JP2021110839A - Laminates, protective layer forming compositions, kits and semiconductor devices - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate in which generation of a residue is suppressed when a protective layer is removed, a composition for forming a protective layer used for forming the protective layer, a kit used for forming the laminate, and the laminate. Providing semiconductor devices formed using. SOLUTION: A base material, an organic layer, a protective layer and a photosensitive layer are included in this order, the protective layer contains a polymer compound, the photosensitive layer is subjected to development using a developing solution, and the protective layer is peeled off. Formation of a laminate having a viscosity of 0.8 mPa · s or less and a dissolution rate of the protective layer in the stripping solution of 100 nm / s or more, and the protective layer, which are subjected to removal using a liquid. A composition for forming a protective layer used in the above, a kit used for forming the above-mentioned laminate, and a semiconductor device formed by using the above-mentioned laminate. [Selection diagram] None

Description

The present invention relates to laminates, protective layer forming compositions, kits and semiconductor devices.

In recent years, devices using patterned organic layers, such as semiconductor devices using organic semiconductors, have been widely used.
For example, an organic semiconductor device has an advantage that it can be manufactured by a simple process as compared with a conventional electronic device using an inorganic semiconductor such as silicon. Further, the material properties of an organic semiconductor can be easily changed by changing its molecular structure. 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 electroluminescent devices, gas sensors, organic rectifying devices, organic inverters, and information recording devices. There is sex.
It is known that such patterning of an organic layer such as an organic semiconductor is performed using a laminate including an organic layer and a layer such as a photosensitive layer (for example, a resist layer).

For example, Patent Document 1 has an organic semiconductor film, a protective film on the organic semiconductor film, and a resist film on the protective film, and the resist film is an organic acid having a pKa of a generated acid of -1 or less. Laminated with a photosensitive resin composition containing a photoacid generator (A) that generates The body is listed.

Japanese Unexamined Patent Publication No. 2015-087609

The present invention relates to a laminate in which the generation of residues when the protective layer is removed is suppressed, a composition for forming a protective layer used for forming the protective layer, a kit used for forming the laminate, and the laminate. It is an object of the present invention to provide a semiconductor device formed by utilizing a body.

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 a polymer compound and contains
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, and is used for removal.
The viscosity of the stripping solution is 0.8 mPa · s or less.
A laminate in which the dissolution rate of the protective layer in the stripping solution is 100 nm / s or more.
<2> The laminate according to <1>, wherein the protective layer has a thickness of 10 μm or less.
<3> The maximum value of the width of the pattern of the protective layer formed by the etching, which is subjected to etching to remove a part of the protective layer and the organic layer after the development, is 10 μm or more, <1> or <2>.
<4> The minimum value of the width of the region where the protective layer does not exist, which is subjected to etching to remove a part of the protective layer and the organic layer after the development, is 5 μm or less. <1> The laminate according to any one of ~ <3>.
<5> The laminate according to any one of <1> to <4>, wherein the stripping solution contains a fluorine-based stripping solution. <6> The content of water with respect to the total mass of the stripping solution is 70% by mass. The laminate according to any one of <1> to <5> described above.
<7> The laminate according to any one of <1> to <5>, wherein the content of water with respect to the total mass of the stripping solution is 80% by mass or more.
<8> The laminate according to any one of <1> to <5>, wherein the content of water with respect to the total mass of the stripping solution is 90% by mass or more.
<9> Contains polymer compounds and solvents
A composition for forming a protective layer used for forming the protective layer contained in the laminate according to any one of <1> to <8>.
<10> A composition for forming a protective layer for forming the protective layer, and
The kit used for forming the laminate according to any one of <1> to <8>, which includes the composition for forming a photosensitive layer for forming the photosensitive layer.
<11> A semiconductor device including an organic layer patterned using the laminate according to any one of <1> to <8>.

According to the present invention, a laminate in which the generation of residues when the protective layer is removed is suppressed, a composition for forming a protective layer used for forming the protective layer, a kit used for forming the laminate, and A semiconductor device formed by using the above-mentioned laminate is provided.

It is sectional drawing which shows typically an example of the processing process of the laminated body which applied the composition for forming a protective layer.

Hereinafter, typical embodiments of the present invention will be described. Each component will be described based on this representative embodiment for convenience, but the present invention is not limited to such embodiments.

In the present specification, the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
In the present specification, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
Regarding the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution means to include those having a substituent as well as those having no substituent. For example, when simply described as "alkyl group", this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). Means. Further, when simply described as "alkyl group", this means that it may be chain-like or cyclic, and in the case of chain-like, it may be linear or branched. These are also synonymous with other groups such as "alkenyl group", "alkylene group" and "alkenylene group".
In the present specification, "exposure" means not only drawing using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Examples of energy rays used for drawing include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, active rays such as extreme ultraviolet rays (EUV light) and X-rays, and particle beams such as electron beams and ion beams. Be done.
In the present specification, "light" includes not only light having wavelengths in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, and infrared regions, electromagnetic waves, but also radiation, unless otherwise specified. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet rays (EUV), and X-rays. Further, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. As these lights, monochrome light (single wavelength light) that has passed through an optical filter may be used, or light containing a plurality of wavelengths (composite light) may be used.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or , And "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.
In the present specification, the solid content in the composition means other components other than the solvent, and the content (concentration) of the solid content in the composition is, unless otherwise specified, based on the total mass of the composition. It is represented by the mass percentage of other components excluding the solvent.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101325 Pa (1 atm), and the relative humidity is 50% RH.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are shown as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. For the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, and TSKgel are used as columns. It can be obtained by using Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, the measurement is carried out using THF (tetrahydrofuran) as the eluent. Unless otherwise specified, a UV ray (ultraviolet) wavelength 254 nm detector is used for detection in GPC measurement.
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.

(Laminated body)
The laminate of the present invention contains a base material, an organic layer, a protective layer and a photosensitive layer in this order, the protective layer contains a polymer compound, and the photosensitive layer is subjected to development using a developing solution to provide the protection. The layer is subjected to removal using a stripping solution, the viscosity of the stripping solution is 0.8 mPa · s or less, and the dissolution rate of the protective layer in the stripping solution is 100 nm / s or more.

According to the laminate of the present invention, the generation of residue when the protective layer is removed is suppressed. The reason why the above effect is obtained is presumed as follows.

Conventionally, in a laminate having an organic layer, a protective layer, and a photosensitive layer in this order, a resist pattern of a resist layer is formed, etching is performed, and then the protective layer and the photosensitive layer are removed with a stripping solution such as water. It has been done.
However, there is still room for improvement in terms of suppressing the residue in the above removal.
Therefore, as a result of diligent studies, the present inventors have obtained a protective layer that is subjected to peeling with a stripping solution having a viscosity of 0.8 mPa · s or less and has a dissolution rate in the stripping solution of 100 nm / s or more. It has been found that the use of the residue suppresses the generation of the residue.
This is because the stripping liquid having a low viscosity easily flows even in a narrow region where a protective layer between the organic layer and the resist layer exists, so that the stripping liquid easily permeates, and the laminate of the present invention has the low viscosity. Since the dissolution rate of the protective layer in the stripping solution is 100 nm / s or more, it is presumed that the protective layer is excellent in removability and the generation of residue is suppressed.
Patent Document 1 does not describe or suggest the use of a laminate containing a protective layer having a high dissolution rate in such a low-viscosity stripping solution.

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 an example of 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. Further, after the development, the photosensitive layer 1a may be further heated or exposed.
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 in the laminated body in the state shown in FIG. 1C have a viscosity of 0.8 mPa · s or less, and the dissolution rate of the protective layer in a stripping solution is 100 nm / s or more. The photosensitive layer 1a and the protective layer 2 on the organic layer 3a after processing are removed by washing with a stripping solution or the like.
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.
The base material that may be contained in the laminate is formed of, for example, various materials such as silicon, quartz, ceramic, glass, polyester film such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), and polyimide film. Any base material may be selected depending on the intended use. 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 (board). The thickness of the substrate is also not particularly limited.

<Organic layer>
The laminate in the present invention contains an organic layer.
The organic layer is a layer containing an organic material. The specific organic material is appropriately selected according to the use and function of the organic layer. Assumed functions of the organic layer include, for example, semiconductor characteristics, light emission characteristics, photoelectric conversion characteristics, light absorption characteristics, electrical insulation, ferroelectricity, transparency, insulation and the like. In the laminate, 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 further contained between the organic layer and the base material. May be.

The thickness of the organic layer is not particularly limited and varies depending on the type of electronic device used and the like, but is preferably 1 nm to 50 μm, more preferably 1 nm to 5 μm, and further preferably 1 nm to 500 nm.
In particular, an example in which the organic layer is an organic semiconductor layer will be described in detail below. The organic semiconductor layer is a layer containing an organic material exhibiting the characteristics of a semiconductor.

The organic semiconductor layer is an organic layer containing an organic semiconductor, and the organic semiconductor is an organic compound exhibiting the characteristics of a semiconductor. Similar to the case of semiconductors made of inorganic compounds, organic semiconductors include p-type semiconductors that conduct holes as carriers and n-type semiconductors 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, in general, the carrier mobility ^{is preferably high, preferably 10-7} cm ² / Vs or more, more preferably ^10-6 cm ² / Vs or more, and ^10-5 cm ^{2 or more.} It is more preferably / Vs or more. The carrier mobility can be determined based on the characteristics when the field effect transistor (FET) element is manufactured and the measured value by the flight time measurement (TOF) method.

As the p-type organic semiconductor that can be used in the organic semiconductor layer, any material may be used as long as it has hole transportability. The p-type organic semiconductor is preferably any one of a p-type π-conjugated polymer, a condensed polycyclic compound, a triarylamine compound, a hetero 5-membered ring compound, a phthalocyanine compound, a porphyrin compound, carbon nanotubes, and graphene. Further, as the p-type organic semiconductor, a plurality of kinds of compounds among these compounds may be used in combination. The p-type organic semiconductor is more preferably at least one of a p-type π-conjugated polymer, a condensed polycyclic compound, a triarylamine compound, a hetero 5-membered ring compound, a phthalocyanine compound, and a porphyrin compound, and more preferably. It is at least one of a p-type π-conjugated polymer and a condensed polycyclic compound.

The p-type π-conjugated polymer is, for example, substituted or unsubstituted polythiophene (for example, poly (3-hexylthiophene) (P3HT, manufactured by Sigma Aldrich Japan LLC)), polyselenophene, polypyrrole, polyparaphenylene, poly. Paraphenylene vinylene, polythiophene vinylene, polyaniline, etc. Condensed polycyclic compounds include, for example, substituted or unsubstituted anthracene, tetracene, pentacene, anthradithiophene, hexabenzocoronene and the like.

Triarylamine compounds include, for example, m-MTDATA (4,4', 4''-Tris [(3-methylphenyl) biphenyllamine), 2-TNATA (4,4', 4''-Tris [2- naphthyl (phenyl) amine), NPD (N, N'-Di (1-naphthyl) -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine), TPD (N) , N'-Diphenyl-N, N'-di (m-tool) benzidine), mCP (1,3-bis (9-carbazolyl) benzene), CBP (4,4'-bis (9-carbazolyl) -2 , 2'-biphenyl) and the like.

The hetero 5-membered ring compound is, for example, a substituted or unsubstituted oligothiophene, TTF (Tetrathiafulvalene), or the like.

Phthalocyanine compounds include substituted or unsubstituted phthalocyanines having various central metals, naphthalocyanines, anthracyanines, tetrapyrazinoporphyrazine and the like. Porphyrin compounds are substituted or unsubstituted porphyrins having various central metals. Further, the carbon nanotube may be a carbon nanotube whose surface is modified with a semiconductor polymer.

As the n-type organic semiconductor that can be used for the organic semiconductor layer, any material may be used as long as it has an electron transporting property. The n-type organic semiconductor is preferably a fullerene compound, an electron-deficient phthalocyanine compound, a fused polycyclic compound (naphthalene tetracarbonyl compound, perylene tetracarbonyl compound, etc.), a TCNQ compound (tetracyanoquinodimethane compound), and a polythiophene compound. , Benzidine-based compound, carbazole-based compound, phenanthroline-based compound, pyridinephenyl ligand iridium-based compound, quinolinol ligand alumnium-based compound, n-type π-conjugated polymer, and graphene. Further, as the n-type organic semiconductor, a plurality of kinds of compounds among these compounds may be used in combination. The n-type organic semiconductor is more preferably at least one of a fullerene compound, an electron-deficient phthalocyanine compound, a fused polycyclic compound, and an n-type π-conjugated polymer, and particularly preferably a fullerene compound and a condensed polycyclic ring. It is at least one of a compound and an n-type π-conjugated polymer.

The fullerene compound means 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 and the like. The fullerene compound is preferably substituted or unsubstituted C ₆₀ , C ₇₀ , C ₈₆ fullerene, and particularly preferably PCBM ([6,6] -phenyl-C61-butyric acid methyl ester, manufactured by Sigma Aldrich Japan GK. etc.) and its analogs (e.g., those with substitution of C ₆₀ part C _70, C _86, etc., those with substitution of the benzene ring substituent in other aromatic ring or a hetero ring, n- butyl ester methyl ester, It is replaced with i-butyl ester or the like).

The electron-deficient phthalocyanine compound is a substituted or unsubstituted phthalocyanine, naphthalocyanine, anthracianine, tetrapyrazinoporphyrazine and the like having four or more electron-attracting groups bonded and having various central metals. Electron-deficient phthalocyanine compounds include, for example, fluorinated phthalocyanine (F ₁₆ MPc) and chlorinated phthalocyanine (Cl ₁₆ MPc). Here, M represents a central metal and Pc represents a phthalocyanine.

Any naphthalene tetracarbonyl compound may be used, but naphthalene tetracarboxylic dianhydride (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 compound (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. The TCNQ compounds include, for example, TCNQ, TCNAQ (Tetracyanoquinodimethane), TCN3T (2,2'-((2E, 2''E) -3', 4'-Alkyl subscribed-5H, 5''H. -[2,2': 5', 2''-terthiophene] -5,5''-diylidene) dimalononirile derivatives) and the like.

The polythiophene-based compound is a compound having a polythiophene structure such as poly (3,4-ethylenedioxythiophene). The polythiophene-based compound is, for example, PEDOT: PSS (complex composed of poly (3,4-ethylenedioxythiophene) (PEDOT) and polystyrene sulfonic acid (PSS)).

The benzidine-based compound is a compound having a benzidine structure in the molecule. Benzidine compounds include, for example, N, N'-bis (3-methylphenyl) -N, N'-diphenylbenzidine (TPD), N, N'-di-[(1-naphthyl) -N, N'-. Diphenyl] -1,1'-biphenyl) -4,4'-diamine (NPD) and the like.

The carbazole-based compound is a compound having a carbazole ring structure in the molecule. Carbazole compounds include, for example, 4,4'-bis (N-carbazolyl) -1,1'-biphenyl (CBP).

The phenanthroline-based compound is a compound having a phenanthroline ring structure in the molecule, and is, for example, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).

The pyridinephenyl ligand iridium-based compound is a compound having an iridium complex structure having a phenylpyridine structure as a ligand. Pyridinephenyl ligands The iridium-based compounds include, for example, bis (3,5-difluoro-2- (2-pyridylphenyl- (2-carboxypyridyl) iridium (III) (FIrpic)) and tris (2-phenylpyridinato). ) Iridium (III) (Ir (ppy) ₃ ) and the like.

The quinolinol ligand alumnium-based compound is a compound having an aluminum complex structure having a quinolinol structure as a ligand, and is, for example, tris (8-quinolinolato) aluminum.

A particularly preferable example of the n-type organic semiconductor material is shown below. 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, still more preferably 6 to 14 carbon atoms). In the structural formula, Me represents a methyl group and M represents a metal atom.

The organic semiconductor contained in the organic semiconductor layer may be one type or two or more types. Further, the organic semiconductor layer may be a laminated or mixed layer of a p-type layer and an n-type layer.

The method for forming the organic layer may be a vapor phase method or a liquid phase method. In the case of the vapor phase method, a physical vapor deposition (PVD) method such as a vapor deposition method (vacuum vapor deposition method, molecular beam epitaxy method, etc.), a sputtering method, an ion plating method, or a chemical vapor deposition method such as a plasma polymerization method is used. A growth (CVD) method can be used, with a vapor deposition method being particularly preferred.

On the other hand, in the case of the liquid phase method, for example, the organic material is blended in a solvent to form a composition for forming an organic layer (composition for forming an organic layer). Then, this composition is supplied onto the substrate and dried to form an organic layer. As a supply method, coating is preferable. Examples of supply 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 thereof include a spin coat method, a Langmuir-Blodgett (LB) method, and an edge cast method (for details, see Patent No. 6179930). 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 an organic layer having a smooth surface and a large area at low cost.

Further, as the solvent used in the composition for forming an organic layer, an organic solvent is preferable. Examples of the organic solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene and 1,2-dichlorobenzene; for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like. Ketone-based solvent; for example, halogenated hydrocarbon-based solvent such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, etc .; eg, ester of ethyl acetate, butyl acetate, amyl acetate, etc. Solvents; alcohol solvents such as, for example, methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol; and ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole; for example. , N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, dimethylsulfoxide and other polar solvents. Only one kind of these solvents may be used, or two or more kinds may be used. The proportion of the organic material in the composition for forming an organic layer is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, whereby a film having an arbitrary thickness can be formed.

Further, a resin binder may be added to the composition for forming an organic layer. In this case, the material forming the film and the binder resin can be dissolved or dispersed in the above-mentioned suitable solvent to prepare a coating liquid, and a thin film can be formed by various coating methods. Resin binders include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulphon, polymethylmethacrylate, polymethylacrylate, cellulose, polyethylene, 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 resin binder may be used alone or in combination of two or more. Considering the mechanical strength of the thin film, a resin binder having a high glass transition temperature is preferable, and considering charge mobility, a resin binder having a structure containing no polar group or a conductive polymer is preferable.

When the resin binder is blended, the blending amount thereof is preferably 0.1 to 30% by mass in the organic layer. The resin binder may be used alone or in combination of a plurality of types. In the case of a combination of a plurality of types, it is preferable that the total amount thereof is within the above range.

Depending on the application, the organic layer may be a blended film composed of a plurality of material types, using a single solution or a mixed solution to which various organic materials and additives are added. For example, when producing a photoelectric conversion layer, a mixed solution using a plurality of types of semiconductor materials can be used.

Further, the base material may be heated or cooled at the time of film formation, and it is possible to control the film quality and the packing of molecules in the film 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 properties of the formed organic layer can be adjusted by post-treatment. For example, it is possible to improve the properties by changing the morphology of the membrane and the packing of molecules in the membrane by heat treatment or exposure to a vaporized solvent. Further, by exposing to an oxidizing or reducing gas, solvent, substance or the like, or by using these methods in combination, an oxidation or reduction reaction can occur, and the carrier density in the membrane can be adjusted.

<Protective layer>
The protective layer in the present invention is subjected to removal using a stripping solution.
Examples of the removing method include the methods described as a step of removing the protective layer using a stripping solution in the method for producing a laminate and the method for patterning an organic layer, which will be described later.

In the present invention, the stripping solution used for stripping the protective layer has a viscosity of 0.8 mPa · s or less, more preferably 0.75 mPa · s or less, and a viscosity of 0.72 mPa · s or less. Is more preferable. The lower limit of the viscosity is not particularly limited, and can be, for example, 0.10 mPa · s or more.

The viscosity can be measured by a known method, and is measured by, for example, a RE-80L type rotational viscometer manufactured by Toki Sangyo Co., Ltd. The rotation speed may be set as appropriate, but can be set to, for example, 100 rpm.
The viscosity of the stripping solution is adjusted by, for example, the structure of the compound used as the solvent contained in the stripping solution, the temperature of the stripping solution, the mixing ratio of the solvent contained in the stripping solution, and the like.

Further, the protective layer used in the present invention has a dissolution rate of 100 nm / s or more, preferably 120 nm / s or more, and more preferably 150 nm / s or more in the stripping solution used for removing the protective layer. preferable. The upper limit of the dissolution rate is not particularly limited, and can be, for example, 1,000 nm / s or less.

The dissolution rate is measured, for example, by the following method.
The photosensitive layer is removed from the laminate to prepare a laminate from which the photosensitive layer has been removed.
The photosensitive layer can be removed, for example, by removing the photosensitive layer with a developing solution without performing either exposure or heating.
The film thickness (film thickness A) of the laminate from which the photosensitive layer has been removed is measured.
The laminate from which the photosensitive layer has been removed is immersed in the stripping solution for 5 seconds and then taken out, and the film thickness (film thickness B) of the laminate is measured again.
The dissolution rate (nm / s) of the protective layer in the stripping solution is calculated by dividing the difference between the film thickness A and the film thickness B by the immersion time (5 seconds).

Examples of the stripping solution include water, an organic solvent, or a mixture thereof.
The stripping solution preferably contains a fluorine-based stripping solution.
As the fluorine-based stripping solution, an ether compound having an alkyl fluoride group is preferable, and a compound in which an alkyl fluoride group and an alkyl group are ether-bonded is more preferable.
The alkyl fluoride group may be any one in which at least one hydrogen atom of the alkyl group is substituted with a fluorine atom, but it is preferable that all of the alkyl groups are substituted with a fluorine atom.
Further, as the fluorinated alkyl group, a fluorinated alkyl group having 2 to 10 carbon atoms is preferable, a fluorinated alkyl group having 2 to 5 carbon atoms is more preferable, and a fluorinated alkyl group having 3 or 4 carbon atoms is further preferable. ..
The alkyl fluoride group may be linear or branched chain, may be cyclic, or may contain a cyclic structure, but must be linear or branched. Is preferable, and linearity is more preferable.
Further, as the alkyl group in the compound in which the fluorinated alkyl group and the alkyl group are ether-bonded, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is preferable. More preferred.
The alkyl group may be linear or branched chain, may be cyclic, or may contain a cyclic structure, but is preferably linear or branched. It is more preferable that it is linear.

Among these, the fluorine-based stripping solution preferably contains _{C 3} F ₇ OCH ₃ , C ₄ F ₉ OCH ₃ , or C ₄ F ₉ OC ₂ H _5.
As the fluorine-based release agent, a commercially available product may be used. Examples of commercially available products include Novec (registered trademark) 7000, 7100, and 7200 (all manufactured by 3M Co., Ltd.).
When the stripping solution contains a fluorine-based stripping solution, the content of the fluorine-based stripping solution is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass, based on the total mass of the stripping solution. It is more preferably mass% or more. The upper limit of the content is not particularly limited, and may be 100% by mass.
Further, the stripping solution may be in a mode in which components other than the fluorine-based stripping solution are substantially not contained. In the above aspect, the content of the fluorine-based stripping solution is preferably 98% by mass or more, more preferably 99% by mass or more, and 99.9% by mass or more, based on the total mass of the stripping solution. Is even more preferable. The upper limit of the content is not particularly limited, and may be 100% by mass.

Further, the stripping solution may be in a form containing water.
In the above aspect, the content of water with respect to the total mass of the stripping liquid is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. The upper limit of the content is not particularly limited and may be 100% by mass or less.
Further, in the mode in which the stripping liquid contains water, it is also possible to make the mode substantially free of components other than water. In the above aspect, the content of water is preferably 98% by mass or more, more preferably 99% by mass or more, and further preferably 99.9% by mass or more, based on the total mass of the stripping solution. preferable. The upper limit of the content is not particularly limited, and may be 100% by mass.
The temperature of the stripping solution may be adjusted so that the viscosity of the stripping solution is within the above range. For example, the temperature of the stripping solution containing water is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and even more preferably 50 ° C. or higher. The upper limit of the temperature can be, for example, 100 ° C. or lower, preferably 90 ° C. or lower, and more preferably 80 ° C. or lower.

Further, the stripping solution may further contain a water-soluble solvent.
In particular, in the embodiment in which the stripping solution contains water, the stripping solution may further contain a water-soluble solvent.
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 solution may contain a surfactant in order to improve the removability of the protective layer.
Known compounds can be used as the surfactant, and nonionic surfactants are preferably mentioned.

From the viewpoint that the effect of the present invention becomes more remarkable, the thickness of the protective layer is preferably 10 μm or less, more preferably 5.0 μm or less, further preferably 3.0 μm or less, and particularly preferably 2.0 μm or less. preferable.
The thinner the protective layer, the more difficult it is for the release liquid to invade, and the more likely it is that a residue will be generated when the protective layer is removed.
However, since the protective layer in the laminate of the present invention is subjected to removal using a stripping solution having a viscosity of 0.8 mPa · s or less, even if the protective layer is a thin layer, the stripping solution easily permeates, and the protective layer can be used. It is considered that the residue when removed is unlikely to be generated.
The lower limit of the thickness of the protective layer is not particularly limited, but is preferably 0.1 μm or more, and more preferably 0.5 μm or more.

The laminate of the present invention is preferably subjected to etching after the photosensitive layer is subjected to development, and from the viewpoint that the effect of the present invention becomes more remarkable, the width of the pattern of the protective layer formed by the etching is wide. Of these, the maximum value (hereinafter, also referred to as "maximum value of the protective layer pattern width") is more preferably 2.0 μm or more.
The maximum value of the protective layer pattern width is more preferably 5.0 μm or more, and further preferably 10.0 μm or more. The maximum value of the protective layer pattern width is preferably 30 μm or less.

The pattern of the protective layer formed by the etching may be a plurality of patterns in which the protective layer is divided by etching, or may be a pattern including only one region formed by etching.
When the pattern of the protective layer formed by the etching is the plurality of patterns, the maximum value of the protective layer pattern width means the maximum value among the widths of the plurality of patterns.
When the pattern of the protective layer formed by the etching is a pattern including only one region, the maximum value of the protective layer pattern width means the width of the region.
The etching is preferably an etching using the pattern of the photosensitive layer after development as a mask.
Examples of the etching method include the methods described in the step of removing the protective layer and the organic layer of the non-masked portion in the method for producing a laminate and the method for patterning an organic layer, which will be described later.
The width of the protective layer pattern is, for example, the length in the width direction (short direction) of the line portion on the surface of the protective layer on the organic layer side when the pattern of the protective layer after etching is a line and space pattern. Say.
For example, when the shape of the pattern of the protective layer after etching on the surface on the organic layer side is circular, the width of the pattern of the protective layer is the diameter of the circle.
For example, when the shape of the pattern of the protective layer after etching on the surface on the organic layer side is rectangular, the width of the pattern of the protective layer is the short side of the rectangle.
For example, when the shape of the pattern of the protective layer after etching on the surface on the organic layer side is square, the width of the pattern of the protective layer is one side of the square.

That is, the maximum value of the protective layer pattern width is the maximum value of the width of the region to be peeled off by the stripping liquid in the protective layer pattern formed after etching. Therefore, the larger the maximum value of the protective layer pattern width, the larger the distance that the stripping liquid must permeate, which makes peeling by the stripping liquid difficult, and a residue is likely to be generated when the protective layer is removed.
In the present invention, the viscosity of the stripping solution is 0.8 mPa · s or less, and the dissolution rate of the protective layer in the stripping solution is 100 nm / s or more, so that the maximum value of the protective layer pattern width is large. However, it is considered that the release liquid easily permeates and the generation of residue when the protective layer is removed is suppressed.

Further, from the viewpoint that the effect of the present invention becomes more remarkable, the minimum value among the widths of the regions where the protective layer formed by the etching does not exist (hereinafter, also referred to as "minimum value of the width of the removed portion"). Is preferably 10.0 μm or less.
The minimum width of the removed portion is more preferably 5.0 μm or less, and further preferably 2.0 μm or less. The lower limit of the minimum value of the width of the removed portion is preferably 0.5 μm or more.

The width of the region where the protective layer does not exist formed by etching is, for example, the space portion on the plane including the interface between the organic layer and the protective layer when the pattern of the protective layer after etching is a line and space pattern. The length in the width direction (short direction) of.
For example, when the shape on the plane including the interface between the organic layer and the protective layer in the region where the protective layer does not exist is rectangular, the width of the region where the protective layer does not exist formed by etching is a short rectangular shape. It is a side.
For example, when the shape on the plane including the interface between the organic layer and the protective layer in the region where the protective layer does not exist is circular, the width of the region where the protective layer does not exist formed by etching is the diameter of the circle. Is.

That is, the minimum value of the width of the removal portion is the minimum value of the region where the release liquid must penetrate in the pattern of the protective layer formed after etching. Therefore, the smaller the minimum value of the width of the removing portion, the more difficult it is for the stripping liquid to penetrate, and the more likely it is that a residue will be generated when the protective layer is removed.
In the present invention, since the viscosity of the stripping solution is 0.8 mPa · s or less and the dissolution rate of the protective layer in the stripping solution is 100 nm / s or more, the minimum value of the width of the removing portion is small. However, it is considered that the release liquid easily penetrates and the generation of the residue when the protective layer is removed is suppressed.

Further, the protective layer in the present invention is preferably a layer having a dissolution rate in a developing solution of 10 nm / s or less at 23 ° C., and more preferably 1 nm / s or less. The lower limit of the dissolution rate is not particularly limited, and may be more than 0 nm / s.

[Polymer compound]
The protective layer in the present invention contains a polymer compound.
As the polymer compound, a water-soluble polymer compound is preferable, and a water-soluble resin is more preferable.

-Water-soluble resin-
The water-soluble resin refers to a resin that dissolves 1 g or more in 100 g of water at 23 ° C. The water-soluble resin is preferably a resin that dissolves 5 g or more with respect to 100 g of water at 23 ° C., more preferably a resin that dissolves 10 g or more, and further preferably a resin that dissolves 30 g or more. There is no particular upper limit on the amount of dissolution, but it is practically about 100 g.

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

Specific examples of the water-soluble resin include polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and water-soluble polysaccharides (water-soluble cellulose (methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxy). (Propylmethyl cellulose, propylmethyl cellulose, etc.), purulan or purulan derivatives, starch (hydroxypropyl starch, carboxymethyl starch, etc.), chitosan, cyclodextrin), polyethylene oxide, polyethyloxazoline, methylolmelamine, polyacrylamide, phenolic resin, styrene / malein. Acid semi-esters 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. In the present invention, the protective layer preferably contains at least one selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, water-soluble polysaccharides, pullulan and pullulan derivatives among these resins, and polyvinylpyrrolidone and polyvinyl alcohol. And at least one selected from the group consisting of water-soluble polysaccharides. The water-soluble polysaccharide is particularly preferably cellulose, more preferably hydroxyethyl cellulose.

Specifically, in the present invention, the water-soluble resin contained in the protective layer is preferably a resin containing a repeating unit represented by any of the formulas (P1-1) to (P4-1).

Wherein ^{(P1-1) ~ (P4-1),} R P1 is hydrogen or ^{methyl, R P2} represents a hydrogen atom or a methyl ^group, the R p31 ^{to R p33} are each independently a substituent or hydrogen Representing an atom, R ^{p41 to} R ^p49 independently represent a substituent or a hydrogen atom.

式（Ｐ１−２）中、Ｒ^Ｐ１１はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ^Ｐ１２は置換基を表し、ｎｐ１及びｎｐ２は質量基準での分子中の構成比率を表す。
式（Ｐ１−２）中、Ｒ^Ｐ１１は式（Ｐ１−１）におけるＲ^Ｐ１と同義であり、好ましい態様も同様である。
式（Ｐ１−２）中、Ｒ^Ｐ１２としては−Ｌ^Ｐ−Ｔ^Ｐで表される基が挙げられる。Ｌ^Ｐは単結合又は後述する連結基Ｌである。Ｔ^Ｐは置換基であり、後述する置換基Ｔの例が挙げられる。なかでも、Ｒ^Ｐ１２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）、又は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）等の炭化水素基が好ましい。これらのアルキル基、アルケニル基、アルキニル基、アリール基、アリールアルキル基は本発明の効果を奏する範囲で更に置換基Ｔで規定される基を有していてもよい。
式（Ｐ１−２）中、ｎｐ１及びｎｐ２は質量基準での分子中の構成比率を表し、それぞれ独立に、１０質量％以上１００質量％未満である。ただしｎｐ１＋ｎｐ２が１００質量％を超えることはない。ｎｐ１＋ｎｐ２が１００質量％未満の場合、その他の繰返し単位を含むコポリマーであることを意味する。 << Resin containing a repeating unit represented by the formula (P1-1) >>
Wherein ^{(P1-1), R P1} is preferably a hydrogen atom.
The resin containing the repeating unit represented by the formula (P1-1) may further contain a repeating unit different from the repeating unit represented by the formula (P1-1).
The resin containing the repeating unit represented by the formula (P1-1) preferably contains the repeating unit represented by the formula (P1-1) in an amount of 10 mol% to 100 mol% with respect to all the repeating units of the resin. , 30 mol% to 70 mol% is more preferable.
Examples of the resin containing the repeating unit represented by the formula (P1-1) include a resin containing two repeating units represented by the following formula (P1-2).

Wherein ^{(P1-2), R P11} each independently represent a hydrogen atom or a methyl ^{group, R P12} represents a substituent, np1 and np2 represent composition ratio in the molecule in mass.
Wherein ^{(P1-2), R P11} has the same meaning as ^{R P1} in formula (P1-1), preferable embodiments thereof are also the same.
Wherein ^(P1-2), include groups represented by ^-L P -T ^P as ^{R P12.} L ^P is a linking group L to a single bond or later. T ^P is a substituent, and examples of the substituent T described later can be mentioned. Among them, ^{as RP12} , an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms are more preferable). Preferably, 2-3 are more preferred), an alkynyl group (preferably 2-12 carbon atoms, more preferably 2-6, more preferably 2-3), an aryl group (preferably 6-22 carbon atoms, 6-18 carbon atoms). Is more preferable, 6 to 10 is more preferable), or a hydrocarbon group such as an arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, and 7 to 11 is more preferable) is preferable. These alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and arylalkyl groups may further have a group defined by a substituent T as long as the effects of the present invention are exhibited.
In the formula (P1-2), np1 and np2 represent the composition ratio in the molecule on a mass basis, and are independently 10% by mass or more and less than 100% by mass. However, np1 + np2 does not exceed 100% by mass. When np1 + np2 is less than 100% by mass, it means that the copolymer contains other repeating units.

式（Ｐ２−２）中、Ｒ^Ｐ２１はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ^Ｐ２２は置換基を表し、ｍｐ１及びｍｐ２は質量基準での分子中の構成比率を表す。
式（Ｐ２−２）中、Ｒ^Ｐ２１は式（Ｐ２−１）におけるＲ^Ｐ２と同義であり、好ましい態様も同様である。
式（Ｐ２−２）中、Ｒ^Ｐ２２としては−Ｌ^Ｐ−Ｔ^Ｐで表される基が挙げられる。Ｌ^Ｐは単結合又は後述する連結基Ｌである。Ｔ^Ｐは置換基であり、後述する置換基Ｔの例が挙げられる。なかでも、Ｒ^Ｐ２２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）、又は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）等の炭化水素基が好ましい。これらのアルキル基、アルケニル基、アルキニル基、アリール基、アリールアルキル基は本発明の効果を奏する範囲で更に置換基Ｔで規定される基を有していてもよい。
式（Ｐ２−２）中、ｍｐ１及びｍｐ２は質量基準での分子中の構成比率を表し、それぞれ独立に、１０質量％以上１００質量％未満である。ただしｍｐ１＋ｍｐ２が１００質量％を超えることはない。ｍｐ１＋ｍｐ２が１００質量％未満の場合、その他の繰返し単位を含むコポリマーであることを意味する。 << Resin containing a repeating unit represented by the formula (P2-1) >>
Wherein ^{(P2-1), R P2} is preferably a hydrogen atom.
The resin containing the repeating unit represented by the formula (P2-1) may further contain a repeating unit different from the repeating unit represented by the formula (P2-1).
The resin containing the repeating unit represented by the formula (P2-1) preferably contains the repeating unit represented by the formula (P2-1) in an amount of 10% by mass to 100% by mass based on the total mass of the resin. It is more preferable to contain 30% by mass to 70% by mass.
Examples of the resin containing the repeating unit represented by the formula (P2-1) include a resin containing two repeating units represented by the following formula (P2-2).

Wherein ^{(P2-2), R P21} each independently represent a hydrogen atom or a methyl ^{group, R P22} represents a substituent, mp1 and mp2 represent composition ratio in the molecule in mass.
Wherein ^{(P2-2), R P21} has the same meaning as ^{R P2} in formula (P2-1), preferable embodiments thereof are also the same.
Wherein ^(P2-2), include groups represented by ^-L P -T ^P as ^{R P22.} L ^P is a linking group L to a single bond or later. T ^P is a substituent, and examples of the substituent T described later can be mentioned. Among them, ^{as RP22} , an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms are more preferable). Preferably, 2-3 are more preferred), an alkynyl group (preferably 2-12 carbon atoms, more preferably 2-6, even more preferably 2-3), an aryl group (preferably 6-22 carbon atoms, 6-18 carbon atoms). Is more preferable, 6 to 10 is more preferable), or a hydrocarbon group such as an arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, and 7 to 11 is more preferable) is preferable. These alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and arylalkyl groups may further have a group defined by a substituent T as long as the effects of the present invention are exhibited.
In the formula (P2-2), mp1 and mp2 represent the composition ratio in the molecule on a mass basis, and are independently 10% by mass or more and less than 100% by mass. However, mp1 + mp2 does not exceed 100% by mass. When mp1 + mp2 is less than 100% by mass, it means that the copolymer contains other repeating units.

<< Resin containing a repeating unit represented by the formula (P3-1) >>
In the formula (P3-1), R ^{p31 to} R ^p33 are each independently a hydrocarbon group or an acyl group which may have a substituent,-(CH ₂ CH ₂ O) _ma H, -CH ₂ COONa or hydrogen. It preferably represents an atom, more preferably a hydrocarbon group, a hydrocarbon group having a hydroxy group as a substituent, an acyl group or a hydrogen atom, and even more preferably a hydrogen atom. ma is or 2.
The number of carbon atoms of the hydrocarbon group which may have the above-mentioned substituent is preferably 1 to 10, and more preferably 1 to 4.
As the hydrocarbon group having a hydroxy group as a substituent, a hydrocarbon group having one hydroxy group and having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having 1 hydroxy group and having 1 to 4 carbon atoms is more preferable. -CH ₂ (OH), -CH ₂ CH ₂ (OH) or -CH ₂ CH (OH) CH ₃ are more preferred.
As the acyl group, an alkylcarbonyl group having 1 to 4 carbon atoms of the alkyl group is preferable, and an acetyl group is more preferable.
The resin containing the repeating unit represented by the formula (P3-1) may further contain a repeating unit different from the repeating unit represented by the formula (P3-1).
The resin containing the repeating unit represented by the formula (P3-1) preferably contains the repeating unit represented by the formula (P3-1) in an amount of 10% by mass to 100% by mass based on the total mass of the resin. It is more preferable to contain 30% by mass to 70% by mass.
Further, the hydroxy group described in the formula (P3-1) may be appropriately substituted with a substituent T or a group combining the substituent L with the substituent L. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the ring in the formula with or without the linking group L to form a ring.

<< Resin containing a repeating unit represented by the formula (P4-1) >>
In the formula (P4-1), R ^{P41 to} R ^P49 are each independently a hydrocarbon group or an acyl group which may have a substituent,-(CH ₂ CH ₂ O) _ma H, -CH ₂ COONa or hydrogen. It preferably represents an atom, more preferably a hydrocarbon group, a hydrocarbon group having a hydroxy group as a substituent, an acyl group or a hydrogen atom, and even more preferably a hydrogen atom. ma is 1 or 2.
The number of carbon atoms of the hydrocarbon group which may have the above-mentioned substituent is preferably 1 to 10, and more preferably 1 to 4.
As the hydrocarbon group having a hydroxy group as a substituent, a hydrocarbon group having one hydroxy group and having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having 1 hydroxy group and having 1 to 4 carbon atoms is more preferable. , -CH ₂ (OH), -CH ₂ CH ₂ (OH) or -CH ₂ CH (OH) CH ₃ is more preferred.
The resin containing the repeating unit represented by the formula (P4-1) may further contain a repeating unit different from the repeating unit represented by the formula (P4-1).
The resin containing the repeating unit represented by the formula (P4-1) preferably contains the repeating unit represented by the formula (P4-1) in an amount of 10% by mass to 100% by mass based on the total mass of the resin. It is more preferable to contain 30% by mass to 70% by mass.
Further, the hydroxy group described in the formula (P4-1) may be appropriately substituted with a substituent T or a group combining the substituent L with the substituent L. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the ring in the formula with or without the linking group L to form a ring.

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), hydroxyl 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 number). 6 to 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), an alkoxyl group (1 to 12 carbon atoms is preferable, 1 to 6 is more preferable, 1 to 3 is more preferable), and an aryloxy group. (Preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), acyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms). Acyloxy group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), allylloyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms). ), 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 to 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 6 carbon atoms). Is more preferable, 1-3 is 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 heteroaryl group (1 to 12 carbon atoms is preferable). , 1-8 are more preferred, 2-5 are even more preferred, and preferably contain a 5- or 6-membered ring), (meth) acryloyl group, (meth) acryloyloxy group, halogen atom (eg, fluorine atom, etc.). chlorine atom, bromine atom, 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, further 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.

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. In the present specification, the "(oligo) alkyleneoxy group" means a divalent linking group having one or more "alkyleneoxy" which is a constituent unit. The number of carbon atoms of the alkylene chain in the structural unit may be the same or different for each structural unit. The alkylene group may have a substituent T. For example, the alkylene group may have a hydroxyl 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.

Other examples of the water-soluble resin include polyethylene oxide, hydroxyethyl cellulose, carboxymethyl cellulose, water-soluble methylol melamine, polyacrylamide, phenol resin, styrene / maleic acid semi-ester, poly-N-vinylacetamide and the like.
A commercially available product may be used as the water-soluble resin, and the commercially available products include the Pittscol series (K-30, K-50, K-90, etc.) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. and UVITEC manufactured by BASF. Series (VA64P, VA6535P, etc.), Japan Vam & Poval Co., Ltd. PXP-05, JL-05E, JP-03, JP-03, AMPS (2-acrylamide-2-methylpropanesulfonic acid copolymer), Examples thereof include Nanocry manufactured by Aldrich.
Among these, it is preferable to use Pittscol K-90 or PXP-05.

For water-soluble resins, the resins described in WO 2016/175220 are cited and incorporated herein by reference.

The weight average molecular weight of the water-soluble resin is appropriately selected according to the type of the water-soluble resin. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the water-soluble resin are the values converted to polyether oxide by GPC measurement. In particular, when the water-soluble resin is a resin containing a repeating unit represented by the formula (p1-1) (for example, polyvinyl alcohol (PVA)), the weight average molecular weight is 10,000 to 100,000. Is preferable. The upper limit of this numerical range is preferably 80,000 or less, and more preferably 60,000 or less. Further, the lower limit of this numerical range is preferably 13,000 or more, and more preferably 15,000 or more. When the water-soluble resin is a resin represented by the formula (p2-2) (for example, polyvinylpyrrolidone (PVP)), the weight average molecular weight is preferably 20,000 to 2,000,000. The upper limit of this numerical range is preferably 1,800,000 or less, and more preferably 1,500,000 or less. Further, the lower limit of this numerical range is preferably 30,000 or more, and more preferably 40,000 or more. When the water-soluble resin is a resin containing a repeating unit represented by the formula (P3-1) or the formula (p4-1) (for example, a water-soluble polysaccharide), the weight average molecular weight is 50,000 to 2 , 000,000 is preferable. The upper limit of this numerical range is preferably 1,500,000 or less, and more preferably 1,300,000 or less. Further, the lower limit of this numerical range is preferably 70,000 or more, and more preferably 90,000 or more.

The molecular weight dispersion of the water-soluble resin (weight average molecular weight / number average molecular weight, also simply referred to as “dispersity”) is preferably 1.0 to 5.0, more preferably 2.0 to 4.0.

Further, in the present invention, the protective layer is a water-soluble resin having a high molecular weight resin (for example, a water-soluble resin having a weight average molecular weight of 10,000 or more) and a weight average molecular weight smaller than the weight average molecular weight of the high molecular weight resin. It is also preferable that the weight average molecular weight of the low molecular weight resin is half or less of the weight average molecular weight of the high molecular weight resin. As a result, the low molecular weight resin is rapidly eluted in the removing liquid (particularly water), and the high molecular weight resin is easily removed starting from the portion where the low molecular weight resin is eluted. The effect of further reduction can be obtained. Further, when the protective layer is formed by using the protective layer, it is possible to suppress the occurrence of cracks in the protective layer.

In the present invention, whether or not the protective layer contains the high molecular weight resin and the low molecular weight resin has two peak tops (maximum values) when, for example, the molecular weight distribution of the protective layer or the entire water-soluble resin is measured. Judgment can be made based on whether or not the above can be confirmed.

The weight average molecular weight of the high molecular weight resin is preferably 20,000 or more, and preferably 45,000 or more. The weight average molecular weight of the high molecular weight resin is preferably 2,000,000 or less, and may be 1,500,000 or less. The molecular weight ratio of the low molecular weight resin to the high molecular weight resin (= weight average molecular weight of the low molecular weight resin / weight average molecular weight of the high molecular weight resin) is preferably 0.4 or less. The upper limit of the molecular weight ratio is more preferably 0.3 or less, and further preferably 0.2 or less. The lower limit of the molecular weight ratio is not particularly limited, but is preferably 0.001 or more, and may be 0.01 or more.

Further, in the molecular weight distribution of the entire water-soluble resin used in the present invention, there are two or more peak tops, and among the two or more peak tops, the molecular weight corresponding to one peak top is the other one. It is also preferable that the molecular weight is less than half of the molecular weight corresponding to the peak top. As a result, the same effect as when the weight average molecular weight of the low molecular weight resin is half or less of the weight average molecular weight of the high molecular weight resin can be obtained. The water-soluble resin having the above molecular weight distribution can be obtained, for example, by mixing the above high molecular weight resin and the above low molecular weight resin. When multiple peaks are confirmed in the molecular weight distribution, two sets of peak tops are selected from those peak tops, and for at least one set of peak tops, the molecular weight corresponding to one peak top is determined. It may be less than half the molecular weight corresponding to the other peak top.

The larger of the corresponding molecular weights (peak top molecular weights) of the peak tops is preferably 20,000 or more, and preferably 45,000 or more. Further, the one having the larger peak top molecular weight is preferably 2,000,000 or less, and may be 1,500,000 or less. The smaller molecular weight ratio (= smaller peak top molecular weight / larger peak top molecular weight) to the larger peak top molecular weight is preferably 0.4 or less. The upper limit of the molecular weight ratio is more preferably 0.3 or less, and further preferably 0.2 or less. The lower limit of the molecular weight ratio is not particularly limited, but is preferably 0.001 or more, and may be 0.01 or more.

The difference between the weight average molecular weight of the high molecular weight resin and the weight average molecular weight of the low molecular weight resin (the molecular weight distance between the peaks when the molecular weight distribution of the entire water-soluble resin is taken) is when PVA is included as the high molecular weight resin. It is preferably 10,000 to 80,000, more preferably 20,000 to 60,000. When PVP is contained as the high molecular weight resin, the above difference is preferably 50,000 to 1,500,000, more preferably 100,000 to 1,200,000. When the high molecular weight resin contains a water-soluble polysaccharide, the above difference is preferably 50,000 to 1,500,000, more preferably 100,000 to 1,200,000.

In particular, in the present invention, the water-soluble resin preferably contains PVA having a weight average molecular weight of 20,000 or more as the high molecular weight resin. In this case, the weight average molecular weight is more preferably 30,000 or more, and further preferably 40,000 or more. Further, in the present invention, the water-soluble resin preferably contains PVP having a weight average molecular weight of 300,000 or more as the high molecular weight resin. In this case, the weight average molecular weight is more preferably 400,000 or more, and further preferably 500,000 or more. Further, in the present invention, the water-soluble resin preferably contains a water-soluble polysaccharide having a weight average molecular weight of 300,000 or more as the high molecular weight resin. In this case, the weight average molecular weight is more preferably 400,000 or more, and further preferably 500,000 or more.

A preferable combination of the high molecular weight resin and the low molecular weight resin is as follows, for example. The water-soluble resin may satisfy only one requirement of the following combination, but may also satisfy the requirements of two or more combinations at the same time.
-A combination of PVA (high molecular weight resin) having a weight average molecular weight Mw of 30,000 to 100,000 and PVA (low molecular weight resin) having a weight average molecular weight Mw of 10,000 to 40,000.
-A combination of PVP (high molecular weight resin) having an Mw of 500,000 to 1,500,000 and PVP (low molecular weight resin) having an Mw of 30,000 to 600,000.
-A combination of a water-soluble polysaccharide (high molecular weight resin) having an Mw of 500,000 to 1,500,000 and a water-soluble polysaccharide (low molecular weight resin) having an Mw of 50,000 to 600,000.
-A combination of PVP (high molecular weight resin) having an Mw of 500,000 to 1,500,000 and PVA (low molecular weight resin) having an Mw of 10,000 to 100,000.
-A combination of a water-soluble polysaccharide (high molecular weight resin) having an Mw of 500,000 to 1,500,000 and a PVA (low molecular weight resin) having an Mw of 10,000 to 100,000.
-A combination of a PVP (high molecular weight resin) having an Mw of 500,000 to 1,500,000 and a water-soluble polysaccharide (low molecular weight resin) having an Mw of 50,000 to 600,000.
-A combination of a water-soluble polysaccharide (high molecular weight resin) having an Mw of 500,000 to 1,500,000 and a PVP (low molecular weight resin) having an Mw of 30,000 to 600,000.

The content of the high molecular weight resin is preferably 50% by mass or less with respect to the total water-soluble resin. The upper limit of this numerical range is more preferably 40% by mass or less, and further preferably 30% by mass or less. Further, the lower limit of this numerical value range is more preferably 5% by mass or more, and further preferably 10% by mass or more.

On the other hand, the water-soluble resin may be in an embodiment that does not substantially contain the low molecular weight resin. In the present invention, "substantially free of low molecular weight resin" means that the content of the low molecular weight resin is 3% by mass or less with respect to the total water-soluble resin. In this embodiment, the content of the low molecular weight resin is preferably 1% by mass or less based on the total water-soluble resin.

-Other polymer compounds-
The protective layer may contain other polymeric compounds. Examples of other polymer compounds include resins containing fluorine atoms and polymer compounds containing fluorine atoms.

式（Ｆ−１）又は式（Ｆ−２）中、Ｘは−Ｏ−又は−Ｃ（Ｒ^２）_２−を表し、Ｒ^１はそれぞれ独立に、水素原子又はフッ素原子を表し、Ｒ^２はそれぞれ独立に、水素原子、フッ素原子、又は、少なくとも１つのフッ素原子で置換された炭素数１〜５のアルキル基を表し、Ｒ^１およびＲ^２の少なくとも１つはフッ素原子を含み、２つのＲ^２は互いに結合して、環構造を形成していてもよい。 -Resin containing fluorine atoms-
The resin containing a fluorine atom is not particularly limited, and may be a linear fluorocarbon resin such as polytetrafluoroethylene, but a fluorine-based resin having a cyclic structure is preferable.
Examples of the fluororesin having a cyclic structure include resins having a repeating unit represented by the following formula (F-1) or formula (F-2).

In formula (F-1) or formula (F-2), X represents -O- or -C (R ² ) _2- , R ¹ independently represents a hydrogen atom or a fluorine atom, and R ^{2 represents a hydrogen atom or a fluorine atom.} Each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms substituted with at least one fluorine atom, and at least one of R ¹ and R ² contains a fluorine atom and two Rs. ² may be bonded to each other to form a ring structure.

Wherein (F-1), X is -C ^(R ₂₎ 2 - is preferably.
In formula (F-2), X is preferably −O−.
In the formula (F-1) or the formula (F-2), R ¹ is preferably a fluorine atom. R ² is a fluorine atom, or at least one fluorine is preferably alkyl group having 1 to 5 carbon atoms replaced by an atom, at least one fluorine atom alkyl having 1 to 5 carbon atoms substituted with It is more preferably a group, more preferably a methyl group or an ethyl group substituted with at least one fluorine atom, further preferably a perfluoromethyl group or an ethyl group substituted with at least three fluorine atoms. It is preferably a perfluoromethyl group, even more preferably.

Wherein (F-1) or Formula (F-2), 2 two ^{R 2} is it is preferable not to form a ring structure.
In the resin having a repeating unit represented by the formula (F-1) or the formula (F-2), the repeating unit represented by the formula (F-1) or the formula (F-2) contains a fluorine atom. Alternatively, it may contain a repeating unit other than the repeating unit represented by the formula (F-1) or the formula (F-2), and the other repeating unit may contain a fluorine atom. It is preferable that the repeating unit represented by F-1) or the formula (F-2) contains a fluorine atom.
As the other repeating unit, an alkylene group optionally substituted with at least one fluorine atom is preferable, and an alkylene group substituted with at least one fluorine atom is more preferable. Examples of the alkylene group include an alkylene group having 1 to 3 carbon atoms, and an ethylene group is preferable. The other repeating unit in the resin is particularly preferably a perfluoroethylene group.
The molar ratio of the repeating unit represented by the formula (F-1) or the formula (F-2) to the other repeating unit is preferably 50 to 95:50 to 5, and is preferably 55 to 90:45 to 10. Is more preferable.
Specific examples of the resin having a repeating unit represented by the formula (F-1) or the formula (F-2) include CYTOP CTL-809A manufactured by AGC, CYTOP CTX-809A, Teflon manufactured by Mitsui DuPont Fluorochemical Co., Ltd. (Registered trademark), AF-1600 and the like are exemplified.

The ratio of fluorine atoms in the resin containing fluorine atoms is preferably 1 to 80%, more preferably 20 to 70%. The ratio of fluorine atoms in the resin containing fluorine atoms is represented by (the number of fluorine atoms constituting the resin containing fluorine atoms / the number of all atoms constituting the resin containing fluorine atoms) × 100 (%).
The resin containing a fluorine atom is preferably a resin composed of only a fluorine atom, a carbon atom, an oxygen atom and a hydrogen atom.
The weight average molecular weight of the resin containing a fluorine atom in the present invention is preferably 2,000 to 200,000, more preferably 3,000 to 100,000. The dispersity (weight average molecular weight / number average molecular weight) of the resin containing a fluorine atom used in the present invention is preferably 1.0 to 5.0, more preferably 2.0 to 4.0.

-Polymer compound containing fluorine atom-
Examples of the polymer compound containing a fluorine atom include fluorinated calixarene protected by an acid unstable group.
In the present invention, the fluorinated calixarene is an oligomer in which a plurality of aromatic ring structures having a phenolic hydroxy group are bonded via a methylene group to form a cyclic structure and having a fluorine atom.
As the aromatic ring structure having a phenolic hydroxy group, an aromatic ring structure having a phenolic hydroxy group and having 6 to 20 carbon atoms is preferable, and a benzene ring structure having a phenolic hydroxy group is more preferable.
Examples of the aromatic ring structure having a phenolic hydroxy group include a phenol structure, a cresol structure, a catechol structure, a resorcinol structure, and the like, and a resorcinol structure is preferable.
The number of aromatic ring structures having a phenolic hydroxy group bonded via the methylene group is preferably 4 to 16, and more preferably 4 to 8.
Further, the fluorinated calixarene protected by an acid unstable group preferably has a structure in which the phenolic hydroxy group is protected by an acid unstable group.
As the acid-labile group, a known protecting group desorbed by an acid can be used without particular limitation, but a t-butoxycarbonyl group is preferable.
The methylene group may have a substituent. Examples of the substituent include a group containing an alkyl fluoride group, and a group in which an alkyl fluoride group and a linking group are bonded is more preferable.
Examples of the linking group include an alkylene group, an arylene group, -O-, -C (= O)-, or a group in which two or more of these are bonded.
As the alkyl fluoride group, an alkyl fluoride group having 1 to 20 carbon atoms is preferable, and an alkyl fluoride group having 4 to 10 carbon atoms is more preferable.
Further, the above-mentioned alkyl fluoride group may be an alkyl group in which a part of the hydrogen atom of the alkyl group is substituted with a fluorine atom, but an alkyl group in which all the hydrogen atoms of the alkyl group are substituted with a fluorine atom. More preferably.
The alkyl fluoride group may be linear or branched chain, may be cyclic, or may contain a cyclic structure, but must be linear or branched. Is preferable, and linearity is more preferable.

The proportion of fluorine atoms in the polymer compound containing fluorine atoms is preferably 1 to 80%, more preferably 20 to 70%. The ratio of fluorine atoms in the polymer compound containing fluorine atoms is (the number of fluorine atoms constituting the polymer compound containing fluorine atoms / the number of all atoms constituting the polymer compound containing fluorine atoms) × 100 (%). Indicated by.
The polymer compound containing a fluorine atom is preferably a polymer compound composed of only a fluorine atom, a carbon atom, an oxygen atom and a hydrogen atom.

The molecular weight of the polymer compound containing a fluorine atom is preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 3,000 or more.
The upper limit of the molecular weight is not particularly limited, and can be, for example, 100,000 or less.

Specific examples of the polymer compound containing a fluorine atom include the compound R-1 used in the examples.

-Content-
The content of the polymer compound in the protective layer may be appropriately adjusted as necessary, but is preferably 20% by mass or more, more preferably 50% by mass or more, based on the total mass of the protective layer. , 70% by mass or more is more preferable. The upper limit of the content is preferably 100% by mass or less, more preferably 99% by mass or less, and further preferably 98% by mass or less.
The protective layer may contain only one type of polymer compound, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.

[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、置換基としては上述の置換基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 above-mentioned substituent T.

-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, and 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 above-mentioned 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 linking group L below 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 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.

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 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 further 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 Fineke Chemical Co., Ltd.), among which Surfinol 104 series, acetylenol E00, E40 and E13T are preferable, and acetylenol 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.
As the other surfactant, any surfactant such as nonionic type, anion type, amphoteric fluorine type, etc. may be used 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 sulfate, 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 at least one of a surfactant containing an acetylene group and at least one of the other surfactants, the total amount of the surfactant containing the acetylene group and the other surfactant is the total amount of the surfactant added. It is preferably 0.05 to 20% by mass, more preferably 0.07 to 15% by mass, and further preferably 0.1 to 10% by mass with respect to the total mass of the protective 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 surface tension of the 0.1% by mass aqueous solution of another surfactant at 23 ° C. is preferably 45 mN / m or less, more preferably 40 mN / m or less, and more preferably 35 mN / m or less. More preferred. 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 other surfactant to be selected.

[Preservatives, fungicides (preservatives, etc.)]
It is also a preferred embodiment that the protective layer contains an antiseptic or antifungal agent.
The preservative and antifungal agent (hereinafter, preservative and the like) preferably contain at least one additive having an antibacterial or antifungal action and 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.

Examples of the natural antibacterial agent or antifungal agent include chitosan, which is a basic polysaccharide obtained by hydrolyzing chitin contained in the crustacean of crab or 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 may contain 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.

[Composition for forming a protective layer]
The composition for forming a protective layer of the present invention is a composition containing a polymer compound and a solvent 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 a protective layer forming composition on 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 (immersion) 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 contains components contained in the above-mentioned protective layer (for example, a water-soluble resin, a surfactant containing an acetylene group, another surfactant, a preservative, a light-shielding agent, etc.), and a solvent. Is preferable.
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.
Further, when the polymer compound contained in the composition for forming a protective layer is the above-mentioned resin containing a fluorine atom or the above-mentioned polymer compound containing a fluorine atom, a fluorine-based solvent can also be used as the solvent.
The fluorine-based solvent is an organic solvent containing a fluorine atom.
The fluorine atom content in the fluorine-based solvent used in the present invention is preferably 10 to 80%, more preferably 15 to 75%, and even more preferably 20 to 70%. The fluorine atom content here is represented by (the number of fluorine atoms constituting the fluorine-based solvent / the number of all atoms constituting the fluorine solvent) × 100 (%).
The boiling point of the fluorine-based solvent used in the present invention is 101325 Pa, preferably 40 to 250 ° C., more preferably 50 to 200 ° C., and even more preferably 55 to 180 ° C.

The fluorine-based solvent is preferably an alcohol, and more preferably an alcohol composed of an alkyl group and an OH group substituted with at least one fluorine atom. By using alcohol, a resin having polarity and not containing a fluorine atom such as resin A1 can be easily dissolved. The number of carbon atoms of the alkyl group substituted with at least one fluorine atom is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 10. The number of fluorine atoms in the alkyl group substituted with at least one fluorine atom is preferably 1 to 30, more preferably 3 to 20, and even more preferably 4 to 12.
Specific examples of the fluorine-based solvent include 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3,4,5,5-octafluoro-1-pentanol, 2, 2,3,3,3-pentafluoro-1-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,4,5,4-heptafluoro- Examples thereof include 1-butanol, 1H, 1H, 7H-dodecafluoro-1-heptanol, nonafluorobutyl ethyl ether, perfluorotributylamine and the like.

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.} , Sp value (solubility parameter) ^{is preferably less than 19.0 (MPa) 1/2, and} less than 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 whose dissolution rate in a developing solution changes due to the action of an acid (hereinafter, also referred to as "specific resin for a photosensitive layer").
The change in the dissolution rate of the specific resin for the photosensitive layer is preferably a decrease in the dissolution rate.
The dissolution rate of the specific resin for the photosensitive layer 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 for the photosensitive layer 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 for the photosensitive layer is also soluble in an organic solvent having an sp value (solubility parameter) of 18.0 (MPa) ^1/2 or less and the dissolution rate changes before the dissolution rate changes. After that, it is preferable that the resin is sparingly soluble in an organic solvent having an sp value of 18.0 (MPa) ^{1/2 or less.}
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 at 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 for a photosensitive layer 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 for the photosensitive layer and the photoacid generator will be described.

[Specific resin for photosensitive layer]
The photosensitive layer in the present invention preferably contains a specific resin for the photosensitive layer.
The specific resin for the photosensitive layer 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 a repeating unit derived from (meth) acrylic acid or an ester thereof in an amount of 50 mol% or more, more preferably 80 mol% or more, 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 for the photosensitive layer, a resin having a repeating unit having a structure in which an acid group is protected by an acid-degradable group is preferably mentioned.
Examples of the structure in which the acid group is protected by the acid-degradable group include a structure in which the carboxy group is protected by the acid-degradable group, a structure in which the phenolic hydroxy group is protected by the 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-A) or a repeating unit represented by the following formula (1-B) 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, 2-6 is more preferable, 2-3 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 equation (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 the repeating unit (1) or the repeating unit (2)) having a structure in which the acid group is protected by the acid-degradable group contained in the specific resin for the photosensitive layer is 5 to 80 mol. % Is preferred, 10 to 70 mol% is more preferred, and 10 to 60 mol% is even more preferred. 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 for the photosensitive layer 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 for the photosensitive layer preferably contains a repeating unit (repeating unit (3)) containing a crosslinkable group, but preferably has a configuration 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 the repeating units of the specific resin for the photosensitive layer.

The specific resin for the photosensitive layer 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 JP-A-2004-264623. 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 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 repeating unit (4) may be used alone or in combination of two or more. Among all the monomer units constituting the specific resin for the photosensitive layer, the content of the monomer unit forming the repeating unit (4) when the repeating unit (4) is contained is preferably 1 to 60 mol%, preferably 5 to 50 mol%. % Is more preferred, and 5-40 mol% is even more preferred. When two or more types are used, the total amount is preferably in the above range.

Various methods are known for synthesizing the specific resin for the photosensitive layer. For example, a radically polymerizable unit used to form at least a repeating unit (1), a repeating unit (2), or the like. It can be synthesized by polymerizing a radically polymerizable monomer mixture containing a body in an organic solvent using a radical polymerization initiator.
As a specific resin for the photosensitive layer, 2,3-dihydrofuran is added to an acid anhydride group in a precursor copolymer copolymerized with unsaturated polyvalent carboxylic acid anhydrides at room temperature in the absence of an acid catalyst. A copolymer obtained by addition at a temperature of (25 ° C.) to about 100 ° C. is also preferable.
The following resins are also mentioned as preferable examples of the specific resin for the photosensitive layer.
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 for the photosensitive layer 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 for the photosensitive layer is preferably 20 to 99% by mass, preferably 40 to 99% by mass, based on the total mass of the photosensitive layer. Is more preferable, and 70 to 99% by mass is further preferable. The specific resin for the photosensitive layer 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 for the photosensitive layer is preferably 10% by mass or more, more preferably 50% by mass or more, and 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 for the photosensitive layer 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 for the photosensitive layer is preferably 10% by mass or less, preferably 5% by mass or less, based on the total mass of the specific resin for the photosensitive layer. Is more preferable.
The molecular weight dispersion (weight average molecular weight / number average molecular weight) of the specific resin for the photosensitive layer is preferably 1.0 to 4.0, more preferably 1.1 to 2.5.

[Photoacid generator]
The photosensitive layer preferably further 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.
A photosensitive layer is formed on a silicon wafer substrate using the composition for forming a photosensitive layer, 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。 -Oxime sulfonate compound-
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. ^{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, or 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 condensed 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 JP2011-209692 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-methylmorpholin, 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 with respect to 100 parts by mass of the specific resin for the photosensitive layer, and 0.002 to 0. More preferably, it is 5 parts by mass.
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 alkyl phenyl 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-07-230165, JP-A-08-062834, JP-A09-054432, JP-A09-005988, 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、感光層用特定樹脂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. Represents an alkyl group of 4 or more, L ⁴ represents an alkylene group having 3 or more and 6 or less carbon atoms, p4 and q4 are mass percentages representing a polymerization ratio, and p4 is a numerical value of 10% by mass or more and 80% by mass or less. 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, preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the specific resin for the photosensitive layer. Is more preferable, and 0.01 to 1 part by mass is further 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]
The photosensitive layer further contains, if necessary, 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.

〔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 value 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 acetate, ethyl formate, butyl acetate, propyl acetate, 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 "substantially free of water" 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 photosensitive layer or in the developing cup is suppressed, and the temperature uniformity in the surface of the photosensitive layer is improved, resulting in photosensitivity after development. Dimensional uniformity of the layer is improved.
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 formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Amyl solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic solvent 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 above can be taken into consideration.

The composition for forming a photosensitive layer includes the above-mentioned components contained in the photosensitive layer (for example, a specific resin for a photosensitive layer, a photoacid generator, a basic compound, a surfactant, and other components), a solvent, and the like. Is preferably included. 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 butylate, 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 for the photosensitive layer. It is more preferably 10 parts by mass, and further preferably 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.

<Manufacturing method of laminated body and patterning method of organic layer>
The following steps (1) to (6) are a series of work steps related to patterning of the organic layer. The method for producing the laminate includes at least the following step (1). The method for patterning the organic layer includes at least the following step (5).
(1) A step of forming a protective layer on an organic layer on a substrate.
(2) A step of forming a photosensitive layer on the protective layer.
(3) A 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) A step of removing the protective layer using a stripping solution.

[(1) Step of forming a protective layer on the organic layer]
The method for patterning an 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 in between 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 method of applying the protective layer forming composition in the above-mentioned laminate.

[(2) Step of forming a photosensitive layer on 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 method of applying the composition for forming a photosensitive layer in the above-mentioned laminate.

[(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-ray (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used, and i-ray is more preferable.

When a laser generator is used as a light source, an active light having a wavelength of 343 nm and 355 nm is preferably used for a solid-state (YAG) laser, and 193 nm (ArF line), 248 nm (KrF line), and 351 nm (KrF line) for an 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]
In the step (3), after exposing the photosensitive layer through a photomask, 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, defects in the pattern derived from the resist residue after development can be significantly reduced.

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 the 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 organic layer to be formed 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 (nitrogen gas (O 2) 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 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 greater than 0% and 50% or less. Is preferable, and 10 to 20% is more preferable. 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 it is preferably 30% or less of the total etching treatment time in the etching process in terms of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched (organic layer), and 5 to 5 It is more preferably 25%, and particularly preferably 10 to 15%.

[(6) Step of removing the protective layer using a stripping solution]
After etching, the protective layer is removed using a stripping solution (eg, water). The details of the stripping solution are as described in the above description of the protective layer.

Examples of the method of removing the protective layer with a stripping solution include a method of spraying the stripping solution onto the resist pattern from a spray-type or shower-type injection nozzle to remove the protective layer. 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 to inject the release liquid during the process of removing the protective layer. 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.

(kit)
The kit of the present invention is a composition for forming a protective layer for forming a protective layer contained in the laminate of the present invention, and a composition for forming a photosensitive layer for forming a photosensitive layer contained in the laminate of the present invention. It is a kit used for forming the laminated body of the present invention including.
Examples of the protective layer forming composition and the photosensitive layer forming composition included in the kit of the present invention include the protective layer forming composition and the photosensitive layer forming composition shown in the above description of the laminate.
In addition, the laminate forming kit of the present invention may further contain the above-mentioned organic layer forming composition.

(Semiconductor device)
The semiconductor device of the present invention includes an organic layer patterned by utilizing the laminate of the present invention.
As a method of using the laminate in the semiconductor device of the present invention, a method of using the laminate including the above-mentioned steps (3) to (6) is preferable. Moreover, the utilization method including the above-mentioned steps (1) to (6) may be used.
That is, in the semiconductor device of the present invention, the protective layer may be removed and may not remain.
Here, the semiconductor 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. 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, an organic electroluminescent transistor, an organic electroluminescent element, and an organic electroluminescent element are preferable, an organic field effect transistor and an organic photoelectric conversion element are more preferable, and an organic electroluminescent transistor is particularly preferable.
Further, the laminate of the present invention is preferably used for manufacturing the above-mentioned semiconductor device.

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 examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the examples, unless otherwise specified, "parts" and "%" are based on mass, and the environmental temperature (room temperature) of each step is 23 ° C.
The weight average molecular weight (Mw) of the resin in the resin composition for forming a photosensitive layer was calculated as a polystyrene-equivalent value measured by GPC. HLC-8220 (manufactured by Tosoh Corporation) was used, and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) was used as a column.

<Preparation of composition for forming protective layer>
Each raw material was mixed so as to have the compounding ratio (part by mass) shown in Table 1 below.
After mixing, each of the protective layer forming compositions was stirred using a stirrer (hot magnet stirrer, C-MAG HS4, manufactured by IKA) under the following stirring conditions. After stirring is completed, a PVDF (polyvinylidene fluoride) membrane filter (Durapore, manufactured by Merck) with a pore size of 5 μm is installed in a stainless pressure filter holder (manufactured by Sartorius), and the pressure is applied at 2 MPa using this. While filtering each composition.
[Stirring conditions]
・ Atmosphere: Atmosphere ・ Stirring time: 240 minutes ・ Stirring temperature: 50 ° C
-Rotation speed of stirring member: 500 rpm (revolutions per minutes)

Details of the abbreviations listed in Table 1 are as follows.
[Polymer compound]
-R-1: A compound having a structure represented by the following formula (A-1)-R-2: CYTOP CTL-809A (manufactured by AGC Inc.)
-R-3: CYTOP CTX-809A (manufactured by AGC)
-PVA: PVA-205 manufactured by Kuraray, Mw = 24,000.
-PVP: Pittscol K-90 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Mw = 1,200,000.
-HEC: 2-Hydroxyethyl cellulose manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Mw = 720,000.

[Surfactant]
E-1: Acetylenol E00
・ E-2: EMALEX 710

〔solvent〕
-S-1: pure water-S-2: ethanol-X-3: Novec7200 (manufactured by 3M Co., Ltd.)

・塩基性化合物（化合物Ｙ（下記構造）、ＤＳＰ五協フード＆ケミカル株式会社製）：０．０８質量部

・界面活性剤（ＯＭＮＯＶＡ社製、ＰＦ−６３２０）：０．０８質量部
・ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）：６９．５質量部 <Preparation of composition for forming photosensitive layer>
In each Example and Comparative Example, the following components were mixed to prepare a composition for forming a photosensitive layer.
-Resin A-1: 30.09 parts by mass-Photoacid generator (Compound X (structure below), R ¹¹ represents a tolyl group, R ¹⁸ represents a methyl group. Daito Chemix Co., Ltd.): 0.26 parts by mass

-Basic compound (Compound Y (structure below), manufactured by DSP Gokyo Food & Chemical Co., Ltd.): 0.08 parts by mass

-Surfactant (manufactured by OMNOVA, PF-6320): 0.08 parts by mass-PGMEA (propylene glycol monomethyl ether acetate): 69.5 parts by mass

[Synthesis of resin A-1]
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 (benzyl methacrylate, 16.65 g), THFMA (tetrahydrofurfuryl methacrylate, 21.08 g), t-BuMA (t-butyl methacrylate, 5.76 g), and V-601 (0.4663 g, Fuji). A solution prepared by dissolving Film Wako Pure Chemical Industries, Ltd. in PGMEA (32.62 g) was added dropwise over 2 hours to prepare a reaction solution. Then, the reaction solution was stirred for 2 hours to terminate the reaction. 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 resin A-2]
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 (benzyl methacrylate, 16.65 g), t-BuMA (t-butyl methacrylate, 26.84 g), and V-601 (0.4663 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to PGMEA (32). A solution dissolved in .62 g) was added dropwise over 2 hours to prepare a reaction solution. Then, the reaction solution was stirred for 2 hours to terminate the reaction. 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 41,000.

<Evaluation>
[Residue evaluation]
-Formation of organic semiconductor film (organic layer)-
In each of the examples and comparative examples, an organic semiconductor coating liquid (composition for forming an organic semiconductor) having the following composition is spin-coated on a 5 cm square glass substrate and dried at 130 ° C. for 10 minutes to be organic. A semiconductor film was formed. The film thickness was 150 nm.
_{Here, the surface of the organic semiconductor film is subjected to a signal intensity I 0} of m / z = 910 using a TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) device (TOF.SIMS5 manufactured by ION-TOF). Was measured.
<< Composition of organic semiconductor coating liquid >>
・ P3HT (manufactured by Sigma-Aldrich Japan GK): 10% by mass
・ PCBM (manufactured by Sigma-Aldrich Japan GK): 10% by mass
-Chloroform (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 80% by mass

-Formation of protective layer-
In each of the Examples and Comparative Examples, the protective layer forming composition was spin-coated on the surface of the organic semiconductor film and dried at 100 ° C. for 1 minute to obtain the “film thickness (μm)” in Table 1. A protective layer having the thickness described in the column of is formed.

-Formation of photosensitive resin layer (photosensitive layer)-
In each of the Examples and Comparative Examples, the above-mentioned photosensitive layer forming composition was spin-coated on the surface of the formed protective layer, dried at 100 ° C. for 1 minute, and a photosensitive resin layer (photosensitive layer) having a thickness of 3 μm was obtained. ) Was formed to form a laminated body.

-Exposure-
In each of the Examples and Comparative Examples, a 1: 1 line-and-space pattern having a line width of 1.0 to 10.0 μm was used as a photomask on the photosensitive layer in the produced laminate using an i-line exposure machine. It was exposed by i-line through a binary mask formed in 0.5 μm width increments. The exposure amount was set so that a line width of 1 μm could be obtained in a 1: 1 line-and-space pattern with a line width of 2 μm.

-Development-
The exposed laminate was heated at 70 ° C. for 60 seconds, developed using butyl acetate (nBA) as a developer for 50 seconds, and spin-dried to obtain a resist pattern.
Further, it was developed with water for 20 seconds and spin-dried to obtain a pattern of a photosensitive layer and a protective layer.

-Etching-
Using the patterns of the photosensitive layer and the protective layer as mask patterns, the substrate was dry-etched under the following conditions to remove the organic layer in the non-mask pattern portion.
Conditions: Source power 500 W, gas: oxygen flow rate 100 ml / min, time 3 minutes Then, the obtained substrate was paddle-washed twice for 60 seconds with the stripping solution shown in Table 1 to obtain patterns for the photosensitive layer and the protective layer. After removal, spin drying was carried out at 1,500 rpm to obtain a substrate in which the organic layer was patterned.
The details of the stripping solution shown in Table 1 are as follows.

X-1: Novec7000 at 25 ° C (manufactured by 3M Co., Ltd.)
X-2: 25 ° C Novec7100 (manufactured by 3M Co., Ltd.)
-X-3: Novec7200 (manufactured by 3M Co., Ltd.)
-X-4: Pure water at 35 ° C.-X-5: Pure water at 70 ° C.-X-6: Novec7300 (manufactured by 3M Co., Ltd.)
-Pure water at X-7: 25 ° C.-10 mass% ethanol aqueous solution at X-8: 50 ° C. Rotation speed of each stripping solution using a RE-80L type rotational viscometer manufactured by Toki Sangyo Co., Ltd. The result of measurement at 100 rpm is shown in the column of "Viscosity (mPa · s)" in Table 1.
In addition, the dissolution rate of the protective layer in the stripping solution in each Example or Comparative Example measured by the following method is shown in the "Dissolution rate" column of Table 1.

<< Dissolution rate measurement method >>
The laminate produced in each Example or Comparative Example was developed with butyl acetate (nBA) as a developing solution for 50 seconds without exposure and heating, and spin-dried to remove the photosensitive layer. Obtained.
The film thickness (film thickness A) of the laminate from which the photosensitive layer was removed was measured.
The laminate from which the photosensitive layer had been removed was immersed in a stripping solution for 5 seconds and then taken out, and the film thickness (film thickness B) of the laminate was measured again.
The dissolution rate (nm / s) of the protective layer in the stripping solution was calculated by dividing the difference between the film thickness A and the film thickness B by the immersion time (5 seconds).

After the vacuum drying, the TOF-SIMS measurement was performed again on the pattern surface of the organic layer on the substrate, and the signal I derived from the organic semiconductor material was measured.
The signal intensity ratio was calculated by the following formula and evaluated according to the following evaluation criteria.
The evaluation result in the part using the binary mask in which the 1: 1 line-and-space pattern with the line width of 2.0 μm was formed as the photomask is shown in the “Residue (2 μm)” column of Table 1 in the column of “Residue (2 μm)” with the line width of 10.0 μm. The evaluation results in the portion using the binary mask in which the one-line and space pattern was formed are described in the column of "residue (10 μm)" in Table 1, respectively.
The maximum value of the protective layer pattern width and the minimum value of the width of the removed portion in the portion using the binary mask in which the 1: 1 line-and-space pattern having a line width of 2.0 μm is formed are both 2.0 μm.
The maximum value of the protective layer pattern width and the minimum value of the width of the removed portion in the portion using the binary mask in which the 1: 1 line-and-space pattern having a line width of 10.0 μm is formed are both 10.0 μm.
It can be said that the larger the signal intensity ratio is, the more the generation of residue when the protective layer is removed is suppressed.
Signal intensity ratio (%) = [I / I ₀ ] x 100
-Evaluation criteria-
A: The signal intensity ratio (%) was 75% or more.
B: The signal intensity ratio (%) was 50% or more and less than 75%.
C: The signal intensity ratio (%) was 25% or more and less than 50%.
D: The signal intensity ratio (%) was less than 25%.
-: The protective layer could not be removed by the stripping solution and could not be evaluated.

From the results shown in Table 1, it can be seen that the composition for forming a protective layer of the present invention suppresses the generation of residues when the protective layer is removed.
Even when the photosensitive layer resin in Example 10 was changed from the above-mentioned resin A-1 to resin A-2, the residue result was exactly the same as the result in Example 10.
The stripping solution used in Comparative Examples 1 to 3 has a viscosity of 1.2 mPa · s and exceeds 0.8 mPa. It can be seen that when such a stripping solution is used, the suppression of the residue when the protective layer is removed is inferior.
The stripping solution used in Comparative Examples 4 to 5 has a viscosity of 0.89 mPa · s and exceeds 0.8 mPa. It can be seen that when such a stripping solution is used, the suppression of the residue when the protective layer is removed is inferior.

A base material on which a gate electrode, a gate insulating film, a source electrode, and a drain electrode were formed was prepared by the same method as in Example 1 of International Publication No. 2018/061821.
An organic semiconductor layer, a protective layer, and a photosensitive layer were formed on the base material by the same method as shown in the residue evaluation in Examples 1 to 16 of the present invention, respectively. After that, the photosensitive layer is developed, the protective layer and the organic semiconductor layer are etched by the same method as the method shown in the residue evaluation, and the organic semiconductor layer is formed so as to be in contact with the source electrode and the drain electrode. Manufactured a transistor.
The organic field effect transistor operated normally.

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 of photosensitive layer after development 5a Removal part of laminate after etching

Claims (11)

The base material, organic layer, protective layer and photosensitive layer are included in this order.
The protective layer contains a polymer compound and contains
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, and is used for removal.
The viscosity of the stripping solution is 0.8 mPa · s or less.
A laminate in which the dissolution rate of the protective layer in the stripping solution is 100 nm / s or more. The laminate according to claim 1, wherein the protective layer has a thickness of 10 μm or less. The first or second aspect of the present invention, wherein the maximum value of the width of the pattern of the protective layer formed by the etching, which is subjected to etching for removing a part of the protective layer and the organic layer after the development, is 10 μm or more. Laminated body. 2. The laminate according to any one item. The laminate according to any one of claims 1 to 4, wherein the stripping solution contains a fluorine-based stripping solution. The laminate according to any one of claims 1 to 5, wherein the content of water with respect to the total mass of the stripping liquid is 70% by mass or more. The laminate according to any one of claims 1 to 5, wherein the content of water with respect to the total mass of the stripping liquid is 80% by mass or more. The laminate according to any one of claims 1 to 5, wherein the content of water with respect to the total mass of the stripping liquid is 90% by mass or more. Contains polymer compounds and solvents
A composition for forming a protective layer used for forming the protective layer contained in the laminate according to any one of claims 1 to 8. A composition for forming a protective layer for forming the protective layer, and
A kit used for forming a laminate according to any one of claims 1 to 8, which includes a composition for forming a photosensitive layer for forming the photosensitive layer. A semiconductor device including an organic layer patterned using the laminate according to any one of claims 1 to 8.

Images