JP6869095B2 - Transfer material, transfer material manufacturing method, pattern forming method, and metal pattern forming method - Google Patents

Description

The present disclosure relates to transfer materials, methods for producing transfer materials, methods for forming patterns, and methods for forming metal patterns.

The photopolymerizable composition is a composition that polymerizes and cures when irradiated with light having a specific wavelength. The photopolymerizable composition generally includes a polymerizable compound having an ethylenically unsaturated bond and a photopolymerization initiator. The photopolymerization initiator is, for example, cleaved by irradiation with light to generate a radical, and this radical promotes the polymerization of a polymerizable compound having an ethylenically unsaturated bond.

Since the portion of the photopolymerizable composition that has been irradiated with light is cured, a desired pattern can be formed by masking the portion that is not cured. In recent years, in technical fields such as semiconductors, there has been a demand for miniaturization of patterns from the viewpoint of increasing the degree of integration, but with the miniaturization of patterns, it is necessary to strictly control the light irradiation portion. .. For example, when the irradiated light is reflected from the substrate, photopolymerization occurs in an undesired place, forming a defective pattern.

For light reflection, an antireflection layer is provided between the layer of the photopolymerizable composition and the base material. For example, a photosensitive material is disclosed in which an organic antireflection film is provided on a substrate and a coating film of a negative resist composition is provided on the organic antireflection film (for example, Patent Document 1).
Also disclosed is a multi-layer system having at least a first layer and a second layer, wherein the first layer contains a photoacid generator that is substantially insoluble in the solvent of the second layer. (For example, Patent Document 2).
Further, an example in which a water-soluble antireflection composition is used when forming an antireflection film is disclosed (for example, Patent Documents 3 and 4).

Japanese Unexamined Patent Publication No. 2001-056555 Japanese Unexamined Patent Publication No. 2011-502276 Japanese Unexamined Patent Publication No. 9-236915 Japanese Unexamined Patent Publication No. 60-129233

However, since the coating film of the organic antireflection film and the negative resist composition described in Patent Document 1 both contains an organic solvent, a coating film of the negative resist composition is provided on the organic antireflection film. In some cases, the interfaces are mixed and the desired effect of each film cannot be obtained.
In the invention described in Patent Document 2, since the film of the upper surface photoresist layer is formed on the antireflection film after the antireflection film is baked, the adhesion between the antireflection film and the coating of the photoresist layer is formed. Insufficient sex.
Patent Documents 3 and 4 do not disclose transfer materials, and the patterns formed by using the inventions described in Patent Documents 3 and 4 have insufficient pattern linearity and pattern shape.

In view of the above, the problem to be solved by one embodiment of the present invention is to provide a transfer material and a method for producing a transfer material, which can form a pattern excellent in pattern linearity and pattern shape and also have excellent adhesion during immersion development. To do.
An object to be solved by another embodiment of the present invention is to provide a method for forming a pattern having excellent pattern linearity, pattern shape, and adhesion during immersion development.
Further, an object to be solved by another embodiment of the present invention is to provide a method for forming a metal pattern having excellent pattern linearity and pattern shape.

Specific means for solving the above problems include the following aspects.
<1> A temporary support having a haze value of 0.3% or less, a polymerizable compound having an ethylenically unsaturated double bond, an alkali-soluble resin, and a photopolymerization initiator arranged on the temporary support. A resin and an ultraviolet absorber that are soluble in a water-based solvent or a lower alcohol-based solvent or a mixed solvent of a water-based solvent and a lower alcohol-based solvent and are arranged on the first layer and the first layer containing the above. A transfer material having a second layer containing and a protective film disposed on top of the second layer.
<2> The transfer material according to <1>, wherein the temporary support is a polyethylene terephthalate film.
<3> The transfer material according to <1> or <2>, wherein the number of fish eyes of ^{0.3 mm 2} or more in the protective film is ^{8 or less per 1000 m 2.}
<4> The transfer material according to any one of <1> to <3>, wherein the protective film is a polyethylene terephthalate film.
<5> The transfer material according to any one of <1> to <4>, wherein the second layer further contains a polymerizable compound having an ethylenically unsaturated double bond and a photopolymerization initiator.
<6> The transfer according to any one of <1> to <5>, wherein the resin soluble in an aqueous solvent, a lower alcohol solvent, or a mixed solvent of the aqueous solvent and the lower alcohol solvent has an acid group. material.
<7> The UV absorber is any one of <1> to <6>, which is a soluble UV absorber in a water-based solvent, a lower alcohol-based solvent, or a mixed solvent of a water-based solvent and a lower alcohol-based solvent. The described transfer material.
<8> The transfer material according to any one of <1> to <7>, wherein the ultraviolet absorber is a benzotriazole-based ultraviolet absorber.
<9> The transfer material according to <8>, wherein the benzotriazole-based ultraviolet absorber is a compound having a structure represented by the following general formula (1).

In the general formula (1), R ¹ independently represents a hydrogen atom or an organic group having 1 to 15 carbon atoms, n ₁ represents an integer of 0 to 4, and R ² independently represents a hydrogen atom. It represents a hydrogen atom or an organic group having 1 to 15 carbon atoms, and n ₂ represents an integer of 0 to 4.
<10> The transfer material according to any one of <1> to <9>, wherein the content of the ultraviolet absorber is 5% by mass or more and less than 80% by mass with respect to the total solid content of the second layer. ..
<11> The transfer material according to any one of <1> to <10>, wherein the photopolymerization initiator contained in the first layer is an oxime-based photopolymerization initiator.
<12> The transfer material according to any one of <1> to <11>, wherein the temporary support has a thickness of 1 μm or more and 25 μm or less.
<13> The transfer material according to any one of <1> to <12>, wherein the thickness of the first layer is 1 μm or more and 15 μm or less.
<14> The transfer material according to any one of <1> to <13>, wherein the thickness of the second layer is 0.05 μm or more and 2 μm or less.
<15> On the temporary support, a polymerizable compound having an ethylenically unsaturated double bond, a photopolymerization initiator, and an alkali-soluble resin are mixed with an ester solvent or a ketone solvent or an ester solvent and a ketone solvent. The step of forming the first layer by applying and drying the first composition dissolved in a solvent, a resin and an ultraviolet absorber are placed on the first layer in an aqueous solvent or a lower alcohol solvent or an aqueous solvent. A step of forming a second layer by applying and drying a second composition dissolved in a mixed solvent of a solvent and a lower alcohol solvent, and attaching a protective film on the second layer. A method for producing a transfer material, including a step of matching.
<16> The step of peeling off the protective film of the transfer material according to any one of <1> to <14>, the temporary support of the transfer material, the first layer, and the second layer are arranged on the substrate. A step of exposing the first layer and the second layer through a temporary support and an exposure mask, a step of peeling off the temporary support, a step of developing the first layer and the second layer, A method of forming a pattern, including.
<17> The method for forming a pattern according to <16>, wherein the exposure step irradiates light in a wavelength range including a wavelength of 365 nm.
<18> The method for forming a pattern according to <16> or <17>, wherein the substrate is a resin substrate.
<19> The step of peeling off the protective film of the transfer material according to any one of <1> to <14>, the temporary support of the transfer material, the first layer, and the second layer on the metal substrate. A step of arranging, a step of exposing the first layer and the second layer via a temporary support and an exposure mask, a step of peeling off the temporary support, a step of developing the first layer and the second layer. A method for forming a metal pattern, which comprises a step of etching a metal substrate and a step of peeling off a first layer and a second layer.

According to one embodiment of the present invention, it is possible to provide a transfer material and a method for producing a transfer material, which can form a pattern excellent in pattern linearity and pattern shape and also have excellent adhesion during immersion development.
According to another embodiment of the present invention, it is possible to provide a method for forming a pattern having excellent pattern linearity, pattern shape, and adhesion during immersion development.
Further, according to another embodiment of the present invention, it is possible to provide a method for forming a metal pattern having excellent pattern linearity and pattern shape.

In the present specification, the numerical range indicated by using "~" means a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively. In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, in the numerical range 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 value shown in the examples.

In the present specification, the ratio of the constituent units of the polymer is a molar ratio unless otherwise specified.

In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. Is done.

In the present specification, "(meth) acrylic acid" is a concept including both acrylic acid and methacrylic acid, and "(meth) acrylate" is a concept including both acrylate and methacrylate, and "( "Meta) acryloyl group" is a concept that includes both an acryloyl group and a methacryloyl group.

<Transfer material>
The transfer materials of the present disclosure include a temporary support having a haze value of 0.3% or less, a polymerizable compound having an ethylenically unsaturated double bond placed on the temporary support, an alkali-soluble resin, and an alkali-soluble resin. A first layer containing a photopolymerization initiator, a resin disposed on the first layer, a resin soluble in an aqueous solvent or a lower alcohol solvent, or a mixed solvent of an aqueous solvent and a lower alcohol solvent, and a resin. It has a second layer containing an ultraviolet absorber and a protective film disposed on top of the second layer.

Traditionally, antireflection films have been widely used in photolithography. Generally, an organic solvent-based material is used for the antireflection film, so when a resist of the organic solvent-based material is further applied on the antireflection film, the antireflection film melts and the interface is mixed. Therefore, there is a problem that the desired effect cannot be obtained. In order to deal with this problem, an acid-crosslinked curing material is used as an antireflection film, and before applying the photoresist, exposure or heat treatment is performed to form an acid-crosslink, and then the photoresist is applied. However, due to the pre-curing of the antireflection film, the adhesion between the antireflection film and the photoresist becomes poor, and peeling is likely to occur.
Further, it has been known that a water-soluble antireflection composition is used for the antireflection film layer, but the pattern linearity and pattern shape of the formed pattern are insufficient.
On the other hand, in the present disclosure, by laminating the water-based second layer on the organic solvent-based first layer, the interface between the first layer and the second layer is not mixed. , A transfer material capable of forming a pattern excellent in pattern linearity and pattern shape is provided in which the function of each layer is suitably maintained.
Further, since the step of applying the photoresist after pre-curing the antireflection film by laminating the first layer and the second layer in advance is not included, the transfer has good adhesion during immersion development. The material is provided.

(Temporary support)
The haze value of the temporary support is 0.3% or less, preferably 0.15% or less. When the haze value is in the above range, it is possible to provide a transfer material capable of reducing undesired light scattering during exposure by a filler or the like contained in the temporary support and forming a pattern having excellent pattern linearity.

The haze value of the present disclosure is measured for a small piece of a temporary support using a haze meter HZ-2 manufactured by Suga Test Instruments Co., Ltd. in accordance with JIS (Japanese Industrial Standards) K 7136 (unit:%). ).

The thickness of the temporary support is preferably 1 μm or more (preferably 3 μm or more) and 25 μm or less (preferably 16 μm or less). For example, the thickness of the temporary support may be 3 μm or more and 16 μm or less. When the thickness of the temporary support is 1 μm or more, the handleability is improved. Further, by providing a transfer material capable of forming a pattern having excellent pattern linearity by reducing undesired light scattering during exposure by a filler or the like contained in the temporary support when the thickness of the temporary support is 25 μm or less. can do.

As the temporary support, a film that is flexible and does not cause significant deformation, shrinkage or elongation under pressure or under pressure and heating can be used, and a resin film is preferable. Examples of such a film include polyethylene terephthalate (PET) film, cellulose triacetate (TAC) film, polystyrene film, polyimide film, and polycarbonate film. Among them, polyethylene terephthalate film is preferable, and biaxially stretched polyethylene terephthalate is preferable. Film is more preferred.

(First layer)
The transfer material of the present disclosure has a first layer, which is placed on a temporary support and contains a polymerizable compound having an ethylenically unsaturated double bond, an alkali-soluble resin, and a photopolymerization initiator.
The first layer is preferably a resist layer, more preferably a negative resist layer.

The thickness of the first layer is preferably 1 μm or more and 15 μm or less, more preferably 1 μm or more and 12 μm or less, and even more preferably 1 μm or more and 10 μm or less. When the thickness of the first layer is 1 μm or more, it is possible to provide a transfer material having excellent laminateability. Further, when the thickness of the first layer is 15 μm or less, a cured film is suitably formed by photopolymerization.

In the present disclosure, "excellent in laminateability" means that there are no bubbles or floats when the temporary support, the first layer and the second layer of the present disclosure are laminated on the substrate, preferably. It means that bubbles and floats are not present in 80% or more of the laminated area, more preferably 90% or more of the laminated area.

-Polymerizable compound with ethylenically unsaturated double bond-
The first layer in the transfer material of the present disclosure contains a polymerizable compound having an ethylenically unsaturated double bond. A polymerizable compound having an ethylenically unsaturated double bond is a compound having one or more ethylenically unsaturated groups, which contributes to the photosensitivity (ie, photocurability) of the first layer and the strength of the cured film. It is an ingredient to be used.

The polymerizable compound having an ethylenically unsaturated double bond, which is preferably contained in the first layer, is a photopolymerization initiator which is soluble in a solvent, preferably an organic solvent.
In the present disclosure, "soluble in solvent" refers to a solvent at 25 ° C., preferably an ester solvent or a ketone solvent, or a mixed solvent of an ester solvent and a ketone solvent, with respect to the total mass of the solvent. It means that it dissolves in an amount of 5% by mass or more, preferably 1% by mass or more, and more preferably 3% by mass or more.

The first layer can contain a monofunctional ethylenically unsaturated compound or a bifunctional or higher functional ethylenically unsaturated compound as a polymerizable compound having an ethylenically unsaturated double bond, and is a bifunctional or higher functional ethylene. It preferably contains a sex unsaturated compound.
Here, the "monofunctional ethylenically unsaturated compound" means a compound having one ethylenically unsaturated group in one molecule, and the "bifunctional or higher functional ethylenically unsaturated compound" means one molecule. It means a compound having two or more ethylenically unsaturated groups in it.

The ethylenically unsaturated group is more preferably a (meth) acryloyl group. Therefore, the (meth) acrylate compound is preferable as the polymerizable compound having an ethylenically unsaturated double bond.

The first layer consists of a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably a trifunctional or higher (meth) acrylate compound). Compound) and, more preferably.

The bifunctional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
Examples of the bifunctional ethylenically unsaturated compound include tricyclodecanedimethanol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,6-hexane. Examples thereof include diol di (meth) acrylate.
More specifically, the bifunctional ethylenically unsaturated compounds include tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimenanol dimethacrylate (DCP, new). Nakamura Chemical Industry Co., Ltd.), 1,9-Nonandiol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) (Manufactured by Kogyo Co., Ltd.) and the like.

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 thereof include acrylates, ditrimethylolpropane tetra (meth) acrylates, isocyanuric acid (meth) acrylates, and (meth) acrylate compounds having a glycerintri (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 that includes tri (meth) acrylate and tetra (meth) acrylate.

Examples of the polymerizable compound having a preferable ethylenically unsaturated double bond include a caprolactone-modified compound of a (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., manufactured by Shin-Nakamura Chemical Industry 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 Industry Co., Ltd., manufactured by Daicel Ornex Co., Ltd.) EBECRYL (registered trademark) 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), carboxylic acid-containing monomer (Aronix (registered trademark) TO-2349, manufactured by Toa Synthetic Co., Ltd.), Trimethylol propanepropylene oxide (PO) -modified triacrylate (Aronix M-310 manufactured by Toa Synthetic Co., Ltd.), Ditrimethylol propanetetraacrylate (AD-TMP manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Bisphenol A-modified dimethacrylate NK ester (new) Nakamura Chemical Industry Co., Ltd. BPE-500), polyfunctional acrylamide monomer (N, N'-{[(2-acrylamide-2-[(3-acrylamide propoxy) methyl] propane-1,3-diyl) bis (oxy) )] Bis (propane-1,3-diyl)} diacrylamide; FAM-401 manufactured by Fujifilm Co., Ltd.) and the like.

Examples of the polymerizable compound having an ethylenically unsaturated double bond include a urethane (meth) acrylate compound (preferably a trifunctional or higher functional urethane (meth) acrylate compound).
Examples of the trifunctional or higher functional urethane (meth) acrylate compound include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.). ) And so on.

The weight average molecular weight (Mw) of the polymerizable compound having an ethylenically unsaturated double bond is preferably 200 to 3000, more preferably 250 to 2600, further preferably 280 to 2200, and particularly preferably 300 to 2200.
Further, among the polymerizable compounds having an ethylenically unsaturated double bond used in the first layer, the proportion of the content of the polymerizable compound having an ethylenically unsaturated double bond having a molecular weight of 300 or less is the first. With respect to all the polymerizable compounds having ethylenically unsaturated double bonds contained in the layer, 30% by mass or less is preferable, 25% by mass or less is more preferable, and 20% by mass or less is further preferable.

The polymerizable compound having an ethylenically unsaturated double bond may be one kind alone or two or more kinds.
The content of the polymerizable compound having an ethylenically unsaturated double bond in the first layer is preferably 1% by mass to 70% by mass, preferably 5% by mass to 50% by mass, based on the total mass of the first layer. More preferably, 10% by mass to 40% by mass is further preferable, and 15% by mass to 30% by mass is particularly preferable.

When the first layer contains a bifunctional ethylenically unsaturated compound and a trifunctional or higher functional ethylenically unsaturated compound, the content of the bifunctional ethylenically unsaturated compound is contained in the first layer. 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 further preferable with respect to all the polymerizable compounds having an ethylenically unsaturated double bond.

-Alkali-soluble resin-
The first layer in the transfer material of the present disclosure contains an alkali-soluble resin.
The "alkali-soluble resin" refers to a resin that is soluble in an alkaline solvent.
In the present disclosure, "alkaline" means pH 7 or more and pH 14 or less, preferably pH 8 or more and pH 14 or less, more preferably pH 9 or more and pH 14 or less, and even more preferably pH 10 or more and pH 14 or less.

In the present disclosure, "soluble in alkaline solvent" means 0.5% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, based on the total mass of the alkaline solvent in the alkaline solvent at 25 ° C. It means to dissolve.
The alkali-soluble resin contained in the first layer is preferably a solvent, preferably an ester-based solvent or a ketone-based solvent, or an alkali-soluble resin soluble in a mixed solvent of the ester-based solvent and the ketone-based solvent.

The alkali-soluble resin is a weight obtained by reacting a hydroxyl group-containing resin such as an acrylic copolymer obtained from a carboxylic acid group-containing acrylic monomer, a cellulose ether, or a polyhydroxyethyl methacrylate with a maleic acid anhydride or a phthalic acid anhydride. Coalescence etc. can be mentioned.

As the acrylic copolymer obtained from the carboxylic acid group-containing acrylic monomer, a copolymer of a carboxylic acid group-containing monomer and another copolymerizable monomer is preferable.
Examples of the carboxylic acid group-containing monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, cinnamic acid, acrylic acid dimer and the like. ) Acrylic acid is particularly preferable.

Other copolymerizable monomers include, for example, acrylic acid ester compounds, methacrylic acid ester compounds, crotonic acid ester compounds, vinyl ester compounds, maleic acid diester compounds, fumaric acid diester compounds, and itaconic acid diesters. Examples thereof include based compounds, (meth) acrylonitrile-based compounds, (meth) acrylamide-based compounds, styrene-based compounds, and vinyl ether-based compounds.

Specifically, for example, the following compounds can be mentioned.
Examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, and acetoxyethyl acrylate. , Phenyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, cyclohexyl acrylate, benzyl acrylate and the like.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate and acetoxyethyl methacrylate. , Phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and the like.

Examples of the crotonic acid ester compound include butyl crotonic acid and hexyl crotonic acid. Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.
Examples of the maleic acid diester compound include dimethyl maleate, diethyl maleate, and dibutyl maleate. Examples of the fumaric acid diester compound include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate. Examples of the itaconic acid diester compound include dimethyl itaconic acid, diethyl itaconic acid, and dibutyl itaconic acid.

Examples of acrylamide-based compounds include acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, n-butyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide, 2-methoxyethyl acrylamide, dimethyl acrylamide, diethyl acrylamide, phenyl acrylamide, and benzyl acrylamide. Can be mentioned.

Examples of methacrylamide compounds include methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, 2-methoxyethyl methacrylamide, and dimethyl methacrylamide. , Diethylmethacrylamide, phenylmethacrylamide, benzylmethacrylamide and the like.

Examples of vinyl ether compounds include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether and the like.

Examples of styrene compounds include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, methyl vinyl benzoate, and alpha. Examples include methyl styrene.
In addition, maleimide, vinylpyridine, vinylpyrrolidone, vinylcarbazole and the like can also be used.
In addition, these compounds may be one kind alone or two or more kinds.

An acrylic copolymer from such a carboxylic acid group-containing monomer can be obtained by copolymerizing each of the monomers by a known method according to a conventional method. For example, these monomers can be obtained by dissolving them in a suitable solvent, adding a radical polymerization initiator to them, and polymerizing them in a solution.
It can also be produced by performing so-called emulsion polymerization in a state where these monomers are dispersed in an aqueous medium. The solvent used for the polymerization can be arbitrarily selected depending on the monomer used and the solubility of the copolymer to be produced, and for example, methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, etc. Acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene and mixtures thereof can be used.
Further, as the polymerization initiator, azo compounds such as 2,2'-azobis (isobutyronitrile) (AIBN) and 2,2'-azobis- (2,4'-dimethylvaleronitrile), such as benzoyl peroxide. Peroxide type, persulfate, etc. can be used.

When the alkali-soluble resin is an acrylic copolymer from a carboxylic acid group-containing monomer, the composition ratio of the carboxylic acid group repeating unit in the acrylic copolymer is 1% by mass to 60% by mass in the total repeating unit of the copolymer. It is preferably by mass%, more preferably 5% by mass to 50% by mass, and particularly preferably 10% by mass to 40% by mass. When the composition ratio of the carboxylic acid group-containing repeating unit is in the above range, it is preferable because the developability to an alkaline aqueous solution can be made sufficient and the stripping solution resistance can be sufficiently maintained.

The molecular weight of the acrylic copolymer can be adjusted arbitrarily, but the weight average molecular weight is preferably 2000 to 20000, and particularly preferably 4000 to 100,000. When the molecular weight is in the above range, the strength of the film can be maintained high, stable production is possible, and the developability is good, which is preferable.

Further, as the alkali-soluble resin, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride or phthalic anhydride can also be used.

A preferable example of the alkali-soluble resin is, for example, a copolymer of methyl methacrylate and methacrylic acid (copolymerization composition ratio (methyl methacrylate / methacrylic acid): 70% by mass to 85% by mass / 30% by mass to 15% by mass, weight. Average molecular weight: 50,000 to 140000), copolymer of benzyl methacrylate and methacrylic acid (copolymerization composition ratio (benzyl methacrylate / methacrylic acid): 65% by mass to 85% by mass / 35% by mass to 15% by mass, weight average molecular weight: 30,000 to 150,000), styrene and maleic acid copolymer (copolymerization composition ratio (styrene / maleic acid): 50% by mass to 70% by mass / 50% by mass to 30% by mass, weight average molecular weight: 1000 to 20000), 2 -Copolymer of hydroxyethyl methacrylate, benzyl methacrylate and methacrylic acid (copolymerization composition ratio (2-hydroxyethyl methacrylate / benzyl methacrylate / methacrylic acid): 10% by mass to 30% by mass / 40% by mass to 60% by mass / 30" Mass% to 10% by mass, weight average molecular weight: 1000 to 20000), or the following compound A (acid value 95 mgKOH / g. The lower right numerical value of each constituent unit is a molar ratio).

In the first layer of the transfer material of the present disclosure, the content of the alkali-soluble resin is preferably 1% by mass to 60% by mass, and 5% by mass to 50% by mass, based on the total mass of the first layer. Is more preferably, 10% by mass to 40% by mass is even more preferable, and 10% by mass to 20% by mass is particularly preferable. When the content of the alkali-soluble resin is in the above range, the solubility in an alkaline solvent becomes good.

-Photopolymerization initiator-
The first layer in the transfer material of the present disclosure contains a photopolymerization initiator. By containing the photopolymerization initiator in the first layer, the polymerization of the polymerizable compound having an ethylenically unsaturated double bond can be promoted.
The photopolymerization initiator contained in the first layer is preferably a solvent, preferably an ester-based solvent or a ketone-based solvent, or a photopolymerization initiator soluble in a mixed solvent of the ester-based solvent and the ketone-based solvent.

The photopolymerization initiator contained in the first layer is not particularly limited, and a known photopolymerization initiator can be used. Preferably, the photopolymerization initiator contained in the first layer is an oxime-based photopolymerization initiator (photopolymerization initiator having an oxime ester structure) or an α-aminoalkylphenone-based photopolymerization initiator (α-aminoalkyl). Photopolymerization initiator having a phenone structure), α-hydroxyalkylphenone-based polymerization initiator (photopolymerization initiator having an α-hydroxyalkylphenone structure), acylphosphine oxide-based photopolymerization initiator (acylphosphine oxide structure) Photopolymerization initiator to have) and the like.

The photopolymerization initiator contained in the first layer is at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, and an α-hydroxyalkylphenone-based polymerization initiator. It preferably contains seeds, more preferably an oxime-based photopolymerization initiator.

Further, as the photopolymerization initiator contained in the first layer, for example, the polymerization initiation described in paragraphs 0031 to 0042 of JP2011-95716A and paragraphs 0064 to 0081 of JP2015-014783. Agents may be used.

Commercially available products of the photopolymerization initiator contained in the first layer include, for example, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (trade name: IRGACURE® OXE-01, manufactured by BASF, Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (Product name: IRGACURE OXE-02, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (trade name: IRGCURE 379, 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-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) 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-phenyl-propane-1-one (trade name: IRGACURE 1173, manufactured by BASF), 1-hydroxycyclohexylphenylketone (trade name: IRGACURE 184,) BASF), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: IRGACURE 651, BASF), 1- [4- (2-hydroxyethoxy) -phenyl] -2- Hydroxy-2-methyl-1-propane-1-one (trade name: IRGACURE 2959, manufactured by BASF), photopolymerization initiator (trade name: FAI-101L, manufactured by Fujifilm Co., Ltd.), oxime ester-based (commodity) Name: Lunar 6, manufactured by DKSH Japan Co., Ltd.) and the like.

The photopolymerization initiator contained in the first layer may be one kind alone or two or more kinds.
The content of the photopolymerization initiator in the first layer is not particularly limited, but is preferably 0.01% by mass or more and 5% by mass or less, and 0.05% by mass or more and 3 by mass, based on the total mass of the first layer. More preferably, it is by mass or less. When the content of the photopolymerization initiator is in the above range, the polymerization of the polymerizable compound having an ethylenically unsaturated double bond can be promoted.

− Solvent −
The coating liquid of the first layer may contain a solvent. By containing the solvent in the coating liquid of the first layer, the adhesion between the first layer and the second layer can be improved.
The solvent may be one kind or a solvent in which two or more kinds are mixed.

The solvent contained in the coating liquid of the first layer is preferably an ester solvent and a ketone solvent.
Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, butyl acetate, isobutyl acetate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, methyl pyruvate and ethyl pyruvate. , Methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethyl acetate, 1-methoxy-2-propyl acetate and the like.
Examples of the ketone solvent include acetone, diacetone alcohol, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone and the like.
Further, a mixed solvent of an ester solvent and a ketone solvent is also preferable, and for example, a mixed solvent of 1-methoxy-2-propyl acetate and methyl ethyl ketone is preferable.

The content of the solvent in the coating liquid of the first layer is preferably 30% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass or less, and 70% by mass with respect to the total mass of the first layer. % Or more and 80% by mass or less are even more preferable.

-Additives-
The following additives can be added to the first layer of the present disclosure, if necessary. Preferably, the additive contained in the first layer is an additive soluble in a solvent (preferably an ester solvent or a ketone solvent or a mixed solvent of an ester solvent and a ketone solvent).

--Sensitizer ---
In the first layer, a compound that absorbs the exposure wavelength can be used as a sensitizer to improve the initiation efficiency of the photopolymerization initiator.

Examples of the sensitizer include known sensitizing dyes, dyes, pigments and the like. The sensitizer may be used alone or in combination of two or more.

Examples of the sensitizing dye include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example, 1, 2). , 4-Triazole), stillben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoaclysin compounds.

Examples of dyes or pigments include fuxin, phthalocyanine green, auramine base, chalcoxide green S, paramagienta, crystal violet, methyl orange, nile blue 2B, Victoria blue, and malachite green (manufactured by Hodogaya Chemical Co., Ltd., Eisen (registered trademark) MALACHITE). GREEN), Basic Blue 20, Diamond Green (manufactured by Hodogaya Chemical Co., Ltd., Eisen (registered trademark) DIAMOND GREEN GH) and the like.

As the dye, a color-developing dye can be used. A color-developing dye is a compound having a function of developing a color by irradiation with light. For example, leuco dye and fluorane dye can be mentioned. Of these, leuco dyes are preferred. Specific examples thereof include tris (4-dimethylamino-2-methylphenyl) methane [leucocrystal violet] and tris (4-dimethylamino-2-methylphenyl) methane [leucoma malachite green].

The leuco dye is preferably used in combination with a halogen compound. Examples of this halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, and tris (2). , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2, 2-bis (p-chlorophenyl) ethane, hexachloroethane, triazine halide compounds, etc. Can be mentioned. Examples of the halogenated triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine. Among them, tribromomethylphenyl sulfone, triazine compound and the like are useful.

Further, as another example of the sensitizer, a thiol compound is preferably mentioned. The thiol compound has actions such as further improving the sensitivity of the photopolymerization initiator to a light source and suppressing the polymerization inhibition of the polymerizable compound by oxygen.
Examples of the thiol compound include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimethylolpropanetristhiopropionate (TMTP), and pentaerythritol tetraxthiopropionate (PETP). ) And other polyfunctional thiol compounds, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, N-phenyl-mercaptobenzimidazole, etc. Examples include monofunctional thiol compounds.
The sensitizer may be a commercially available product, and examples thereof include polyfunctional thiols (trade name: Calends MT (registered trademark) BD1 manufactured by Showa Denko).

Further, as another example of the sensitizer, an amino acid compound (eg, N-phenylglycine, etc.), an organometallic compound described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate, etc.), Tokusho 55-34414. Examples thereof include hydrogen donors described in JP-A, sulfur compounds described in JP-A-6-308727 (eg, tritian, etc.) and the like.

The content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and the chain transfer, 0. The range of 01% by mass to 5% by mass is preferable, and the range of 0.05% by mass to 1% by mass is more preferable.

--Adhesion improver ---
The first layer of the present disclosure may contain an adhesion improver. By including the adhesion improver, the adhesion between the first layer and the second layer can be improved.
The adhesion improver may be an isocyanate compound or a precursor thereof. The isocyanate-based compound includes a monofunctional isocyanate compound and a polyfunctional isocyanate compound. Here, the "monofunctional isocyanate compound" means a compound having only one isocyanate group in one molecule, and the "polyfunctional isocyanate compound" means a compound having two or more isocyanate groups in one molecule. ..

Examples of the monofunctional isocyanate compound include aromatic, aliphatic or alicyclic monofunctional isocyanate compounds. Specifically, for example, ethyl isocyanate, n-propyl isocyanate, i-propyl isocyanate, butyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, 3-i-propenylcumyl isocyanate, 4-methoxyphenyl isocyanate, m-tolyl. Isocyanate, p-tolyl isocyanate, 1-naphthyl isocyanate, dimethylbenzyl isocyanate, additive TI (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Karenz MOI (manufactured by Showa Denko Co., Ltd.), Karenz AOI (manufactured by Showa Denko Co., Ltd.), Karenz BEI (Showa) (Made by Denko Co., Ltd.) and the like.

The monofunctional isocyanate compound is preferably a compound having at least one photopolymerizable ethylenically unsaturated group. By having at least one photopolymerizable ethylenically unsaturated group, the adhesion between the first layer and the second layer can be further improved.

Specific examples of the monofunctional isocyanate compound having a photopolymerizable ethylenically unsaturated group include Karenz MOI (manufactured by Showa Denko KK), Karenz AOI (manufactured by Showa Denko KK), and Karenz BEI (Showa Denko KK). (Made).

Further, the precursor of the monofunctional isocyanate compound is preferably a compound in which the isocyanate group of the monofunctional isocyanate compound is blocked. When the isocyanate group is blocked, the isocyanate group is in a precursor state of the isocyanate group which has reacted with, for example, a substituent desorbed by heat, and the reactivity as the isocyanate group is suppressed. It means that it is.

Specific examples of the monofunctional isocyanate compound in which the isocyanate group is blocked include 2- ([1'-methylpropylideneamino] carboxyamino) ethyl methacrylate (for example, Karenz MOI-BM manufactured by Showa Denko Co., Ltd.). (Registered Trademark)), 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate (for example, Carenz MOI-BP (registered trademark) manufactured by Showa Denko Co., Ltd.) and the like.
Specific examples of the polyfunctional isocyanate compound in which the isocyanate group is blocked include Duranate TPA-B80E (Asahi Kasei Corporation).

The content of the isocyanate compound or its precursor is preferably 0.1% by mass to 10% by mass, more preferably 1% by mass to 5% by mass, based on the total mass of the first layer. .. When the content of the isocyanate compound or its precursor is in the above range, the adhesion between the first layer and the second layer can be effectively improved.

Further, the first layer may contain tetrazole or a derivative thereof, benzotriazole, benzimidazole or the like as an adhesion improver in order to improve the adhesion between the first layer and the second layer. it can.
Examples of tetrazole or derivatives thereof include 1-phenyltetrazole, 5-phenyltetrazole, 5-aminotetrazole, 5-amino-1-methyltetrazole, 5-amino-2-phenyltetrazole, 5-mercapto-1-phenyltetrazole. , 5-Mercapto-1-methyltetrazole and the like, and these may be one kind, or two or more kinds.

The content of tetrazole or a derivative thereof, benzotriazole, and benzimidazole is preferably 0.01% by mass to 1% by mass, and 0.05% by mass to 0.5% by mass, based on the total mass of the first layer. More preferably. When the content of tetrazole or a derivative thereof, benzotriazole, and benzimidazole is in the above range, the adhesion between the first layer and the second layer can be effectively improved.

--Surfactant ---
Surfactants can be included. By including the surfactant, the uniformity of the thickness of the first layer can be enhanced.
Examples of the surfactant include silicone-based surfactants and fluorine-based surfactants.
Examples of the silicone-based surfactant include a surfactant having a siloxane bond. Specifically, for example, Toshiba Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Torre Silicone Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341, KF6001, KF6002, KF6003, X22-160AS (manufactured by Shinetsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Made) and so on.

Moreover, as a fluorine-based surfactant, a surfactant having a fluorocarbon chain can be mentioned. Specifically, all of them are trade names, for example, Fluorinert FC430, Fluorinert FC431 (all manufactured by Sumitomo 3M Co., Ltd.); Megafuck F142D, Megafuck F171, Megafuck F172, Megafuck F173, Megafuck F177, Megafuck. F780F, Mega Fuck F781F, Mega Fuck F479, Mega Fuck F482, Mega Fuck F551A, Mega Fuck F553, Mega Fuck F554, Mega Fuck F486, Mega Fuck F478, Mega Fuck F480, Mega Fuck F484, Mega Fuck F470, Mega Fuck F471, Mega Fuck F483, Mega Fuck F489, Mega Fuck F487, Mega Fuck F444, Mega Fuck F183, Mega Fuck R30 (above, manufactured by DIC Corporation); Ftop EF301, Ftop EF303, Ftop EF351, Ftop EF352 (above, Shin-Akita Kasei Co., Ltd.); Surflon S381, Surflon S382, Surflon SC101, Surflon SC105 (all manufactured by Asahi Glass Co., Ltd.); E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.); BM-1000, BM-1100 (BM Chemie) (Made) and so on.

Further, a silicone-based surfactant having a fluorine atom having a siloxane bond and a fluorocarbon chain can be mentioned. Specifically, all of them are trade names, and examples thereof include MegaFvck R08, MegaFvck BL20, MegaFvck F475, MegaFvck F477, and MegaFvck F443 (all manufactured by DIC Corporation).
These other surfactants may be used alone or in combination of two or more.

(Second layer)
The transfer material of the present disclosure contains an aqueous solvent or a lower alcohol solvent or a resin soluble in a mixed solvent of the aqueous solvent and the lower alcohol solvent and an ultraviolet absorber arranged on the first layer. It has a second layer.
The second layer is preferably an antireflection layer.

The thickness of the second layer is preferably 0.05 μm or more and 2 μm or less, and more preferably 0.05 μm or more and 1 μm or less. When the thickness of the second layer is 0.05 μm or more, the antireflection effect in the second layer is sufficiently exhibited, and it is possible to provide a transfer material capable of forming a pattern excellent in pattern linearity and pattern shape. .. Further, when the thickness of the second layer is 2 μm or less, the formation of undercuts is suppressed, and a transfer material capable of forming a pattern having an excellent pattern shape can be provided.

Since the first layer is solvent-based and the second layer is water-based, the first layer and the second layer are preferably separated. By separating the first layer and the second layer, the function of each layer is maintained without being impaired.

-A resin soluble in an aqueous solvent or a lower alcohol solvent or a mixed solvent of an aqueous solvent and a lower alcohol solvent-
The second layer of the present disclosure contains a resin soluble in an aqueous solvent or a lower alcohol solvent or a mixed solvent of the aqueous solvent and the lower alcohol solvent.
In the present disclosure, "soluble in an aqueous solvent or a lower alcohol solvent or a mixed solvent of an aqueous solvent and a lower alcohol solvent" means an aqueous solvent or a lower alcohol solvent or an aqueous solvent and a lower alcohol solvent at 25 ° C. 0.5% by mass or more, preferably 1% by mass or more, more preferably 3% by mass, based on the total mass of the water-based solvent, the lower alcohol-based solvent, or the mixed solvent of the water-based solvent and the lower alcohol-based solvent. It means to dissolve above.

The resin soluble in an aqueous solvent, a lower alcohol solvent, or a mixed solvent of the aqueous solvent and the lower alcohol solvent contains a water-soluble or lower alcohol-soluble resin as a skeleton. Preferably, the resin soluble in an aqueous solvent, a lower alcohol solvent, or a mixed solvent of the aqueous solvent and the lower alcohol solvent is a resin having a functional group or a functional moiety capable of causing a cross-linking reaction by heating. Examples of the resin containing such a skeleton include polyvinyl alcohol-based resins that have a hydroxy group as a hydrophilic structural unit [for example, polyvinyl alcohol (PVA), acetoacetyl-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, and anion-modified. Polyvinyl alcohol, silanol-modified polyvinyl alcohol, polyvinyl acetal, etc.], Cellular resins [for example, methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl Chitin-based compounds, chitosan-based compounds, starch-based compounds, resins having ether bonds such as methyl cellulose and hydroxypropyl methyl cellulose [for example, polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyvinyl ether (PVE)) Etc.], resins having a carbamoyl group [for example, polyacrylamide (PAAM), polyvinylpyrrolidone (PVP), polyacrylic acid hydrazide, etc.] and the like.

More specifically, the resin soluble in an aqueous solvent, a lower alcohol solvent, or a mixed solvent of the aqueous solvent and the lower alcohol solvent is, for example, a 20% aqueous solution of polyvinyl acetal resin (manufactured by Sekisui Chemical Industry Co., Ltd., Eslek () Registered trademark) KW-1: acetalization degree 9 mol%, hydroxyl group content 90 mol%), polyvinyl acetal resin 10% aqueous solution (manufactured by Kuraray Co., Ltd., PVA205C: saponification degree 88 mol%, hydroxyl group content 88 mol%, polymerization degree 550 10 % Dissolved in water to form an aqueous solution), sodium methacrylate / allyl methacrylate copolymer resin (composition ratio = 40/60, molecular weight 15,000, solid content concentration 5%), methacrylate / methyl methacrylate copolymer resin (Composition ratio = 40/60, molecular weight 15000), partially neutralized sodium polyacrylate (ARONVIS® AH-105X manufactured by Toa Synthetic Co., Ltd.), and a compound having the following structure [molecular weight (Mw) = 10500, Dispersion degree (Mw / Mn) = 1.76; It can be synthesized according to Synthesis Example 1 of JP-A-2008-257188. The numerical value at the lower right of each structural unit is the molar ratio. ] And so on.

The resin soluble in an aqueous solvent, a lower alcohol solvent, or a mixed solvent of the aqueous solvent and the lower alcohol solvent preferably has an acid group. A resin soluble in an aqueous solvent, a lower alcohol solvent, or a mixed solvent of an aqueous solvent and a lower alcohol solvent has an acid group, so that the unexposed portion is excellent in developability and removability.
The acid group can be appropriately selected depending on the intended purpose without any particular limitation. Examples thereof include a carboxyl group, a sulfonic acid group and a phosphoric acid group, and among these, a carboxyl group is preferable.
Examples of the resin soluble in an aqueous solvent having a carboxyl group, a lower alcohol solvent, or a mixed solvent of the aqueous solvent and the lower alcohol solvent include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, and a modification. Examples thereof include epoxy resins, and among them, vinyl copolymers having a carboxyl group are preferable from the viewpoints of solubility in a solvent, solubility in a developing solution, synthetic suitability, and ease of adjusting film physical properties.
Further, from the viewpoint of developability, a copolymer of at least one of styrene and a styrene derivative is also preferable.

--Aqueous solvent or lower alcohol solvent or mixed solvent of aqueous solvent and lower alcohol solvent ---
In the present disclosure, the "aqueous solvent" includes pure water, a solution in which a low-molecular-weight acid or base is dissolved in pure water, and aqueous ammonia (for example, 1% to 5% aqueous ammonia).
Here, the "low molecular weight acid or base" includes, for example, acetic acid, propionic acid, phosphoric acid, monomethanolamine, dimethylamine, trimethylamine, or ammonium salt.
The concentration of the low molecular weight acid or base is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

In the present disclosure, the "lower alcohol solvent" includes monohydric alcohols having 1 to 3 carbon atoms, that is, methanol, ethanol, 1-propanol, and 2-propanol (hereinafter, also referred to as "lower alcohol"). ..

The mixing ratio of the mixed solvent of the aqueous solvent and the lower alcohol solvent can be appropriately set according to the purpose. The mixing ratio of the aqueous solvent and the lower alcohol solvent (aqueous solvent / lower alcohol solvent) may be, for example, 1% by mass to 99% by mass / 99% by mass to 1% by mass, preferably 10% by mass. ~ 90% by mass / 90% by mass / 10% by mass.

-UV absorber-
The second layer of the present disclosure contains an ultraviolet absorber capable of absorbing light in the wavelength region of an exposure light source (preferably including a wavelength of 365 nm) in order to prevent reflection from the substrate.
Preferably, the ultraviolet absorber contained in the second layer is an ultraviolet absorber that is soluble in an aqueous solvent, a lower alcohol solvent, or a mixed solvent of the aqueous solvent and the lower alcohol solvent. The ultraviolet absorber contained in the second layer may be an aqueous solvent such as carbon black, a lower alcohol solvent, or an ultraviolet absorber insoluble in a mixed solvent of the aqueous solvent and the lower alcohol solvent.
The ultraviolet absorber may be used alone or in combination of two or more.

The ultraviolet absorber is preferably an ultraviolet absorber having a large molar extinction coefficient with respect to light having a wavelength of 365 nm.
^{The molar extinction coefficient was prepared by preparing an ultraviolet absorber into a solution of 4 × 10-6} (g / ml) using N, N-dimethylformamide, and measuring this solution with a UV measuring device UV2550 manufactured by Shimadzu Corporation. Therefore, it can be calculated by the formula of [molar extinction coefficient] = [absorbance] / [mass concentration of solution / molecular weight of absorbent compound].

The molar extinction coefficient of the UV absorber is preferably 5000 to 100,000 (l / mol · cm), more preferably 1000 to 80,000 (l / mol · cm), and even more preferably 1500 to 50000 (l / mol). mol · cm). When the molar extinction coefficient is in the above range, the effect of preventing the reflection of light from the exposure light source is sufficiently exhibited, and an undesired polymerization reaction can be prevented.

As the ultraviolet absorber, for example, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based ultraviolet absorber can be used.
Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like.
Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone. , 2-Hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone and the like.

Examples of preferable benzotriazole-based ultraviolet absorbers include compounds having a structure represented by the following general formula (1).

In the general formula (1), R ¹ independently represents a hydrogen atom or an organic group having 1 to 15 carbon atoms, n ₁ represents an integer of 0 to 4, and R ² independently represents a hydrogen atom. It represents a hydrogen atom or an organic group having 1 to 15 carbon atoms, and n ₂ represents an integer of 0 to 4.

The organic group having 1 to 15 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms.

In R ^1, an alkyl group having 1 to 15 carbon atoms may be linear, branched or cyclic substituted or unsubstituted alkyl group. The alkyl group having 1 to 12 carbon atoms is, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, or n-. Pentyl group, i-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, i-octyl group, t-octyl group, dodecyl group, cyclopropyl, 1-ethylcyclopropyl, cyclopentyl, cyclohexyl, etc. Good.

When ^{the alkyl group of R 1} has a substituent, preferred substituents are a halogen atom (F, Cl, Br, I, etc.), a cyano group, an alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, methoxyethoxyethoxy group). Groups, etc.), aryloxy groups (phenoxy groups, etc.), alkylthio groups (methylthio groups, ethylthio groups, etc.), alkoxycarbonyl groups (ethoxycarbonyl groups, etc.), polyoxyethylenecarbonyl groups, carbonate ester groups (ethoxycarbonyloxy groups, etc.) , Acyl group (acetyl group, propionyl group, benzoyl group, etc.), sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.), acyloxy group (acetoxy group, benzoyloxy group, acryloyloxy group, methacryloyloxy group, etc.), sulfonyloxy group (Methanesulfonyloxy group, toluenesulfonyloxy group, etc.), phosphonyl group (diethylphosphonyl group, etc.), amide group (acetylamino group, benzoylamino group, etc.), carbamoyl group (N, N-dimethylcarbamoyl group, etc.), aryl Group (phenyl group, toluyl group, etc.), heterocyclic group (pyridyl group, imidazolyl group, furanyl group, etc.), alkenyl group (vinyl group, 1-propenyl group, etc.), trialkoxysilyl group (triethoxysilyl group, etc.), Examples thereof include a silyloxy group.

In R ^1, a halogen atom, fluorine (F), chlorine (Cl), it may be bromine (Br), or iodine (I).

n ₁ represents an integer from 0 to 4. Preferably, n ₁ is 0.

In R ^2, an alkyl group having 1 to 15 carbon atoms may be linear, branched or cyclic substituted or unsubstituted alkyl group. The alkyl group having 1 to 12 carbon atoms is, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, or n-. Pentyl group, i-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, i-octyl group, t-octyl group, dodecyl group, cyclopropyl, 1-ethylcyclopropyl, cyclopentyl, cyclohexyl, etc. Good. Preferably, R ² is a substituted or unsubstituted butyl group.

When the alkyl group R ² has a substituent, examples of preferred substituents, a halogen atom (F, Cl, Br, I, etc.), a cyano group, an alkoxy group (methoxy group, an ethoxy group, methoxyethoxy group, methoxyethoxyethoxy Groups, etc.), aryloxy groups (phenoxy groups, etc.), alkylthio groups (methylthio groups, ethylthio groups, etc.), alkoxycarbonyl groups (ethoxycarbonyl groups, etc.), polyoxyethylenecarbonyl groups, carbonate ester groups (ethoxycarbonyloxy groups, etc.) , Acyl group (acetyl group, propionyl group, benzoyl group, etc.), sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.), acyloxy group (acetoxy group, benzoyloxy group, acryloyloxy group, methacryloyloxy group, etc.), sulfonyloxy group (Methanesulfonyloxy group, toluenesulfonyloxy group, etc.), phosphonyl group (diethylphosphonyl group, etc.), amide group (acetylamino group, benzoylamino group, etc.), carbamoyl group (N, N-dimethylcarbamoyl group, etc.), aryl Group (phenyl group, toluyl group, etc.), heterocyclic group (pyridyl group, imidazolyl group, furanyl group, etc.), alkenyl group (vinyl group, 1-propenyl group, etc.), trialkoxysilyl group (triethoxysilyl group, etc.), Examples thereof include a silyloxy group.

n ₂ represents an integer from 0 to 4. Preferably n ₂ is 1 or 2.

Examples of preferred benzotriazole-based UV absorbers include 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 2- [2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro -2H-benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5) '-Isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl -5'-propylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methyl Examples thereof include phenyl) benzotriazole and 2- [2'-hydroxy-5'-(1,1,3,3-tetramethyl) phenyl] benzotriazole.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like.
Examples of triazine-based UV absorbers are 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)-. 1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-Triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-Triazine and other mono (hydroxyphenyl) triazine compounds; 2 , 4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4) −propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2,4) -Bis (hydroxyphenyl) triazine compounds such as dimethylphenyl) -1,3,5-triazine; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl)- 1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (2-hydroxy-4- ( Examples thereof include tris (hydroxyphenyl) triazine compounds such as 3-butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-triazine.

In addition, ADEKA Corporation's ADEKA STAB (registered trademark) LA-24, LA-29, LA-31, LA-31RG, LA-31G, LA-32, LA-, which are commercially available compounds and are benzotriazole-based ultraviolet absorbers. 36, LA-36G, LA-46, LA-F70 manufactured by ADEKA Corporation may be used as the triazine-based UV absorber, and 1413 manufactured by ADEKA Corporation may be used as the benzophenone-based UV absorber.

Further, as an ultraviolet absorber having a large molar absorption coefficient with respect to light having a wavelength of 365 nm, for example, 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid, 2- (4-dibutylamino-2-hydroxybenzoyl) Orthoperic acid, 2,2', 4,4'-tetrahydroxybenzophenone, 2,3,3', 4,4', 5'-hexahydroxybenzophenone, usnic acid, phenylfluorone, rosolic acid, 1, 8,9-Trihydroxyanthracene, 2- (4-hydroxyphenylazo) benzoic acid, methyl red, 4,4'-diaminobenzophenone, 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone), 3, 4-Diaminobenzophenone, curcumin, and α-cyano-4-hydroxycinnamic acid, octyl methoxycinnamate, octyl dimethoxybenzylidene dioxoimidazolidine propionate, hexyl diethylaminohydroxybenzoyl benzoate, t-butylmethoxydibenzoylmethane, octyl Examples thereof include triazone and 2-ethylhexyl paramethoxysilicate.

Preferred UV absorbers include, for example, TINUVIN® P, TINUVIN109, TINUVIN171, TINUVIN234, TINUVIN326, TINUVIN326FL, TINUVIN327, TINUVIN328, TINUVIN329, TINUVIN329FL, TINUVIN384, TINUVIN490 (Made) can be mentioned.

Further, the ultraviolet absorber may be a compound capable of absorbing wavelengths in the visible region, and a commercially available dye may be used. For example, a phthalocyanine compound or a black pigment can be added.

The content of the ultraviolet absorber is preferably 5% by mass or more and less than 80% by mass with respect to the total solid content of the second layer. When the content of the ultraviolet absorber is within the above range, the effect of preventing reflection of light from the exposure light source becomes sufficient.

-Polymerizable compound with ethylenically unsaturated double bond-
The second layer can further contain a polymerizable compound having an ethylenically unsaturated double bond. When the second layer contains a polymerizable compound having an ethylenically unsaturated double bond, the adhesion to the first layer can be improved.
The polymerizable compound having an ethylenically unsaturated double bond that can be contained in the second layer is the "polymerizable compound having an ethylenically unsaturated double bond" described in the section of "(first layer)". ". Preferably, the polymerizable compound having an ethylenically unsaturated double bond that can be contained in the second layer is soluble in an aqueous solvent or a lower alcohol solvent or a mixed solvent of the aqueous solvent and the lower alcohol solvent. It is a polymerizable compound having an ethylenically unsaturated double bond.
The content of the polymerizable compound having an ethylenically unsaturated double bond in the second layer is preferably 0.1% by mass to 30% by mass, preferably 0.1% by mass to the total mass of the second layer. 10% by mass is more preferable, 0.5% by mass to 5% by mass is further preferable, and 0.5% by mass to 2% by mass is particularly preferable.

-Photopolymerization initiator-
The second layer can further contain a photopolymerization initiator. By including the photopolymerization initiator in the second layer, the polymerization of the polymerizable compound having an ethylenically unsaturated double bond can be promoted.
The photopolymerization initiator that can be contained in the second layer is the "photopolymerization initiator" described in the section "(first layer)". Preferably, the photopolymerization initiator that can be contained in the second layer is a photopolymerization initiator that is soluble in an aqueous solvent or a lower alcohol solvent or a mixed solvent of the aqueous solvent and the lower alcohol solvent.

The content of the photopolymerization initiator in the second layer is not particularly limited, but is preferably 0.01% by mass or more and 5% by mass or less, and 0.01% by mass or more 3 with respect to the total mass of the second layer. It is more preferably mass% or less, and even more preferably 0.05 mass% or more and 1 mass% or less. When the content of the photopolymerization initiator is in the above range, the polymerization of the polymerizable compound having an ethylenically unsaturated double bond can be promoted.

− Solvent −
The coating liquid of the second layer may contain a solvent.
By containing a solvent, the coating liquid of the second layer can improve the adhesion between the temporary support and the first layer and / or between the first layer and the second layer.
The solvent may be one type alone or a mixture of two or more types.

The solvent contained in the coating liquid of the second layer is preferably an aqueous solvent. Preferred solvents include, for example, water (including ion-exchanged water and pure water), 1% to 5% aqueous ammonia, lower alcohols (eg, methanol, ethanol, 1-propanol, 2-propanol, n-butanol, sec. -Butanol, or tert-butanol), propylene glycol monomethyl ether acetate (PGMEA) and the like.

The content of the solvent in the coating liquid of the second layer is preferably 50% by mass or more and 99% by mass or less, more preferably 60% by mass or more and 98% by mass or less, and 80% by mass with respect to the total mass of the second layer. % To 95% by mass is even more preferable.

(Other layers)
The transfer material of the present disclosure may further include other layers such as a contrast enhancement layer.

(Protective film)
The transfer material of the present disclosure has a protective film placed on top of a second layer.
The protective film has a function of preventing dirt or damage of the second layer and protecting the first layer and the second layer.

The protective film may be made of the same material as the temporary support or may be made of a different material. The protective film is, for example, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polyimide film, polycarbonate film, polyethylene, polypropylene, cellophane, polyethylene naphthalate, silicone paper, polyethylene or paper laminated with polypropylene or the like. Good. Of these, polyethylene terephthalate is preferable from the viewpoint of less fisheye and adhesion to the second layer.
The thickness of the protective film may be 5 μm to 100 μm, preferably 10 μm to 50 μm, and more preferably 12 μm to 40 μm from the viewpoint of flexibility and curl.

-Fish eye-
"Fisheye" refers to foreign matter, undissolved material, gel-like material, when the material for forming the protective film is heat-melted, kneaded, extruded, biaxially stretched, cast, etc. to produce the film. A substantially circular defect that occurs when a deteriorated product is incorporated into the film.

In the present disclosure, the term "number of fish eyes" refers to the number of fish eyes of 0.3 mm ² or more visually counted in a protective film having a size of 300 mm × 200 mm, with 1000 square meters (m ² ) as a unit area. It is a converted value.
The area of the fish eye can be obtained by performing image processing on the defective portion observed with an optical microscope and measuring the area.

The number of fish eyes of 0.3 mm ² or more is preferably 8 or less, more preferably 2 or less, and even more preferably 1 or less per ^{1000 square meters (m 2).} It is particularly preferable that the number is 0. When the number of fish eyes of 0.3 mm ² or more is within the above range, the laminateability when the transfer material of the present disclosure is brought into close contact with the substrate is improved.

<Manufacturing method of transfer material>
In the method for producing a transfer material of the present disclosure, a polymerizable compound having an ethylenically unsaturated double bond, a photopolymerization initiator, and an alkali-soluble resin are placed on a temporary support in an ester solvent, a ketone solvent, or an ester solvent. The step of forming the first layer by applying and drying the first composition dissolved in a mixed solvent of and a ketone solvent, a resin and an ultraviolet absorber are added to the water-based solvent on the first layer. Alternatively, a step of applying and drying a second composition dissolved in a lower alcohol solvent or a mixed solvent of an aqueous solvent and a lower alcohol solvent to form a second layer, and a step of forming the second layer, and The step of laminating the protective film is included on the top.

(Step of forming the first layer)
In the method for producing a transfer material of the present disclosure, a polymerizable compound having an ethylenically unsaturated double bond, a photopolymerization initiator, and an alkali-soluble resin are placed on a temporary support in an ester solvent, a ketone solvent, or an ester solvent. It comprises a step of applying a first composition dissolved in a mixed solvent of and a ketone solvent and drying to form a first layer.

-Temporary support-
The temporary support is the "temporary support" described in the section "<Transfer Material>" of the present disclosure.

-First composition-
The first composition comprises a polymerizable compound having an ethylenically unsaturated double bond, a photopolymerization initiator, and an alkali-soluble resin in an ester solvent or a ketone solvent, or a mixed solvent of an ester solvent and a ketone solvent. Obtained by dissolving in.

--Polymerizable compound with ethylenically unsaturated double bond ---
The polymerizable compound having an ethylenically unsaturated double bond is the “polymerizable compound having an ethylenically unsaturated double bond” described in the section “<Transfer material>” of the present disclosure, and is an ester solvent or a ketone. It is a polymerizable compound having an ethylenically unsaturated double bond that is soluble in a system solvent or a mixed solvent of an ester solvent and a ketone solvent.

In the present disclosure, "soluble in an ester solvent or a ketone solvent or a mixed solvent of an ester solvent and a ketone solvent" means an ester solvent or a ketone solvent or an ester solvent and a ketone solvent at 25 ° C. 0.5% by mass or more, preferably 1% by mass or more, more preferably 3% by mass, based on the total mass of the ester solvent, the ketone solvent, or the mixed solvent of the ester solvent and the ketone solvent. The photopolymerization initiator that dissolves as described above.

--Photopolymerization initiator ---
The photopolymerization initiator used in the method for producing a transfer material is the "photopolymerization initiator" described in the section "<Transfer Material>" of the present disclosure, and is an ester solvent or a ketone solvent or an ester solvent and a ketone solvent. A photopolymerization initiator that is soluble in a mixed solvent with a solvent.

--Alkali-soluble resin ---
The alkali-soluble resin used in the method for producing a transfer material is the "alkali-soluble resin" described in the section "<Transfer material>" of the present disclosure, and includes an ester solvent or a ketone solvent or an ester solvent and a ketone solvent. It is an alkali-soluble resin that is soluble in the mixed solvent of.

--Ester solvent ---
Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, butyl acetate, isobutyl acetate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, methyl pyruvate and ethyl pyruvate. , Methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethyl acetate and the like.

--Ketone solvent ---
Examples of the ketone solvent include acetone, diacetone alcohol, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone and the like.

-Applying-
As a method of applying the first composition, various methods can be used, for example, slit coater coating, bar coater coating, rotary coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, etc. Roll coating and the like can be mentioned.

In order to prevent damage to the lower layer, the coating is preferably a non-contact type, and the coating by the slit method is more preferable.
As a coating method by the slit method, from the viewpoint of maintaining height accuracy and performing uniform coating, it is preferable to perform coating using a slit-shaped nozzle having a slit-shaped hole in the portion where the liquid is discharged. Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-17098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. A slit coater having a slit-shaped nozzle described in Japanese Patent Application Laid-Open No. 2001-310147, etc. is preferably used.
In slit coating, a coating head having a slit (gap) with a width of several tens of μm at the tip and a length corresponding to the coating width of a rectangular substrate has a clearance (gap) with the substrate of several tens of μm to several hundreds of μm. While holding the substrate and the coating head, the substrate and the coating head can be provided with a constant relative velocity, and the coating liquid supplied from the slit can be applied to the substrate at a predetermined discharge amount.

− Drying −
The applied first composition is dried using a hot plate, an oven, etc., for example, in a temperature range of 50 ° C. to 140 ° C., preferably 80 ° C. to 120 ° C. for 10 seconds to 300 seconds, preferably 30. It can be performed under the condition of seconds to 120 seconds.

The drying may be incomplete drying. Here, "incomplete drying" means that the solvent is present in an amount of more than 0% by mass, preferably 0.1% by mass or more and 95% by mass, based on the total mass of the first composition applied. Hereinafter, it is more preferably 1% by mass or more and 90% by mass or less, and even more preferably 10% by mass or more and 50% by mass or less. By applying and drying the second composition in a state where the first composition is incompletely dried, the adhesion between the first layer and the second layer can be improved.
In the present disclosure, the first layer contains an ester solvent or a ketone solvent or a mixed solvent of an ester solvent and a ketone solvent, whereas the second layer is an aqueous solvent or a lower alcohol solvent or an aqueous solvent. Since it contains a mixed solvent of and a lower alcohol solvent, even if the first layer forms the second layer while remaining "incompletely dried", it is still between the first layer and the second layer. The interface is preferably retained so that the functions of the first layer and the second layer are not impaired.

(Step of forming the second layer)
The method for producing a transfer material of the present disclosure is a second method in which a resin and an ultraviolet absorber are dissolved on a first layer in an aqueous solvent or a lower alcohol solvent or a mixed solvent of an aqueous solvent and a lower alcohol solvent. It comprises the steps of applying and drying the composition to form a second layer.

-Second composition-
The second composition is obtained by dissolving the resin and the ultraviolet absorber in an aqueous solvent or a lower alcohol solvent or a mixed solvent of the aqueous solvent and the lower alcohol solvent.

--Resin ---
The resin contained in the second composition is a resin soluble in an aqueous solvent, a lower alcohol solvent, or a mixed solvent of the aqueous solvent and the lower alcohol solvent. The resin contained in the second composition is a resin soluble in the "water-based solvent or lower alcohol-based solvent or a mixed solvent of the water-based solvent and the lower alcohol-based solvent" described in the section "<Transfer material>" of the present disclosure. ".

--UV absorber ---
The ultraviolet absorber contained in the second composition is the "ultraviolet absorber" described in the section "<Transfer Material>" of the present disclosure.

--Aqueous solvent or lower alcohol solvent or mixed solvent of aqueous solvent and lower alcohol solvent ---
The aqueous solvent or lower alcohol solvent contained in the second composition or the mixed solvent of the aqueous solvent and the lower alcohol solvent is the "aqueous solvent or lower alcohol solvent" described in the section "<Transfer Material>" of the present disclosure. It is a solvent or a mixed solvent of an aqueous solvent and a lower alcohol solvent.

-Applying-
The coating is the same as the coating described in the section "(First layer)".

− Drying −
Drying is similar to the drying described in the section "(First Layer)".

(The process of pasting a protective film on the second layer)
The method for producing a transfer material includes a step of laminating a protective film on the second layer.

-Protective film-
The protective film used in the method for producing a transfer material is the "protective film" described in the section "<Transfer material>".

-Lasting-
The bonding can be performed by laminating a protective film on the second layer so that air bubbles do not enter. The bonding is preferably performed while pressurizing.

<Pattern formation method>
The pattern forming method of the present disclosure includes a step of peeling off a protective film of the transfer material of the present disclosure, a step of arranging a temporary support of the transfer material, a first layer, and a second layer on a substrate, and a temporary support. And a step of exposing the first layer and the second layer through an exposure mask, a step of peeling off the temporary support, and a step of developing the first layer and the second layer.

(Step of peeling off the protective film of the transfer material of the present disclosure)
The pattern forming method of the present disclosure includes a step of peeling off the protective film of the transfer material of the present disclosure.
The protective film of the transfer material can be peeled off by using any peeling means.

(Step of arranging the temporary support of the transfer material, the first layer, and the second layer on the substrate)
The pattern forming method of the present disclosure includes a step of arranging a temporary support, a first layer, and a second layer of the transfer material of the present disclosure on the substrate.

The step of arranging the temporary support, the first layer and the second layer of the transfer material of the present disclosure on the substrate is a step of crimping the temporary support, the first layer and the second layer on the substrate. It may be there. When the substrate is a resin substrate, roll-to-roll crimping may be performed.
The method of crimping the substrate with the temporary support, the first layer and the second layer is not particularly limited, and a known transfer method and laminating method can be used.
Specifically, for example, it is preferable to stack the second layer side after peeling off the protective film on the substrate and pressurize with a roll or the like, or pressurize and heat. For bonding, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.

The crimping pressure and temperature in the above steps are not particularly limited and can be appropriately set according to the temporary support, the materials of the first layer and the second layer, the transport speed, and the crimping machine to be used.
For example, the crimping pressure in the above step may be 0.1 MPa to 5 MPa, preferably 0.5 MPa to 3 MPa, and more preferably 0.8 MPa to 1.5 MPa.
For example, the temperature in the above step may be 50 ° C. to 150 ° C., preferably 70 ° C. to 120 ° C., and more preferably 85 ° C. to 105 ° C.

-Board-
The substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the material of the substrate may be a glass substrate, a resin substrate, a metal substrate, a ceramic plate, a silicon wafer used for a semiconductor substrate, or the like. The substrate may have a shape such as a plate shape, a film shape, or a sheet shape. The substrate may be transparent or opaque.

Examples of the metal substrate include an aluminum plate, a copper plate, a nickel plate, a stainless plate, and the like.
Examples of the glass substrate include transparent glass, white plate glass, blue plate glass, and silica-coated blue plate glass. Further, a thin glass substrate having a thickness of 10 μm to several hundred μm, which has been developed in recent years, may be used.
Examples of the resin substrate include polyethylene terephthalate film, polycarbonate film, cellulose triacetate film, polyether sulfone film, polyester film, acrylic resin film, vinyl chloride resin film, aromatic polyamide resin film, polyamideimide film, and polyimide film. Can be mentioned.
Examples of the metal substrate include an aluminum plate, a copper plate, a nickel plate, a stainless plate, and the like.

Further, the substrate may be a substrate having copper layers on both sides or one side of an insulating base material such as a glass substrate or a resin substrate, and may be, for example, a copper-clad laminate (CCL).
The "insulating base material" does not necessarily have to have a complete insulating property, and it is sufficient that the "insulating base material" has an insulating property that can achieve the object of the present disclosure. The insulating base material is preferably a resin substrate from the viewpoint of flexibility, for example, polyethylene terephthalate film, polycarbonate film, cellulose triacetate film, polyether sulfone film, polyester film, acrylic resin film, vinyl chloride resin film, aromatic polyamide. A resin film, a polyamideimide film, a polyimide film and the like can be used, and a polyethylene terephthalate film is preferable from the viewpoint of ease of handling and versatility.

To form the copper layer, for example, the copper foil is heat-bonded to the insulating base material via an adhesive layer, the insulating base material itself is heat-bonded to the copper foil, and the insulating material is cast and heated on the copper foil. This can be done by forming a copper layer by sputtering or plating, and it is preferable to form a copper layer by sputtering.

If desired, the substrate can be subjected to pretreatment such as chemical treatment such as silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction method, vacuum deposition and the like.

The thickness of the substrate is not particularly limited, but is preferably 5 μm to 200 μm, preferably 5 μm to 40 μm, more preferably 5 μm to 25 μm, and 5 μm from the viewpoint of ease of handling and versatility. It is particularly preferably ~ 16 μm.

-Transfer material-
The transfer material used in the pattern forming method is as described in the section "<Transfer material>".

--Temporary support ---
The first layer used in the pattern forming method is the "temporary support" described in the section "<Transfer Material>".

--First layer ---
The first layer used in the pattern forming method is the "first layer" described in the section "<Transfer material>".

--Second layer ---
The second layer used in the pattern forming method is the "second layer" described in the section "<Transfer Material>".

(Step of exposing the first layer and the second layer through the temporary support and the exposure mask)
The pattern forming method of the present disclosure includes a step of exposing the first layer and the second layer via a temporary support and an exposure mask. By exposing the first layer and the second layer through the temporary support and the exposure mask, the first layer and the second layer of the exposed portion are cured, and the curing does not elute into the developing solution. By forming the film, a resist pattern is formed.

As the light source for exposure, any light source in a wavelength range capable of curing the first layer and the second layer (including, for example, a wavelength of 365 nm or 405 nm) can be appropriately selected and used. .. In the exposure step, it is preferable to irradiate light in a wavelength range including a wavelength of 365 nm.
Examples of the light source include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and the like.
Exposure is preferably ^{5mJ / cm 2 ~200mJ / cm 2} , more preferably ^{10mJ / cm 2 ~200mJ / cm 2} . When the exposure amount is in the above range, a cured film containing the first layer and the second layer can be appropriately formed.

In the step of exposure, after exposure and before development, for example, it may be left at room temperature for 30 minutes to 2 hours, or the exposed first layer and second layer are heat-treated (so-called PEB (Post Exposure Bake)). )) May be applied.

Is preferable. After exposure, for example, it may be left at room temperature for 30 minutes to 2 hours, or the exposed first layer and second layer may be heat-treated, and then the temporary support may be peeled off before development. preferable.

(Step of peeling off the temporary support)
The pattern forming method of the present disclosure includes a step of peeling off the temporary support after the step of exposing and before the step of developing. The temporary support can be peeled off by any peeling means.

(Step of developing the first layer and the second layer)
The pattern forming method of the present disclosure includes a step of developing a first layer and a second layer after exposure. In the developing step, the pattern-exposed first layer and the second layer are developed (that is, the unexposed portion is dissolved in a developing solution) to obtain a pattern according to the pattern exposure. ..

The developer used for development is not particularly limited, and a known developer such as the developer described in JP-A-5-72724 can be used.
As the developing solution, it is preferable to use an alkaline aqueous solution.
Examples of the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. , Tetrabutylammonium hydroxide, choline (2-hydroxyethyltrimethylammonium hydroxide), and the like.
The pH of the alkaline aqueous solution at 25 ° C. is preferably more than pH 7 and preferably pH 14 or less, more preferably pH 8 to pH 13, even more preferably pH 9 to pH 12, and particularly preferably pH 10 to pH 12.
The content of the alkaline compound in the alkaline aqueous solution is preferably 0.1% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass, based on the total amount of the alkaline aqueous solution.

The developer may contain an organic solvent that is miscible with water.
Examples of the organic solvent include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol, acetone and methyl ethyl ketone. , Cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone.
The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass with respect to the total mass of the developing solution.
The developer may contain a known surfactant. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass with respect to the total mass of the developing solution.
The liquid temperature of the developing solution is preferably 20 ° C. to 40 ° C.

Examples of the development method include paddle development, shower development, shower and spin development, and dip development.
When shower development is performed, the unexposed portions of the first layer and the second layer are removed by spraying the developing solution on the first layer and the second layer after pattern exposure in a shower shape.
Further, after the development, it is preferable to remove the development residue by rubbing with a brush or the like while spraying a cleaning agent or the like with a shower.
Development is preferably carried out for 10 to 60 seconds.

The developing step may include a step of performing the above-mentioned development and a step of heat-treating the cured film obtained by the above-mentioned development (hereinafter, also referred to as "post-baking").
When the substrate is a resin substrate, the post-baking temperature is preferably 100 ° C. to 160 ° C., more preferably 130 ° C. to 160 ° C.
By this post-baking, the resistance value of the transparent electrode pattern can also be adjusted.
When the first layer and the second layer contain a carboxyl group-containing (meth) acrylic resin, at least a part of the carboxyl group (meth) -containing acrylic resin is changed to a carboxylic acid anhydride by post-baking. be able to.

Further, the developing step may include a step of performing the above-mentioned development and a step of exposing the cured film obtained by the above-mentioned development (hereinafter, also referred to as “post-exposure”).
When the developing step includes a post-exposure step and a post-baking step, it is preferably carried out in the order of post-exposure and post-baking.

The pattern forming method of the present disclosure may include other steps other than the above-mentioned steps. As other steps, for example, a washing step can be applied without particular limitation.

<Metal pattern formation method>
The metal pattern forming method of the present disclosure includes a step of peeling off a protective film of the transfer material of the present disclosure, a step of arranging a temporary support of the transfer material, a first layer, and a second layer on a metal substrate, and a temporary step. A step of exposing the first layer and the second layer through a support and an exposure mask, a step of peeling off the temporary support, a step of developing the first layer and the second layer, and etching of a metal substrate. And a step of peeling off the first layer and the second layer.

(Step of peeling off the protective film of the transfer material of the present disclosure)
The method for forming a metal pattern of the present disclosure includes a step of peeling off a protective film of the transfer material of the present disclosure.
The protective film of the transfer material can be peeled off by using any peeling means.

(Step of arranging the temporary support of the transfer material, the first layer, and the second layer on the metal substrate)
The method of forming a metal pattern of the present disclosure includes a step of arranging a temporary support of a transfer material, a first layer, and a second layer on a metal substrate.
The above step is the same as the "step of arranging the temporary support, the first layer, and the second layer of the transfer material on the substrate" described in the section of "<Pattern forming method>".

-Metal substrate-
The metal substrate may be, for example, an aluminum plate, a copper plate, a nickel plate, a stainless plate, or the like.
Further, the metal substrate may be a metal substrate having a metal on the surface of any base material. For example, the metal substrate may be a metal substrate having copper layers on both sides or one side of an insulating base material such as a transparent glass substrate or a synthetic resin film, and may be, for example, a copper-clad laminate (CCL). The "insulating base material" does not necessarily have to have a complete insulating property, and it is sufficient that the "insulating base material" has an insulating property that can achieve the object of the present disclosure.
As the base material forming the insulating base material, a resin substrate is preferable from the viewpoint of flexibility, for example, polyethylene terephthalate film, polycarbonate film, cellulose triacetate film, polyether sulfone film, polyester film, acrylic resin film, vinyl chloride. A resin film, an aromatic polyamide resin film, a polyamideimide film, a polyimide film and the like can be used, and a polyethylene terephthalate film is preferable from the viewpoint of ease of handling and versatility.

To form the copper layer, for example, the copper foil is heat-bonded to the insulating base material via an adhesive layer, the insulating base material itself is heat-bonded to the copper foil, and the insulating material is cast and heated on the copper foil. This can be done by forming a copper layer by sputtering or plating, and it is preferable to form a copper layer by sputtering.

The thickness of the substrate is not particularly limited, but is preferably 5 μm to 200 μm, preferably 5 μm to 40 μm, more preferably 5 μm to 25 μm, and 5 μm from the viewpoint of ease of handling and versatility. It is particularly preferably ~ 16 μm.

(Step of exposing the first layer and the second layer through the temporary support and the exposure mask)
The method for forming a metal pattern of the present disclosure includes a step of exposing a first layer and a second layer via a temporary support and an exposure mask.
The above step is the same as the "step of exposing the first layer and the second layer through the temporary support and the exposure mask" described in the section of "<Pattern forming method>".

(Step of peeling off the temporary support)
The method for forming a metal pattern of the present disclosure includes a step of peeling off a temporary support. The temporary support can be peeled off by any peeling means.

(Step of developing the first layer and the second layer)
The method for forming a metal pattern of the present disclosure includes a step of developing a first layer and a second layer.
The above step is the same as "(step of developing the first layer and the second layer)" in the section of "<Pattern forming method>".

(Process for etching metal substrate)
This is a step of performing an etching process by using a pattern formed on a metal substrate as an etching resist.
Etching can be applied by a known method such as the method described in paragraphs 0048 to 0054 of JP-A-2010-152155.
For example, as an etching method, a commonly used wet etching method of immersing in an etching solution can be mentioned. As the etching solution used for wet etching, an acidic type or alkaline type etching solution may be appropriately selected according to the etching target.
Examples of the acidic type etching solution include an aqueous solution of an acidic component alone such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, or phosphoric acid, an acidic component and ferric chloride, ammonium fluoride, or permanganese. An example is a mixed aqueous solution of a salt such as potassium acid. As the acidic component, a component in which a plurality of acidic components are combined may be used.
The alkaline type etching solution includes an aqueous solution of an alkaline component alone such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, or a salt of an organic amine such as tetramethylammonium hydroxide, an alkaline component and potassium permanganate. A mixed aqueous solution of salts such as, etc. is exemplified. As the alkaline component, a component in which a plurality of alkaline components are combined may be used.

The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower. In the present disclosure, the pattern used as an etching mask (etching pattern) preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower.

After the above steps, in order to prevent contamination of the process line, a step of cleaning the metal substrate (cleaning step) and a step of drying the metal substrate (drying step) may be included, if necessary.
Examples of the cleaning step include cleaning the substrate with pure water for 10 seconds to 300 seconds at room temperature (10 ° C. to 35 ° C.).
For the drying step, for example using the air blowing may be performed dried by appropriately adjusting the air blow pressure ^{(0.1kg / cm 2 ~5kg / cm} 2 or so).

(Step of peeling the first layer and the second layer)
After the etching step, a step of peeling the first layer and the step of peeling the second layer is included.
It is preferable to use a release liquid for peeling the first layer and the second layer.
As the stripping solution, for example, an inorganic alkaline component such as sodium hydroxide or potassium hydroxide, or an organic alkaline component such as a tertiary amine or a quaternary ammonium salt can be used as water, dimethylsulfoxide, N-methylpyrrolidone, or , A stripping solution dissolved in a mixed solution of these, and the like.
The release liquid can be used for peeling by a spray method, a shower method, a paddle method, or the like.

The metal pattern forming method of the present disclosure may include other steps other than the above-mentioned steps. As other steps, for example, a washing step can be applied without particular limitation.

Hereinafter, the present disclosure will be described in more detail with reference to Examples, but the present disclosure is not limited to the following Examples as long as the gist of the present disclosure is not exceeded.

<Example 1>
[Preparation of transfer material]
-Temporary support-
The following three types of PET films having different thicknesses and haze values were used as the temporary supports of the examples.
A: PET film (thickness 16 μm) Haze value: 0.12%
B: PET film (thickness 25 μm) Haze value: 0.3%
C: PET film (thickness 38 μm) Haze value: 0.48%
The haze value of the temporary support is the total light haze (unit:%) measured in accordance with JIS (Japanese Industrial Standards) K 7136 using a haze meter HZ-2 manufactured by Suga Test Instruments Co., Ltd.
In Example 1, the above-mentioned temporary support A was used.

-First layer-
Material A-1, whose composition is shown in Table 1 below, is applied onto a temporary support A (a PET film having a thickness of 16 μm and a haze of 0.12%) using a slit-shaped nozzle, and is placed in a convection oven at 100 ° C. for 2 minutes. It was dried to form a first layer with a layer thickness of 8.0 μm.

-Second layer-
Next, the material B-1 whose composition is shown in Table 2 below is applied onto the first layer using a bar coater, dried in a convection oven at 100 ° C. for 2 minutes, and the second layer has a layer thickness of 0.1 μm. Formed a layer of.

-Protective film-
As the protective film of the example, the following three types of films having different thicknesses and the number of fish eyes were used.
A: It is a PET film (thickness 16 μm), and the number of fish eyes is 0.
B: PET film (thickness 25 μm), and the number of fish eyes is 0.
C: It is a polypropylene (PP) film (thickness 30 μm), and the number of fish eyes is one.
The "number of fish eyes" is the number of fish eyes described in the "protective film" section of "<transfer material>".

In Example 1, the protective film A was laminated on the second layer to prepare a transfer material.

The pattern linearity (LWR), pattern shape, laminateability, and adhesion during immersion development were evaluated for the produced transfer material as follows. The results are shown in Table 3 below.

(Pattern linearity)
A PET substrate with a copper layer in which a copper layer having a thickness of 500 nm was prepared by a sputtering method on a PET film having a thickness of 188 μm was used. The prepared transfer material was cut into 50 cm squares to prepare sample pieces. The protective film of the sample piece is peeled off, the surface of the exposed second layer is brought into contact with the copper layer, and the transfer material is placed on the copper layer under laminating conditions of a roll temperature of 90 ° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m / min. It was laminated on a PET substrate with. The temporary support, the first layer and the second layer are exposed with an ultra-high pressure mercury lamp via a line-and-space pattern mask (duty ratio 1: 1) having a line width of 3 μm to 20 μm without peeling the temporary support. After leaving it for 1 hour, the temporary support was peeled off and developed. Development was carried out by shower development for 30 seconds using a 1.0 mass% sodium carbonate aqueous solution at 28 ° C.

The pattern widths of 20 randomly selected patterns from the line-and-space patterns formed on the PET substrate with a copper layer were measured. The standard deviation σ was calculated from the obtained pattern width value, and the value obtained by multiplying the standard deviation σ by 3 was defined as LWR (Line Width Roughness) and used as an index for evaluating the pattern linearity.

By definition, the LWR is preferable because the smaller it is, the smaller the line width variation is. For a pattern with a line width of 10 μm, the pattern linearity was evaluated as follows based on the value of LWR.
〔Evaluation criteria〕
A: LWR <0.3, which is very preferable as a circuit wiring board.
B: 0.3 ≦ LWR <0.5, which is preferable as a circuit wiring board.
C: 0.5 ≦ LWR <1.0, and it can be used as a circuit wiring board, but it is not preferable because there is a possibility that a defect may occur.
D: 1.0 ≦ LWR, the line width fluctuates greatly, leading to a circuit defect, and it cannot be used as a circuit wiring board.

(Pattern shape)
The cross-sectional shape on the PET substrate with a copper layer having a line-and-space pattern of 10 μm was observed. The state of the bottom of the pattern was observed using an electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation), and the case where there was no hem shape or undercut shape was designated as "A". When a hemming or undercut of less than 0.5 μm was observed, it was evaluated as “B”, and when a hemming or undercut shape of 0.5 μm or more was observed, it was evaluated as “C”.

(Laminated)
Visually evaluate the area where the first layer and the second layer are in close contact with the copper layer without bubbles or floating, and (the area where the first layer and the second layer are in close contact) / (of the cut transfer material. The area ratio in close contact was determined by (area) × 100 (%). It can be said that the larger the area (%), the better the laminating suitability.
〔Evaluation criteria〕
A: The area (%) is 90% or more.
B: The area (%) is 80% or more and less than 90%.
C: The area (%) is less than 80%.

(Adhesion during immersion development)
After laminating the transfer material on the PET substrate with a copper layer as described above, an ultra-high pressure mercury lamp is used via a line-and-space pattern mask (duty ratio 1: 1) with a line width of 3 μm to 20 μm without peeling off the temporary support. The temporary support, the first layer and the second layer were exposed and left for 1 hour, and then the temporary support was peeled off and developed.
For development, a 1.0% sodium carbonate aqueous solution at 28 ° C. was used, immersion development was performed in 15 seconds, and then air knife treatment was performed. Then, immersion development was further carried out for 15 seconds, the developer was drained by air knife treatment, and then immersion treatment was carried out in pure water for 30 seconds, and further air knife treatment was carried out.

By observing the processed substrate, the one with the remaining pattern was designated as "A", the one with peeling only at the end of the line pattern was designated as "B", and the one with the pattern peeling was designated as "C". ..

As shown in Table 3, the transfer material of Example 1 has all the evaluations of pattern linearity, pattern shape, laminateability, and adhesion during immersion development being A, and has very excellent properties as a transfer material. Was shown.

<Examples 2 to 17>
The same as in Example 1 except that the temporary support, the material and film thickness of the first layer, the material and film thickness of the second layer, and the protective film are as shown in Tables 1 to 3. The pattern linearity, pattern shape, laminateability, and adhesion during immersion development were evaluated. The evaluations in Examples 2 to 17 are shown in Table 3.

In Examples 3 to 5, 7, 8, 10 to 13, 15 and 16, all the evaluations of the pattern linearity, the pattern shape, the laminate property and the adhesion during immersion development were A, which was very excellent as a transfer material. It was shown to have the above-mentioned properties.

In Example 2, it was shown that the evaluation of the pattern linearity and the pattern shape was B, and the evaluation of the laminate property and the adhesion during immersion development was A.
When the thickness of the second layer is 0.02 μm, it is considered that as a result of insufficient antireflection, polymerization at the interface proceeds and hemming occurs.

In Example 6, it was shown that the evaluation of the pattern linearity was B, and the evaluation of the pattern shape, the laminate property, and the adhesion during immersion development was A.
It is considered that this is because the haze value of the temporary support is high and light scattering occurs during exposure, resulting in a decrease in pattern linearity.

In Example 9, it was shown that the evaluation of the pattern linearity, the pattern shape, and the adhesion during immersion development was A, and the evaluation of the laminate property was B.
It is considered that this is because the adhesion was lowered due to the insufficient thickness of the first layer.

In Example 14, it was shown that the evaluation of the pattern linearity was B, and the evaluation of the pattern shape, the laminate property, and the adhesion during immersion development was A.
It is considered that this is because the haze value of the temporary support is high and light scattering occurs during exposure, resulting in a decrease in pattern linearity.

In Example 17, it was shown that the evaluation of the laminate property was B, and the evaluation of the pattern linearity, the pattern shape, and the adhesion during immersion development was A.
It is considered that this is because the material of the protective film was polypropylene and the number of fish eyes was one, so that the laminate property was deteriorated.

<Comparative Examples 1 to 4>
The same as in Example 1 except that the temporary support, the material and film thickness of the first layer, the material and film thickness of the second layer, and the protective film are as shown in Tables 1 to 3. The pattern linearity, pattern shape, laminateability, and adhesion during immersion development were evaluated. The evaluations in Comparative Examples 1 to 3 are shown in Table 3.

In Comparative Example 1, it was shown that the evaluation of the pattern linearity was C, and the evaluation of the pattern shape, the laminate property, and the adhesion during immersion development was A.
It is considered that this is because the haze value of the temporary support is high and light scattering occurs during exposure, resulting in a decrease in pattern linearity.

In Comparative Example 2, it was shown that the evaluation of the pattern linearity was C, the evaluation of the pattern shape was B, and the evaluation of the laminate property and the adhesion during immersion development was A.
It is considered that this is because the haze value of the temporary support is high and light scattering occurs during exposure, resulting in a decrease in pattern linearity. Further, since the second layer is thick, it is considered that the pattern shape is deteriorated as a result of the undercut.

In Comparative Example 3, it was shown that the evaluation of the pattern linearity and the pattern shape was C, and the evaluation of the laminate property and the adhesion during immersion development was A.
It is probable that the pattern linearity and the pattern shape were poor because the exposed light was reflected and the tailing occurred as a result of not including the second layer.

In Comparative Example 4, it was shown that the evaluation of the pattern linearity and the pattern shape was C, and the evaluation of the laminate property and the adhesion during immersion development was A.
It is considered that this is because the second layer does not contain the ultraviolet absorber, and as a result, the exposed light is reflected and the tailing occurs, so that the pattern linearity and the pattern shape are poor.

<Comparative example 5>
In Comparative Example 5, the first layer and the second layer were directly applied onto the PET substrate with a copper layer without preparing a transfer material. Specifically, the material B-6 was applied on a PET substrate with a copper layer with a bar coater and then prebaked at 90 ° C. for 60 seconds to obtain a film having a thickness of 0.1 μm. Material A-1 was applied thereto with a bar coater and then baked at 90 ° C. for 60 seconds to obtain a film having a thickness of 8.0 μm.
The pattern linearity, pattern shape, laminateability, and adhesion during immersion development were evaluated for the above film. The evaluation results are shown in Table 3.
As a result, it was shown that the evaluation of the pattern linearity and the pattern shape was A, and the evaluation of the adhesion during immersion development was C.
It is considered that this is because the adhesion during immersion development was poor as a result of not using the transfer material of the present disclosure.

The transfer material, the transfer material manufacturing method, the pattern forming method, and the metal pattern forming method of the present disclosure are used for producing a resin film with a metal layer for a flexible printed wiring board, producing wiring for a touch sensor film, and the like. It is useful.

Claims (16)

A temporary support with a haze value of 0.3% or less, and
A first layer containing a polymerizable compound having an ethylenically unsaturated double bond, an alkali-soluble resin, and a photopolymerization initiator placed on the temporary support.
A second layer containing a water-based solvent, a lower alcohol-based solvent, or a resin soluble in a mixed solvent of the water-based solvent and the lower alcohol-based solvent, and an ultraviolet absorber, which are arranged on the first layer.
With the protective film placed on the second layer,
Have,
The resin soluble in the aqueous solvent, the lower alcohol solvent, or the mixed solvent of the aqueous solvent and the lower alcohol solvent is a polyvinyl alcohol resin, a cellulose resin, a chitin compound, a chitosan compound, a starch compound, or a polyethylene oxide. , Polypropylene oxide, polyethylene glycol, polyvinyl ether and at least one selected from the group consisting of resins having a carbamoyl group.
The content of the resin soluble in the aqueous solvent or the lower alcohol solvent or the mixed solvent of the aqueous solvent and the lower alcohol solvent in the second layer is 59 mass by mass with respect to the total solid content of the second layer. der least% is,
The ultraviolet absorber, Ru benzotriazole ultraviolet absorber der,
Transfer material. The transfer material according to claim 1, wherein the temporary support is a polyethylene terephthalate film. The transfer material according to claim 1 or ² , wherein the number of fish eyes of 0.3 mm 2 or more in the protective film is ^{8 or less per 1000 m 2.} The transfer material according to any one of claims 1 to 3, wherein the protective film is a polyethylene terephthalate film. The transfer material according to any one of claims 1 to 4, wherein the second layer further contains a polymerizable compound having an ethylenically unsaturated double bond and a photopolymerization initiator. The transfer material according to any one of claims 1 to 5, wherein the resin soluble in the aqueous solvent, the lower alcohol solvent, or the mixed solvent of the aqueous solvent and the lower alcohol solvent has an acid group. The transfer material according to claim 1 , wherein the benzotriazole-based ultraviolet absorber is a compound having a structure represented by the following general formula (1).

In the general formula (1), R ¹ independently represents a hydrogen atom or an organic group having 1 to 15 carbon atoms, n ₁ represents an integer of 0 to 4, and R ² independently represents a hydrogen atom. It represents a hydrogen atom or an organic group having 1 to 15 carbon atoms, and n ₂ represents an integer of 0 to 4. The transfer material according to any one of claims 1 to 7 , wherein the content of the ultraviolet absorber is 5% by mass or more and less than 80% by mass with respect to the total solid content of the second layer. The transfer material according to any one of claims 1 to 8 , wherein the photopolymerization initiator contained in the first layer is an oxime-based photopolymerization initiator. The transfer material according to any one of claims 1 to 9 , wherein the temporary support has a thickness of 1 μm or more and 25 μm or less. The transfer material according to any one of claims 1 to 10 , wherein the thickness of the first layer is 1 μm or more and 15 μm or less. The transfer material according to any one of claims 1 to 11 , wherein the thickness of the second layer is 0.05 μm or more and 2 μm or less. The step of peeling off the protective film of the transfer material according to any one of claims 1 to 12.
The step of arranging the temporary support, the first layer, and the second layer of the transfer material on the substrate,
The step of exposing the first layer and the second layer through the temporary support and the exposure mask.
The step of peeling off the temporary support,
The step of developing the first layer and the second layer,
A method of forming a pattern, including. The method for forming a pattern according to claim 13 , wherein the exposure step irradiates light in a wavelength range including a wavelength of 365 nm. The pattern forming method according to claim 13 or 14 , wherein the substrate is a resin substrate. The step of peeling off the protective film of the transfer material according to any one of claims 1 to 12.
The step of arranging the temporary support, the first layer, and the second layer of the transfer material on the metal substrate,
The step of exposing the first layer and the second layer through the temporary support and the exposure mask.
The step of peeling off the temporary support,
The step of developing the first layer and the second layer,
The process of etching the metal substrate and
The step of peeling the first layer and the second layer,
A method of forming a metal pattern, including.