JPWO2020129873A1 - Laminates, compositions, and laminate forming kits - Google Patents

Abstract

The base material, the organic layer, the protective layer and the photosensitive layer are contained in this order, the protective layer contains polyvinyl alcohol, the saponification degree of the polyvinyl alcohol is 50 mol% or more and 85 mol% or less, and the photosensitive layer contains a developing solution. The laminated body, the composition used for forming the protective layer or the photosensitive layer contained in the laminated body, and the laminated body, which are subjected to the development used and the protective layer is subjected to removal using a stripping solution. A kit for forming a laminate used for forming.

Description

The present invention relates to a laminate, a composition, and a laminate forming kit.

In recent years, devices using patterned organic layers, such as semiconductor devices using organic semiconductors, have been widely used.
For example, devices using organic semiconductors are manufactured by a simpler process than conventional devices using inorganic semiconductors such as silicon, and material properties can be easily changed by changing the molecular structure. have. In addition, there are a wide variety of materials, and it is thought that it will be possible to realize functions and elements that could not be achieved with inorganic semiconductors. Organic semiconductors can be applied to electronic devices such as organic solar cells, organic electroluminescence displays, organic optical detectors, organic field effect transistors, organic field light emitting devices, gas sensors, organic rectifying elements, organic inverters, and information recording elements. There is sex.
It is known that such patterning of an organic layer such as an organic semiconductor is performed using a laminate containing an organic layer and a layer such as a photosensitive layer.

For example, Patent Document 1 includes an organic semiconductor film containing a water-soluble resin layer containing a water-soluble resin and a photosensitive resin layer containing a photosensitive resin in this order, and the water-soluble resin layer and the photosensitive resin layer. The water-soluble resin is at least one of polyvinylpyrrolidone having a weight average molecular weight of 300,000 or more and polyvinyl alcohol having a weight average molecular weight of 15,000 or more. Laminates of 000 or more are listed.
Further, Patent Document 2 describes a step of forming an organic semiconductor layer, a step of laminating a protective layer for protecting the organic semiconductor layer from a mask layer on the organic semiconductor layer, and a mask having a predetermined pattern. A method for patterning an organic semiconductor layer, which comprises a step of laminating and forming the layer on the protective layer and a step of patterning the protective layer and the organic semiconductor layer in the same shape by etching using the mask layer as a mask. Describes a method for patterning an organic semiconductor layer, wherein the protective layer is formed of an organic polymer compound or an insulating inorganic compound which is different in material from the mask layer and has hydrophilicity. ..

International Publication No. 2016/175220 Japanese Unexamined Patent Publication No. 2006-041317

In this way, when patterning an organic layer such as an organic semiconductor, a chemical solution used for patterning the organic layer by forming a protective layer containing polyvinyl alcohol or the like (for example, a developing solution used for developing a photosensitive layer). It is protected from damage caused by such factors.
The protective layer may be removed from the patterned organic layer using a stripping solution. However, it has been found that in such removal, a part of the components contained in the protective layer (for example, a resin component such as polyvinyl alcohol) may remain as a residue without being removed.

The present invention relates to a laminate in which the generation of residues is suppressed in removing the protective layer, a composition used for forming a protective layer or a photosensitive layer contained in the laminate, and a laminate used for forming the laminate. It is an object of the present invention to provide a kit for body formation.

式（１）中、Ｒ⁸は水素原子又はアルキル基を表し、Ｌ¹はカルボニル基又はフェニレン基を表し、Ｒ¹〜Ｒ⁷はそれぞれ独立に、水素原子又はアルキル基を表す。
＜１２＞ けん化度が５０モル％以上８５モル％以下であるポリビニルアルコールを含む、＜１＞〜＜１１＞のいずれか１つに記載の積層体に含まれる上記保護層の形成に用いられる組成物。
＜１３＞ ＜１＞〜＜１１＞のいずれか一つに記載の積層体に含まれる上記感光層の形成に用いられる組成物。
＜１４＞ 下記Ａ及びＢを含む、積層体形成用キット；
Ａ：けん化度が５０モル％以上８５モル％以下のポリビニルアルコールを含む、＜１＞〜＜１１＞のいずれか１つに記載の積層体に含まれる上記保護層の形成に用いられる組成物；
Ｂ：＜１＞〜＜１１＞のいずれか一つに記載の積層体に含まれる上記感光層の形成に用いられる組成物。Typical embodiments of the present invention are shown below.
<1> The base material, the organic layer, the protective layer and the photosensitive layer are included in this order.
The protective layer contains polyvinyl alcohol and contains
The saponification degree of the polyvinyl alcohol is 50 mol% or more and 85 mol% or less.
The photosensitive layer is subjected to development using a developing solution, and is subjected to development.
The protective layer is used for removal using a stripping solution.
Laminated body.
<2> The laminate according to <1>, wherein the content of the polyvinyl alcohol is 50% by mass or more with respect to the total mass of the protective layer.
<3> The laminate according to <1> or <2>, wherein the degree of saponification of the polyvinyl alcohol is 60 mol% or more and 80 mol% or less.
<4> The laminate according to any one of <1> to <3>, wherein the degree of saponification of the polyvinyl alcohol is 65 mol% or more and 75 mol% or less.
<5> The laminate according to any one of <1> to <4>, wherein the photosensitive layer contains a photoacid generator.
<6> The laminate according to any one of <1> to <5>, wherein the development is a negative type.
<7> The laminate according to any one of <1> to <6>, wherein the content of the organic solvent with respect to the total mass of the developer is 90 to 100% by mass.
<8> The laminate according to any one of <1> to <7>, wherein the content of water with respect to the total mass of the stripping liquid is 90 to 100% by mass.
<9> The laminate according to any one of <1> to <8>, wherein the photosensitive layer contains a resin having a repeating unit having a structure in which an acid group is protected by an acid-degradable group.
<10> The laminate according to <9>, wherein the repeating unit is a repeating unit containing a cyclic ether ester structure in a side chain.
<11> The laminate according to <9>, wherein the repeating unit is a repeating unit represented by the following formula (1);

In formula (1), R ⁸ represents a hydrogen atom or an alkyl group, L ¹ represents a carbonyl group or a phenylene group, and R ^{1 to} R ⁷ independently represent a hydrogen atom or an alkyl group.
<12> A composition used for forming the protective layer contained in the laminate according to any one of <1> to <11>, which contains polyvinyl alcohol having a saponification degree of 50 mol% or more and 85 mol% or less. thing.
<13> A composition used for forming the photosensitive layer contained in the laminate according to any one of <1> to <11>.
<14> A laminate forming kit containing the following A and B;
A: A composition used for forming the protective layer contained in the laminate according to any one of <1> to <11>, which contains polyvinyl alcohol having a saponification degree of 50 mol% or more and 85 mol% or less;
B: A composition used for forming the photosensitive layer contained in the laminate according to any one of <1> to <11>.

According to the present invention, it is used for forming a laminate in which the generation of residues is suppressed in removing the protective layer, a composition used for forming the protective layer or the photosensitive layer contained in the laminate, and the laminate. A kit for forming a laminate is provided.

It is sectional drawing which shows typically the processing process of the laminated body which concerns on a preferable embodiment of this invention.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
In the present specification, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either. ) Acryloyl ”represents both acryloyl and methacrylic acid, or either of them.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
Unless otherwise specified, in the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of a water-soluble resin such as polyvinyl alcohol are polyethylene oxide (PEO) measured by a GPC (gel permeation chromatography) method. ) Converted value.
In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of a water-insoluble resin such as (meth) acrylic resin are polystyrene-equivalent values measured by the GPC method.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
In the present specification, when "upper" and "lower" are described, it may be the upper side or the lower side of the structure. That is, other structures may intervene and do not need to be in contact with each other. Unless otherwise specified, the direction of the photosensitive layer side as seen from the organic layer is referred to as "upper", and the direction of the base material side as seen from the organic layer is referred to as "lower".
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the wavy line portion or * (asterisk) in the structural formula represents a binding site with another structure.
Unless otherwise specified, the atmospheric pressure at the time of boiling point measurement in the present invention is 101325 Pa (1 atmospheric pressure). Unless otherwise specified, the temperature in the present invention is 23 ° C.
In the present specification, the combination of preferred embodiments is a more preferred embodiment.

(Laminated body)
The laminate of the present invention
The base material, organic layer, protective layer and photosensitive layer are included in this order.
The protective layer contains polyvinyl alcohol and contains
The saponification degree of the polyvinyl alcohol is 50 mol% or more and 85 mol% or less.
The photosensitive layer is subjected to development using a developing solution, and is subjected to development.
The protective layer is used for removal using a stripping solution.

According to the laminate of the present invention, the generation of residues is suppressed in the removal of the protective layer. The reason why the above effect is obtained is presumed as follows.

According to the study of the present inventor, when a layer containing polyvinyl alcohol (hereinafter, also referred to as “PVA”) is used as the protective layer, a part of the components contained in the protective layer is an organic layer (organic semiconductor film) as a residue. ) It turns out that it may remain on.
Further, as a result of diligent studies, the present inventor has found that it is effective to use PVA having a saponification degree in a specific range of 50 to 85 mol% in order to suppress the generation of the residue.
The reason why the above effect is obtained is not clear, but it is presumed as follows.
When the degree of saponification of PVA contained in the protective layer is 85 mol% or less, the interaction between the protective layer and the organic layer (hydrogen bonds, etc.) is reduced, and the interaction between PVAs (hydrogen bonds, etc.) is reduced. Since the degree of saponification is low, the crystallinity of PVA is low, and the release liquid or the component (for example, water) contained in the stripping liquid is likely to form an infiltration path. Therefore, the removability of the protective layer by the stripping liquid is improved. However, it is considered that the generation of residue is suppressed.
Further, since the saponification degree of PVA contained in the protective layer is 50 mol% or more, the solubility and dispersibility in the stripping solution are improved, so that the generation of residue in the removal of the protective layer using the stripping solution is suppressed. It is thought that it will be done.
Further, according to the present invention, it is considered that when the saponification degree of PVA is 85 mol% or less, the permeation of the acid generated from the photoacid generator into the protective layer is likely to be suppressed. Therefore, it is considered that the occurrence of undercut and the like of the photosensitive layer is suppressed even during the development of the photosensitive layer, and the pattern shape of the photosensitive layer tends to be good.

Here, in Patent Document 1, there is no description or suggestion that the saponification degree of polyvinyl alcohol is set to a specific value, and no study has been made.
Further, Patent Document 2 describes a mode in which a layer containing PVA is left as a protective layer in a device finally manufactured. In such an embodiment, since it is necessary to increase the strength of the layer containing PVA, a PVA having a saponification degree of more than 85 mol% (for example, a saponification degree of 98 mol% or more) should be used. Is normal. That is, there is no description or suggestion in Patent Document 2 that PVA having a saponification degree of 85 mol% or less used in the present invention is used, and there is no description or suggestion regarding the use of PVA having a saponification degree of 85 mol% or less. There is nothing that can be motivating.

The laminate of the present invention can be used for patterning the organic layer contained in the laminate.
FIG. 1 is a schematic cross-sectional view schematically showing a processing process of a laminated body according to a preferred embodiment of the present invention. In one embodiment of the present invention, the organic layer 3 (for example, an organic semiconductor layer) is arranged on the base material 4 as in the example shown in FIG. 1 (a). Further, the protective layer 2 that protects the organic layer 3 is arranged on the surface of the protective layer 2 in contact with the protective layer 2. Another layer may be provided between the organic layer 3 and the protective layer 2, but from the viewpoint that the effect of the present invention can be more easily obtained, the organic layer 3 and the protective layer 2 are in direct contact with each other. However, an example of a preferred embodiment is given. Further, the photosensitive layer 1 is arranged on the protective layer. The photosensitive layer 1 and the protective layer 2 may be in direct contact with each other, or another layer may be provided between the photosensitive layer 1 and the protective layer 2.
FIG. 1B shows an example of a state in which a part of the photosensitive layer 1 is exposed and developed. For example, the photosensitive layer 1 is partially exposed by a method such as using a predetermined mask, and after the exposure, the photosensitive layer 1 is removed and exposed by developing with a developing solution such as an organic solvent. The photosensitive layer 1a after development is formed. At this time, the protective layer 2 remains because it is difficult to be removed by the developer, and the organic layer 3 is protected from damage by the developer by the remaining protective layer 2.
FIG. 1C shows an example of a state in which a part of the protective layer 2 and the organic layer 3 is removed. For example, by removing the protective layer 2 and the organic layer 3 in the removing portion 5 without the photosensitive layer (resist) 1a after development by dry etching treatment or the like, the removing portion 5a is formed in the protective layer 2 and the organic layer 3. Will be done. In this way, the organic layer 3 can be removed in the removing portion 5a. That is, the organic layer 3 can be patterned.
FIG. 1D shows an example in which the photosensitive layer 1a and the protective layer 2 are removed after the patterning. For example, the photosensitive layer 1a and the protective layer 2 on the organic layer 3a after processing are washed with a stripping solution containing water, for example, by washing the photosensitive layer 1a and the protective layer 2 in the laminated body in the state shown in FIG. 1C. Is removed.
As described above, according to the preferred embodiment of the present invention, it is possible to form a desired pattern on the organic layer 3 and remove the photosensitive layer 1 as a resist and the protective layer 2 as a protective film. Details of these steps will be described later.

<Base material>
The laminate of the present invention contains a base material.
Examples of the base material include a base material formed of various materials such as silicon, quartz, ceramic, glass, polyester film such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), and polyimide film. Any substrate may be selected depending on the situation. For example, when used for a flexible element, a base material formed of a flexible material can be used. Further, the base material may be a composite base material formed of a plurality of materials or a laminated base material in which a plurality of materials are laminated.
Further, the shape of the base material is not particularly limited and may be selected according to the intended use, and examples thereof include a plate-shaped base material (hereinafter, also referred to as “base material”). The thickness of the substrate is also not particularly limited.

<Organic layer>
The laminate in the present invention contains an organic layer.
Examples of the organic layer include an organic semiconductor layer and a resin layer.
In the laminate according to the present invention, the organic layer may be contained above the base material, the base material may be in contact with the organic layer, or another layer may be provided between the organic layer and the base material. May be further included.

[Organic semiconductor layer]
The organic semiconductor layer is a layer containing an organic material (also referred to as an "organic semiconductor compound") exhibiting the characteristics of a semiconductor.

-Organic semiconductor compound-
Similar to the case of semiconductors made of inorganic materials, organic semiconductor compounds include p-type organic semiconductor compounds that conduct holes as carriers and n-type organic semiconductor compounds that conduct electrons as carriers.
The ease of carrier flow in the organic semiconductor layer is represented by the carrier mobility μ. Although it depends on the application, the mobility is generally higher, ^{preferably 10-7} cm ² / Vs or more, more preferably ^10-6 cm ² / Vs or more, and ^10-5 cm ² / Vs or more. It is more preferably Vs or more. The mobility μ can be obtained by the characteristics when the field effect transistor (FET) element is manufactured and the flight time measurement (TOF) method.

As the p-type organic semiconductor compound that can be used for the organic semiconductor layer, any material among organic semiconductor materials may be used as long as it is a material exhibiting hole transportability, but a p-type π-conjugated polymer is preferable. Compounds (eg, substituted or unsubstituted polythiophene (eg, poly (3-hexylthiophene) (P3HT, manufactured by Sigma Aldrich Japan LLC), etc.), polyselenophen, polypyrrole, polyparaphenylene, polyparaphenylene vinylene, polythiophenine vinylene. , Polyaniline, etc.), fused polycyclic compounds (eg, substituted or unsubstituted anthracene, tetracene, pentacene, anthradithiophene, hexabenzocoronene, etc.), triarylamine compounds (eg, m-MTDATA (4,4', 4). '' -Tris [(3-methylphenyl) compound] triphenylamine), 2-TNATA (4,4', 4''-Tris [2-naphthyl (phenyl) amino] triphenyllamine), NPD (N, N'-Di [ (1-naphyl) -N, N'-diphenyl] -1,1'-biphenyl) -4,4'-diamine), TPD (N, N'-Diphenyl-N, N'-di (m-polyl) benzidine, mCP (1,3-bis (9-carbazolyl) benzene), CBP (4,4'-bis (9-carbazolyl) -2,2'-biphenyl), etc.), hetero 5-membered ring compounds (eg, substitutions) Alternatively, unsubstituted oligothiophene, TTF (Tetrasia fullvalene), phthalocyanine compounds (substituted or unsubstituted various central metals phthalocyanine, naphthalocyanine, anthracianin, tetrapyrazinoporphyrazine), porphyrin compounds (various substituted or unsubstituted). Porphyrin), carbon nanotubes, semiconductor polymer-modified carbon nanotubes, and graphene, more preferably p-type π-conjugated polymer compounds, condensed polycyclic compounds, triarylamine compounds, and hetero 5-membered ring compounds. , A phthalocyanine compound or a porphyrin compound, more preferably a p-type π-conjugated polymer compound.

The n-type semiconductor compound that can be used in the organic semiconductor layer may be any organic semiconductor material as long as it has electron transportability, but is preferably a fullerene compound, an electron-deficient phthalocyanine compound, or a naphthalenetetracarbonyl compound. , Perylene tetracarbonyl compound, TCNQ compound (tetracyanoquinodimethane compound), n-type π-conjugated polymer compound, more preferably fullerene compound, electron-deficient phthalocyanine compound, naphthalene tetracarbonyl compound, perylene tetracarbonyl compound, n It is a type π-conjugated polymer compound, and particularly preferably a fullerene compound and an n-type π-conjugated polymer compound. In the present invention, the fullerene compound refers to a substituted or unsubstituted fullerene, and the fullerenes are C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₀ , C ₈₂ , C ₈₄ , C ₈₆ , C ₈₈ , C _90. , C ₉₆ , C ₁₁₆ , C ₁₈₀ , C ₂₄₀ , C ₅₄₀ fullerenes, etc., but are preferably substituted or unsubstituted C ₆₀ , C ₇₀ , C ₈₆ fullerenes, and particularly preferably PCBM ([6,]. 6] -Phenyl-C _61- butyl methyl ester, manufactured by Sigma Aldrich Japan LLC, etc.) and its analogs (C ₆₀ portion _{substituted with C 70} , C _86, etc., benzene ring of substituent is another aromatic ring Alternatively, a heterocycle is substituted, or a methyl ester is substituted with n-butyl ester, i-butyl ester, or the like). _{The electron-deficient phthalocyanines are phthalocyanines (F 16} MPc, FPc-S8, etc., which are various central metals in which four or more electron attracting groups are bonded, where M is the central metal, Pc is phthalocyanine, and S8 is (. (Representing an n-octylsulfonyl group), naphthalocyanine, anthracyanine, substituted or unsubstituted tetrapyrazinoporphyrazine and the like. Any naphthalene tetracarbonyl compound may be used, but naphthalene tetracarboxylic acid anhydride (NTCDA), naphthalene bisimide compound (NTCDI), and perinone pigments (Pigment Orange 43, Pigment Red 194, etc.) are preferable. Any perylenetetracarbonyl compound may be used, but perylenetetracarboxylic dianhydride (PTCDA), perylenebisimide compound (PTCDI), and benzimidazole fused ring (PV) are preferable. The TCNQ compound is a substituted or unsubstituted TCNQ and a compound in which the benzene ring portion of TCNQ is replaced with another aromatic ring or heterocycle. For example, TCNQ, TCNAQ (tetracyanoquinodimethane), TCN3T (2, 2'-((2E, 2''E) -3', 4'-Alkyl substationed-5H, 5''H- [2,2': 5', 2''-terthiophene] -5,5'' -Diylidene) dimalononirile derivatives) and the like. Further, graphene can be mentioned. A particularly preferable example of the n-type organic semiconductor compound is shown below by the structural formula.

The R in the formula may be any, but is hydrogen atom, substituted or unsubstituted, branched or linear alkyl group (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably. 1 to 8), substituted or unsubstituted aryl groups (preferably those having 6 to 30, more preferably 6 to 20, and even more preferably 6 to 14 carbon atoms). Me in the structural formula is a methyl group, and M is a metal element.

有機半導体層に含まれる有機半導体化合物は、１種でもよいし、２種以上であってもよい。
有機半導体層の全質量に対する有機半導体化合物の含有量は、１〜１００質量％であることが好ましく、１０〜１００質量％であることがより好ましい。

The organic semiconductor compound contained in the organic semiconductor layer may be one kind or two or more kinds.
The content of the organic semiconductor compound with respect to the total mass of the organic semiconductor layer is preferably 1 to 100% by mass, more preferably 10 to 100% by mass.

-Binder resin-
The organic semiconductor layer may further contain a binder resin.
Binder resins include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulphon, polymethylmethacrylate, polymethylacrylate, cellulose, polyethylene, and polypropylene, and their co-weights. Examples thereof include photoconductive polymers such as coalescing, polyvinylcarbazole and polysilane, and conductive polymers such as polythiophene, polypyrrole, polyaniline and polyparaphenylene vinylene.
The organic semiconductor layer may contain only one type of binder resin, or may contain two or more types of binder resin. Considering the mechanical strength of the organic semiconductor layer, a binder resin having a high glass transition temperature is preferable, and considering charge mobility, a binder resin having a structure having no polar group or a conductive polymer is preferable.
When the organic semiconductor layer contains a binder resin, the content of the binder resin is preferably 0.1 to 30% by mass with respect to the total mass of the organic semiconductor layer.

− Film thickness −
The film thickness of the organic semiconductor layer is not particularly limited and varies depending on the type of device to be finally produced and the like, but is preferably 5 nm to 50 μm, more preferably 10 nm to 5 μm, and further preferably 20 nm to 500 nm.

-Composition for forming an organic semiconductor layer-
The organic semiconductor layer is formed by using, for example, a composition for forming an organic semiconductor layer containing a solvent and an organic semiconductor compound.
As an example of the forming method, a method of applying the composition for forming an organic semiconductor layer in a layer on a substrate and drying to form a film can be mentioned. As the application method, for example, the description of the application method of the composition for forming a protective layer in the protective layer described later can be taken into consideration.

Solvents contained in the composition for forming an organic semiconductor layer include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene and 1-methylnaphthalene; and ketones such as acetone, methylethylketone, methylisobutylketone and cyclohexanone. Solvents: Halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate; methanol, propanol , Butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol and other alcohol solvents; dibutyl ether, tetrahydrofuran, dioxane, anisole and other ether solvents; N, N-dimethylformamide, N, N- Examples thereof include polar solvents such as dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, and dimethylsulfoxide. Only one kind of these solvents may be used, or two or more kinds may be used.
The content of the organic semiconductor compound with respect to the total mass of the composition for forming the organic semiconductor layer is preferably 0.1 to 80% by mass, more preferably 0.1 to 30% by mass. The content of the organic semiconductor may be appropriately set according to the thickness of the organic semiconductor layer to be formed and the like.

Further, the composition for forming an organic semiconductor layer may further contain the above-mentioned binder resin.
The binder resin may be dissolved or dispersed in a solvent contained in the composition for forming an organic semiconductor layer.
When the composition for forming an organic semiconductor layer contains a binder resin, the content of the binder resin is preferably 0.1 to 30% by mass with respect to the total solid content of the composition for forming an organic semiconductor layer.

The composition for forming an organic semiconductor layer may contain a semiconductor material other than the above-mentioned organic semiconductor compound, or may further contain other additives. By using the other semiconductor material or the composition for forming an organic semiconductor layer containing the other additive, it is possible to form a blend film containing the other semiconductor material or the other additive. be.
For example, when producing a photoelectric conversion layer, a composition for forming an organic semiconductor layer further containing another semiconductor material can be used.
Further, during film formation, the base material may be heated or cooled, and the film quality of the organic semiconductor layer and the packing of molecules in the film can be controlled by changing the temperature of the base material. The temperature of the base material is not particularly limited, but is preferably −200 ° C. to 400 ° C., more preferably −100 ° C. to 300 ° C., and even more preferably 0 ° C. to 200 ° C.
The characteristics of the formed organic semiconductor layer can be adjusted by post-treatment. For example, the formed organic semiconductor layer is heat-treated, exposed to a vaporized solvent, or the like to change the morphology of the film or the packing of molecules in the film to obtain desired properties. Is also possible. Further, the carrier density in the film is adjusted by exposing the formed organic semiconductor layer to a substance such as an oxidizing or reducing gas or a solvent, or by mixing these to cause an oxidation or reduction reaction. be able to.

[Resin layer]
The resin layer is an organic layer other than the organic semiconductor layer, and is a layer containing a resin.
The resin contained in the resin layer is not particularly limited, but is (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether. Examples thereof include phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyurethane resin, polyurea resin, and the like.
Among these, (meth) acrylic resin is preferably mentioned from the viewpoint that the effect of the present invention can be easily obtained.
The resin contained in the resin layer is preferably a water-insoluble resin, more preferably a resin having a dissolution amount of 0.1 g or less in 100 g of water at 25 ° C., and a dissolution amount of 0.01 g or less. The resin is more preferable.

In addition to the resin, the resin layer may contain known additives such as a colorant, a dispersant, and a refractive index adjuster. The types and contents of these additives may be appropriately designed according to the intended use with reference to known techniques.
Examples of the use of the resin layer include a colored layer such as a color filter, a high refractive index layer or a low refractive index layer such as a refractive index adjusting layer, and an insulating layer for wiring.

− Film thickness −
The film thickness of the resin layer is not particularly limited and varies depending on the type of the device to be finally produced or the type of the organic layer itself, but is preferably 5 nm to 50 μm, more preferably 10 nm to 5 μm, and further preferably 20 nm to 20 nm. It is 500 nm.

-Composition for forming a resin layer-
The resin layer is formed by using, for example, a composition for forming a resin layer containing a resin and a solvent. An example of the forming method is a method in which the composition for forming a resin layer is applied in a layered manner on a substrate and dried to form a film. As the application method, for example, the description of the application method of the composition for forming a protective layer in the protective layer described later can be taken into consideration.
Further, the resin layer may be formed by using a resin layer forming composition containing a resin raw material. For example, as a raw material for the resin, a composition for forming a resin layer containing a resin that is a precursor of the resin, a polymerizable compound (a compound having a polymerizable group) constituting a monomer unit in the resin, and, if necessary, a polymerizable compound. Examples thereof include a method in which a resin layer forming composition containing a polymerization initiator or the like is applied in a layered manner on a substrate, and at least one of drying and curing is performed to form a film. As the application method, for example, the description of the application method of the composition for forming a protective layer in the protective layer described later can be taken into consideration. As the curing method, known methods such as heating and exposure may be used depending on the type of resin precursor, the type of polymerization initiator and the like.

<Protective layer>
The laminate of the present invention contains a protective layer, the protective layer contains polyvinyl alcohol, the saponification degree of the polyvinyl alcohol is 50 mol% or more and 85 mol% or less, and the protective layer is used for removal using a stripping solution. Be forced.
Hereinafter, polyvinyl alcohol having a saponification degree of 50 mol% or more and 85 mol% or less contained in the protective layer is also referred to as "specific polyvinyl alcohol".

[Specific polyvinyl alcohol]
The saponification degree of the specific polyvinyl alcohol is 50 mol% or more and 85 mol% or less, preferably 60 mol% or more and 80 mol% or less, and more preferably 65 mol% or more and 75 mol% or less.
In the present invention, the saponification degree of polyvinyl alcohol is measured by the method described in paragraphs 0020 to 0023 of JP-A-2006-028233.

The weight average molecular weight (Mw) of the specific polyvinyl alcohol contained in the protective layer is preferably 5,000 to 100,000, more preferably 8,000 to 50,000, and 10,000 to 30, It is more preferably 000, and particularly preferably 12,000 to 25,000.

The content of the specific polyvinyl alcohol is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more, based on the total mass of the protective layer. The upper limit of the content is not particularly limited and may be 100% by mass or less.

[Other water-soluble resins]
The protective layer may contain a water-soluble resin other than the specific polyvinyl alcohol.
In the present specification, the water-soluble resin refers to a resin having a dissolution amount of 1 g or more in 100 g of water at 23 ° C., preferably 5 g or more, more preferably 10 g or more, and 30 g or more. Is more preferable. There is no upper limit to the amount of dissolution, but it can be, for example, 100 g or less. Further, in the present specification, the water-insoluble resin means a resin having a dissolution amount of less than 1 g in 100 g of water at 23 ° C.

Further, in the present invention, an alcohol-soluble resin can also be used as the water-soluble resin. Examples of the alcohol-soluble resin include polyvinyl acetal. As the alcohol that can be used as a solvent, an alcohol that is usually used may be selected, and examples thereof include isopropyl alcohol. The alcohol-soluble resin refers to a resin having a solubility in 100 g of alcohol (for example) at 23 ° C. of 1 g or more, preferably a resin having a solubility of 10 g or more, and more preferably 20 g or more. There is no upper limit, but it is practical that it is 30 g or less. Unless otherwise specified, the alcohol-soluble resin is included in the water-soluble resin in the present invention.

The other water-soluble resin is preferably a resin containing a hydrophilic group, and examples of the hydrophilic group include a hydroxy group, a carboxy group, a sulfonic acid group, a phosphoric acid group, an amide group, and an imide group.

Specific examples of other water-soluble resins include polyvinylpyrrolidone (PVP), water-soluble polysaccharides (water-soluble cellulose (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, etc.), pullulan or Pullulan derivatives, starch, hydroxypropyl starch, carboxymethyl starch, chitosan, cyclodextrin), polyethylene oxide, polyethyloxazoline and the like can be mentioned. Further, two or more kinds may be selected and used from these, or may be used as a copolymer.
The protective layer in the present invention is, as another water-soluble resin, polyvinyl alcohol other than the specific polyvinyl alcohol (polyvinyl alcohol having a saponification degree of more than 85 mol% or less than 50 mol%, hereinafter, "other polyvinyl alcohol". However, from the viewpoint of suppressing the generation of residues in the removal of the protective layer, the content of other polyvinyl alcohol is 5% by mass or less based on the total mass of the protective layer. It is preferably 3% by mass or less, more preferably 1% by mass or less, particularly preferably 0.1% by mass or less, and most preferably 0% by mass (not contained). preferable.

As for other water-soluble resins, the water-soluble resins described in International Publication No. 2016/175220 can also be used.

The weight average molecular weight of the other water-soluble resin is preferably 50,000 to 400,000 in the case of polyvinylpyrrolidone, and preferably 15,000 to 100,000 in the case of other polyvinyl alcohol. In the case of other resins, it is preferably in the range of 10,000 to 300,000.
The molecular weight dispersion (weight average molecular weight / number average molecular weight) of the other water-soluble resin used in the present invention is preferably 1.0 to 5.0, more preferably 2.0 to 4.0.

When the protective layer used in the present invention contains another water-soluble resin, the content of the other water-soluble resin is preferably 0.1 to 50% by mass, preferably 0 to 50% by mass, based on the total mass of the protective layer. .1 to 40% by mass is more preferable, and 0.1 to 20% by mass is further preferable.

[Surfactant containing acetylene group]
From the viewpoint of suppressing the generation of residues, the protective layer preferably contains a surfactant containing an acetylene group.
The number of acetylene groups in the molecule in the surfactant containing an acetylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 2, and even 1 to 2. Is more preferable.

The molecular weight of the surfactant containing an acetylene group is preferably relatively small, preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less. There is no particular lower limit, but it is preferably 200 or more.

式中、Ｒ^９１及びＲ^９２は、それぞれ独立に、炭素数３〜１５のアルキル基、炭素数６〜１５の芳香族炭化水素基、又は、炭素数４〜１５の芳香族複素環基である。芳香族複素環基の炭素数は、１〜１２が好ましく、２〜６がより好ましく、２〜４が更に好ましい。芳香族複素環は５員環又は６員環が好ましい。芳香族複素環が含むヘテロ原子は窒素原子、酸素原子、又は硫黄原子が好ましい。
Ｒ^９１及びＲ^９２は、それぞれ独立に、置換基を有していてもよく、置換基としては下記置換基Ｔが挙げられる。-Compound represented by formula (9)-
The surfactant containing an acetylene group is preferably a compound represented by the following formula (9).

In the formula, R ⁹¹ and R ⁹² are independently an alkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, or an aromatic heterocyclic group having 4 to 15 carbon atoms. .. The aromatic heterocyclic group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The aromatic heterocycle is preferably a 5-membered ring or a 6-membered ring. The hetero atom contained in the aromatic heterocycle is preferably a nitrogen atom, an oxygen atom, or a sulfur atom.
R ⁹¹ and R ⁹² may each independently have a substituent, and examples of the substituent include the following substituent T.

As the substituent T, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) and an arylalkyl group (preferably 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms). , 7-11 is more preferred), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 and even more preferably 2 to 6), an alkynyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2-3 are more preferable), hydroxy group, amino group (preferably 0 to 24 carbon atoms, more preferably 0 to 12 and even more preferably 0 to 6), thiol group, carboxy group, aryl group (carbon). Numbers 6 to 22 are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable), alkoxyl groups (1 to 12 carbon atoms are preferable, 1 to 6 are more preferable, and 1 to 3 are more preferable), aryloxy. Group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10), acyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3) , Acyloxy group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), allyloyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms). (Preferably), allyloyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11), carbamoyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms 1). ~ 3 is more preferable), sulfamoyl group (preferably 0 to 12 carbon atoms, more preferably 0 to 6 and even more preferably 0 to 3), sulfo group, alkylsulfonyl group (preferably 1 to 12 carbon atoms, 1 to 1). 6 is more preferable, 1 to 3 are more preferable), an arylsulfonyl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), and a heterocyclic group (1 to 12 carbon atoms is preferable). Preferably, 1 to 8 are more preferable, 2 to 5 are even more preferable, and a 5-membered ring or a 6-membered ring is preferably contained), a (meth) acryloyl group, a (meth) acryloyloxy group, a halogen atom (for example, a fluorine atom). , a chlorine atom, a bromine atom, an iodine atom), oxo (= O), imino (= ^NR N), an alkylidene group _{^{(= C (R N) 2}} ) , and the like. ^RN is a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and a hydrogen atom, a methyl group, an ethyl group, or a propyl group is preferable. The alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be chain or cyclic, and may be linear or branched. When the substituent T is a group capable of taking a substituent, it may further have a substituent T. For example, the alkyl group may be an alkyl halide group, a (meth) acryloyloxyalkyl group, an aminoalkyl group or a carboxyalkyl group. When the substituent is a group capable of forming a salt such as a carboxy group or an amino group, the group may form a salt.

-Compound represented by formula (91)-
The compound represented by the formula (9) is preferably a compound represented by the following formula (91).

R ^{93 to} R ⁹⁶ are each independently a hydrocarbon group having 1 to 24 carbon atoms, n9 is an integer of 1 to 6, m9 is an integer twice n9, and n10 is an integer of 1 to 6. It is an integer, m10 is an integer twice n10, and l9 and l10 are independently numbers of 0 or more and 12 or less.
R ^{93 to} R ⁹⁶ are hydrocarbon groups, and among them, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and an alkenyl group (2 to 12 carbon atoms are preferable). Preferably, 2 to 6 are more preferable, 2 to 3 are more preferable), an alkynyl group (2 to 12 carbon atoms are preferable, 2 to 6 are more preferable, 2 to 3 are more preferable), and an aryl group (6 to 3 carbon atoms is more preferable). 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), and an arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable). .. The alkyl group, alkenyl group, and alkynyl group may be linear or cyclic, and may be linear or branched. R ^{93 to} R ⁹⁶ may have a substituent T as long as the effects of the present invention are exhibited. Further, R ^{93 to} R ⁹⁶ may be bonded to each other or form a ring via the following connecting group L. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the hydrocarbon group in the formula with or without the following linking group L to form a ring.
R ⁹³ and R ⁹⁴ are preferably alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). Of these, a methyl group is preferable.
R ⁹⁵ and R ⁹⁶ are preferably alkyl groups (preferably 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 3 to 6 carbon atoms). Of these, − (C _n11 R ⁹⁸ _m11 ) -R ⁹⁷ is preferable. R ⁹⁵ and R ⁹⁶ are particularly preferably isobutyl groups.
n11 is an integer of 1 to 6, preferably an integer of 1 to 3. m11 is twice the number of n11.
R ⁹⁷ and R ⁹⁸ are each independently preferably a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms).
n9 is an integer of 1 to 6, preferably an integer of 1 to 3. m9 is an integer that is twice n9.
n10 is an integer of 1 to 6, preferably an integer of 1 to 3. m10 is an integer that is twice n10.
l9 and l10 are independently numbers 0-12, respectively. However, l9 + l10 is preferably a number from 0 to 12, more preferably a number from 0 to 8, further preferably a number from 0 to 6, even more preferably a number exceeding 0 and less than 6, and exceeding 0. A number of 3 or less is even more preferable. Regarding l9 and l10, the compound of the formula (91) may be a mixture of compounds having different numbers, and in that case, the numbers of l9 and l10, or l9 + l10 are the numbers including the decimal point. You may.

As the linking group L, an alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) and an alkenylene group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). 2-3 are more preferred), alkynylene groups (2-12 carbon atoms are preferred, 2-6 are more preferred, 2-3 are more preferred), (oligo) alkyleneoxy groups (alkylene groups in one repeating unit. The number of carbon atoms is preferably 1-12, more preferably 1-6, still more preferably 1-3; the number of repetitions is preferably 1-50, more preferably 1-40, even more preferably 1-30), arylene group ( 6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, and 6 to 10 are more preferable), oxygen atom, sulfur atom, sulfonyl group, carbonyl group, thiocarbonyl group, -NR ^N- , and combinations thereof. Linking groups can be mentioned. The alkylene group may have the following substituent T. For example, the alkylene group may have a hydroxy group. The number of atoms contained in the linking group L is preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30, excluding hydrogen atoms. The number of linked atoms means the number of atoms located in the shortest path among the atomic groups involved in the linking. For example, in the case of -CH _2- (C = O) -O-, the number of atoms involved in the connection is 6, and even excluding the hydrogen atom, it is 4. On the other hand, the shortest atom involved in the connection is -C-C-O-, which is three. The number of connected atoms is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6. The alkylene group, alkenylene group, alkynylene group, and (oligo) alkyleneoxy group may be chain-like or cyclic, and may be linear or branched. When the linking group is a group ^{capable of forming a salt such as −NR N−} , the group may form a salt.

Ｒ^９３、Ｒ^９４、Ｒ^９７〜Ｒ^１００は、それぞれ独立に、炭素数１〜２４の炭化水素基であり、ｌ１１及びｌ１２は、それぞれ独立に、０以上１２以下の数である。
Ｒ^９３、Ｒ^９４、Ｒ^９７〜Ｒ^１００はなかでもアルキル基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３が更に好ましい）、アルケニル基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３が更に好ましい）、アルキニル基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３が更に好ましい）、アリール基（炭素数６〜２２が好ましく、６〜１８がより好ましく、６〜１０が更に好ましい）、アリールアルキル基（炭素数７〜２３が好ましく、７〜１９がより好ましく、７〜１１が更に好ましい）であることが好ましい。アルキル基、アルケニル基、アルキニル基は鎖状でも環状でもよく、直鎖でも分岐でもよい。Ｒ^９３、Ｒ^９４、Ｒ^９７〜Ｒ^１００は本発明の効果を奏する範囲で置換基Ｔを有していてもよい。また、Ｒ^９３、Ｒ^９４、Ｒ^９７〜Ｒ^１００は互いに結合して、又は連結基Ｌを介して環を形成していてもよい。置換基Ｔは、複数あるときは互いに結合して、あるいは連結基Ｌを介して又は介さずに式中の炭化水素基と結合して環を形成していてもよい。
Ｒ^９３、Ｒ^９４、Ｒ^９７〜Ｒ^１００は、それぞれ独立に、アルキル基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３が更に好ましい）であることが好ましい。なかでもメチル基が好ましい。
ｌ１１＋ｌ１２は０〜１２の数であることが好ましく、０〜８の数であることがより好ましく、０〜６の数が更に好ましく、０を超え６未満の数が一層好ましく、０を超え５以下の数がより一層好ましく、０を超え４以下の数が更に一層好ましく、０を超え３以下の数であってもよく、０を超え１以下の数であってもよい。なお、ｌ１１、ｌ１２は、式（９２）の化合物がその数において異なる化合物の混合物となる場合があり、そのときはｌ１１及びｌ１２の数、あるいはｌ１１＋ｌ１２が、小数点以下が含まれた数であってもよい。-Compound represented by formula (92)-
The compound represented by the formula (91) is preferably a compound represented by the following formula (92).

R ⁹³ , R ⁹⁴ , and R ^{97 to} R ¹⁰⁰ are each independently a hydrocarbon group having 1 to 24 carbon atoms, and l11 and l12 are each independently a number of 0 or more and 12 or less.
Among them, R ⁹³ , R ⁹⁴ , and R ^{97 to} R ¹⁰⁰ are alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and alkenyl groups (preferably 2 to 12 carbon atoms). , 2-6 are more preferred, 2-3 are more preferred), alkynyl groups (2-12 carbon atoms are preferred, 2-6 are more preferred, 2-3 are more preferred), aryl groups (6-22 carbon atoms are preferred). Is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), and an arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable). The alkyl group, alkenyl group, and alkynyl group may be chain or cyclic, and may be linear or branched. R ⁹³ , R ⁹⁴ , and R ^{97 to} R ¹⁰⁰ may have a substituent T as long as the effects of the present invention are exhibited. Further, R ⁹³ , R ⁹⁴ , and R ^{97 to} R ¹⁰⁰ may be bonded to each other or form a ring via a connecting group L. When there are a plurality of the substituents T, they may be bonded to each other, or may be bonded to the hydrocarbon group in the formula with or without the linking group L to form a ring.
R ⁹³ , R ⁹⁴ , and R ^{97 to} R ¹⁰⁰ are each independently preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms). Of these, a methyl group is preferable.
The number of l11 + l12 is preferably 0 to 12, more preferably 0 to 8, further preferably 0 to 6, more preferably more than 0 and less than 6, more than 0 and 5 or less. The number of is even more preferable, the number of more than 0 and less than 4 is even more preferable, the number of more than 0 and less than 3 or more than 0 and less than or equal to 1. In addition, l11 and l12 may be a mixture of compounds having different numbers in the compound of the formula (92), and in that case, the numbers of l11 and l12, or l11 + l12 are the numbers including the decimal point. May be good.

Surfactants containing an acetylene group include Surfynol 104 series (trade name, Nisshin Kagaku Kogyo Co., Ltd.), Acetyrenol E00, E40, E13T, and 60 (all trade names, rivers). (Manufactured by Ken Finechem Co., Ltd.), among which Surfinol 104 series, Acetyleneol E00, E40 and E13T are preferable, and Acetyleneol E40 and E13T are more preferable. The Surfinol 104 series and acetylenol E00 are surfactants having the same structure.

[Other surfactants]
The protective layer may contain other surfactants other than the above-mentioned surfactant containing an acetylene group for the purpose of improving the coatability of the protective layer forming composition described later.
The other surfactant may be any other surfactant, such as nonionic surfactant, anionic surfactant, and amphoteric fluorine surfactant, as long as it lowers the surface tension.
Examples of other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene nonylphenyl ether. Polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan triole Nonionic surfactants such as sorbitan alkyl esters such as ate, monoglyceride alkyl esters such as glycerol monostearate and glycerol monooleate, oligomers containing fluorine or silicon; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate. , Alkylnaphthalene sulfonates such as sodium butylnaphthalene sulfonate, sodium pentylnaphthalene sulfonate, sodium hexylnaphthalene sulfonate, sodium octylnaphthalene sulfonate, alkyl sulfates such as sodium lauryl sulphate, alkyl sulfonic acid such as sodium dodecyl sulfonate, etc. Anionic surfactants such as salts and sulfosuccinate salts such as sodium dilauryl sulfosuccinate; and amphoteric surfactants such as alkyl betaines such as lauryl betaine and stearyl betaine and amino acids can be used.

When the protective layer contains a surfactant containing an acetylene group and another surfactant, the total amount of the surfactant containing an acetylene group and the other surfactant is used, and the amount of the surfactant added is protective. The amount is preferably 0.05 to 20% by mass, more preferably 0.07 to 15% by mass, still more preferably 0.1 to 10% by mass, based on the total mass of the layer. These surfactants may be used alone or in combination of two or more. When a plurality of items are used, the total amount is within the above range.
Further, in the present invention, the structure may be substantially free of other surfactants. The term "substantially free" means that the content of the other surfactant is 5% by mass or less of the content of the surfactant containing an acetylene group, preferably 3% by mass or less, and 1% by mass or less. Is more preferable.

The protective layer may contain both a surfactant containing an acetylene group and another surfactant as the surfactant, or may contain only one of them.
In the protective layer, the content of the surfactant is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, still more preferably 0.1% by mass or more, based on the total mass of the protective layer. .. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less. As the surfactant, one type or a plurality of types may be used. When a plurality of products are used, the total amount is preferably in the above range.

The surface tension of the 0.1% by mass aqueous solution of the surfactant at 23 ° C. is preferably 45 mN / m or less, more preferably 40 mN / m or less, and further preferably 35 mN / m or less. .. As the lower limit, it is preferably 5 mN / m or more, more preferably 10 mN / m or more, and further preferably 15 mN / m or more. The surface tension of the surfactant may be appropriately selected depending on the type of the surfactant to be selected.

[Preservatives, fungicides (preservatives, etc.)]
It is also a preferred embodiment that the protective layer contains an antiseptic or antifungal agent.
As the preservative and antifungal agent (hereinafter, preservative and the like), it is preferable that the additive having an antibacterial or antifungal action contains at least one selected from water-soluble or water-dispersible organic compounds. Examples of the additive having an antibacterial or antifungal action such as an antiseptic include an organic antibacterial agent or an antifungal agent, an inorganic antibacterial agent or an antifungal agent, a natural antibacterial agent or an antifungal agent and the like. For example, as the antibacterial or antifungal agent, those described in "Antibacterial / Antifungal Technology" published by Toray Research Center Co., Ltd. can be used.
In the present invention, by blending a preservative or the like in the protective layer, the effect of suppressing the increase of coating defects due to the growth of bacteria inside the solution after long-term storage at room temperature is more effectively exhibited.

Examples of preservatives include phenol ether compounds, imidazole compounds, sulfone compounds, N. haloalkylthio compounds, anilide compounds, pyrrol compounds, quaternary ammonium salts, alcine compounds, pyridine compounds, and triazine compounds. , Benzoisothiazolin-based compounds, isothiazoline-based compounds and the like. Specifically, for example, 2 (4 thiocyanomethyl) benzimidazolone, 1,2 benzothiazolone, 1,2-benzisothiazolin-3-one, N-fluorodichloromethylthio-phthalimide, 2,3,5,6-tetrachloro. Isophthalonitrile, N-trichloromethylthio-4-cyclohexene-1,2-dicarboxyimide, copper 8-quinophosphate, bis (tributyltin) oxide, 2- (4-thiazolyl) benzimidazole, 2-benzimidazole carbamate Methyl, 10,10'-oxybisphenoxyarcin, 2,3,5,6-tetrachloro-4- (methylsulphon) pyridine, bis (2-pyridylthio-1-oxide) zinc, N, N-dimethyl-N '-(Fluorodichloromethylthio) -N'-Phenylsulfamide, Poly- (Hexamethylenebiguanide) Hydrochloride, Dithio-2-2'-Bis, 2-Methyl-4,5-Trimethylene-4-isothiazolin-3 -On, 2-bromo-2-nitro-1,3-propanediol, hexahydro-1,3-tris- (2-hydroxyethyl) -S-triazine, p-chloro-m-xylenol, 1,2-benz Examples thereof include isothiazolin-3-one and methylphenol.

As a natural antibacterial and antifungal agent, there is chitosan, a basic polysaccharide obtained by hydrolyzing chitin contained in the crustacean of crabs and shrimp. Nikko's "trade name Holon Killer Bees Cera", which is composed of an amino metal in which a metal is compounded on both sides of an amino acid, is preferable.

The content of the preservative or the like in the protective layer is preferably 0.005 to 5% by mass, more preferably 0.01 to 3% by mass, and 0.05 to 0.05 to the total mass of the protective layer. It is more preferably 2% by mass, and even more preferably 0.1 to 1% by mass. As the preservative or the like, one kind or a plurality of preservatives may be used. When a plurality of items are used, the total amount is within the above range.
The antibacterial effect of preservatives and the like can be evaluated in accordance with JIS Z 2801 (antibacterial processed product-antibacterial test method / antibacterial effect). In addition, the antifungal effect can be evaluated in accordance with JIS Z 2911 (mold resistance test).

[Shading agent]
The protective layer preferably contains a light-shielding agent. By blending a light-shielding agent, the influence of light damage to the organic layer and the like can be further suppressed.
As the light-shielding agent, for example, a known colorant or the like can be used, and examples thereof include organic or inorganic pigments or dyes, preferably inorganic pigments, and more preferably carbon black, titanium oxide, titanium nitride and the like. ..
The content of the light-shielding agent is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and further preferably 5 to 25% by mass with respect to the total mass of the protective layer. As the light-shielding agent, one type or a plurality of types may be used. When a plurality of items are used, the total amount is within the above range.

〔thickness〕
The thickness of the protective layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1.0 μm or more, and even more preferably 2.0 μm or more. The upper limit of the thickness of the protective layer is preferably 10 μm or less, more preferably 5.0 μm or less, still more preferably 3.0 μm or less.

[Stripping liquid]
The protective layer in the present invention is subjected to removal using a stripping solution.
The method of removing the protective layer using the stripping liquid will be described later.
Examples of the stripping solution include water, a mixture of water and a water-soluble solvent, a water-soluble solvent, and the like, and water or a mixture of water and a water-soluble solvent is preferable.
The content of water with respect to the total mass of the stripping liquid is preferably 90 to 100% by mass, and preferably 95 to 100% by mass. Further, the stripping liquid may be a stripping liquid consisting only of water.
In the present specification, water, a mixture of water and a water-soluble solvent, and a water-soluble solvent may be collectively referred to as an aqueous solvent.
As the water-soluble solvent, an organic solvent having a solubility in water at 23 ° C. of 1 g or more is preferable, an organic solvent having a solubility of 10 g or more is more preferable, and an organic solvent having a solubility of 30 g or more is further preferable.
Examples of the water-soluble solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol and glycerin; ketone solvents such as acetone; and amide solvents such as formamide.
In addition, the stripping liquid may contain a surfactant in order to improve the removability of the protective layer.
As the surfactant, a known compound can be used, but a nonionic surfactant is preferable.

[Composition for forming a protective layer]
The composition for forming a protective layer of the present invention is a composition containing a specific polyvinyl alcohol and used for forming a protective layer contained in the laminate of the present invention.
In the laminate of the present invention, the protective layer can be formed, for example, by applying the protective layer forming composition onto the organic layer and drying it.
As a method of applying the composition for forming a protective layer, coating is preferable. Examples of application methods include slit coating method, casting method, blade coating method, wire bar coating method, spray coating method, dipping coating method, bead coating method, air knife coating method, curtain coating method, inkjet method, etc. Examples include the spin coat method and the Langmuir-Blodgett (LB) method. It is more preferable to use the casting method, the spin coating method, and the inkjet method. Such a process makes it possible to produce a protective layer having a smooth surface and a large area at low cost.
Further, the protective layer forming composition can also be formed by a method of transferring a coating film previously formed on a temporary support by the above-mentioned applying method or the like onto an application target (for example, an organic layer).
Regarding the transfer method, the description of paragraphs 0023, 0036 to 0051 of JP-A-2006-023696, paragraphs 096 to 0108 of JP-A-2006-047592, and the like can be referred to.

The composition for forming a protective layer is a component contained in the above-mentioned protective layer (for example, a specific polyvinyl alcohol, another water-soluble resin, a surfactant containing an acetylene group, another surfactant, a preservative, a light-shielding agent, etc.). , And preferably contain a solvent.
Regarding the content of the components contained in the protective layer forming composition, the content of each component with respect to the total mass of the protective layer may be read as the content with respect to the solid content of the protective layer forming composition. preferable.

Examples of the solvent contained in the composition for forming a protective layer include the above-mentioned aqueous solvent, and water or a mixture of water and a water-soluble solvent is preferable, and water is more preferable.
When the aqueous solvent is a mixed solvent, it is preferably a mixed solvent of an organic solvent having a solubility in water at 23 ° C. of 1 g or more and water. The solubility of the organic solvent in water at 23 ° C. is more preferably 10 g or more, further preferably 30 g or more.

The solid content concentration of the protective layer forming composition is preferably 0.5 to 30% by mass from the viewpoint of being more uniform in thickness when the protective layer forming composition is applied and being easy to apply. It is more preferably 0 to 20% by mass, and even more preferably 2.0 to 14% by mass.

<Photosensitive layer>
The laminate of the present invention includes a photosensitive layer.
In the present invention, the photosensitive layer is a layer to be subjected to development using a developing solution.
The development is preferably a negative type development.
As the photosensitive layer, a known photosensitive layer (for example, a photoresist layer) used in the present technical field can be appropriately used.
In the laminated body of the present invention, the photosensitive layer may be a negative type photosensitive layer or a positive type photosensitive layer.

It is preferable that the exposed portion of the photosensitive layer is sparingly soluble in a developing solution containing an organic solvent. The poorly soluble means that the exposed portion is difficult to dissolve in the developing solution.
It is preferable that the dissolution rate of the photosensitive layer in the exposed portion in the developing solution is smaller (difficult to dissolve) than the dissolution rate of the photosensitive layer in the developing solution in the unexposed portion.
Specifically, the polarity is changed by exposing light having at least one wavelength having a wavelength of 365 nm (i line), a wavelength of 248 nm (KrF line) and a wavelength of 193 nm (ArF line) at ^{an irradiation amount of 50 mJ / cm 2 or more.} , It is preferable that the sp value (solubility parameter) is ^{poorly soluble in a solvent of less than 19.0 (MPa) 1/2} , and is poorly soluble in a solvent of 18.5 (MPa) ^1/2 or less. It is more preferable that the solvent is poorly soluble in a solvent of ^{18.0 (MPa) 1/2 or less.}
In the present invention, the solubility parameter (sp value) is a value [unit: (MPa) ^1/2 ] obtained by the Okitsu method. The Okitsu method is one of the well-known methods for calculating the sp value. For example, Vol. 29, No. 6 (1993) The method described in detail on pages 249-259.
Further, by exposing light having at least one wavelength having a wavelength of 365 nm (i line), a wavelength of 248 nm (KrF line) and a wavelength of 193 nm (ArF line) at ^{an irradiation amount of 50 to 250 mJ / cm 2} , the polarity can be changed as described above. It is more preferable to change.

The photosensitive layer preferably has a photosensitivity to i-ray irradiation.
The photosensitivity means that the dissolution rate in an organic solvent (preferably butyl acetate) is changed by irradiation with at least one of active rays and radiation (irradiation with i-rays if the photosensitivity is with respect to i-ray irradiation). To do.

Examples of the photosensitive layer include a photosensitive layer containing a resin (hereinafter, also referred to as “specific resin”) whose dissolution rate in a developing solution changes due to the action of an acid.
The change in the dissolution rate in the specific resin is preferably a decrease in the dissolution rate.
The dissolution rate of the specific resin in an organic solvent having an sp value of 18.0 (MPa) ^1/2 or less before the dissolution rate changes is more preferably 40 nm / sec or more.
The dissolution rate of the specific resin in an organic solvent having an sp value of 18.0 (MPa) ^1/2 or less after the dissolution rate is changed is more preferably less than 1 nm / sec.
The specific resin is also soluble in an organic solvent having an sp value (solubility parameter) of 18.0 (MPa) ^1/2 or less before the dissolution rate changes, and after the dissolution rate changes. , A resin having a sp value of 18.0 (MPa) ^1/2 or less, which is poorly soluble in an organic solvent, is preferable.
Here, "soluble in an organic solvent having an sp value (solubility parameter) of 18.0 (MPa) ^1/2 or less" means that a solution of a compound (resin) is applied onto a substrate and the temperature is 100 ° C. for 1 minute. The dissolution rate of a coating film (thickness 1 μm) of a compound (resin) formed by heating when immersed in a developing solution at 23 ° C. is 20 nm / sec or more, which means that the “sp value”. Is sparingly soluble in an organic solvent of 18.0 (MPa) ^1/2 or less "means a compound (resin) formed by applying a solution of a compound (resin) on a substrate and heating at 100 ° C. for 1 minute. ), The dissolution rate of the coating film (thickness 1 μm) in the developing solution at 23 ° C. is less than 10 nm / sec.

Examples of the photosensitive layer include a photosensitive layer containing a specific resin and a photoacid generator, a photosensitive layer containing a polymerizable compound, a photopolymerization initiator, and the like.
Further, the photosensitive layer is preferably a chemically amplified photosensitive layer from the viewpoint of achieving both high storage stability and fine pattern formation.
Hereinafter, an example of the photosensitive layer containing the specific resin and the photoacid generator will be described.

[Specific resin]
The photosensitive layer in the present invention preferably contains a specific resin.
The specific resin is preferably an acrylic polymer.
The "acrylic polymer" is an addition polymerization type resin, a polymer containing a repeating unit derived from (meth) acrylic acid or an ester thereof, and other than the repeating unit derived from (meth) acrylic acid or an ester thereof. The repeating unit of the above, for example, a repeating unit derived from styrenes, a repeating unit derived from a vinyl compound, and the like may be included. The acrylic polymer preferably contains 50 mol% or more, more preferably 80 mol% or more, of repeating units derived from (meth) acrylic acid or an ester thereof, based on all the repeating units in the polymer. It is particularly preferable that the polymer consists only of repeating units derived from (meth) acrylic acid or an ester thereof.

As the specific resin, a resin having a repeating unit having a structure in which an acid group is protected by an acid-degradable group is preferably mentioned. As a structure in which the acid group is protected by an acid-degradable group, a carboxy group is acid-decomposable. Examples thereof include a structure protected by a group, a structure in which a phenolic hydroxy group is protected by an acid-degradable group, and the like.
Further, as the repeating unit having a structure in which the acid group is protected by an acid-degradable group, a repeating unit having a structure in which the carboxy group in the monomer unit derived from (meth) acrylic acid is protected by an acid-degradable group, p. Examples thereof include a repeating unit having a structure in which a phenolic hydroxy group in a monomer unit derived from hydroxystyrenes such as −hydroxystyrene and α-methyl-p-hydroxystyrene is protected by an acid-degradable group.

Examples of the repeating unit having a structure in which the acid group is protected by an acid-degradable group include a repeating unit containing an acetal structure, and a repeating unit containing a cyclic ether ester structure in the side chain is preferable. As the cyclic ether ester structure, it is preferable that the oxygen atom in the cyclic ether structure and the oxygen atom in the ester bond are bonded to the same carbon atom to form an acetal structure.

式（１）中、Ｒ^８は水素原子又はアルキル基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３が更に好ましい）を表し、Ｌ^１はカルボニル基又はフェニレン基を表し、Ｒ^１〜Ｒ^７はそれぞれ独立に、水素原子又はアルキル基を表す。
式（１）中、Ｒ^８は、水素原子又はメチル基であることが好ましく、メチル基であることがより好ましい。
式（１）中、Ｌ^１は、カルボニル基又はフェニレン基を表し、カルボニル基であることが好ましい。
式（１）中、Ｒ^１〜Ｒ^７はそれぞれ独立に、水素原子又はアルキル基を表す。Ｒ^１〜Ｒ^７におけるアルキル基は、Ｒ^８と同義であり、好ましい態様も同様である。また、Ｒ^１〜Ｒ^７のうち、１つ以上が水素原子であることが好ましく、Ｒ^１〜Ｒ^７の全てが水素原子であることがより好ましい。Further, as the repeating unit having a structure in which the acid group is protected by an acid-degradable group, the repeating unit represented by the following formula (1) is preferable.
Hereinafter, the “repetition unit represented by the equation (1)” and the like are also referred to as the “repetition unit (1)” and the like.

In the formula (1), R ⁸ represents a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and L ¹ represents a carbonyl group or a phenylene group. , R ^{1 to} R ⁷ independently represent a hydrogen atom or an alkyl group.
In the formula (1), R ⁸ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
In the formula (1), L ¹ represents a carbonyl group or a phenylene group, and is preferably a carbonyl group.
In formula (1), R ^{1 to} R ⁷ independently represent a hydrogen atom or an alkyl group. The alkyl groups in R ^{1 to} R ^{7 are synonymous with R 8} and the preferred embodiments are the same. ^Further, among R 1 to R ^7, preferably more than one is a hydrogen ^atom, more preferably all of R 1 to R ⁷ is a hydrogen atom.

As the repeating unit (1), a repeating unit represented by the following formula (1-1) or a repeating unit represented by the following formula (1-2) is preferable.

As the radically polymerizable monomer used for forming the repeating unit (1), a commercially available one may be used, or one synthesized by a known method may be used. For example, it can be synthesized by reacting (meth) acrylic acid with a dihydrofuran compound in the presence of an acid catalyst. Alternatively, it can also be formed by reacting a carboxy group or a phenolic hydroxy group with a dihydrofuran compound after polymerization with a precursor monomer.

式（２）中、Ａは、水素原子又は酸の作用により脱離する基を表す。酸の作用により脱離する基としては、アルキル基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３が更に好ましい）、アルコキシアルキル基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３が更に好ましい）、アリールオキシアルキル基（総炭素数７〜４０が好ましく、７〜３０がより好ましく、７〜２０が更に好ましい）、アルコキシカルボニル基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３が更に好ましい）、アリールオキシカルボニル基（炭素数７〜２３が好ましく、７〜１９がより好ましく、７〜１１が更に好ましい）が好ましい。Ａは更に置換基を有していてもよく、置換基として上記置換基Ｔの例が挙げられる。
式（２）中、Ｒ^１０は置換基を表し、置換基Ｔの例が挙げられる。Ｒ^９は式（１）におけるＲ^８と同義の基を表す。
式（２）中、ｎｘは、０〜３の整数を表す。Further, as the repeating unit having a structure in which the acid group is protected by an acid-degradable group, a repeating unit represented by the following formula (2) is also preferably mentioned.

In formula (2), A represents a group eliminated by the action of a hydrogen atom or an acid. As the group desorbed by the action of the acid, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and an alkoxyalkyl group (preferably 2 to 12 carbon atoms, 2). ~ 6 is more preferred, 2-3 is more preferred), aryloxyalkyl group (total carbon number 7-40 is preferred, 7-30 is more preferred, 7-20 is more preferred), alkoxycarbonyl group (carbonyl 2). ~ 12 is preferable, 2 to 6 is more preferable, 2 to 3 is more preferable), and an aryloxycarbonyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable) is preferable. A may further have a substituent, and examples of the above-mentioned Substituent T can be mentioned as the substituent.
In the formula (2), R ¹⁰ represents a substituent, and an example of the substituent T can be given. R ⁹ represents a group synonymous with ^{R 8} in the formula (1).
In equation (2), nx represents an integer from 0 to 3.

As the group desorbed by the action of an acid, among the compounds described in paragraphs 0039 to 0049 of JP-A-2008-197480, a repeating unit containing a group desorbed by an acid is also preferable, and JP-A-2012- The compounds described in paragraphs 0052 to 0056 of Japanese Patent No. 159830 (Patent No. 5191567) are also preferred, and their contents are incorporated herein.

Specific examples of the repeating unit (2) are shown below, but the present invention is not construed as being limited thereto.

The content of the repeating unit (preferably, repeating unit (1) or repeating unit (2)) having a structure in which the acid group is protected by an acid-degradable group contained in the specific resin is preferably 5 to 80 mol%. , 10 to 70 mol% is more preferable, and 10 to 60 mol% is further preferable. The acrylic polymer may contain only one type of repeating unit (1) or repeating unit (2), or may contain two or more types. When two or more types are used, the total amount is preferably in the above range.

The specific resin may contain a repeating unit containing a crosslinkable group. For details of the crosslinkable group, the description in paragraphs 0032 to 0046 of JP2011-209692A can be referred to, and these contents are incorporated in the present specification.
The specific resin preferably contains a repeating unit (repeating unit (3)) containing a crosslinkable group, but preferably has a structure that does not substantially contain the repeating unit (3) containing a crosslinkable group. With such a configuration, the photosensitive layer can be removed more effectively after patterning. Here, substantially not contained means, for example, 3 mol% or less, preferably 1 mol% or less, of all repeating units of the specific resin.

The specific resin may contain other repeating units (repeating units (4)). Examples of the radically polymerizable monomer used for forming the repeating unit (4) include the compounds described in paragraphs 0021 to 0024 of JP2004-246623A. A preferred example of the repeating unit (4) is a repeating derived from at least one selected from the group consisting of a hydroxy group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene, and an N-substituted maleimide. The unit is mentioned. Among these, benzyl (meth) acrylate, tricyclo (meth) acrylate [5.2.1.0 ^2,6 ] decane-8-yl, tricyclo (meth) acrylate [5.2.1.0 ^{2,] 6} ] (Meta) acrylic acid esters containing alicyclic structure such as decane-8-yloxyethyl, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, or Hydrophobic monomers such as styrene are preferred.
The repetition unit (4) may be used alone or in combination of two or more. Among all the monomer units constituting the specific resin, the content of the monomer unit forming the repeating unit (4) when the repeating unit (4) is contained is preferably 1 to 60 mol%, more preferably 5 to 50 mol%. It is preferable, and more preferably 5 to 40 mol%. When two or more types are used, the total amount is preferably in the above range.

Various methods are known for synthesizing a specific resin, and for example, it contains at least a radically polymerizable monomer used for forming a repeating unit (1), a repeating unit (2), and the like. It can be synthesized by polymerizing a radically polymerizable monomer mixture in an organic solvent with a radical polymerization initiator.
As a specific resin, 2,3-dihydrofuran was added to an acid anhydride group in a precursor copolymer copolymerized with unsaturated polyvalent carboxylic acid anhydrides at room temperature (25 ° C.) in the absence of an acid catalyst. ) To a copolymer obtained by adding at a temperature of about 100 ° C. is also preferable.
The following resins are also mentioned as preferable examples of the specific resin.
BzMA / THFMA / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
BzMA / THFAA / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
BzMA / THPMA / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
BzMA / PEES / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
BzMA is benzyl methacrylate, THFMA is tetrahydrofuran-2-yl methacrylate, t-BuMA is t-butyl methacrylate, THFAA is tetrahydrofuran-2-yl acrylate, THPMA is tetrahydro-2H. -Pyran-2-yl methacrylate, PEES is p-ethoxyethoxystyrene.

Further, as the specific resin used for positive type development, those described in JP2013-011678A are exemplified, and these contents are incorporated in the present specification.

From the viewpoint of improving the pattern forming property during development, the content of the specific resin is preferably 20 to 99% by mass, more preferably 40 to 99% by mass, based on the total mass of the photosensitive layer. , 70 to 99% by mass, more preferably. The specific resin may contain only one type, or may contain two or more types. When two or more types are used, the total amount is preferably in the above range.
The content of the specific resin is preferably 10% by mass or more, more preferably 50% by mass or more, and more preferably 90% by mass or more, based on the total mass of the resin components contained in the photosensitive layer. Is more preferable.

The weight average molecular weight of the specific resin is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 35,000 or more. The upper limit value is not particularly specified, but is preferably 100,000 or less, and may be 70,000 or less, or 50,000 or less.
Further, the amount of the component having a weight average molecular weight of 1,000 or less contained in the specific resin is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the specific resin.
The molecular weight dispersion (weight average molecular weight / number average molecular weight) of the specific resin is preferably 1.0 to 4.0, more preferably 1.1 to 2.5.

[Photoacid generator]
The photosensitive layer preferably contains a photoacid generator. The photoacid generator is preferably a photoacid generator that decomposes by 80 mol% or more when the photosensitive layer is exposed to an exposure amount of 100 mJ / cm ^{2 at a wavelength of 365 nm.}
The degree of decomposition of the photoacid generator can be determined by the following method. Details of the following composition for forming a photosensitive layer will be described later.
Using the composition for forming a photosensitive layer, a photosensitive layer is formed on a silicon wafer substrate, heated at 100 ° C. for 1 minute, and after heating, the photosensitive layer is exposed ^{to 100 mJ / cm 2 using light having a wavelength of 365 nm.} To expose. The thickness of the photosensitive layer after heating is 700 nm. Then, the silicon wafer substrate on which the photosensitive layer is formed is immersed in a methanol / tetrahydrofuran (THF) = 50/50 (mass ratio) solution for 10 minutes while applying ultrasonic waves. After the immersion, the extract extracted into the solution is analyzed by HPLC (high performance liquid chromatography) to calculate the decomposition rate of the photoacid generator from the following formula.
Decomposition rate (%) = decomposition product amount (mol) / amount of photoacid generator contained in the photosensitive layer before exposure (mol) x 100
The photoacid generator preferably decomposes by 85 mol% or more when the photosensitive layer is exposed to an exposure amount of 100 mJ / cm ^{2 at a wavelength of 365 nm.}

式（ＯＳ−１）中、Ｘ^３は、アルキル基、アルコキシル基、又は、ハロゲン原子を表す。Ｘ^３が複数存在する場合は、それぞれ同一であってもよいし、異なっていてもよい。上記Ｘ^３におけるアルキル基及びアルコキシル基は、置換基を有していてもよい。上記Ｘ^３におけるアルキル基としては、炭素数１〜４の、直鎖状又は分岐状アルキル基が好ましい。上記Ｘ^３におけるアルコキシル基としては、炭素数１〜４の直鎖状又は分岐状アルコキシル基が好ましい。上記Ｘ^３におけるハロゲン原子としては、塩素原子又はフッ素原子が好ましい。
式（ＯＳ−１）中、ｍ３は、０〜３の整数を表し、０又は１が好ましい。ｍ３が２又は３であるとき、複数のＸ^３は同一でも異なっていてもよい。
式（ＯＳ−１）中、Ｒ^３４は、アルキル基又はアリール基を表し、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、炭素数１〜５のハロゲン化アルキル基、炭素数１〜５のハロゲン化アルコキシル基、Ｗで置換されていてもよいフェニル基、Ｗで置換されていてもよいナフチル基又はＷで置換されていてもよいアントラニル基であることが好ましい。Ｗは、ハロゲン原子、シアノ基、ニトロ基、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、炭素数１〜５のハロゲン化アルキル基又は炭素数１〜５のハロゲン化アルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のハロゲン化アリール基を表す。The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound").
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-) It is preferably an oxime sulfonate compound represented by 105).

Wherein (OS-1), ^{X 3} is an alkyl group, an alkoxyl group, or a halogen atom. If X ³ there are a plurality, each be the same or may be different. Alkyl group and an alkoxyl group represented by X ³ may have a substituent. The alkyl group in the above X ^3, 1 to 4 carbon atoms, straight-chain or branched alkyl group is preferable. The alkoxyl group represented by X ^3, preferably a linear or branched alkoxyl group having 1 to 4 carbon atoms. The halogen atom in the X ^3, a chlorine atom or a fluorine atom is preferable.
In the formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X ³ may be the same or different.
In the formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxyl group of numbers 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxyl halide having 1 to 5 carbon atoms. It represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.

Wherein (OS-1), m3 is 3, ^{X 3} is a methyl group, the substitution position of ^{X 3} is ^ortho, a linear alkyl group ^{R 34} is 1 to 10 carbon atoms, 7, A compound having a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group is particularly preferable.

式（ＯＳ−１０３）〜式（ＯＳ−１０５）中、Ｒ^ｓ１はアルキル基、アリール基又はヘテロアリール基を表し、複数存在する場合のあるＲ^ｓ２はそれぞれ独立に、水素原子、アルキル基、アリール基又はハロゲン原子を表し、複数存在する場合のあるＲ^ｓ６はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基又はアルコキシスルホニル基を表し、ＸｓはＯ又はＳを表し、ｎｓは１又は２を表し、ｍｓは０〜６の整数を表す。
式（ＯＳ−１０３）〜式（ＯＳ−１０５）中、Ｒ^ｓ１で表されるアルキル基（炭素数１〜３０が好ましい）、アリール基（炭素数６〜３０が好ましい）又はヘテロアリール基（炭素数４〜３０が好ましい）は、置換基Ｔを有していてもよい。Specific examples of the oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-209692A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents are incorporated herein.

In formulas (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and R ^{s2, which may be present in a plurality of R s2,} independently represents a hydrogen atom, an alkyl group and an aryl group. ^{R s6} , which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and Xs represents O or S. Represented, ns represents 1 or 2, ms represents an integer from 0 to 6.
In formulas (OS-103) to (OS-105), ^{an alkyl group represented by R s1} (preferably having 1 to 30 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms) or a heteroaryl group (carbon). (Preferably numbers 4 to 30) may have a substituent T.

In formulas (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable. ^{Of the R s2} that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom. The alkyl group or aryl group represented by ^{R s2 may have a substituent T.}
In the formula (OS-103), the formula (OS-104), or the formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

In formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
In formulas (OS-103) to (OS-105), the ^{alkyl group represented by R s6} (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) have substituents. You may have.
In the formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.

式（ＯＳ−１０６）〜式（ＯＳ−１１１）中、Ｒ^ｔ１はアルキル基、アリール基又はヘテロアリール基を表し、Ｒ^ｔ７は、水素原子又は臭素原子を表し、Ｒ^ｔ８は水素原子、炭素数１〜８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、Ｒ^ｔ９は水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、Ｒ^ｔ２は水素原子又はメチル基を表す。
式（ＯＳ−１０６）〜式（ＯＳ−１１１）中、Ｒ^ｔ７は、水素原子又は臭素原子を表し、水素原子であることが好ましい。
式（ＯＳ−１０６）〜式（ＯＳ−１１１）中、Ｒ^ｔ８は、水素原子、炭素数１〜８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、炭素数１〜８のアルキル基、ハロゲン原子又はフェニル基であることが好ましく、炭素数１〜８のアルキル基であることがより好ましく、炭素数１〜６のアルキル基であることが更に好ましく、メチル基であることが特に好ましい。
式（ＯＳ−１０６）〜式（ＯＳ−１１１）中、Ｒ^ｔ９は、水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、水素原子であることが好ましい。
Ｒ^ｔ２は、水素原子又はメチル基を表し、水素原子であることが好ましい。
また、上記オキシムスルホネート化合物において、オキシムの立体構造（Ｅ，Ｚ）については、いずれか一方であっても、混合物であってもよい。
上記式（ＯＳ−１０３）〜式（ＯＳ−１０５）で表されるオキシムスルホネート化合物の具体例としては、特開２０１１−２０９６９２号公報の段落番号００８８〜００９５、特開２０１５−１９４６７４号公報の段落番号０１６８〜０１９４に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。The compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111). The compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.

In formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, and R ^t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups, R ^t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups, and R ^t2 represents a hydrogen atom or a methyl group.
In formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
In formulas (OS-106) to (OS-111), R ^t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, and a phenyl group. Alternatively, it represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is more preferable to have a methyl group, and it is particularly preferable to have a methyl group.
In formulas (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ^t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
Specific examples of the oxime sulfonate compound represented by the above formulas (OS-103) to (OS-105) include paragraphs 008 to 0995 of JP2011-209692A and paragraphs of JP2015-194674A. The compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.

式（ＯＳ−１０１）又は式（ＯＳ−１０２）中、Ｒ^ｕ９は、水素原子、アルキル基、アルケニル基、アルコキシル基、アルコキシカルボニル基、アシル基、カルバモイル基、スルファモイル基、スルホ基、シアノ基、アリール基又はヘテロアリール基を表す。Ｒ^ｕ９がシアノ基又はアリール基である態様がより好ましく、Ｒ^ｕ９がシアノ基、フェニル基又はナフチル基である態様が更に好ましい。
式（ＯＳ−１０１）又は式（ＯＳ−１０２）中、Ｒ^ｕ２ａは、アルキル基又はアリール基を表す。
式（ＯＳ−１０１）又は式（ＯＳ−１０２）中、Ｘｕは、−Ｏ−、−Ｓ−、−ＮＨ−、−ＮＲ^ｕ５−、−ＣＨ_２−、−ＣＲ^ｕ６Ｈ−又はＣＲ^ｕ６Ｒ^ｕ７−を表し、Ｒ^ｕ５〜Ｒ^ｕ７はそれぞれ独立に、アルキル基又はアリール基を表す。
式（ＯＳ−１０１）又は式（ＯＳ−１０２）中、Ｒ^ｕ１〜Ｒ^ｕ４はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシル基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基又はアリール基を表す。Ｒ^ｕ１〜Ｒ^ｕ４のうちの２つがそれぞれ互いに結合して環を形成してもよい。このとき、環が縮環してベンゼン環ともに縮合環を形成していてもよい。Ｒ^ｕ１〜Ｒ^ｕ４としては、水素原子、ハロゲン原子又はアルキル基が好ましく、また、Ｒ^ｕ１〜Ｒ^ｕ４のうちの少なくとも２つが互いに結合してアリール基を形成する態様も好ましい。中でも、Ｒ^ｕ１〜Ｒ^ｕ４がいずれも水素原子である態様が好ましい。上記した置換基は、いずれも、更に置換基を有していてもよい。
上記式（ＯＳ−１０１）で表される化合物は、式（ＯＳ−１０２）で表される化合物であることがより好ましい。
また、上記オキシムスルホネート化合物において、オキシムやベンゾチアゾール環の立体構造（Ｅ，Ｚ等）についてはそれぞれ、いずれか一方であっても、混合物であってもよい。
式（ＯＳ−１０１）で表される化合物の具体例としては、特開２０１１−２０９６９２号公報の段落番号０１０２〜０１０６、特開２０１５−１９４６７４号公報の段落番号０１９５〜０２０７に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。
上記化合物の中でも、ｂ−９、ｂ−１６、ｂ−３１、ｂ−３３が好ましい。
市販品としては、ＷＰＡＧ−３３６（富士フイルム和光純薬（株）製）、ＷＰＡＧ−４４３（富士フイルム和光純薬（株）製）、ＭＢＺ−１０１（みどり化学（株）製）等を挙げることができる。Other preferable embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

In formula (OS-101) or formula (OS-102), ^Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Represents an aryl group or a heteroaryl group. The ^{embodiment in which R u9} is a cyano group or an aryl group is more preferable, and the embodiment in which R ^u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
In formula (OS-101) or formula (OS-102), ^Ru2a represents an alkyl or aryl group.
In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, ^-NH- , -NR u5-, -CH _2- , -CR ^u6 H- or CR ^u6 R ^u7. Represents −, and R ^{u5 to} R ^u7 independently represent an alkyl group or an aryl group.
In the formula (OS-101) or the formula (OS-102), ^{Ru1 to Ru4} are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group. 2 in turn, each may be bonded to each other to form a ring of the R ^u1 to R ^u4. At this time, the ring may be condensed to form a fused ring together with the benzene ring. The R ^u1 to R ^u4, hydrogen atom, preferably a halogen atom or an alkyl group, ^also aspects to form the at least two aryl groups bonded to each other of R u1 ^{to R u4} preferred. Above ^all, embodiments R u1 ^{to R u4} are both hydrogen atom. Any of the above-mentioned substituents may further have a substituent.
The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP2011-209692A and paragraph numbers 0195 to 0207 of JP2015-194674. These contents are incorporated herein by reference.
Among the above compounds, b-9, b-16, b-31, and b-33 are preferable.
Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Chemical Co., Ltd.), and the like. Can be done.

As the photoacid generator sensitive to active light, those containing no 1,2-quinonediazide compound are preferable. The reason is that the 1,2-quinonediazide compound produces a carboxy group by a sequential photochemical reaction, but its quantum yield is 1 or less, which is lower in sensitivity than the oxime sulfonate compound.
On the other hand, the oxime sulfonate compound acts as a catalyst for the deprotection of the protected acid group by the acid generated in response to the active light, so that a large number of acids are produced by the action of one photon. Contributes to the deprotection reaction of, the quantum yield exceeds 1, and becomes a large value such as a power of 10, and it is presumed that high sensitivity can be obtained as a result of so-called chemical amplification.
Further, since the oxime sulfonate compound has a broad π-conjugated system, it has absorption even on the long wavelength side, and not only far ultraviolet rays (DUV), ArF rays, KrF rays, and i rays, but also It also shows very high sensitivity in the g-line.
By using a tetrahydrofuranyl group as the acid-decomposable group in the photosensitive layer, it is possible to obtain acid-decomposability equal to or higher than that of acetal or ketal. As a result, the acid-degradable group can be reliably consumed by post-baking in a shorter time. Further, by using the oxime sulfonate compound which is a photoacid generator in combination, the sulfonic acid generation rate is increased, so that the acid production is promoted and the decomposition of the acid-degradable group of the resin is promoted. Further, since the acid obtained by decomposing the oxime sulfonate compound is a sulfonic acid having a small molecule, it has high diffusibility in the cured membrane and can be made more sensitive.
The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and 0.5 to 10% by mass with respect to the total mass of the photosensitive layer. It is more preferable to use 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.
As the photoacid generator, one type may be used alone, or two or more types may be used in combination. When two or more types are used, the total amount is preferably in the above range.

[Basic compound]
The photosensitive layer preferably contains a basic compound from the viewpoint of liquid storage stability of the composition for forming a photosensitive layer, which will be described later.
As the basic compound, it can be arbitrarily selected and used from those used in known chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.
Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, and the like. 4-Dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinolin, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, cyclohexylmorpholinoethylthiourea, piperazine, morpholin, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonen, 1,8-diazabicyclo [5.3] .0] -7-Undesen and the like.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide and the like.
Examples of the quaternary ammonium salt of the carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
When the photosensitive layer contains a basic compound, the content of the basic compound is preferably 0.001 to 1 part by mass, and 0.002 to 0.5 part by mass with respect to 100 parts by mass of the specific resin. Is more preferable.
As the basic compound, one type may be used alone or two or more types may be used in combination, but it is preferable to use two or more types in combination, more preferably two types in combination, and a heterocyclic amine. It is more preferable to use two kinds in combination. When two or more types are used, the total amount is preferably in the above range.

[Surfactant]
The photosensitive layer preferably contains a surfactant from the viewpoint of improving the coatability of the composition for forming a photosensitive layer, which will be described later.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but the preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, polyoxyethylene glycol higher fatty acid diesters, fluorine-based and silicone-based surfactants. ..
It is more preferable that the surfactant contains a fluorine-based surfactant or a silicone-based surfactant.
Examples of these fluorine-based surfactants or silicone-based surfactants include JP-A-62-0366663, JP-A-61-226746, JP-A-61-226745, and JP-A-62-170950. , JP-A-63-034540, JP-A-7-230165, JP-A-8-062834, JP-A-9-054432, JP-A-9-005988, JP-A-2001-330953. Activators can be mentioned, and commercially available surfactants can also be used.
As commercially available surfactants that can be used, for example, Ftop EF301, EF303 (above, manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (above, manufactured by Sumitomo 3M Co., Ltd.), Megafuck F171, F173, F176. , F189, R08 (above, manufactured by DIC Co., Ltd.), Surfron S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox series such as PF-6320 ( Fluorine-based surfactants such as OMNOVA) or silicone-based surfactants can be mentioned. Further, the polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone-based surfactant.

式（４１）中、Ｒ^４１及びＲ^４３はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ^４２は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ^４４は水素原子又は炭素数１以上４以下のアルキル基を表し、Ｌ^４は炭素数３以上６以下のアルキレン基を表し、ｐ４及びｑ４は重合比を表す質量百分率であり、ｐ４は１０質量％以上８０質量％以下の数値を表し、ｑ４は２０質量％以上９０質量％以下の数値を表し、ｒ４は１以上１８以下の整数を表し、ｎ４は１以上１０以下の整数を表す。
式（４１）中、Ｌ^４は、下記式（４２）で表される分岐アルキレン基であることが好ましい。式（４２）におけるＲ^４５は、炭素数１以上４以下のアルキル基を表し、被塗布面に対する濡れ性の点で、炭素数１以上３以下のアルキル基が好ましく、炭素数２又は３のアルキル基がより好ましい。
−ＣＨ_２−ＣＨ（Ｒ^４５）− （４２）
上記共重合体の重量平均分子量は、１，５００以上５，０００以下であることがより好ましい。
感光層が界面活性剤を含む場合、界面活性剤の添加量は、特定樹脂１００質量部に対して、１０質量部以下であることが好ましく、０．０１〜１０質量部であることがより好ましく、０．０１〜１質量部であることが更に好ましい。
界面活性剤は、１種を単独で、又は２種以上を混合して使用することができる。２種以上用いる場合、合計量が上記範囲となることが好ましい。Further, as a surfactant, a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography when a repeating unit A and a repeating unit B represented by the following formula (41) is contained and tetrahydrofuran (THF) is used as a solvent. A copolymer having (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.

In formula (41), R ⁴¹ and R ⁴³ independently represent a hydrogen atom or a methyl group, R ⁴² represents a linear alkylene group having 1 to 4 ^{carbon atoms, and R 44} represents a hydrogen atom or 1 carbon atom. above 4 represents an alkyl group, L ⁴ represents an alkylene group having 3 to 6 carbon atoms, p4 and q4 is the mass percentage representing the polymerization ratio, p4 is a number from 10% by weight to 80% by weight Represented, q4 represents a numerical value of 20% by mass or more and 90% by mass or less, r4 represents an integer of 1 or more and 18 or less, and n4 represents an integer of 1 or more and 10 or less.
In the formula (41), L ⁴ is preferably a branched alkylene group represented by the following formula (42). ^{R 45} in the formula (42) represents an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl having 2 or 3 carbon atoms is preferable in terms of wettability to the surface to be coated. Groups are more preferred.
-CH _2- CH (R ⁴⁵ )-(42)
The weight average molecular weight of the copolymer is more preferably 1,500 or more and 5,000 or less.
When the photosensitive layer contains a surfactant, the amount of the surfactant added is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the specific resin. , 0.01 to 1 part by mass is more preferable.
As the surfactant, one type may be used alone, or two or more types may be mixed and used. When two or more types are used, the total amount is preferably in the above range.

[Other ingredients]
Further, if necessary, the photosensitive layer contains an antioxidant, a plasticizer, a thermal radical generator, a thermoacid generator, an acid growth agent, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. One or more known additives such as, etc. can be added, respectively. For these details, the description in paragraphs 0143 to 0148 of JP2011-209692A can be referred to, and these contents are incorporated in the present specification.

Further, as the photosensitive layer, there is also an embodiment in which a photosensitive layer containing a polymerizable compound, a photopolymerization initiator and the like is used.
Such a photosensitive layer is described in JP-A-2015-087610, which comprises a photoradical polymerization initiator (A) as the photopolymerization initiator and a radical polymerizable compound (B) as the polymerizable compound. The resist film of is preferably used. The photosensitive layer may further contain other compounds described in JP-A-2015-087610, such as the sensitizing dye (C) and the binder polymer (D). The description of the resist membrane in the above document is incorporated herein.
Hereinafter, each component contained in such a photosensitive layer will be described.

[Photoradical polymerization initiator (A)]
The photoradical initiator (A) is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) in the radically polymerizable compound (B) described later, and is appropriately selected from known polymerization initiators. can do. For example, those having photosensitivity to light rays in the ultraviolet region to the visible region are preferable. Further, it may be an activator that produces an active radical by causing some action with a photoexcited sensitizing dye (for example, a sensitizing dye (C) described later).
Further, the photoradical polymerization initiator (A) preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 nm to 800 nm (preferably 330 nm to 500 nm).

As the photoradical polymerization initiator (A), a known compound can be used, and for example, a halogenated hydrocarbon derivative (for example, one having a triazine skeleton, one having an oxadiazole skeleton, or one having a trihalomethyl group) can be used. Etc.), acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenone , Azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes and the like.
As these compounds, for example, the compounds described in paragraphs 0045 to 0049 of Japanese Patent Application Laid-Open No. 2015-087610 are preferably used.

The photoradical polymerization initiator (A) is more preferably an oxime compound. As specific examples of the oxime-based initiator, the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, and the compounds described in JP-A-2006-342166 can be used. ..

Examples of the oxime compound such as an oxime derivative preferably used as the photoradical polymerization initiator (A) include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, and 3-propionyloxy. Iminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4) -Toluenesulfonyloxy) iminobutane-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like can be mentioned.

Examples of the oxime ester compound include J.I. C. S. Perkin II (1979) pp. 1653-1660), J. Mol. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. In each of the compounds described in each document of 202-232, the compounds described in JP-A-2000-066385, JP-A-2000-080068, JP-A-2004-534977, and JP-A-2006-342166. The described compounds and the like can be mentioned.
As commercially available products, Irgacure OXE 01 (manufactured by BASF), Irgacure OXE 02 (manufactured by BASF), and N-1919 are also preferably used.

Further, as an oxime ester compound other than the above, the compound described in JP-A-2009-5199004, in which an oxime is linked to the N-position of the carbazole ring, and US Pat. No. 6,626,957 in which a heterosubstituted group is introduced at the benzophenone moiety. The compound described, the compound described in Japanese Patent Application Laid-Open No. 2010-015025 in which a nitro group is introduced into a dye moiety, and the compound described in US Patent Application Publication No. 2009-292039, and the ketooxime-based compound described in International Publication No. 2009-131189. , A compound described in US Pat. No. 7,556,910, which contains a triazine skeleton and an oxime skeleton in the same molecule, Japanese Patent Application Laid-Open No. 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source. The compound described in 1 and the like may be used.

Preferably, it can also be preferably used for the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744. Among the cyclic oxime compounds, the cyclic oxime compound fused to the carbazole dye described in JP-A-2010-032985 and JP-A-2010-185072 has high light absorption and is highly sensitive. preferable.
Further, the compound described in JP-A-2009-242469, which has an unsaturated bond at a specific site of the oxime compound, can also be suitably used because it can achieve high sensitivity by regenerating the active radical from the polymerization inactive radical. can.

Particularly preferably, an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061 can be mentioned.
As the other photoradical polymerization initiator (A), triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate and the like can also be used. ..

The molar absorption coefficient of the compound can be measured by using a known method. Specifically, for example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of 0.01 g / L.

The photoradical polymerization initiator (A) may be ionic or nonionic, but is preferably a nonionic photoradical initiator from the viewpoint of exposure sensitivity and avoiding mixing with the protective film.
Nonionic photoradical initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, and benzothiazole compounds. , A benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxaziazole compound, and a 3-aryl substituted coumarin compound.

More preferably, it is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triarylimidazole dimer, a benzophenone compound, an acetophenone compound, and a trihalomethyltriazine compound, an α-aminoketone compound, an oxime. At least one compound selected from the group consisting of a compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and an oxime compound is further preferable.
Further, at least one compound selected from the group consisting of an oxime compound, an α-aminoketone compound, a titanosen compound, a phosphine oxide compound, a ketone compound and an onium salt compound is preferable, and an oxime compound, an α-aminoketone compound, a titanosen compound and a phosphine are preferable. At least one compound selected from the group consisting of oxide compounds and ketone compounds is more preferable.

The content of the photoradical polymerization initiator (A) in the photosensitive layer is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 0.1% by mass or more and 30% by mass or less with respect to the total mass of the photosensitive layer. , 0.1% by mass or more and 20% by mass or less is more preferable, and 1% by mass or more and 10% by mass or less is particularly preferable.
Only one type of photoradical polymerization initiator (A) may be used alone, or two or more types may be used in combination. When two or more kinds of photoradical polymerization initiators (A) are used in combination, the total amount thereof is preferably in the above range.

[Radical polymerizable compound (B)]
The radically polymerizable compound (B) in the photosensitive layer can be arbitrarily selected from the radically polymerizable compounds described below.
The radically polymerizable compound (B) is a compound having a radically polymerizable group. The radically polymerizable group is a group that can be polymerized by irradiation with active light or radiation or by the action of radicals, and is preferably an ethylenically unsaturated group.

The radically polymerizable group is preferably, for example, a functional group capable of an addition polymerization reaction. Examples of the functional group capable of the addition polymerization reaction include an ethylenically unsaturated bond group. As the ethylenically unsaturated bond group, a vinylphenyl group, a (meth) acryloyl group and an allyl group are preferable, and a (meth) acryloyl group is more preferable. That is, the radically polymerizable compound (B) used in the present invention is preferably a (meth) acrylate compound, and more preferably an acrylate compound.

The radically polymerizable compound (B) may be in any chemical form such as, for example, a monomer or prepolymer, that is, a dimer, a trimer and an oligomer, a polymer, or a mixture thereof and a multimer thereof. It is preferable, but a monomer and / or an oligomer is preferable, and a monomer is more preferable.
The monomer is typically a low molecular weight compound, preferably having a molecular weight of 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight is usually 100 or more.
The oligomer is typically a polymer with a relatively low molecular weight, preferably a polymer in which 10 to 100 monomers are bonded. The weight average molecular weight is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 2,000 to 10,000.
The polymer is a polymer having a high molecular weight, and the weight average molecular weight is preferably 20,000 or more.

The radically polymerizable compound (B) is preferably substantially insoluble in water in order to avoid mixing with the protective film. Substantially insoluble in water is a coating obtained by dissolving only the radically polymerizable compound (B) in a solvent such as butyl acetate and applying a composition having a solid content concentration of 3.5% by mass on a silicon wafer. When the coating film (thickness 100 nm) is formed, the coating film is immersed in ion-exchanged water at room temperature (25 ° C.) measured using a QCM (quartz crystal microbalance) sensor or the like for 1000 seconds. It shows that the average dissolution rate (decrease rate of film thickness) is 1 nm / s or less, preferably 0.1 nm / s or less.
The radically polymerizable compound (B) used in the present invention preferably has a solubility in water at 25 ° C. of less than 1 g / 100 g of water, and more preferably a solubility of less than 0.1 g / 100 g of water. With such a configuration, even when a water-soluble resin is used for the protective film, the radically polymerizable compound (B) is less likely to permeate into the protective film, and the effect of the present invention is more effectively exhibited.

The polymerizable group equivalent (mmol / g) of the radically polymerizable compound (B) in the photosensitive resin composition is preferably 0.1 to 7.0, more preferably 1.0 to 6.0, and 2.0. ~ 5.0 is more preferable. When the polymerizable radical equivalent of the radically polymerizable compound (B) is within the above range, the generation of cracks in the photosensitive layer due to curing shrinkage during curing is suppressed, and the curability is likely to be sufficient. (Mmol / g) represents the number of (mmol) of polymerizable radicals contained in the total solid content mass of the photosensitive resin composition.

Examples of the case where the radically polymerizable compound (B) is a monomer or an oligomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters thereof. Examples thereof include amides and multimers thereof, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, amides of unsaturated carboxylic acids and polyvalent amine compounds, and multimers thereof. ..
Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and a halogen group. Substitution reaction products of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
Further, as another example, it is also possible to use a compound group in which the above-mentioned unsaturated carboxylic acid is replaced with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like.

Specific examples of the monomer of the ester of the polyhydric alcohol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate as acrylic acid esters. , Propylene glycol diacrylate, Neopentyl glycol diacrylate, Trimethylol propan triacrylate, Trimethylol propantri (acryloyloxypropyl) ether, Trimethylol ethanetriacrylate, Hexandiol diacrylate, 1,4-Cyclohexanediol diacrylate, Tetra Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri ( Acryloyloxyethyl) isocyanurate, isocyanurate ethylene oxide (EO) modified triacrylate, polyester acrylate oligomer and the like.

Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylpropantrimethacrylate, trimethylol ethanetrimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate. Hexylenediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacrylicyloxy-). 2-Hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (methacrylicoxyethoxy) phenyl] dimethylmethane and the like.
In addition, as the radically polymerizable compound (B), the ester compound described in JP-A-2015-087610 or an amide-based monomer is also preferably used.
Further, as the radically polymerizable compound (B), the urethane-based addition polymerizable monomer described in JP-A-2015-087610 is also preferably used.

The radically polymerizable compound (B) is an ethylenically unsaturated group having at least one addition-polymerizable ethylene group described in JP-A-2015-087610 and having a boiling point of 100 ° C. or higher under normal pressure. Compounds with are also preferred.
In addition, as the radically polymerizable compound (B), the radically polymerizable polymer described in JP-A-2015-087610 is also preferably used.

[Sensitizing dye (C)]
The photosensitive layer can contain a sensitizing dye (C) in order to accelerate the decomposition of the photoradical polymerization initiator (A).
The sensitizing dye (C) absorbs active light rays or radiation and becomes an electron-excited state. The sensitizing dye (C) in the electron-excited state comes into contact with the photoradical polymerization initiator to cause actions such as electron transfer, energy transfer, and heat generation. As a result, the photoradical polymerization initiator undergoes a chemical change and decomposes to generate radicals.
Examples of the preferable sensitizing dye (C) include compounds belonging to the following compounds and having an absorption maximum wavelength in any of the 350 nm to 450 nm ranges.

Multinuclear aromatics (eg pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (For example, fluoressein, eosin, erythrosin, rhodamine B, rosebengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (for example) For example, merocyanines, carbomerocyanins), rhodacyanines, oxonors, thiazines (eg, thionin, methylcoumarin, toluisin blue), acridins (eg, acrydin orange, chloroflavin, acryflabin), acridons (eg, acrydon, etc.) 10-Butyl-2-chloroacrydone), anthracenes (eg, anthracene), squaryliums (eg, squarylium), styryls, base styryls (eg, 2- [2- [4- (dimethylamino) phenyl]] Ethenyl] benzoxazole), coumarins (eg, 7-diethylamino4-methylcoumarin, 7-hydroxy4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H- [1] Benzopyrano [6,7,8-ij] quinolidine-11-one).

Among these sensitizing dyes (C), polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Among the polynuclear aromatics, anthracene derivatives are the most preferable.
As a commercially available product of the sensitizing dye (C), for example, Anthracure UVS-1331 (manufactured by Kawasaki Kasei Chemicals Co., Ltd.) can be used.

The blending amount of the sensitizing dye (C) is 0.1 for the mass ratio of the sensitizing dye (C) and the photoradical polymerization initiator (A) (sensitizing dye (C) / photoradical polymerization initiator (A)). /1.0 to 10 / 1.0 is preferable, and 0.2 / 1.0 to 5.0 / 1.0 is more preferable. Only one type of sensitizing dye (C) may be used, or two or more types may be used. When two or more types are used, the total amount is within the above range.

[Binder polymer (D)]
The binder polymer (D) may be added to the photosensitive layer used in the present invention for the purpose of improving sensitivity, developability and resistance to dry etching in a well-balanced manner.
Examples of such a binder polymer (D) include (meth) acrylic polymers, polyurethane resins, polyvinyl alcohol resins, polyvinyl acetal resins (preferably polyvinyl butyral resins), polyvinyl formal resins, polyamide resins, polyester resins, and epoxy resins. , And novolak resin and the like are used.

In the present invention, the "(meth) acrylic polymer" refers to (meth) acrylic acid, (meth) acrylic acid ester (alkyl ester, aryl ester, allyl ester, etc.), (meth) acrylamide and (meth) acrylamide derivative. It refers to a copolymer having a (meth) acrylic acid derivative as a polymerization component. For example, polymethyl methacrylate, a copolymer of benzyl methacrylate and methyl methacrylate and the like can be mentioned.
The "polyurethane resin" refers to a polymer produced by a condensation reaction of a compound having two or more isocyanate groups and a compound having two or more hydroxy groups.

The "polyvinyl butyral resin" refers to a polymer synthesized by reacting polyvinyl alcohol obtained by saponifying part or all of polyvinyl acetate with butylaldehyde under acidic conditions (acetalization reaction), and further. A polymer in which an acid group or the like is introduced by a method of reacting the remaining hydroxy group with a compound having an acid group or the like is also included.

"Novolak resin" refers to a polymer produced by the condensation reaction of phenols (phenol, cresol, etc.) and aldehydes (formaldehyde, etc.). Further, a polymer in which a substituent is introduced by a method of reacting the remaining hydroxy group with another compound or the like is also included.
Preferable examples of novolak resin are phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, or m- / p). -Mixed) Novolac resin such as mixed formaldehyde resin can be mentioned. Novolac resins having a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 10,000 are preferable. Further, a compound in which a substituent is introduced by reacting a hydroxy group in a novolak resin with another compound can also be preferably used.

The binder polymer (D) preferably has a weight average molecular weight of 5,000 or more, and more preferably 10,000 to 300,000. The number average molecular weight is preferably 1,000 or more, more preferably 2,000 to 250,000. The degree of polydispersity (weight average molecular weight / number average molecular weight) is preferably 1.1 to 10.

The content of the binder polymer (D) is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and 20 to 80% by mass, based on the total solid content of the photosensitive resin composition, from the viewpoint of good sensitivity. Mass% is more preferred.
The binder polymer may be used alone or in combination of two or more.
The form of the binder polymer (D) may be any of a random type, a block type, a graft type, and a star type. The binder polymer (D) can be synthesized, for example, by radical, cationic, or anionic polymerization of unsaturated monomers corresponding to each structure. It is also possible to obtain the desired resin by carrying out a polymer reaction after polymerizing using an unsaturated monomer corresponding to a precursor of each structure.

[Other ingredients]
The photosensitive layer containing the polymerizable compound, the photopolymerization initiator and the like may further contain other components.
Examples of other components include surfactants and polymerization inhibitors, and other components described in JP-A-2015-087610 are preferably used.

〔thickness〕
From the viewpoint of improving the resolving power, the thickness (thickness) of the photosensitive layer in the present invention is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 0.75 μm or more, and particularly preferably 0.8 μm or more. .. The upper limit of the thickness of the photosensitive layer is preferably 10 μm or less, more preferably 5.0 μm or less, still more preferably 2.0 μm or less.
The total thickness of the photosensitive layer and the protective layer is preferably 0.2 μm or more, more preferably 1.0 μm or more, and further preferably 2.0 μm or more. The upper limit is preferably 20.0 μm or less, more preferably 10.0 μm or less, and further preferably 5.0 μm or less.

[Developer]
The photosensitive layer in the present invention is subjected to development using a developing solution.
As the developing solution, a developing solution containing an organic solvent is preferable.
The content of the organic solvent with respect to the total mass of the developing solution is preferably 90 to 100% by mass, more preferably 95 to 100% by mass. Further, the developing solution may be a developing solution containing only an organic solvent.
The method for developing the photosensitive layer using a developing solution will be described later.

-Organic solvent-
Sp value of the organic solvent contained in the developer is preferably less than ^{19 MPa 1/2,} and more preferably ^{18 MPa 1/2} or less.
Examples of the organic solvent contained in the developing solution include polar solvents such as ketone solvents, ester solvents and amide solvents, and hydrocarbon solvents.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methylamyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and the like. Examples thereof include methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Can be mentioned.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
The organic solvent may be used alone or in combination of two or more. Further, it may be used by mixing with an organic solvent other than the above. However, the content of water with respect to the total mass of the developing solution is preferably less than 10% by mass, and more preferably substantially no water. The term "substantial" as used herein means that, for example, the content of water with respect to the total mass of the developing solution is 3% by mass or less, more preferably not more than the measurement limit.
That is, the amount of the organic solvent used with respect to the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the developing solution.
In particular, the organic developer preferably contains at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent and an amide solvent.
Further, the organic developer may contain an appropriate amount of a basic compound, if necessary. Examples of the basic compound include those described in the above section of the basic compound.
The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less at 23 ° C. By reducing the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is improved. Gender improves.
Specific examples of solvents having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, 2-heptanone (methylamylketone), 4-heptanone, 2-hexanone, and diisobutyl. Ketone solvents such as ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylisobutylketone, butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol Ester solvents such as monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl nitate, propyl silicate, ethyl lactate, butyl lactate, propyl lactate, etc. Amido-based solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as octane and decane. Can be mentioned.
Specific examples of the solvent having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, and the like. Ketone solvents such as methylcyclohexanone and phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, Ester solvents such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl Examples thereof include amide-based solvents such as formamide, aromatic hydrocarbon-based solvents such as xylene, and aliphatic hydrocarbon-based solvents such as octane and decane.

-Surfactant-
The developer may contain a surfactant.
The surfactant is not particularly limited, but for example, the surfactant described in the above section of the protective layer is preferably used.
When a surfactant is blended in the developing solution, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0, based on the total amount of the developing solution. It is 0.01 to 0.5% by mass.

[Composition for forming a photosensitive layer]
The composition for forming a photosensitive layer of the present invention is a composition used for forming a photosensitive layer contained in the laminate of the present invention.
In the laminate of the present invention, the photosensitive layer can be formed, for example, by applying a composition for forming a photosensitive layer onto a protective layer and drying it. As the application method, for example, the description of the application method of the composition for forming a protective layer in the protective layer described later can be taken into consideration.

The composition for forming a photosensitive layer is a component contained in the above-mentioned photosensitive layer (for example, a specific resin, a photoacid generator, a basic compound, a surfactant, and other components, or a photoradical polymerization initiator (A). ), The radically polymerizable compound (B), the sensitizing dye (C), the binder polymer (D), and other components), and a solvent. The components contained in these photosensitive layers are preferably dissolved or dispersed in a solvent, and more preferably dissolved.
Regarding the content of the components contained in the composition for forming a photosensitive layer, the content of each component with respect to the total mass of the photosensitive layer may be read as the content with respect to the solid content of the composition for forming a photosensitive layer. preferable.

-Organic solvent-
As the organic solvent used in the composition for forming a photosensitive layer, a known organic solvent can be used, and ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl. Ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers Examples thereof include acetates, esters, ketones, amides, lactones and the like.
As an organic solvent, for example
(1) Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
(2) Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether;
(3) Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate;
(4) Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;
(5) Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether and propylene glycol diethyl ether;
(6) Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate;
(7) Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
(8) Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monobutyl ether acetate;
(9) Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether;
(10) Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether;
(11) Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate;
(12) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, and isoamyl lactate;
(13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, propion Alibocarboxylic acid esters such as isobutyl acid, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate;
(14) Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl Other esters such as butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;
(15) Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
(16) Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
(17) Examples of lactones such as γ-butyrolactone can be mentioned.
Further, if necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, capric acid, 1-octanol, 1- Organic solvents such as nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate can also be added.
Among the above-mentioned organic solvents, propylene glycol monoalkyl ether acetates or diethylene glycol dialkyl ethers are preferable, and diethylene glycol ethyl methyl ether or propylene glycol monomethyl ether acetate is particularly preferable.
When the composition for forming a photosensitive layer contains an organic solvent, the content of the organic solvent is preferably 1 to 3,000 parts by mass, preferably 5 to 2,000 parts by mass, per 100 parts by mass of the specific resin. It is more preferable, and it is further preferable that the amount is 10 to 1,500 parts by mass.
These organic solvents may be used alone or in admixture of two or more.
When two or more types are used, the total amount is preferably in the above range.

(Laminated body formation kit)
The laminate forming kit of the present invention includes the following A and B.
A: A composition used for forming the protective layer contained in the laminate of the present invention, which contains polyvinyl alcohol having a saponification degree of 50 mol% or more and 85 mol% or less;
B: A composition used for forming the photosensitive layer contained in the laminate of the present invention.
Here, A is synonymous with the above-mentioned composition for forming a protective layer, and B is synonymous with the above-mentioned composition for forming a photosensitive layer, and the preferred embodiments are also the same.
Further, the laminate forming kit of the present invention may further include the above-mentioned organic semiconductor layer forming composition or resin layer forming composition.

(Method of patterning organic layer)
The following forms can be mentioned as a patterning method that can be suitably adopted in the present invention.
The method of patterning the organic layer of the present embodiment is
(1) A process of forming a protective layer on the organic layer,
(2) A step of forming a photosensitive layer on the side opposite to the organic layer of the protective layer.
(3) Step of exposing the photosensitive layer,
(4) A step of developing a photosensitive layer with a developing solution containing an organic solvent to prepare a mask pattern.
(5) A step of removing the protective layer and the organic layer of the non-masked portion,
(6) Step of removing the protective layer with a stripping solution,
including.

<(1) Step of forming a protective layer on the organic layer>
The method for patterning the organic layer of the present embodiment includes a step of forming a protective layer on the organic layer. Usually, this step is performed after forming an organic layer on the base material. In this case, the protective layer is formed on the surface of the organic layer opposite to the surface on the substrate side. The protective layer is preferably formed so as to be in direct contact with the organic layer, but other layers may be provided between the protective layers as long as the gist of the present invention is not deviated. Examples of the other layer include a fluorine-based undercoat layer and the like. Further, only one protective layer may be provided, or two or more protective layers may be provided. As described above, the protective layer is preferably formed using a composition for forming a protective layer.
For details of the forming method, refer to the above-mentioned method of applying the protective layer forming composition in the laminate of the present invention.

<(2) Step of forming a photosensitive layer on the side opposite to the organic layer of the protective layer>
After the step (1) above, a photosensitive layer is formed on the surface of the protective layer opposite to the organic layer side (preferably on the surface).
As described above, the photosensitive layer is preferably formed by using the composition for forming the photosensitive layer.
For details of the forming method, refer to the above-mentioned method of applying the composition for forming a photosensitive layer in the laminate of the present invention.

<(3) Step of exposing the photosensitive layer>
After forming the photosensitive layer in the step (2), the photosensitive layer is exposed. Specifically, for example, at least a part of the photosensitive layer is irradiated (exposed) with active light rays.
It is preferable that the exposure is performed so as to have a predetermined pattern. Further, the exposure may be performed through a photomask, or a predetermined pattern may be drawn directly.
As the wavelength of the active ray at the time of exposure, an active ray having a wavelength of 180 nm or more and 450 nm or less, more preferably 365 nm (i line), 248 nm (KrF line) or 193 nm (ArF line) can be used. can.

As the light source of the active light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a laser generator, a light emitting diode (LED) light source, or the like can be used.
When a mercury lamp is used as a light source, active rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. In the present invention, it is preferable to use the i-ray because the effect is preferably exhibited.
When a laser generator is used as the light source, active light having a wavelength of 343 nm and 355 nm is preferably used for the solid-state (YAG) laser, and 193 nm (ArF line), 248 nm (KrF line) and 351 nm (KrF line) for the excimer laser. An active ray having a wavelength of (Xe line) is preferably used, and further, an active ray having a wavelength of 375 nm or 405 nm is preferably used in a semiconductor laser. Among these, active rays having a wavelength of 355 nm or 405 nm are more preferable from the viewpoint of stability, cost and the like. The laser can irradiate the photosensitive layer once or in a plurality of times.

The exposure amount is preferably 40 to 120 mJ, more preferably 60 to 100 mJ.
The energy density per pulse of the laser ^{is preferably 0.1 mJ / cm 2} or more and 10,000 mJ / cm ² or less. In order to sufficiently cure the coating film, 0.3 mJ / cm ² or more is more preferable, and 0.5 mJ / cm ² or more is further preferable. From the viewpoint of suppressing decomposition of the photosensitive layer due ablation phenomenon, the exposure amount is preferably set to 1,000 mJ / cm ² or less, 100 mJ / cm ² or less being more preferred.
The pulse width is preferably 0.1 nanosecond (hereinafter referred to as “ns”) or more and 30,000 ns or less. In order to prevent the color coating film from being decomposed by the ablation phenomenon, 0.5 ns or more is more preferable, and 1 ns or more is more preferable. In order to improve the matching accuracy during scan exposure, 1,000 ns or less is more preferable, and 50 ns or less is further preferable.

When a laser generator is used as the light source, the frequency of the laser is preferably 1 Hz or more and 50,000 Hz or less, and more preferably 10 Hz or more and 1,000 Hz or less.
Further, in order to shorten the exposure processing time, the laser frequency is more preferably 10 Hz or higher, further preferably 100 Hz or higher, and further preferably 10,000 Hz or lower in order to improve the matching accuracy during scan exposure. It is more preferably 000 Hz or less.
The laser is preferable in that it is easier to focus than the mercury lamp, and the use of a photomask can be omitted in pattern formation in the exposure process.

The exposure apparatus is not particularly limited, but commercially available ones include Callisto (manufactured by V Technology Co., Ltd.), AEGIS (manufactured by V Technology Co., Ltd.), and DF2200G (Dainippon Screen Mfg. Co., Ltd.). It is possible to use (manufactured by). In addition, devices other than the above are also preferably used.
Further, if necessary, the amount of irradiation light can be adjusted through a spectroscopic filter such as a long wavelength cut filter, a short wavelength cut filter, and a bandpass filter.
Further, after the above exposure, a post-exposure heating step (PEB) may be performed if necessary.

<(4) Step of developing the photosensitive layer with a developing solution containing an organic solvent to prepare a mask pattern>
After exposing the photosensitive layer through a photomask in the step (3), the photosensitive layer is developed using a developing solution.
Negative type is preferable for development.
The details of the developer are as described in the above description of the photosensitive layer.
Examples of the developing method include a method of immersing the base material in a tank filled with a developing solution for a certain period of time (dip method), and a method of developing by raising the developing solution on the surface of the base material by surface tension and allowing it to stand still for a certain period of time. (Paddle method), a method of spraying the developer on the surface of the base material (spray method), a method of continuing to discharge the developer while scanning the developer discharge nozzle at a constant speed on the base material rotating at a constant speed (spray method) Dynamic dispense method) etc. can be applied.
When the above-mentioned various developing methods include a step of discharging the developer from the developing nozzle of the developing device toward the photosensitive layer, the discharge pressure of the discharged developer (flow velocity per unit area of the discharged developer) is determined. It is preferably 2 mL / sec / mm ² or less, more preferably 1.5 mL / sec / mm ² or less, and further preferably 1 mL / sec / mm ² or less. There is no particular lower limit on the discharge pressure, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput. By setting the discharge pressure of the developer to be discharged within the above range, it is possible to significantly reduce the defects of the pattern derived from the resist residue after development.
The details of this mechanism are not clear, but probably, by setting the discharge pressure within the above range, the pressure applied to the photosensitive layer by the developer becomes small, and the resist pattern on the photosensitive layer is inadvertently scraped or broken. It is thought that this is because it is suppressed.
The discharge pressure of the developer (mL / sec / mm ² ) is a value at the outlet of the developing nozzle in the developing apparatus.
Examples of the method of adjusting the discharge pressure of the developing solution include a method of adjusting the discharge pressure with a pump and the like, a method of adjusting the pressure by supplying from a pressure tank, and the like.
Further, after the step of developing with a developing solution containing an organic solvent, a step of stopping the development while substituting with another organic solvent may be carried out.

<(5) Step of removing the protective layer and organic layer of the non-masked portion>
After developing the photosensitive layer to prepare a mask pattern, at least the protective layer and the organic layer in the non-masked portion are removed by an etching process. The non-masked portion refers to a region not masked by a mask pattern formed by developing the photosensitive layer (a region in which the photosensitive layer has been removed by development).
The etching process may be performed in a plurality of stages. For example, the protective layer and the organic layer may be removed by a single etching treatment, or after at least a part of the protective layer is removed by the etching treatment, the organic layer (and, if necessary, the protective layer) The balance) may be removed by etching.
Further, the etching process may be a dry etching process or a wet etching process, and the etching may be divided into a plurality of times to perform the dry etching process and the wet etching process. For example, the removal of the protective layer may be by dry etching or wet etching.
Examples of the method for removing the protective layer and the organic layer include a method A in which the protective layer and the organic layer are removed by a single dry etching treatment, and at least a part of the protective layer is removed by a wet etching treatment. After that, a method such as method B for removing the organic layer (and, if necessary, the rest of the protective layer) by dry etching can be mentioned.
The dry etching process in the method A, the wet etching process and the dry etching process in the method B can be performed according to a known etching method.
Hereinafter, details of one aspect of the above method A will be described. As a specific example of the above method B, the description of JP-A-2014-098889 can be referred to.

In the above method A, specifically, the protective layer and the organic layer of the non-masked portion can be removed by performing dry etching using the resist pattern as an etching mask (mask pattern). Typical examples of dry etching are JP-A-59-126506, JP-A-59-046628, JP-A-58-009108, JP-A-58-002809, and JP-A57. There is a method described in Japanese Patent Application Laid-Open No. 148706 and Japanese Patent Application Laid-Open No. 61-041102.

The dry etching is preferably performed in the following form from the viewpoint of forming the cross section of the pattern of the formed organic layer closer to a rectangle and further reducing the damage to the organic layer.
Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), etching is performed to the region (depth) where the organic layer is not exposed, and after this first-stage etching, nitrogen gas () A _{second-stage etching that uses a mixed gas of N 2} ) and oxygen gas (O ₂ ), preferably etching to the vicinity of the region (depth) where the organic layer is exposed, and over-etching that is performed after the organic layer is exposed. A form including and is preferable. Hereinafter, a specific method of dry etching, as well as first-stage etching, second-stage etching, and over-etching will be described.

The etching conditions in dry etching are preferably performed while calculating the etching time by the following method.
(A) The etching rate (nm / min) in the first-stage etching and the etching rate (nm / min) in the second-stage etching are calculated respectively.
(B) The time for etching the desired thickness in the first-stage etching and the time for etching the desired thickness in the second-stage etching are calculated, respectively.
(C) The first-stage etching is performed according to the etching time calculated in (B) above.
(D) The second stage etching is performed according to the etching time calculated in (B) above. Alternatively, the etching time may be determined by endpoint detection, and the second-stage etching may be performed according to the determined etching time.
(E) The overetching time is calculated with respect to the total time of the above (C) and (D), and the overetching is performed.

The mixed gas used in the first-stage etching preferably contains _{a fluorine-based gas and an oxygen gas (O 2} ) from the viewpoint of processing the organic material to be etched into a rectangular shape. Further, in the first-stage etching, the laminated body is etched to a region where the organic layer is not exposed. Therefore, it is considered that the organic layer is not damaged or the damage is very slight at this stage.

Further, in the second-stage etching and the over-etching, it is preferable to perform the etching treatment using a mixed gas of nitrogen gas and oxygen gas from the viewpoint of avoiding damage to the organic layer.

It is important that the ratio of the etching amount in the first-stage etching to the etching amount in the second-stage etching is determined so as to have excellent rectangularity in the cross section of the pattern of the organic layer in the first-stage etching.
The ratio of the etching amount in the second stage etching to the total etching amount (the sum of the etching amount in the first stage etching and the etching amount in the second stage etching) is larger than 0% and 50% or less. It is preferably present, and more preferably 10 to 20%. The etching amount refers to an amount calculated from the difference between the remaining film thickness of the film to be etched and the film thickness before etching.

Further, the etching preferably includes an over-etching treatment. The over-etching treatment is preferably performed by setting the over-etching ratio.
The over-etching ratio can be set arbitrarily, but from the viewpoint of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched (organic layer), it is preferably 30% or less of the total etching treatment time in the etching process, and 5 to 5 It is more preferably 25%, and particularly preferably 10 to 15%.

<(6) Step of removing the protective layer with a stripping solution,>
After etching, the protective layer is removed using a stripping solution (eg, water).
The details of the stripping liquid are as described in the above description of the protective layer.
Examples of the method of removing the protective layer with the stripping liquid include a method of spraying the stripping liquid onto the resist pattern from a spray-type or shower-type injection nozzle to remove the protective layer. Pure water can be preferably used as the stripping liquid. Further, examples of the injection nozzle include an injection nozzle in which the entire base material is included in the injection range, and a movable injection nozzle in which the movable range includes the entire base material. Another embodiment is a mode in which the protective layer is mechanically peeled off and then the residue of the protective layer remaining on the organic layer is dissolved and removed.
When the injection nozzle is movable, the resist pattern is removed more effectively by moving from the center of the base material to the end of the base material twice or more during the process of removing the protective layer and injecting the release liquid. be able to.
It is also preferable to perform a step such as drying after removing the protective layer. The drying temperature is preferably 80 to 120 ° C.

(Use)
The laminate of the present invention can be used for manufacturing an electronic device using an organic semiconductor. Here, the electronic device is a device containing a semiconductor and having two or more electrodes, and controlling the current flowing between the electrodes and the generated voltage by electricity, light, magnetism, chemical substances, or the like, or It is a device that generates light, electric field, magnetic field, etc. by the applied voltage and current.
Examples include organic photoelectric conversion elements, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifying elements, organic inverters, information recording elements, and the like.
The organic photoelectric conversion element can be used for both optical sensor applications and energy conversion applications (solar cells).
Among these, the applications are preferably organic field effect transistors, organic photoelectric conversion elements, and organic field light emitting elements, more preferably organic field effect transistors and organic photoelectric conversion elements, and particularly preferably organic field effect transistors. ..

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Unless otherwise specified, "%" and "part" are based on mass.

The weight average molecular weight (Mw) of a water-soluble resin such as polyvinyl alcohol was calculated as a value converted to polyether oxide by GPC measurement. HLC-8220 (manufactured by Tosoh Corporation) was used as an apparatus, and SuperMultipore PW-N (manufactured by Tosoh Corporation) was used as a column.
The weight average molecular weight (Mw) of a water-insoluble resin such as (meth) acrylic resin was calculated as a polystyrene-equivalent value measured by GPC. HLC-8220 (manufactured by Tosoh Corporation) was used as an apparatus, and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) was used as a column.

(Synthesis of PVA (polyvinyl alcohol))
PVA was synthesized by the synthesis method described below. The saponification degree and weight average molecular weight (Mw) of the obtained PVA are shown in Tables 1 to 4 described later.

<Synthesis Example 1: Synthesis of PVA-1>
Vinyl acetate: 800 parts by mass, methanol: 200 parts by mass, and 2,2'-azobisisobutyronitrile: 0.1 parts by mass as a polymerization initiator are charged into a reactor equipped with a stirrer and a reflux condenser. , The temperature of the system was maintained at 60 ° C. and the reaction was carried out for 6 hours. The obtained polymerization solution was supplied to a demonomer column having a large number of perforated plates in the column, and methanol vapor was blown from the lower part of the column to bring it into contact with the polymerization solution to remove unreacted vinyl acetate monomer. After adding 4.4 parts by mass of 5% by mass sodium hydroxide-methanol solution and 5.6 parts by mass of water to 500 parts by mass of this polyvinyl acetate-methanol solution, the mixture is well stirred and kept at 40 ° C. for a saponification reaction. Was done. An aqueous citric acid solution was added to the pulverized slurry of the obtained gel to neutralize the system to pH 9. The neutralized slurry was separated into solid and liquid, and the solid component was dried to obtain PVA-1.

<Synthesis Example 2: Synthesis of PVA-2>
6. 3.0 parts by mass of 5% by mass sodium hydroxide-methanol solution and water 7. After adding 0 parts by mass, the saponification reaction was carried out by stirring well and keeping the temperature at 40 ° C. An aqueous citric acid solution was added to the pulverized slurry of the obtained gel to neutralize the system to pH 9. The neutralized slurry was separated into solid and liquid, and the solid component was dried to obtain PVA-2.

<Synthesis Example 3: Synthesis of PVA-3>
2. 2.5 parts by mass of 5% by mass sodium hydroxide-methanol solution and 2.5 parts by mass of 5 parts by mass of a polyvinyl acetate-methanol solution obtained by polymerization and demonomerization in the same manner as in the synthesis of PVA-1. After adding 5 parts by mass, the saponification reaction was carried out by stirring well and keeping the temperature at 40 ° C. An aqueous citric acid solution was added to the pulverized slurry of the obtained gel to neutralize the system to pH 9. The neutralized slurry was separated into solid and liquid, and the solid component was dried to obtain PVA-3.

<Synthesis Example 4: Synthesis of PVA-4>
2. 2 parts by mass of 5% by mass sodium hydroxide-methanol solution and 2.2 parts by mass of water with respect to 500 parts by mass of the polyvinyl acetate-methanol solution obtained by polymerization and demonomerization in the same manner as in the synthesis of PVA-1. After adding 8 parts by mass, the saponification reaction was carried out by stirring well and keeping the temperature at 40 ° C. An aqueous citric acid solution was added to the pulverized slurry of the obtained gel to neutralize the system to pH 9. The neutralized slurry was separated into solid and liquid, and the solid component was dried to obtain PVA-4.

<Synthesis Example 5: Synthesis of PVA-5>
1. 1.8 parts by mass of 5% by mass sodium hydroxide-methanol solution and 1.8 parts by mass of water with respect to 500 parts by mass of the polyvinyl acetate-methanol solution obtained by polymerization and demonomerization in the same manner as in the synthesis of PVA-1. After adding 2 parts by mass, the saponification reaction was carried out by stirring well and keeping the temperature at 40 ° C. An aqueous citric acid solution was added to the pulverized slurry of the obtained gel to neutralize the system to pH 9. The neutralized slurry was separated into solid and liquid, and the solid component was dried to obtain PVA-5.

<Synthesis Example 6: Synthesis of PVA-6>
8. 1.5 parts by mass of 5% by mass sodium hydroxide-methanol solution and 1.5 parts by mass of water with respect to 500 parts by mass of the polyvinyl acetate-methanol solution obtained by polymerization and demonomerization in the same manner as in the synthesis of PVA-1. After adding 5 parts by mass, the saponification reaction was carried out by stirring well and keeping the temperature at 40 ° C. An aqueous citric acid solution was added to the pulverized slurry of the obtained gel to neutralize the system to pH 9. The neutralized slurry was separated into solid and liquid, and the solid component was dried to obtain PVA-6.

<Synthesis Example 7: Synthesis of PVA-7>
1. 1.2 parts by mass of 5% by mass sodium hydroxide-methanol solution and water 8. After adding 8 parts by mass, the saponification reaction was carried out by stirring well and keeping the temperature at 40 ° C. An aqueous citric acid solution was added to the pulverized slurry of the obtained gel to neutralize the system to pH 9. The neutralized slurry was separated into solid and liquid, and the solid component was dried to obtain PVA-7.

<Synthesis Example 8: Synthesis of PVA-8>
1. 1 part by mass of 5% by mass sodium hydroxide-methanol solution and 1.1 parts by mass of water with respect to 500 parts by mass of the polyvinyl acetate-methanol solution obtained by polymerization and demonomerization by the same method as the synthesis of PVA-1. After adding 9 parts by mass, the saponification reaction was carried out by stirring well and keeping the temperature at 40 ° C. An aqueous citric acid solution was added to the pulverized slurry of the obtained gel to neutralize the system to pH 9. The neutralized slurry was separated into solid and liquid, and the solid component was dried to obtain PVA-8.

<Synthesis Example 9: Synthesis of PVA-9>
1. 1.0 part by mass of 5% by mass sodium hydroxide-methanol solution and 1.0 part by mass of water with respect to 500 parts by mass of the polyvinyl acetate-methanol solution obtained by polymerization and demonomerization by the same method as the synthesis of PVA-1. After adding 0 parts by mass, the saponification reaction was carried out by stirring well and keeping the temperature at 40 ° C. An aqueous citric acid solution was added to the pulverized slurry of the obtained gel to neutralize the system to pH 9. The neutralized slurry was separated into solid and liquid, and the solid component was dried to obtain PVA-9.

<Synthesis Example 10: Synthesis of PVA-10>
9. 0.7 parts by mass of 5% by mass sodium hydroxide-methanol solution and 0.7 parts by mass of water with respect to 500 parts by mass of the polyvinyl acetate-methanol solution obtained by polymerization and demonomerization in the same manner as in the synthesis of PVA-1. After adding 3 parts by mass, the saponification reaction was carried out by stirring well and keeping the temperature at 40 ° C. An aqueous citric acid solution was added to the pulverized slurry of the obtained gel to neutralize the system to pH 9. The neutralized slurry was separated into solid and liquid, and the solid component was dried to obtain PVA-10.

<Synthesis Example 11: Synthesis of PVA-11>
9. 0.6 parts by mass of 5% by mass sodium hydroxide-methanol solution and 0.6 parts by mass of water with respect to 500 parts by mass of the polyvinyl acetate-methanol solution obtained by polymerization and demonomerization in the same manner as in the synthesis of PVA-1. After adding 4 parts by mass, the saponification reaction was carried out by stirring well and keeping the temperature at 40 ° C. An aqueous citric acid solution was added to the pulverized slurry of the obtained gel to neutralize the system to pH 9. The neutralized slurry was separated into solid and liquid, and the solid component was dried to obtain PVA-11.

<Synthesis Example 12: Synthesis of PVA-12>
Vinyl acetate: 700 parts by mass, methanol: 300 parts by mass, 2,2'-azobisisobutyronitrile: 0.5 parts by mass in a reactor equipped with a stirrer, a reflux condenser, a continuous addition device and a continuous discharge device. Was continuously introduced, and the temperature of the system was maintained at 60 ° C., and the same amount of polyvinyl acetate-methanol solution was continuously discharged for continuous reaction. When the average residence time was 5 hours, the polymerization yield at the reactor outlet was 85% by mass. The obtained polymerization solution was demonomerized, saponified, neutralized, and solid-liquid separated by the same method as in the synthesis of PVA-6, and the solid component was dried to obtain PVA-12.

<Synthesis Example 13: Synthesis of PVA-13>
A reactor equipped with a stirrer and a reflux condenser is charged with vinyl acetate: 800 parts by mass, methanol: 200 parts by mass, and 2,2'-azobisisobutyronitrile: 0.07 parts by mass as a polymerization initiator. The temperature was maintained at 60 ° C. and the reaction was carried out for 6 hours. The obtained polymerization solution was supplied to a demonomer column having a large number of perforated plates in the column, and methanol vapor was blown from the lower part of the column to bring it into contact with the polymerization solution to remove unreacted vinyl acetate monomer. The obtained polymerization solution was demonomerized, saponified, neutralized, and solid-liquid separated by the same method as in the synthesis of PVA-6, and the solid component was dried to obtain PVA-13.

<Synthesis Example 14: Synthesis of PVA-14>
A reactor equipped with a stirrer and a reflux condenser is charged with vinyl acetate: 800 parts by mass, methanol: 200 parts by mass, and 2,2'-azobisisobutyronitrile: 0.04 parts by mass as a polymerization initiator. The temperature was maintained at 60 ° C. and the reaction was carried out for 6 hours. The obtained polymerization solution was supplied to a demonomer column having a large number of perforated plates in the column, and methanol vapor was blown from the lower part of the column to bring it into contact with the polymerization solution to remove unreacted vinyl acetate monomer. The obtained polymerization solution was demonomerized, saponified, neutralized, and solid-liquid separated by the same method as in the synthesis of PVA-6, and the solid component was dried to obtain PVA-14.

<Synthesis Example 15: Synthesis of PVA-15>
Polyvinyl acetate-methanol solution obtained by polymerization and demonomerization by the same method as the above synthesis of PVA-1: 5.0 parts by mass of 5% by mass sodium hydroxide-methanol solution and 5 parts by mass of water with respect to 500 parts by mass. After adding 0.0 part by mass, the saponification reaction was carried out by stirring well and keeping the temperature at 40 ° C. An aqueous citric acid solution was added to the pulverized slurry of the obtained gel to neutralize the system to pH 9. The neutralized slurry was separated into solid and liquid, and the solid component was dried to obtain PVA-15.

<Synthesis Example 16: Synthesis of PVA-16>
Polyvinyl acetate-methanol solution obtained by polymerization and demonomerization by the same method as the above synthesis of PVA-1: 0.4 parts by mass of 5% by mass sodium hydroxide-methanol solution and water 9 with respect to 500 parts by mass. After adding 6 parts by mass, the saponification reaction was carried out by stirring well and keeping the temperature at 40 ° C. An aqueous citric acid solution was added to the pulverized slurry of the obtained gel to neutralize the system to pH 9. The neutralized slurry was separated into solid and liquid, and the solid component was dried to obtain PVA-16.

(Synthesis of specific resin)
The specific resin was synthesized by the synthesis method described below.

<Synthesis of specific resin A-1 (Mw = 45,000)>
PGMEA (propylene glycol monomethyl ether acetate, 32.62 g) was placed in a three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. Here, BzMA (benzyl methacrylate, 16.65 g), THFMA (tetrahydrofuran methacrylate, 21.08 g), t-BuMA (t-butyl methacrylate, 5.76 g), and V-601 (0.4663 g,). A solution prepared by Fujifilm Wako Pure Chemical Industries, Ltd. in PGMEA (32.62 g) was added dropwise over 2 hours. Then, the reaction solution was stirred for 2 hours to terminate the reaction. The specific resin A-1 was obtained by recovering the white powder produced by re-precipitating the reaction solution in heptane by filtration. The weight average molecular weight (Mw) was 45,000.

<Synthesis of specific resin A-2 (Mw = 45,000)>
PGMEA (32.62 g) was placed in a three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. Here, BzMA (16.65 g), THFAA (tetrahydro-2-yl acrylate, 19.19 g), t-BuMA (5.76 g), and V-601 (0.4663 g, 0.75 mol% with respect to the monomer). ) Was dissolved in PGMEA (32.62 g) and added dropwise over 2 hours. Then, the reaction solution was stirred for 2 hours to terminate the reaction. The specific resin A-2 was obtained by recovering the white powder produced by re-precipitating the reaction solution in heptane by filtration. The weight average molecular weight (Mw) was 45,000.
The amount of the component having Mw of 1,000 or less was 3% by mass.

(Other ingredients)
Among the components of the protective layer forming composition or the photosensitive layer forming composition shown in Tables 1 to 4, details of components other than those described above are as follows.

<Composition for forming a protective layer>
-Additive C-1: Polyvinylpyrrolidone K15 (manufactured by Tokyo Chemical Industry Co., Ltd.)
-Additive C-2: HEC Daicel SP200 (Hydroxyethyl cellulose, manufactured by Daicel Finechem Co., Ltd.)
-Surfactant EOO: Acetyleneol E00, manufactured by Kawaken Fine Chemicals Co., Ltd., compound represented by the following formula (EOO) -Solvent water: Pure water

<Composition for forming a photosensitive layer>
-Resin (Binder polymer (D) described above) A-3: Benzyl methacrylate / methacrylic acid copolymer (ratio (molar ratio) 70/30 weight average molecular weight 15,000)
-Photosensitizer (photoacid generator) P-1: In the following formula (OS-107), ^{a compound having R 11} = tolyl group and R ¹⁸ = methyl group was adopted.
-Photosensitizer (photoacid generator) P-2: Triphenylsulfonium nonafluoropropylsulfonate-Photosensitizer (photoradical polymerization initiator (A)) P-3: IRGACURE OXE 01 (manufactured by BASF)
Quencher (basic compound) Y: A thiourea derivative represented by the following formula (Y1).
・ Quencher (polymerization inhibitor) Z: p-methoxyphenol ・ Surfactant PF-6320: OMNOVA, PF-6320
-Crosslinking agent (radical polymerizable compound (B)) B: A-TMPT (trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
-Solvent PGMEA: Propylene glycol monomethyl ether acetate

(Examples and comparative examples)
In each Example and Comparative Example, a composition for forming a protective layer, a composition for forming a photosensitive layer, an organic semiconductor layer, a protective layer, and a photosensitive layer are formed to produce a laminate. bottom.

<Preparation of composition for forming protective layer>
The components shown in Tables 1 to 4 are mixed at the ratios (parts by mass) shown in Tables 1 to 4 to obtain a uniform solution, and then filtered using a Savana PP cartridge filter (equivalent to 0.1 μm) manufactured by Entegris. Then, a water-soluble resin composition was prepared.
In Tables 1 to 4, the unit of saponification degree is "mol%".
In Tables 1 to 4, the description of "-" indicates that the corresponding component is not contained.

<Preparation of composition for forming photosensitive layer>
The components shown in Tables 1 to 4 are mixed at the ratios (parts by mass) shown in Tables 1 to 4 to obtain a uniform solution, and then filtered using a Savana PP cartridge filter (equivalent to 0.1 μm) manufactured by Entegris. To prepare a composition for forming a photosensitive layer.

<Preparation of organic layer>
A composition for forming an organic semiconductor layer or a composition for forming a resin layer having the following composition is spin-coated on a 5 cm square glass substrate, and in the "Bake conditions" column of "Organic layer" in Tables 1 to 4. An organic layer was formed by drying at the described temperature for 10 minutes. The film thickness was 150 nm.
In Example 25, a silicon wafer (6 inch silicon wafer manufactured by SUMCO Corporation, 1 inch is 2.54 cm) was used as a substrate instead of the glass substrate.
In the examples described as "P3HT / PCBM" in the column of the type of organic layer in Tables 1 to 4, the composition for forming an organic semiconductor layer having the following composition was used. Further, in the example described as "Cyclomer P (ACA) Z200M", a resin layer forming composition having the following composition was used.
[Composition of composition for forming organic semiconductor layer]
・ P3HT (Poly (3-hexylthiophene), manufactured by Sigma-Aldrich Japan LLC): 10% by mass
-PCBM ([6,6] -Phenyl-C _61- Methyl butyrate, manufactured by Sigma-Aldrich Japan LLC): 10% by mass
-Chloroform (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 80% by mass
[Composition of composition for forming a resin layer]
-Cyclomer P (ACA) Z200M (manufactured by Daicel Ornex Co., Ltd.): 50% by mass
-Propylene glycol monomethyl ether: 50% by mass

<Formation of protective layer>
The composition for forming a protective layer is spin-coated on the surface of the organic layer, dried at the temperature described in the "Bake condition" column of "Protective layer" in Tables 1 to 4 for 1 minute, and dried in Tables 1 to Table 1. A protective layer having the thickness (thickness (μm)) shown in 4 was formed.

<Formation of intermediate layer>
In Example 23, after the protective layer was formed, parylene (polyparaxylylene) was deposited by CVD (chemical vapor deposition) at the thickness shown in Table 3. In other examples, no intermediate layer was formed.

<Formation of photosensitive layer>
A composition for forming a photosensitive layer was spin-coated on the surface of the formed protective layer (the surface of the intermediate layer in Example 23), and in the "Bake conditions" column of the "photosensitive layer" in Tables 1 to 4. It was dried at the described temperature for 1 minute to form a photosensitive layer having the thickness (thickness (μm)) shown in Tables 1 to 4.

<Evaluation of residual strength>
In each Example or Comparative Example, the photosensitive layer in the manufactured laminate was exposed to the i-line through a predetermined mask using an i-line parallel exposure machine so that the exposure amount was 80 mJ.
After that, post-baking (PEB) was performed at the temperatures shown in Tables 1 to 4 under the conditions of 60 seconds, and the developing solution shown in Tables 1 to 4 was used for 80 seconds to develop a 1 cm square hole. An opening was obtained. At the opening of the hole, the protective layer was exposed.
200 mL of the stripping solution shown in any of Tables 1 to 4 was applied to the surface of the laminate having the hole openings on the photosensitive layer side, and the mixture was held for 60 seconds. The release liquid was brought into contact with the protective layer exposed at the opening of the hole. After 15 seconds, spin drying was performed. Further, in Comparative Example 3, peeling using the above peeling liquid was not performed.
TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry, TOF. The _{evaluation value was calculated by comparing the signal intensity of C 4} H ₅ O ⁻ with the signal intensity ratio after the protective layer was formed and before the photosensitive layer was formed. The C ₄ H ₅ O ⁻ signal is presumed to be a PVA-derived signal.
The evaluation values were calculated by the following formulas and are listed in the "residue" column of Tables 1 to 4. It can be said that the smaller the evaluation value, the more the generation of the residue is suppressed.
Evaluation value (%) = ( _{Signal intensity of C 4} H ₅ O ⁻ _{after spin drying) / (Signal intensity of C 4} H ₅ O ^{− on} the surface of the protective layer after formation of the protective layer and before formation of the photosensitive layer) × 100

Details of the developers shown in Tables 1 to 4 are as follows.
-NBA: n-butyl acetate-0.38% TMAHaq: 0.38% by mass aqueous solution of tetramethylammonium hydroxide

<Evaluation of light emission>
In Examples 1 to 25 and Comparative Examples 1 to 3, a model of an organic electroluminescent device was prepared and the presence or absence of light emission was evaluated.
A washed ITO (indium tin oxide) substrate (30 mm × 30 mm) was placed in a vapor deposition apparatus, and copper phthalocyanine was vapor-deposited at 10 nm. Diphenyl) -benzidine) was deposited at 40 nm to form an NPD layer. The organic semiconductor layer forming composition is applied to the entire surface of the NPD layer, and the organic layer is dried at the temperature described in the "Bake condition" column of "Organic layer" in Tables 1 to 4 for 10 minutes to form the organic layer. Formed. The film thickness was 150 nm.
The composition for forming a protective layer is spin-coated on the surface of the organic layer, dried at the temperature described in the "Bake condition" column of "Protective layer" in Tables 1 to 4 for 1 minute, and dried in Tables 1 to Table 1. A protective layer having the thickness (thickness (μm)) shown in 4 was formed.
In Example 23, after the protective layer was formed, parylene (polyparaxylylene) was deposited by CVD to the thickness shown in Table 3. In other examples, no intermediate layer was formed.
The surface of the formed protective layer (the surface of the intermediate layer in Example 23) is spin-coated with the composition for forming a photosensitive layer, and the temperature of 100 ° C. It was dried at the temperature described in the column for 1 minute to form a photosensitive layer having the thickness (thickness (μm)) shown in Tables 1 to 4.
The photosensitive layer was exposed to the i-line through a predetermined mask using an i-line parallel exposure machine so that the exposure amount was 80 mJ. Then, post-baking (PEB) was performed at the temperatures shown in Tables 1 to 4 under the conditions of 60 seconds, and the developing solution shown in Tables 1 to 4 was used for 80 seconds of development to form a 20 μm square shape. A pattern was formed in which the photosensitive layer remained. In the part not included in the square, the protective layer was exposed.
The laminated body including the square-shaped photosensitive layer was dry-etched to remove the protective layer and the organic layer in the region where the photosensitive layer did not exist.
Then, 200 mL of the stripping solution shown in Tables 1 to 4 was applied and held for 60 seconds to remove the photosensitive layer and the protective layer, leaving a 20 μm square organic layer on the NPD layer. The laminated body was prepared. Further, in Comparative Example 3, the photosensitive layer and the protective layer were not removed.
BAlq (bis- (2-methyl-8-quinolinolate) -4- (phenylphenolate) aluminum) was deposited on the surface of the organic layer (the surface of the protective layer in Comparative Example 3) to a thickness of 40 nm. , Formed an electron transport layer. After 3 nm of lithium fluoride was vapor-deposited on the electron transport layer, 60 nm of aluminum was vapor-deposited to prepare an organic electroluminescent device.
Using a Toyo Technica source measure unit 2400 type, apply it between the electrodes of the element that obtained a DC constant voltage (3V) (between the ITO substrate and the above-deposited aluminum), and check the presence or absence of light emission according to the following evaluation criteria. bottom. The evaluation results are shown in the "light emission" column of Tables 1 to 4. Since the light emission was not evaluated in Example 26, it is described as “−” in Table 4.
〔Evaluation criteria〕
OK: Light emission was observed NG: No light emission was observed

<Evaluation of pattern shape>
In each Example or Comparative Example, a 1: 1 line-and-space pattern binary with a line width of 10 μm was used for the photosensitive layer in the laminate produced by the same method as the evaluation of the residual strength using an i-line parallel exposure machine. The i-line was exposed through the mask so as to have an exposure amount of 80 mJ.
Then, after heating at 110 ° C. for 60 seconds, it was developed with butyl acetate for 15 seconds and spin-dried to obtain a 1: 1 line-and-space resist pattern having a line width of 10 μm. The cross section of the resist pattern was observed using a scanning electron microscope, and the pattern shape of the photosensitive layer was evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
OK: The taper angle of the pattern is 80 ° C to 100 ° C.
NG: The taper angle of the pattern is out of the range described in "OK" above.

From the results shown in Tables 1 to 4, when the laminate of the present invention according to each example was used, the residue at the time of removing the protective layer was compared with the case where the laminate according to the comparative example was used. It can be seen that the occurrence is suppressed.
Since the laminated body according to Comparative Example 1 contains only PVA having a saponification degree of 87 mol% in the protective layer, it can be seen that the generation of residue at the time of removing the protective layer is not suppressed.
Since the laminated body according to Comparative Example 2 contains only PVA having a saponification degree of 49 mol% in the protective layer, it can be seen that the generation of residue at the time of removing the protective layer is not suppressed.
In Comparative Example 3, the protective layer was not subjected to removal using a stripping solution. Therefore, it is impossible to evaluate the residue after removing the protective layer. Further, in such an embodiment, since the protective layer remains in the obtained device without being removed, it can be seen that it cannot be used for forming the organic electroluminescent element used for the above-mentioned evaluation of light emission, for example.

1 Photosensitive layer 1a Photosensitive layer after exposure development 2 Protective layer 3 Organic layer 3a Organic layer after processing 4 Base material 5 Removal part 5a Removal part after etching

Claims (14)

The base material, organic layer, protective layer and photosensitive layer are included in this order.
The protective layer contains polyvinyl alcohol
The saponification degree of the polyvinyl alcohol is 50 mol% or more and 85 mol% or less.
The photosensitive layer is subjected to development using a developing solution, and is subjected to development.
The protective layer is subjected to removal using a stripping solution.
Laminated body. The laminate according to claim 1, wherein the content of the polyvinyl alcohol is 50% by mass or more with respect to the total mass of the protective layer. The laminate according to claim 1 or 2, wherein the degree of saponification of the polyvinyl alcohol is 60 mol% or more and 80 mol% or less. The laminate according to any one of claims 1 to 3, wherein the degree of saponification of the polyvinyl alcohol is 65 mol% or more and 75 mol% or less. The laminate according to any one of claims 1 to 4, wherein the photosensitive layer contains a photoacid generator. The laminate according to any one of claims 1 to 5, wherein the development is a negative type. The laminate according to any one of claims 1 to 6, wherein the content of the organic solvent with respect to the total mass of the developing solution is 90 to 100% by mass. The laminate according to any one of claims 1 to 7, wherein the content of water with respect to the total mass of the stripping liquid is 90 to 100% by mass. The laminate according to any one of claims 1 to 8, wherein the photosensitive layer contains a resin having a repeating unit having a structure in which an acid group is protected by an acid-degradable group. The laminate according to claim 9, wherein the repeating unit is a repeating unit containing a cyclic ether ester structure in a side chain. The laminate according to claim 9, wherein the repeating unit is a repeating unit represented by the following formula (1);

In formula (1), R ⁸ represents a hydrogen atom or an alkyl group, L ¹ represents a carbonyl group or a phenylene group, and R ^{1 to} R ⁷ independently represent a hydrogen atom or an alkyl group. The composition used for forming the protective layer contained in the laminate according to any one of claims 1 to 11, which contains polyvinyl alcohol having a saponification degree of 50 mol% or more and 85 mol% or less. A composition used for forming the photosensitive layer contained in the laminate according to any one of claims 1 to 11. A laminate forming kit containing the following A and B;
A: A composition used for forming the protective layer contained in the laminate according to any one of claims 1 to 11, which contains polyvinyl alcohol having a saponification degree of 50 mol% or more and 85 mol% or less;
B: A composition used for forming the photosensitive layer contained in the laminate according to any one of claims 1 to 11.

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