generator [component (C)]>
The resist layer composition according to the present disclosure preferably contains a photoacid generator.
The photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiation with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
The photoacid generator used in the present disclosure is preferably a compound that generates an acid in response to an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but its chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be used as a sensitizer as long as it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
The 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. It is particularly preferred that The lower limit value of the pKa of the acid generated from the photoacid generator is not particularly defined, but is preferably, for example, -10.0 or more, and more preferably -4.0 or more from the viewpoint of sensitivity and visibility. Preferably, -3.5 or more is more preferable, and -3.0 or more is particularly preferable.

  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 more preferably sulfonic acid. Preferably, it is a sulfonic acid represented by the following formula C1 or C2.

In formula C1 and formula C2, 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, n is 1, each X ^S independently represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and ms represents an integer of 0 to 5.

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 number of carbon atoms of the alkyl group in ^RS is preferably 1-20, and more preferably 2-16.
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 each independently is preferably an alkyl group, more preferably an alkyl group having 1 to 20 carbon atoms, still more preferably an alkyl group having 1 to 8 carbon atoms, and a methyl group. Is particularly preferred.
ms is preferably an integer of 0 to 3, more preferably 0 or 1, and particularly preferably 1.

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

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

  As the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure, a compound having an oxime sulfonate structure represented by the following formula C3 is preferable.

In Formula C3, R ²¹ represents an alkyl group or an aryl group, and * represents a bonding site with another atom or another group.

In the compound having an oxime sulfonate structure represented by the formula C3, any group may be substituted, and the alkyl group in R ²¹ may be linear or branched, or may have a ring structure. You may have. Acceptable substituents are described below.
The alkyl group for R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group). , Preferably a bicycloalkyl group or the like) or a halogen atom.
As the aryl group for R ^21, an aryl group having 6 to 18 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a halogen atom.

The compound having an oxime sulfonate structure represented by Formula C3 is also preferably an oxime sulfonate compound described in paragraphs 0078 to 0111 of JP-A-2014-85643.
And compounds described in paragraphs 0080 to 0081 of JP-A No. 2015-151347.

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

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

A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
The content of the photoacid generator in the resist layer composition is preferably 0.1% by mass to 15% by mass with respect to the total solid content of the resist layer composition from the viewpoint of sensitivity and resolution. More preferably, it is 0.5 mass%-10 mass%.

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

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

The said basic compound may be used individually by 1 type, or may use 2 or more types together.
The content of the basic compound is preferably 0.001% by mass to 5% by mass and more preferably 0.005% by mass to 3% by mass with respect to the total solid content of the resist layer composition. preferable.

<Solvent>
The resist layer composition according to the present disclosure preferably further contains a solvent (S).
Moreover, in order to easily form a resist layer, which will be described later, the resist layer composition once contains a solvent to adjust the viscosity of the resist layer composition, and then apply and dry the resist layer composition containing the solvent, A resist layer can be suitably formed.
As the solvent used in the present disclosure, a known solvent can be used. Solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers , Diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones, ethyl acetate, acetic acid Propyl, isopropyl acetate, isobutyl acetate, butyl acetate, tert-butyl acetate Le, cyclopentyl methyl ether, diisopropyl ether, propylene glycol monoethyl ether, methyl n- butyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl n- propyl ketone, methyl isopropyl ketone or toluene and the like. Specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A, the contents of which are incorporated in the present disclosure.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, -Solvents such as nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, or propylene carbonate can also be added.
Only 1 type may be used for a solvent and 2 or more types may be used for it.
The solvent which can be used for this indication may be used individually by 1 type, and it is more preferable to use 2 types together. When two or more solvents are used, for example, combined use of propylene glycol monoalkyl ether acetates and dialkyl ethers, combined use of diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates A combination with the above is preferred.

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

The content of the solvent in applying the resist layer composition is preferably 50 parts by weight to 1,900 parts by weight, and 100 parts by weight to 900 parts by weight per 100 parts by weight of the total solid content in the resist layer composition. More preferably, it is a part.
In addition, the content of the solvent in the resist layer described later is preferably 2% by mass or less, more preferably 1% by mass or less, and 0.5% by mass or less with respect to the total mass of the resist layer. More preferably it is.

<Other additives>
The resist layer composition according to the present disclosure may contain known additives as necessary in addition to the above-described components such as the specific polymer and the photoacid generator.

-Plasticizer-
The resist layer composition according to the present disclosure may contain a plasticizer for the purpose of improving plasticity.
The plasticizer preferably has a weight average molecular weight smaller than that of the specific polymer.
The weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and still more preferably 800 or more and less than 4,000 from the viewpoint of imparting plasticity.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the specific polymer and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

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

  For example, a chemically amplified positive resist layer obtained by mixing compound X, a specific polymer and a photoacid generator, even if it is a compound having an alkyleneoxy group having the above structure (referred to as “compound X”). When the composition does not improve the plasticity as compared with the chemically amplified positive resist layer composition formed without containing the compound X, it does not fall under the plasticizer in the present disclosure. For example, an optional surfactant is not used as a plasticizer in the present disclosure because it is generally not used in an amount that provides plasticity to the resist layer composition.

The content of the plasticizer is preferably 1% by mass to 50% by mass with respect to the total solid content of the resist layer composition from the viewpoint of adhesion of the resist layer formed by the resist layer composition. It is more preferable that it is 2 mass%-20 mass%.
The said resist layer composition may contain only 1 type of plasticizers, and may contain 2 or more types.

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

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

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

  The content of the sensitizer is preferably 0% by mass to 10% by mass, and more preferably 0.1% by mass to 10% by mass, based on the total solid content of the resist layer composition. .

-Heterocyclic compound-
The resist layer composition according to the present disclosure may include a heterocyclic compound.
There is no restriction | limiting in particular in the heterocyclic compound in this indication. For example, compounds having an epoxy group or oxetanyl group in the molecule described below, alkoxymethyl group-containing heterocyclic compounds, other oxygen-containing monomers such as various cyclic ethers and cyclic esters (lactones), nitrogen-containing monomers such as cyclic amines and oxazolines Furthermore, 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 resist layer composition is preferably 0.01% by mass to 50% by mass with respect to the total solid content of the resist layer composition. The content is more preferably 0.1% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. It is preferable in the said range from a viewpoint of adhesiveness and etching tolerance. Only 1 type may be used for a heterocyclic compound and it can also use 2 or more types together.

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

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

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

  Specific examples of the compound having an oxetanyl group in the molecule include Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei) 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 resist layer composition according to the present disclosure, the heterocyclic compound is preferably a compound having an epoxy group from the viewpoint of etching resistance and line width stability of the resulting pattern.

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

-Surfactant-
The resist layer 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-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (manufactured by Toray Dow Corning Co., Ltd.).
Moreover, the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography when tetrahydrofuran (THF) is used as a surfactant contains the structural unit A and the structural unit B represented by the following formula I-1. A preferred example is a copolymer having (Mw) of 1,000 or more and 10,000 or less.

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

L is preferably a branched alkylene group represented by the following formula (I-2). R ⁴⁰⁵ in formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred. The sum 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 paragraphs 0060 to 0071 of JP 2009-237362 A can also be used.

Surfactant may be used individually by 1 type and may use 2 or more types together.
The addition amount of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass with respect to the total solid content of the resist layer composition, It is still more preferable that it is 3 mass%-3 mass%.

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

Moreover, the said resist layer can contain preferably each component in the said resist layer composition other than the said solvent.
Furthermore, in the resist layer, the preferable content of each component with respect to the total mass of the resist layer is the same as the preferable content of each component with respect to the total solid content of the resist layer composition in the resist layer composition.

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

-Formation method of resist layer-
It is possible to prepare a resist layer composition for forming a resist layer by mixing each component and a solvent in a predetermined ratio and by an arbitrary method, and dissolving by stirring. For example, it is possible to prepare a composition by preparing each solution of each component in advance in a solvent and then mixing the obtained solution at a predetermined ratio. The composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

  The photosensitive transfer material according to the present disclosure having the intermediate layer and the resist layer on the temporary support can be obtained by applying the resist layer composition onto the temporary support on which the intermediate layer is formed 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, and inkjet coating.

[Temporary support]
The photosensitive transfer material according to the present disclosure has a temporary support.
The temporary support is a support that supports the intermediate layer and the resist layer and can be peeled off.
In the case where the intermediate layer and the resist layer are subjected to pattern exposure, the temporary support used in the present disclosure preferably has light transmittance from the viewpoint that the intermediate layer and the resist layer can be exposed through the temporary support.
Having light transmittance means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is a viewpoint of improving exposure sensitivity. Therefore, 60% or more is preferable, and 70% or more is more preferable. Examples of the method for measuring the transmittance include a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoints of strength and flexibility. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of a temporary support body is not specifically limited, The range of 5 micrometers-200 micrometers is preferable, and the range of 10 micrometers-150 micrometers is more preferable at points, such as ease of handling and versatility.
The thickness of the temporary support is selected according to the material from the viewpoints of strength as a support, flexibility required for bonding to a circuit wiring forming substrate, light transmittance required in the first exposure process, etc. do it.

  Preferred embodiments of the temporary support are described, for example, in paragraphs 0017 to 0018 of JP-A-2014-85643, and the contents of this publication are incorporated in the present disclosure.

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

The photosensitive transfer material according to the present disclosure has an intermediate layer and a resist layer in this order on a temporary support.
Here, with reference to FIG.1 and FIG.2, an example of the layer structure of the photosensitive transfer material which concerns on this indication is shown roughly.
In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 12, a laminate 14 (see FIG. 2) of a resist layer 14-1 and an intermediate layer 14-2, and a cover film 16 are laminated in this order. . The intermediate layer 14-2 contains a pigment.
Hereinafter, constituent materials and the like of the photosensitive transfer material according to the present disclosure will be described. Note that the above configuration in the present disclosure may be referred to as follows in the present disclosure.
A polymer having a structural unit having an acid group protected with an acid-decomposable group may be referred to as a “specific polymer”.
When the resist layer is a positive resist layer, it may be referred to as a “positive resist layer”. When the resist layer is a negative resist layer, it may be referred to as a “negative resist layer”.

(Method for manufacturing circuit wiring)
A first embodiment of a circuit wiring manufacturing method using the photosensitive transfer material according to the present disclosure will be described.
The first embodiment of the circuit wiring manufacturing method is as follows:
A step of bonding the resist layer of the photosensitive transfer material according to the present disclosure to the substrate in contact with the substrate (bonding step);
A step of exposing the intermediate layer and the resist layer of the photosensitive transfer material after the bonding step (exposure step);
The resist layer after the pattern exposure process is developed to form a pattern (development process), and the process of etching the substrate in the region where the pattern is not disposed (etching process) is included in this order.
The substrate in the first embodiment of the circuit wiring manufacturing method may be a substrate in which a layer such as a desired conductive layer is provided on a base material such as glass, silicon, or a film.
According to the first embodiment of the circuit wiring manufacturing method, a fine pattern can be formed on the substrate surface.

The second embodiment of the circuit wiring manufacturing method is
And a plurality of conductive layers including a first conductive layer and a second conductive layer having different constituent materials from each other, and on the surface of the base material, in the order farthest from the surface of the base material, Bonding the resist layer of the photosensitive transfer material according to the present disclosure in contact with the first conductive layer to a substrate on which the first conductive layer and the second conductive layer which are layers are laminated Process,
A first exposure step of pattern exposing the intermediate layer and the resist layer through the temporary support of the photosensitive transfer material after the bonding step;
A first development step of developing the intermediate layer and the resist layer after the first exposure step to form a first pattern after peeling the temporary support from the intermediate layer and the resist 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 pattern exposing the first pattern after the first etching step with a pattern different from the first pattern;
A second development step of developing the first pattern after the second exposure step to form a second pattern;
A second etching step of etching at least the first conductive layer among the plurality of conductive layers in the region where the second pattern is not disposed. As the second embodiment, International Publication No. 2006/190405 can be referred to, and the contents thereof are incorporated in the present disclosure.

The third embodiment of the circuit wiring manufacturing method is a mode in which the first embodiment is repeated twice.
That is, a step of bonding the resist layer of the photosensitive transfer material according to the present disclosure to the substrate in contact with the substrate (bonding step);
A step of exposing the intermediate layer and the resist layer of the photosensitive transfer material after the bonding step (exposure step);
Developing the resist layer after the pattern exposing step to form a pattern (developing step);
A step of etching the substrate in the region where the pattern is not disposed (etching step);
In this order, the resist layer of the photosensitive transfer material according to the present disclosure is bonded to the remaining resist layer after the etching step in contact with the remaining resist layer (bonding). Combining step) and
A step of exposing the intermediate layer and the resist layer of the photosensitive transfer material after the bonding step (exposure step);
Developing the resist layer after the pattern exposing step to form a pattern (developing step);
A step of etching the substrate in the region where the pattern is not disposed (etching step);
Are included in this order.
The first and second photosensitive transfer materials may be the same or different. The photosensitive transfer material used in the first bonding step is preferably a positive type, and the photosensitive transfer material used in the second bonding step may be a positive type or a negative type. Also good.

Specifically, the third embodiment of the circuit wiring manufacturing method can be implemented by, for example, the following method.
An ITO film is formed on the base material by sputtering, and copper is formed thereon by a vacuum vapor deposition method to form a conductive pattern forming substrate.
Next, a photosensitive transfer material is bonded onto the copper layer to form a laminate. The laminated body is subjected to pattern exposure using a photomask provided with a pattern A having a configuration in which conductive layer pads are connected in one direction without peeling off the temporary support. Thereafter, the temporary support is peeled off, developed and washed with water to obtain a resin pattern drawn with pattern A. Next, after the copper layer is etched using a copper etchant, the ITO layer is etched using an ITO etchant to obtain a substrate on which both copper and ITO are drawn in the pattern A.
Next, a photosensitive transfer material is bonded onto the remaining resist layer. In this state, pattern exposure is performed using a photomask provided with openings of pattern B in the aligned state, and the temporary support of the photosensitive transfer material is peeled off, followed by development and washing with water. Thereafter, the copper wiring is etched, and the remaining resist layer is stripped using a stripping solution to obtain a circuit wiring board having a conductive pattern.

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

<Lamination process>
An example of the bonding process is schematically shown in FIG.
First, in the bonding step, the substrate 22 has a plurality of conductive layers including the first conductive layer 24 and the second conductive layer 26 having different constituent materials, and the substrate 22 is formed on the surface of the substrate 22. The photosensitive transfer material according to the present disclosure described above is applied to the substrate (circuit wiring forming substrate) 20 in which the first conductive layer 24 and the second conductive layer 26 which are the outermost surface layers are laminated in order from the surface of the substrate. 100 resist layers 14-1 (see FIG. 1) are brought into contact with the first conductive layer 24 and bonded together. Such a bonding of the circuit wiring forming substrate and the photosensitive transfer material may be referred to as “transfer” or “laminate”.

When the cover film 16 is provided on the positive resist layer 14 of the photosensitive transfer material 100 as shown in FIGS. 1 to 2, the cover film 16 is removed from the photosensitive transfer material 100 (positive resist layer 14). Thereafter, the resist layer 14-1 of the photosensitive transfer material 100 is brought into contact with the first conductive layer 24 and bonded thereto.
The bonding (transfer) of the photosensitive transfer material onto the first conductive layer is performed by stacking the resist layer side of the photosensitive transfer material on the first conductive layer, and applying pressure and heating with a roll or the like. Is preferred. For laminating, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
When the base material of the circuit wiring forming substrate is a resin film, roll-to-roll bonding can also be performed.

〔Base material〕
As for the board | substrate with which the some electroconductive layer was laminated | stacked on the base material, it is preferable that a base material is a glass base material or a film base material, and it is more preferable that it is a film base material. When the circuit wiring manufacturing method according to the present disclosure is a circuit wiring for a touch panel, the substrate is particularly preferably a sheet-shaped resin composition.
Moreover, it is preferable that a base material is transparent. The term “transparent” means that the transmittance in the visible light region of 400 nm to 800 nm is 90% or more.
The refractive index of the substrate is preferably 1.50 to 1.52.
The base material may be composed of a light-transmitting base material such as a glass base material, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. Moreover, as the above-mentioned transparent substrate, the materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
When a film substrate is used as the substrate, it is more preferable to use a substrate that is not optically distorted and a substrate having high transparency. Specific examples of the material include polyethylene terephthalate (PET), Examples thereof include polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

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

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

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

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

  As examples of the exposure step, the development step, and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present disclosure.

For example, a mask 30 having a predetermined pattern is disposed above the photosensitive transfer material 100 disposed on the first conductive layer 24 (on the side opposite to the side in contact with the first conductive layer 24), and then For example, a method of exposing with ultraviolet rays from above the mask through the mask 30 may be used.
In the present disclosure, the detailed arrangement and specific size of the pattern are not particularly limited. Since it is desired to improve the display quality of a display device (for example, a touch panel) including an input device having a circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure and to make the area occupied by the extraction wiring as small as possible, At least a part (particularly, the electrode pattern of the touch panel and the part of the extraction wiring) is preferably a fine wire of 100 μm or less, and more preferably 70 μm or less.
Here, the light source used for exposure can be appropriately selected and used as long as it can irradiate light (for example, 365 nm, 405 nm, etc.) in a wavelength region where the exposed portion of the photosensitive transfer material can be dissolved in the developer. . Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned.
Energy of exposure preferably ² ~200mJ / cm 2 of about ^{5 mJ} / cm, more preferably 10mJ ^/ cm ² ~100mJ ^/ cm 2 approximately.
It is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. By a process called PEB (Post Exposure Bake), pattern edge roughness due to standing waves generated in the resist layer during exposure can be reduced.

  The pattern exposure may be performed after the temporary support is peeled off from the intermediate layer and the resist layer, or before the temporary support is peeled off, it is exposed through the temporary support, and then the temporary support is removed. It may be peeled off. In order to prevent mask contamination due to contact between the intermediate layer and the mask, and to avoid the influence on the exposure caused by foreign matters attached to the mask, it is preferable to expose the temporary support without peeling off. The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.

<Development process (first development process)>
In the first embodiment, the developing step is performed, and in the second embodiment, the first developing step is performed. An example of the development process (first development process) is schematically shown in FIG.
In the development process (first development process), the temporary support 12 is peeled from the positive resist layer 14 after the exposure process (first exposure process), and then the positive resist layer 14 after the exposure process (first exposure process). Is developed to form the first pattern 14A.

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

  The development method is not particularly limited, and any of paddle development, shower development, shower and spin development, dip development, and the like may be used. Here, the shower development will be described. The exposed portion can be removed by spraying a developer onto the positive resist layer after exposure. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The liquid temperature of the developer is preferably 20 ° C to 40 ° C.

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

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

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

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

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

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

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

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

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

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

<Second etching process>
In the second embodiment, the second exposure process 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 among the plurality of conductive layers in the region where the second pattern 14B is not disposed is etched.

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

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

Although there is no restriction | limiting in particular as a method of removing the remaining positive type resist layer, The method of removing by chemical treatment can be mentioned.
As a method for removing the positive resist layer, for example, a substrate having a positive resist layer or the like in a stripping solution being stirred at preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 1 minute to 30 minutes. The method of immersing for a minute is mentioned.

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

  The method for 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.

<Process for attaching protective film>
The second embodiment may further include a step of attaching a light-transmitting protective film (not shown) on the first pattern after the first etching step and before the second exposure step. Good.
In this case, it is preferable that in the second exposure step, the first pattern is subjected to pattern exposure via the protective film, and after the second exposure step, the protective film is peeled off from the first pattern, and then the second development step is performed.

<Step of reducing visible light reflectance>
The manufacturing method of the circuit wiring which concerns on this indication can include the process of reducing the visible light reflectance of some or all of the some conductive layers on a base material.
Examples of the treatment for reducing the visible light reflectance include an oxidation treatment. For example, visible light reflectance can be reduced by oxidizing copper to copper oxide and blackening.
Regarding preferred embodiments of the processing for reducing the visible light reflectance, paragraphs 0017 to 0025 of JP2014-150118A, and paragraphs 0041, 0042, 0048 and 0058 of JP2013-206315A are described. The content of this publication is incorporated into the present disclosure.

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

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

  Moreover, although not shown in FIG. 2, the manufacturing method of the circuit wiring which concerns on this indication WHEREIN: The base material has a some conductive layer in both surfaces, respectively, and the conductive layer formed in both surfaces of the base material It is also preferable to form circuits sequentially or simultaneously. With such a configuration, it is possible to form a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface. Moreover, it is also preferable to form the circuit wiring for touch panels of such a structure from both surfaces of a base material by roll-to-roll.

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

(Input device and display device)
An input device is mentioned as an apparatus provided with the circuit wiring manufactured by the manufacturing method of the circuit wiring concerning this indication.
The input device in the present disclosure is preferably a capacitive touch panel.
The display device according to the present disclosure preferably includes the input device according to the present disclosure.
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, touch panel display device and manufacturing method thereof)
The touch panel according to the present disclosure is a touch panel having at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure. In addition, the touch panel according to the present disclosure preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
The touch panel display device according to the present disclosure is a touch panel display device having at least circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure, and is preferably a touch panel display device including the touch panel according to the present disclosure.
The method for manufacturing a touch panel or a touch panel display device according to the present disclosure preferably includes a method for manufacturing a circuit wiring according to the present disclosure.
The manufacturing method of the touch panel or the touch panel display device according to the present disclosure includes a step of bringing the resist layer of the photosensitive transfer material obtained by the method of manufacturing the photosensitive transfer material into contact with the substrate and bonding, and after the bonding step Pattern exposing the resist layer of the photosensitive transfer material, developing the resist layer after the pattern exposing step, forming a pattern, and etching the substrate in a region where the pattern is not disposed It is preferable that the process to include is included in this order. The details of each process are synonymous with the details of each process in the above-described circuit wiring manufacturing method, and the preferred embodiments are also the same.
As a detection method in the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among these, the electrostatic capacity method is preferable.
As the touch panel type, a so-called in-cell type (for example, those described in FIGS. 5, 6, 7, and 8 of JP-T-2012-517051), a so-called on-cell type (for example, JP 2013-168125 A). 19 of the publication, those described in FIGS. 1 and 5 of JP2012-89102A, OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP No. 2013-54727 shown in FIG. 2), other configurations (for example, those shown in FIG. 6 of JP 2013-164471A), various out-cell types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.).
As the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, “latest touch panel technology” (July 6, 2009, issued by Techno Times Co., Ltd.), supervised by Yuji Mitani, “Touch Panel Technology and Development”, The configurations disclosed in CM Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. can be applied.

  The embodiment of the present disclosure will be described more specifically with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the embodiment of the present disclosure. Therefore, the scope of the embodiment of the present disclosure is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass. The “maximum absorption wavelength” in this example is a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development.

The abbreviation regarding the component used in the Example represents the following compounds, respectively.
-Intermediate layer-
[Polymer (Binder polymer for intermediate layer)]
Polymer B-11: Nissan HPC-SSL (Hydroxypropylcellulose Nippon Soda Co., Ltd.)
Polymer B-12: Metroz 60SH-03 (hydroxypropylmethylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd.)
[Dye]
A-1: Bromophenol blue (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., maximum absorption wavelength: 606 nm, water-soluble)
A-2: Bromocresol Green (Fuji Film Wako Pure Chemical Industries, Ltd., maximum absorption wavelength: 626 nm, water-soluble)
A-3: VPB-NAPS (Victoria Pure Blue naphthalene sulfonate) (manufactured by Hodogaya Chemical Co., Ltd., maximum absorption wavelength: 616 nm, water-soluble)

-Confirmation of pH sensitivity of pigments-
The pH sensitivity of coloring of the dye in an aqueous solution was confirmed by the following method.
0.1 g of the dye was dissolved in 100 mL of a mixed solution of ethanol and water (ethanol / water = 1/2 [mass ratio]), and 0.1 mol / l (1N) aqueous hydrochloric acid was added to adjust to pH = 1. Titration was carried out with a 0.01 mol / l (0.01 N) aqueous solution of sodium hydroxide to confirm the color change and the pH when the color change. The results are shown below.
The pH was measured at 25 ° C. using a pH meter (model number: HM-31, manufactured by Toa DKK).
A-1: Color development (that is, maximum absorption wavelength) changed at pH 4.0 or higher.
A-2: Color development (that is, maximum absorption wavelength) changed at pH 5.4 or higher.
A-3: Even when the pH was changed at pH 1 to 14, the color development (that is, the maximum absorption wavelength) did not change.

[PH adjuster]
G-1: 0.1N sodium hydroxide aqueous solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
G-2: 0.1N potassium hydroxide aqueous solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
G-3: 0.1N lithium hydroxide aqueous solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
G-4: Tetrabutylammonium hydroxide (40% by mass aqueous solution) (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
G-5: Hexadecyltrimethylammonium hydroxide (10% by mass aqueous solution) (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
G-6: Choline (50% by mass aqueous solution) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
G-7: benzyltrimethylammonium (40 mass% methanol solution) (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
[Inorganic filler]
H-1: Snowtex O (Nissan Chemical Industry Co., Ltd.)
H-2: Snowtex C (Nissan Chemical Co., Ltd.)
H-3: Snowtex N (manufactured by Nissan Chemical Industries, Ltd.)
[Surfactant]
E-11: Megafuck F-444 (manufactured by DIC Corporation)

-Resist layer-
(Polymer)
In the following examples, the following abbreviations represent the following compounds, respectively.
ATHF: 2-tetrahydrofuranyl acrylate (synthetic product)
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
ATHP: Tetrahydro-2H-pyran-2-yl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
MATHP: Tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
TBMA: t-butyl methacrylate (Fuji Film Wako Pure Chemical Industries, Ltd.)
AA: Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
MAA: Methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
EA: Ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
MMA: Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
CHA: cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
CHMA: cyclohexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
Normal propyl acetate (manufactured by Showa Denko KK)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by FUJIFILM 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 adding 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 spreading Kyoward 200 (aluminum hydroxide adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (hydrotalcite-based adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) in the order of Nutsche, the reaction solution is filtered. As a result, a filtrate was obtained. Hydroquinone monomethyl ether (MEHQ, 0.0012 parts) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ° C., whereby 140.8 parts of tetrahydrofuran-2-yl acrylate (ATHF) was obtained as a colorless oil. Obtained (yield 99.0%).

-Synthesis of MATHF-
Methacrylic acid (86.0 parts, 1.0 molar equivalent) and hexane (72.1 parts) were added to a three-necked flask and cooled to 20 ° C. After adding camphorsulfonic acid (0.00070 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 spreading Kyoward 200 (aluminum hydroxide adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (hydrotalcite-based adsorbent, manufactured by Kyowa Chemical Industry Co., Ltd.) in the order of Nutsche, the reaction solution is filtered. As a result, a filtrate was obtained. Hydroquinone monomethyl ether (MEHQ, 0.0012 parts) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ° C., so that 152.9 parts of tetrahydrofuran-2-yl methacrylate (MATHF) was obtained as a colorless oil. Obtained (yield 98.0%).

-Synthesis example of polymer B-1-
Normal propyl acetate (75.0 parts) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. A mixed solution of ATHF (38.70 parts), AA (1.47 parts), CHA (59.83 parts), V-601 (4.1 parts), and normal propyl acetate (75.0 parts) The solution was added dropwise to the three-necked flask solution maintained within the range of ± 2 ° C over 2 hours. After completion of dropping, the solution was stirred for 2 hours in a range of 90 ° C. ± 2 ° C. to obtain a solution of polymer B-1 (solid content concentration 40.0% by mass).

-Synthesis example of polymers B-2 to B-8-
Polymers B-2 to B-8 were synthesized in the same manner as in the synthesis of polymer A-1 except that the types of monomers were changed as shown in Table 1 below.
The solid content concentration of the polymer was 40% by mass.
In addition, the notation of “-” in Table 1 indicates that the corresponding component is not included.

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

C-2: Compound having the structure shown below (synthesized according to the method described in paragraph 0210 of JP-A-2014-197155)

C-3: The following compound (Irgacure PAG-103, manufactured by BASF)

  C-4: CPI-310TS (triarylsulfonium salt, manufactured by San Apro Co., Ltd.)

[Basic compounds]
D-1: Compound (CMTU) having the structure shown below

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: F-552 (fluorinated nonionic surfactant, manufactured by DIC Corporation)
E-2: F-554 (fluorine-based nonionic surfactant, manufactured by DIC Corporation)

Example 1
<Preparation of intermediate layer composition 1>
The following components were mixed and filtered with a polytetrafluoroethylene filter having a pore size of 5.0 μm to prepare an intermediate layer composition 1.

Water: 891.5 parts by mass Methanol: 891.5 parts by mass Polymer B-11: 80.0 parts by mass Dye A-1: 1.2 parts by mass pH adjuster G-1: 35.8 parts by mass Inorganic filler H -1: 100.0 parts by mass Surfactant E-11: 0.05 parts by mass

<Preparation of resist layer forming composition 1>
The following components were mixed and filtered through a polytetrafluoroethylene filter having a pore size of 1.0 μm to prepare a resist layer forming composition 1.

MEK (methyl ethyl ketone: manufactured by Maruzen Petrochemical Co., Ltd.): 306.0 parts by mass Normal propyl acetate (manufactured by Showa Denko KK): 459.9 parts by mass Polymer B-1 solution: 423.5 parts by mass Photoacid generation Agent C-1: 9.00 parts by mass Basic compound D-1: 1.35 parts by mass Surfactant E-1: 0.24 parts by mass

<Preparation of photosensitive transfer material>
An intermediate layer composition 1 is formed on a polyethylene terephthalate film (hereinafter also referred to as “PET (A)”) having a thickness of 16 μm, which is a temporary support, with a dry film thickness of 1.8 μm using a slit nozzle. Was applied. Then, it was dried in a convection oven at 100 ° C. for 2 minutes.
On the formed intermediate layer, the resist layer forming composition 1 was applied in an amount such that the dry film thickness was 3.0 μm using a slit nozzle. Finally, a polypropylene film (manufactured by Oji F-Tex Co., Ltd., Alphan PK-002) was pressure bonded as a cover film to prepare a photosensitive transfer material.

(Examples 2-27 and Example 201)
A mixed solvent of water and methanol (water / methanol = 891.5 parts by mass / 891.5 parts by mass) was added to the pigment, polymer, pH adjuster, inorganic filler, and surfactant, as shown in Table 2 below. The intermediate layer compositions 2 to 18 were prepared by dissolving and mixing in a part) and filtering through a polytetrafluoroethylene filter having a pore size of 1.0 μm.
Moreover, as shown in Table 3, the intermediate layer composition 19 was prepared in the same manner as the intermediate layer composition 1 except that 2.0 parts by mass of the photoacid generator C-4 was further added.

In addition, a polymer, a photoacid generator, a basic compound, a surfactant, and other components are mixed solvents of n-propyl acetate and methyl ethyl ketone so that the solid content ratio (mass ratio) shown in Table 4 below is obtained. (Sodium acetate n-propyl / methyl ethyl ketone = 70/30 [volume%]) is dissolved and mixed at a solid content concentration of 14% by mass and filtered through a polytetrafluoroethylene filter having a pore size of 1.0 μm for resist layer formation. Compositions 2-10 were prepared.
Moreover, the following component was mixed and the composition 11 for resist layer formation was prepared by filtering with the filter made from a polytetrafluoroethylene with a hole diameter of 1.0 micrometer.

41% by mass (solid content) MEK of a copolymer having a composition of methacrylic acid / styrene / benzyl methacrylate (polymerization ratio 30/20/50), an acid equivalent weight of 290, and a weight average molecular weight of 55,000. (Methyl ethyl ketone) solution: 55.0 parts by mass Polyethylene glycol dimethacrylate (Shin-Nakamura Chemical Co., BPE-500) obtained by adding an average of 5 moles of ethylene oxide to both ends of bisphenol A: 25.0 parts by mass, average 12 Polyalkylene glycol dimethacrylate in which 3 moles of ethylene oxide was further added on both ends to polypropylene glycol to which moles of propylene oxide had been added: 20.0 parts by mass 4,4′-bis (diethylamino) benzophenone: 0.1 mass Part 2- (o-chlorophenyl)- , 5-diphenyl imidazole dimer: 3.0 parts by Diamond Green: 0.1 parts by weight Leuco Crystal Violet: 0.3 parts by weight

  In Example 1, the intermediate layer composition 1 was replaced with the intermediate layer compositions 2 to 19, respectively, and the resist layer forming composition 1 was replaced with the resist layer forming compositions 2 to 11, respectively. In the same manner as in Example 1, a photosensitive transfer material was produced.

(Comparative Example 1)
In Example 1, the intermediate layer composition 1 was replaced with the comparative intermediate layer composition 1 prepared without adding the dye A-1 and the pH adjuster G-1 used for the preparation of the intermediate layer composition 1. A photosensitive transfer material of Comparative Example 1 was produced in the same manner as Example 1 except for the above.

(Comparative Example 2)
A mixed solvent of water and methanol (water / methanol = 891.5 parts by mass / 891.5 parts by mass) was added to the pigment, polymer, pH adjuster, inorganic filler, and surfactant, as shown in Table 2 below. Part), and the mixture was filtered through a polytetrafluoroethylene filter having a pore diameter of 1.0 μm to prepare a comparative intermediate layer composition 2.

  A photosensitive transfer material was prepared in the same manner as in Example 1 except that the intermediate layer composition 1 was replaced with the comparative intermediate layer composition 2 in Example 1.

(Comparative Example 3)
In Example 201, instead of the intermediate layer composition 19, as shown in Table 3, it was prepared without adding the dye A-1 and the photoacid generator C-4 used for the preparation of the intermediate layer composition 19. A photosensitive transfer material was produced in the same manner as in Example 201 except that the comparative intermediate layer composition 3 was used.

[Performance evaluation 1]
A PET substrate with a copper layer was used in which a copper layer was formed by sputtering at a thickness of 200 nm on a polyethylene terephthalate (PET) film having a thickness of 100 μm.

<Visibility>
The produced photosensitive transfer material was subjected to a roll temperature of 90 ° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m / min. It laminated on the PET board | substrate with a copper layer on the lamination conditions of these. The temporary support of the photosensitive transfer material is contacted with a glass mask having a line-and-space pattern (duty ratio of 1: 1) having a line width of 10 μm without peeling off the temporary support, and ultrahigh pressure is passed through the mask. The resist layer was exposed with an exposure dose of 200 mJ / cm ^{2 with} a mercury lamp. After leaving for 4 hours, the exposed line and space pattern was observed with an optical microscope and evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: It was confirmed that the line and space pattern was distinguishable with a sufficient color density.
B: A line and space pattern could not be confirmed.

(Examples 28 to 33)
In Example 1, a photosensitive transfer material was produced in the same manner as in Example 1 except that the intermediate layer composition and the resist layer forming composition were changed to have the structure shown in Table 6 below.

[Performance evaluation 2]
<Adhesion>
A PET substrate with a copper layer in which a copper layer was formed by a sputtering method at a thickness of 200 nm on a polyethylene terephthalate (PET) film having a thickness of 100 μm was used.
The produced photosensitive transfer material was cut into a size of 50 cm × 50 cm to obtain a sample piece, and the cover film of the obtained sample piece was peeled off, and the roll temperature was 90 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 4.0 m / min. The film was laminated on a PET film with a copper layer under the following laminating conditions. Subsequently, the temporary support is peeled off, the portion where the intermediate layer and the resist layer are attached to the copper layer is marked using an oil-based magic, the entire PET substrate is photographed, and image analysis software (ImageJ (National Institute of America, USA) (Health)), the area where the intermediate layer and the resist layer were attached to the copper layer and the area of the entire sample were calculated. And area ratio was calculated | required from the following formula and evaluated according to the following evaluation criteria.
Area ratio (%) = area where the intermediate layer and resist layer are attached / area of the entire sample piece × 100
<Evaluation criteria>
5: 95% or more 4: 90% or more and less than 95% 3: 85% or more and less than 90% 2: 80% or more and less than 85% 1: less than 80%

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

Next, pattern alignment was performed using a photomask provided with openings of the pattern shown in FIG. 4 (hereinafter also referred to as “pattern B”) in the aligned state, and development and washing were performed.
In the pattern B shown in FIG. 4, the gray portion G is a light shielding portion, and the dotted line portion DL is a virtual alignment alignment frame.
Thereafter, the copper layer was etched using Cu-02, and the remaining resist layer was stripped using a stripping solution (10% by mass sodium hydroxide aqueous solution) to obtain a circuit wiring board.
As a result, a circuit wiring board was obtained. When observed with a microscope, there was no peeling or chipping, and the pattern was clean.

(Example 102)
On a 100 μm-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by vacuum deposition at a thickness of 200 nm. The film was formed into a circuit forming 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 resist layer was subjected to pattern exposure using a photomask provided with a pattern A shown in FIG. 3 having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Next, after etching the copper layer using a copper etchant (Kanto Chemical Co., Ltd. Cu-02), the ITO layer is etched using an ITO etchant (Kanto Chemical Co., Ltd. ITO-02), A substrate on which copper (solid line portion SL) and ITO (gray portion G) were both drawn with the pattern A was obtained.
Next, PET (A) was laminated as a protective layer on the remaining resist. In this state, pattern alignment was performed using a photomask provided with an opening of the pattern B shown in FIG. 4 in the aligned state, and after developing the PET (A), development and washing were performed.
Thereafter, the copper wiring was etched using Cu-02, and the remaining resist layer was stripped using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.

  When observed with a microscope, it was a clean pattern with no peeling or chipping.

DESCRIPTION OF SYMBOLS 12 Temporary support body 14 Laminated body 14-1 of intermediate | middle layer and resist layer 14-2 Resist layer 14-2 1st pattern 14B 2nd pattern 16 Cover film 20 Substrate 22 for circuit formation Base material 24 1st conductive layer 24A 1st Conductive layer (after the first etching step)
24B 1st conductive layer (after 2nd etching process)
26 2nd conductive layer 26A 2nd conductive layer (after 1st etching process and 2nd etching process)
30 Mask 40 Mask 100 Photosensitive transfer material SL Solid line part G Gray part DL Dotted line part

Claims (14)

Having a temporary support, an intermediate layer and a resist layer in this order,
The intermediate layer is a photosensitive transfer material containing the following component (A).
Component (A): a dye having a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm during color development, and the maximum absorption wavelength being changed by an acid, a base, or a radical   The photosensitive transfer material according to claim 1, wherein the dye as the component (A) is a pH-sensitive dye.   The photosensitive transfer material according to claim 1, wherein the dye as the component (A) has a triarylmethane skeleton. The dye as the component (A) contains at least one selected from a dye represented by the following formula I, a ring-opened product of the dye represented by the following formula I, and a neutralized product of the ring-opened product. The photosensitive transfer material of any one of Claims 1-3.


In formula I, Ar and Ar ′ each independently represent an aromatic group. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent. The photosensitive transfer material according to claim 1, wherein the resist layer contains the following components (B) and (C).
(B) Component: Polymer (C) component containing a structural unit having a group in which an acid group is protected with an acid-decomposable group: Photoacid generator   The maximum absorption wavelength in a wavelength range of 400 nm to 780 nm at the time of color development of the dye as the component (A) is changed by the acid released from the photoacid generator as the component (C) by exposure. Photosensitive transfer material.   7. The maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of coloring of the dye as the component (A) is shortened by the acid released from the photoacid generator as the component (C) by exposure. Photosensitive transfer material.   The photosensitivity according to any one of claims 5 to 7, wherein the acid generated from the photoacid generator as component (C) is phosphoric acid or sulfonic acid, and pKa is 4 or less. Transfer material. The structural unit having the group in which the polymer as the component (B) has a group in which the acid group is protected by an acid-decomposable group is a structural unit represented by the following formula II. The photosensitive transfer material of any one of Claims 1.



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 Alternatively, it represents an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether. R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. The photosensitive transfer material according to claim 1, wherein the intermediate layer further contains the following component (G).
(G) component: pH adjuster   The photosensitive transfer material according to claim 10, wherein the pH adjuster is a quaternary ammonium salt. The photosensitive transfer material according to any one of claims 1 to 11, wherein the resist layer further contains the following component (D).
Component (D): basic compound A step of bringing the resist layer of the photosensitive transfer material according to any one of claims 1 to 12 into contact with the substrate and bonding the substrate to the substrate;
Pattern exposing the resist layer of the photosensitive transfer material after the bonding step;
Developing the resist layer after the pattern exposing step to form a pattern;
Etching the substrate in a region where the pattern is not disposed;
A method of manufacturing circuit wiring including the above in this order. A step of bringing the resist layer of the photosensitive transfer material according to any one of claims 1 to 12 into contact with the substrate and bonding the substrate to the substrate;
Pattern exposing the resist layer of the photosensitive transfer material after the bonding step;
Developing the resist layer after the pattern exposing step to form a pattern;
Etching the substrate in a region where the pattern is not disposed;
The manufacturing method of the touch panel which contains these in this order.