WO2019163951A1

WO2019163951A1 - Photosensitive layer, laminate, photosensitive resin composition, and kit

Info

Publication number: WO2019163951A1
Application number: PCT/JP2019/006811
Authority: WO
Inventors: 誠也増田
Original assignee: 富士フイルム株式会社
Priority date: 2018-02-26
Filing date: 2019-02-22
Publication date: 2019-08-29
Also published as: TW201936396A; JPWO2019163951A1; KR20200110425A; CN111819494A

Abstract

Provided are a photosensitive layer, a laminate, a photosensitive resin composition, and a kit. The photosensitive layer is included in a laminate having a water-soluble resin layer and the photosensitive layer, and is formed from a photosensitive resin composition containing: a compound capable of generating an acid upon irradiation with actinic rays or radiation; and a resin of which the dissolution rate in butyl acetate varies according to the action of an acid. The resin of which the dissolution rate in butyl acetate varies according to the action of an acid has a weight average molecular weight of 10,000-50,000, and is a hydrophobic resin which is soluble in butyl acetate at 23°C and in which 50-100 mol% of units soluble in an aqueous alkali solution among the total constituent units are protected by a hydrophobic protection group. The dissolution rate of the unirradiated photosensitive layer when immersed in butyl acetate at 23°C is 20-200 nm/s. The static contact angle of the photosensitive resin composition on the water-soluble resin layer is 60° or less.

Description

Photosensitive layer, laminate, photosensitive resin composition, kit

The present invention relates to a photosensitive layer, a laminate, a photosensitive resin composition, and a kit.

In recent years, electronic devices using organic semiconductors have been widely used. A device using an organic semiconductor has an advantage that it can be manufactured by a simple process as compared with a conventional device using an inorganic semiconductor such as silicon. Furthermore, the organic semiconductor can be easily changed in material properties by changing its molecular structure. In addition, there are a wide variety of materials, and it is thought that functions and elements that could not be achieved with inorganic semiconductors can be realized. Organic semiconductors can be applied to electronic devices such as organic solar cells, organic electroluminescence displays, organic photodetectors, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifying elements, organic inverters, information recording elements, etc. There is sex.

The patterning of organic semiconductors has been performed by printing techniques so far. However, patterning by printing technology has a limit in fine processing. Another problem is that organic semiconductors are easily damaged.

Therefore, an organic semiconductor patterning method using a water-soluble resin as a protective film has been studied. For example, Patent Document 1 discloses a laminate including a specific water-soluble resin layer and a photosensitive layer in this order on an organic semiconductor layer, and the water-soluble resin layer and the photosensitive layer are in contact with each other. Thus, it is described that a fine pattern by exposure and development of the photosensitive layer can be realized and cracks in the laminate can be suppressed.

Patent Documents

2 and 3 are laminates having a water-soluble resin layer and a photosensitive layer on the surface of an organic semiconductor layer, and a specific photoacid generator and a specific resin are blended in the photosensitive resin composition. A laminate is disclosed. Thereby, it is described that a good pattern can be formed on the organic semiconductor.

International Publication WO2016 / 175220 Pamphlet Japanese Patent Laying-Open No. 2015-194673 Japanese Patent Laying-Open No. 2015-087609

By the above-described technique, the water-soluble resin layer is interposed between the organic semiconductor layer and the photosensitive layer, thereby ensuring the protection of the organic semiconductor layer.
Here, when producing a thick photosensitive layer, it is required to use a resin having a high molecular weight for the photosensitive layer. This is to suppress the occurrence of cracks. Further, when patterning is performed a plurality of times, a thick photosensitive layer is required to suppress the influence of the step.
However, a resin having a high molecular weight has a much slower dissolution rate in a hydrophobic developer. Therefore, it is required to increase the dissolution rate from the viewpoint of production efficiency. In order to increase the dissolution rate, it is conceivable to increase the hydrophobicity of the resin of the photosensitive layer. However, if this is done, the adhesion between the photosensitive layer and the water-soluble resin layer will be reduced, causing pattern peeling and the like. SUMMARY OF THE INVENTION The present invention aims to solve such problems, and a photosensitive layer, a laminate, a photosensitive resin composition, and a kit that can form a pattern appropriately even when a resin having a high molecular weight is used for the photosensitive layer. The purpose is to provide.

In order to solve the above-mentioned problems, the present inventors have studied, improved, and tested various materials and structures. As a result, by designing the dissolution rate of the photosensitive layer and the static contact angle of the photosensitive resin composition with respect to the water-soluble resin layer in a well-balanced manner, a pattern can be appropriately formed even when a resin having a high molecular weight is used for the photosensitive layer. As a result, the present invention has been completed. That is, the present invention provides the following means.

<1> a photosensitive layer included in a laminate having a water-soluble resin layer and a photosensitive layer,
The photosensitive layer is formed from a photosensitive resin composition containing a compound that generates an acid upon irradiation with actinic rays or radiation, and a resin that changes its dissolution rate with respect to butyl acetate by the action of the acid. The resin in which the dissolution rate changes with respect to the resin has a weight average molecular weight of 10,000 to 50,000, and among all the structural units, 50 mol% to 100 mol% of the group soluble in the alkaline aqueous solution is hydrophobic. A hydrophobic resin soluble in butyl acetate at 23 ° C., protected by a protecting group,
The dissolution rate when the unirradiated photosensitive layer is immersed in butyl acetate at 23 ° C. is 20 nm / s or more and 200 nm / s or less,
The photosensitive layer whose static contact angle of the said photosensitive resin composition on the said water-soluble resin layer is 60 degrees or less.
<2> The photosensitive layer according to <1>, wherein the photosensitive layer has photosensitivity to i-ray irradiation.
<3> The photosensitive layer according to <1> or <2>, wherein the water content in the photosensitive resin composition is 0.01% by mass or more and 1% by mass or less.
<4> The photosensitive layer according to any one of <1> to <3>, wherein the change in dissolution rate is a decrease in dissolution rate.
<5> The photosensitive layer according to any one of <1> to <4>, wherein the resin contained in the photosensitive layer has a structural unit represented by the following formula (1):

In the formula, R ⁸ represents a hydrogen atom or an alkyl group, L ¹ represents a carbonyl group or a phenylene group, and R ¹ to R ⁷ each independently represents a hydrogen atom or an alkyl group.
<6> The photosensitive layer according to any one of <1> to <5>, wherein the total content of sodium ion, potassium ion and calcium ion in the photosensitive resin composition is 1 mass ppt to 1000 mass ppb. .
<7> The photosensitive layer according to any one of <1> to <6>, which is used for processing an organic semiconductor layer.
<8> A laminate having the photosensitive layer according to any one of <1> to <7> and a water-soluble resin layer.
<9> The laminate according to <8>, further comprising an organic semiconductor layer, wherein the organic semiconductor layer, the water-soluble resin layer, and the photosensitive layer are laminated in this order.
<10> The resin in which the dissolution rate in butyl acetate is changed by the action of the acid is a mixture of a resin having a high dissolution rate in butyl acetate and a resin having a low dissolution rate in butyl acetate, <8> or <8>9>.
<11> A photosensitive resin composition for forming a photosensitive layer,
The photosensitive layer is a layer that forms a laminate in combination with a water-soluble resin layer, and the dissolution rate when the unexposed photosensitive layer is immersed in butyl acetate is 20 nm / s or more and 200 nm / second or less,
The photosensitive resin composition contains a compound that generates an acid upon irradiation with actinic rays or radiation, and a resin that causes a change in the dissolution rate in butyl acetate by the action of the acid,
Resins in which the dissolution rate in butyl acetate is changed by the action of the acid have a weight average molecular weight of 10,000 to 50,000, and 50 mol% to 100 mol% of all structural units are groups soluble in an aqueous alkali solution. Is a hydrophobic resin soluble in butyl acetate and protected by a hydrophobic protecting group, and having a static contact angle of 60 ° or less on the water-soluble resin layer. object.
<12> The photosensitive resin composition according to <11>, which is used for processing an organic semiconductor layer.
<13> A kit for forming a water-soluble resin layer and a photosensitive layer in this order, comprising the photosensitive resin composition according to <11> or <12> and the water-soluble resin composition.
<14> The kit according to <13>, which is for processing an organic semiconductor layer.

According to the present invention, it is possible to provide a photosensitive layer laminate, a photosensitive resin composition, and a kit that can form an appropriate pattern even when a resin having a high molecular weight is used for the photosensitive layer.

FIG. 2 is a cross-sectional view schematically showing a process of exposure and development of a photosensitive layer according to a preferred embodiment of the present invention, in which (a) shows a state before development and (b) shows a state after development.

The description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “active light” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. In this specification, “exposure” means not only exposure by far ultraviolet rays, X-rays, EUV light typified by mercury lamps and excimer lasers, but also drawing by particle beams such as electron beams and ion beams, unless otherwise specified. Including.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In this specification, the term “process” not only means an independent process, but if the intended action of the process is achieved even if it cannot be clearly distinguished from other processes, the process Is included in this term.
In this specification, solid content concentration is the percentage of the mass of the other components excluding the solvent with respect to the total mass of the composition.
In this specification, when “upper” and “lower” are described, they may be above or below the structure. That is, other structures may be interposed and do not need to be in contact with each other. Unless otherwise specified, the photosensitive layer side is referred to as the upper side, and the substrate or organic semiconductor layer side is referred to as the lower side.

The photosensitive layer of the present invention is a photosensitive layer contained in a laminate having a water-soluble resin layer and a photosensitive layer, and this photosensitive layer is a compound that generates an acid upon irradiation with actinic rays or radiation (in this specification, A compound (sometimes referred to as an “acid generator”), and a resin (acid-reactive resin) in which the rate of dissolution in butyl acetate is changed by the action of an acid, having a weight average molecular weight of 10,000 to 50,000 And photosensitivity including a hydrophobic resin soluble in butyl acetate in which 50 mol% to 100 mol% of all structural units are protected with a hydrophobic protecting group in a group soluble in an alkaline aqueous solution When the unexposed photosensitive layer formed from the resin composition is immersed in butyl acetate at 23 ° C., the dissolution rate is 20 nm / second or more and 200 nm / second or less, and the photosensitive layer forming composition is the water-soluble resin. On the layer Definitive static contact angles being between 60 ° or less.
With such a configuration, a pattern can be appropriately formed even when a resin having a high molecular weight is used for the photosensitive layer.
That is, a resin having a high molecular weight has a significantly slow dissolution rate in a hydrophobic developer. In order to increase the dissolution rate, it is conceivable to increase the hydrophobicity of the resin. However, if this is done, the adhesiveness with the water-soluble resin layer is lowered, causing pattern peeling and the like. Here, in order to suppress pattern peeling, it can be considered that adjustment is made so as not to include bubbles that are likely to trigger pattern peeling. Therefore, by adjusting the contact angle of the photosensitive resin composition with respect to the water-soluble resin layer to a predetermined range, a pattern can be appropriately formed even when a resin having a large molecular weight is used.

The photosensitive layer of the present invention is preferably used in combination with a water-soluble resin layer and disposed in contact with both. In an embodiment of the present invention, an organic semiconductor layer 3 is disposed on a substrate 4 as in the example shown in FIG. Further, a water-soluble resin layer 2 that protects the organic semiconductor layer 3 is disposed on the surface in contact therewith. Next, the photosensitive layer 1 is disposed thereon in contact with the water-soluble resin layer. In the example shown in FIG. 1B, the improved photosensitive layer 1 is formed, and even if this is exposed and developed with a predetermined mask, no defect occurs in the removal portion 5. Thus, the photosensitive layer of the present invention exhibits a particularly high effect when it is laminated on the water-soluble resin layer.
In FIG. 1, the form provided on the organic semiconductor layer is shown as an example. However, a water-soluble resin layer and a photosensitive layer may be used in combination on the surface of another material. In the present invention, the organic semiconductor layer is preferably used for processing.
The laminate of the present invention is a laminate having the photosensitive layer of the present invention and a water-soluble resin layer, and preferably further includes an organic semiconductor layer, the organic semiconductor layer, the water-soluble resin layer, and the photosensitive layer. It is the laminated body laminated | stacked in order of the layer. These layers are preferably in contact with each other.
Hereinafter, features of each layer and materials constituting the layer will be described.

<Organic semiconductor layer>
The organic semiconductor layer is a layer containing an organic material exhibiting semiconductor characteristics. As in the case of a semiconductor made of an inorganic material, there are a p-type organic semiconductor that conducts holes as carriers and an n-type organic semiconductor that conducts electrons as carriers. The ease of carrier flow in the organic semiconductor layer is represented by carrier mobility μ. Although it depends on the application, in general, the mobility should be higher, preferably 10 ⁻⁷ cm ² / Vs or more, more preferably 10 ⁻⁶ cm ² / Vs or more, more preferably 10 ⁻⁵ cm ² / Vs. More preferably, it is Vs or higher. The mobility can be obtained by characteristics when a field effect transistor (FET) element is manufactured or by a time-of-flight measurement (TOF) method.

As described above, the organic semiconductor layer is preferably used after being formed on a substrate. That is, it is preferable to have a substrate on the surface of the organic semiconductor layer far from the water-soluble resin layer. Examples of the substrate include various materials such as silicon, quartz, ceramic, glass, polyester film such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), and polyimide film. May be selected. For example, when used for a flexible element, a flexible substrate can be used. Further, the thickness of the substrate is not particularly limited.

As a p-type semiconductor material that can be used for the organic semiconductor layer, any material of organic semiconductor materials may be used as long as it exhibits a hole (hole) transport property, but preferably a p-type π-conjugated polymer ( For example, substituted or unsubstituted polythiophene (for example, poly (3-hexylthiophene) (P3HT, Sigma Aldrich Japan GK), etc.), polyselenophene, polypyrrole, polyparaphenylene, polyparaphenylene vinylene, polythiophene vinylene, polyaniline Etc.), condensed polycyclic compounds (eg, substituted or unsubstituted anthracene, tetracene, pentacene, anthradithiophene, hexabenzocoronene, etc.), triarylamine compounds (eg, m-MTDATA (4,4 ′, 4 ″) -Tris [(3-methylph nyl) phenylamino] triphenylamine), 2-TNATA (4,4 ′, 4 ″ -Tris [2-naphthyl (phenyl) amino] triphenylamine), NPD (N, N′-Di [(1-naphthyl) -N, N′-diphenyl] -1,1′-biphenyl) -4,4′-diaminine), TPD (N, N′-Diphenyl-N, N′-di (m-tolyl) benzidine, mCP (1,3- bis (9-carbazolyl) benzene), CBP (4,4′-bis (9-carbazolyl) -2,2′-biphenyl), etc.), hetero 5-membered ring compounds (eg, substituted or unsubstituted oligothiophene, TTF) (Tetrath iafulvalene), etc.), phthalocyanine compounds (substituted or unsubstituted central metal phthalocyanines, naphthalocyanines, anthracocyanines, tetrapyrazinoporphyrazine), porphyrin compounds (substituted or unsubstituted various central metal porphyrins), carbon nanotubes, Either a carbon nanotube or graphene modified with a semiconductor polymer, more preferably a p-type π-conjugated polymer, a condensed polycyclic compound, a triarylamine compound, a hetero 5-membered ring compound, a phthalocyanine compound, or a porphyrin compound And more preferably a p-type π-conjugated polymer.

The n-type semiconductor material that can be used for the organic semiconductor layer may be any organic semiconductor material as long as it has an electron transporting property, but is preferably a fullerene compound, an electron-deficient phthalocyanine compound, or a naphthalene tetracarbonyl compound. Perylene tetracarbonyl compound, TCNQ compound (tetracyanoquinodimethane compound), n-type π-conjugated polymer, more preferably fullerene compound, electron-deficient phthalocyanine compound, naphthalene tetracarbonyl compound, perylene tetracarbonyl compound, n-type π-conjugated polymers, particularly preferably fullerene compounds and n-type π-conjugated polymers. In the present invention, the fullerene compound refers to a substituted or unsubstituted fullerene, and the fullerene is 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 fullerene and the like may be used, preferably substituted or unsubstituted C ₆₀ , C ₇₀ , C ₈₆ fullerene, and particularly preferably PCBM ([6, 6] -Phenyl-C61-butyric acid methyl ester, Sigma-Aldrich Japan GK, etc.) and analogs thereof (substitute the C ₆₀ moiety with C ₇₀ , C _86, etc., the benzene ring of the substituent being another aromatic ring or Substituted with a heterocyclic ring, and methyl ester substituted with n-butyl ester, i-butyl ester, etc.). Electron-deficient phthalocyanines are phthalocyanines of various central metals (F ₁₆ MPc, FPc-S8, etc., in which four or more electron withdrawing groups are bonded, where M is a central metal, Pc is phthalocyanine, and S8 is ( n-octylsulfonyl group)), naphthalocyanine, anthracocyanine, substituted or unsubstituted tetrapyrazinoporphyrazine and the like. Any naphthalene tetracarbonyl compound may be used, but naphthalene tetracarboxylic anhydride (NTCDA), naphthalene bisimide compound (NTCDI), and perinone pigment (Pigment Orange 43, Pigment Red 194, etc.) are preferable. Any perylene tetracarbonyl compound may be used, but perylene tetracarboxylic acid anhydride (PTCDA), perylene bisimide compound (PTCDI), and benzimidazole condensed ring (PV) are preferable. The TCNQ compound is a compound in which a substituted or unsubstituted TCNQ and a benzene ring portion of TCNQ are replaced with another aromatic ring or a heterocyclic ring. For example, TCNQ, TCAQ (tetracyanoquinodimethane), TCN3T (2, 2 ′-((2E, 2 ″ E) -3 ′, 4′-Alkyl substituted-5H, 5 ″ H- [2,2 ′: 5 ′, 2 ″ -tertiophene] -5,5 ″ -Diylidene) dimalononitrile derivative)) and the like. In addition, graphene is also included. Particularly preferred examples of the n-type organic semiconductor material are shown below.

R in the formula may be any, but is a hydrogen atom, a substituted or unsubstituted, branched or straight chain alkyl group (preferably having 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8) and a substituted or unsubstituted aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 14 carbon atoms). Me is a methyl group.

The organic material showing the characteristics of the semiconductor contained in the organic semiconductor layer may be one type or two or more types.

The above materials are usually blended in a solvent, applied in layers on a substrate, dried and formed into a film. As an application method, description of a water-soluble resin layer described later can be referred to.
Examples of the solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, and 1-methylnaphthalene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Halogenated hydrocarbon solvents such as chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene; for example, ester solvents such as ethyl acetate, butyl acetate, and amyl acetate; for example, methanol, propanol Alcohol solvents such as butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol; Ether solvents such as tetrahydrofuran, dioxane and anisole; for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, dimethylsulfoxide Examples include polar solvents such as side. These solvent may use only 1 type and may use 2 or more types.
The ratio of the organic semiconductor in the composition for forming the organic semiconductor layer (composition for forming an organic semiconductor) is preferably 0.1 to 80% by mass, more preferably 0.1 to 30% by mass. A film having a thickness can be formed.

Moreover, a resin binder may be blended in the composition for forming an organic semiconductor. In this case, the material for forming the film and the binder resin can be dissolved or dispersed in the above-mentioned appropriate solvent to form a coating solution, and the thin film can be formed by various coating methods. Resin binders include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, polypropylene, and other insulating polymers, and their co-polymers. Examples thereof include photoconductive polymers such as coalescence, polyvinyl carbazole and polysilane, and conductive polymers such as polythiophene, polypyrrole, polyaniline and polyparaphenylene vinylene. The resin binder may be used alone or in combination. In consideration of the mechanical strength of the thin film, a resin binder having a high glass transition temperature is preferable, and in consideration of charge mobility, a resin binder made of a photoconductive polymer or a conductive polymer having a structure containing no polar group is preferable.

When the resin binder is blended, the blending amount is preferably 0.1 to 30% by mass in the organic semiconductor layer. Only one type of resin binder may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
Depending on the application, a single layer or a mixed solution to which various semiconductor materials and additives are added may be applied onto a substrate or the like to form a blend film composed of a plurality of material types. For example, when a photoelectric conversion layer is manufactured, a mixed solution with another semiconductor material can be used.
In film formation, the substrate may be heated or cooled, and the film quality and packing of molecules in the film can be controlled by changing the temperature of the substrate. The temperature of the substrate is not particularly limited, but is preferably −200 ° C. to 400 ° C., more preferably −100 ° C. to 300 ° C., and further preferably 0 ° C. to 200 ° C.
The characteristics of the formed organic semiconductor layer can be adjusted by post-processing. For example, it is possible to improve the characteristics by changing the film morphology and the molecular packing in the film by exposing to a heat treatment or a vaporized solvent. Further, by exposing to an oxidizing or reducing gas, solvent, substance, or the like, or mixing them, an oxidation or reduction reaction can be caused to adjust the carrier density in the film.
The thickness of the organic semiconductor layer is not particularly limited and varies depending on the type of electronic device used, but is preferably 5 nm to 50 μm, more preferably 10 nm to 5 μm, and still more preferably 20 nm to 500 nm.

<Water-soluble resin layer (water-soluble resin composition)>
The water-soluble resin layer preferably contains a water-soluble resin and is formed from a water-soluble resin composition. The water-soluble resin refers to a resin in which the amount of the resin that can be dissolved in 100 g of water at 20 ° C. is 1 g or more, preferably a resin that is 5 g or more, more preferably 10 g or more, and 30 g or more. More preferably. There is no upper limit, but it is practical to be 20 g.

Specific examples of the water-soluble resin include polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), water-soluble polysaccharides (water-soluble cellulose (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, etc. ), Pullulan or a pullulan derivative, starch, hydroxypropyl starch, carboxymethyl starch, chitosan, cyclodextrin), polyethylene oxide, polyethyloxazoline and the like. PVP and PVA are preferable, and PVA is more preferable. Of these, two or more different main chain structures may be selected and used, or may be used as a copolymer.

The weight average molecular weight of the water-soluble resin is not particularly limited, but the weight average molecular weight of the polyvinylpyrrolidone used in the present invention is preferably 50,000 to 400,000. The weight average molecular weight of the polyvinyl alcohol used in the present invention is preferably 15000 to 100,000. For other resins, it is preferably in the range of 10,000 to 300,000.
Further, the dispersity (weight average molecular weight / number average molecular weight) of the water-soluble resin (PVP, PVA) used in the present invention is preferably 1.0 to 5.0, more preferably 2.0 to 4.0.

The content of the water-soluble resin in the water-soluble resin composition may be appropriately adjusted as necessary, but is preferably 30% by mass or less, more preferably 25% by mass or less, and 20% by mass or less. More preferably it is. As a minimum, it is preferred that it is 1 mass% or more, it is more preferred that it is 2 mass% or more, and it is still more preferred that it is 4 mass% or more.

The thickness of the water-soluble resin layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1.0 μm or more, and further preferably 2.0 μm or more. As an upper limit of the thickness of a water-soluble resin layer, 10 micrometers or less are preferable, 5.0 micrometers or less are more preferable, and 3.0 micrometers or less are further more preferable.
The water-soluble resin layer can be formed, for example, by applying a water-soluble resin composition containing one or more of the above water-soluble resins on the organic semiconductor layer and drying it. Usually, the water-soluble resin composition contains water as a solvent and may further contain other additives.
The solid content concentration of the water-soluble resin composition is preferably 0.5 to 30% by mass, more preferably 1.0 to 20% by mass, and further preferably 2.0 to 14% by mass. preferable. It can apply | coat more uniformly by making solid content concentration into the said range.

Application is preferred as the application method. Examples of application methods include slit coating, casting, blade coating, wire bar coating, spray coating, dipping (dip) coating, bead coating, air knife coating, curtain coating, ink jet, Examples thereof include a spin coating method and a Langmuir-Blodgett (LB) method. It is more preferable to use a casting method, a spin coating method, and an ink jet method. Such a process makes it possible to produce a water-soluble resin layer having a smooth surface and a large area at a low cost.

The water-soluble resin composition preferably further contains a surfactant for improving coatability.
As the surfactant, any surfactant such as nonionic, anionic, and amphoteric fluorine may be used as long as it reduces the surface tension. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and other polyoxyethylene alkyl ethers. Oxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, etc. Sorbitan alkyl esters, monoglyceride alkyl esters such as glycerol monostearate and glycerol monooleate Nonionic surfactants such as oligomers containing fluorine or silicon, acetylene glycol, ethylene oxide adducts of acetylene glycol, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, sodium butyl naphthalene sulfonate, pentyl naphthalene sulfonic acid Alkyl naphthalene sulfonates such as sodium, sodium hexyl naphthalene sulfonate, sodium octyl naphthalene sulfonate, alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium dodecyl sulfonate, sulfosuccinic acid such as sodium dilauryl sulfosuccinate Anionic surfactants such as ester salts; alkylbetaines such as lauryl betaine and stearyl betaine, amino Classes such as the amphoteric surfactant can be used.

When the water-soluble resin composition contains a surfactant, the addition amount of the surfactant is preferably 0.001 to 20% by mass, more preferably 0.001 to 5% by mass, and still more preferably 0% in the solid content. .01 to 1% by mass. These surfactants may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.

<Photosensitive layer (photosensitive resin composition)>
The photosensitive layer is formed from a photosensitive layer forming composition containing an acid generator and a resin. The weight average molecular weight of the acid-reactive resin in the photosensitive layer is 10,000 or more, preferably 15,000 or more, and more preferably 20,000 or more. As an upper limit, it is 50,000 or less, and it is preferable that it is 45,000 or less. The present invention is highly valuable in that a pattern can be appropriately formed even when such a resin having a large molecular weight is used.
Further, the amount of the component having a weight average molecular weight of 1,000 or less contained in the acid-reactive resin is preferably 10% by mass or less, more preferably 5% by mass or less of the total acid-reactive resin component. By adopting such a configuration, it is possible to reduce fluctuations in sensitivity between resin production lots.
The dispersity (weight average molecular weight / number average molecular weight) of the acid-reactive resin is preferably 1.0 to 4.0, more preferably 1.1 to 2.5.
In the present invention, the value measured by the method shown in the Examples is adopted as the weight molecular weight.

The photosensitive resin composition forming the photosensitive layer may contain a solvent. An embodiment in which the amount of the solvent contained in the photosensitive resin composition is 1 to 10% by mass is exemplified. The photosensitive layer is preferably a chemically amplified photosensitive layer. When the photosensitive layer is of a chemical amplification type, high storage stability and fine pattern formation can be achieved.

The content of the acid reactive resin in the photosensitive layer is preferably 20 to 99.9% by mass, more preferably 40 to 99% by mass, and further preferably 70 to 99% by mass. 1 type, or 2 or more types of acid reactive resin may be contained. When using 2 or more types, it is preferable that a total amount becomes the said range.
In the present invention, the acid-reactive resin may be a mixture of a resin having a high dissolution rate in butyl acetate and a resin having a low dissolution rate in butyl acetate. For example, a mixture of an acid-reactive resin having a dissolution rate of less than 20 nm / s and a resin having a dissolution rate of more than 200 nm / s is exemplified. The dissolution rate in this case refers to the dissolution rate measured by the method described in the example described later in Example 1, which will be described later, and the composition in which the acid reactive resin is replaced with the acid reactive resin.
The photosensitive layer is preferably hardly soluble in a developing solution containing an organic solvent in the exposed portion. Slightly soluble means that the exposed portion is hardly soluble in the developer, and specifically, 50 mJ / cm in at least one of a wavelength of 365 nm (i-line), a wavelength of 248 nm (KrF line), and a wavelength of 193 nm (ArF line). It is preferable that the polarity changes due to exposure at an irradiation dose of ² or more, and the sp value (solubility parameter value) is hardly soluble in a solvent of less than 19 (MPa) ^1/2 , and 18.5 (MPa) It is more preferable that it is hardly soluble in a solvent of ^1/2 or less, and it is more preferable that it is hardly soluble in a solvent of 18.0 (MPa) ^1/2 or less. Furthermore, the polarity changes as described above by exposing at a dose of 50 to 250 mJ / cm ² at at least one of a wavelength of 365 nm (i-line), a wavelength of 248 nm (KrF line) and a wavelength of 193 nm (ArF line). Is more preferable.

The photosensitive layer may be a negative photosensitive layer or a positive photosensitive layer, but a negative photosensitive layer is preferable because it enables formation of finer trenches and hole patterns. .
From the viewpoint of improving resolution, the thickness of the photosensitive layer is preferably 0.5 μm or more, may exceed 1.0 μm, may be 1.5 μm or more, or may be 1.8 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, and may be 3.0 μm or less.
Furthermore, the total thickness of the photosensitive layer and the water-soluble resin layer is preferably 2.0 μm or more. The upper limit is preferably 20.0 μm or less, more preferably 10.0 μm or less, and even more preferably 5.0 μm or less.

The photosensitive layer preferably has photosensitivity to i-ray irradiation. The photosensitivity is a property that a material is altered by irradiation with at least one of actinic rays and radiation (if it has photosensitivity to i-ray irradiation), the material is altered in the present invention. Is accompanied by a change in dissolution rate in butyl acetate.
The over development coefficient of the photosensitive layer is preferably from 1.0 to 4.0, more preferably from 1.1 to 1.9. By setting it as such a range, the effect of suppressing pattern footing and undercutting can be exhibited effectively. The over-development coefficient is measured and calculated according to the description in the examples described later.

The photosensitive resin composition is preferably a chemically amplified photosensitive resin composition containing at least an acid reactive resin and a photoacid generator.

<< Dissolution rate >>
In the present invention, the dissolution rate when the unirradiated photosensitive layer is immersed in butyl acetate at 23 ° C. is defined as 20 nm / second or more and 200 nm / second or less. The dissolution rate is preferably 180 nm / second or less, more preferably 150 nm / second or less, and further preferably 120 nm / second or less. The lower limit is preferably 25 nm / second or more, more preferably 40 nm / second or more, and further preferably 70 nm / second or more. By setting the dissolution rate within the above range, in combination with the definition of the static contact angle of the photosensitive resin composition described below, the occurrence of undercut of the photosensitive layer is suppressed or prevented, and the pattern collapse resulting therefrom. In addition to this, peeling of the photosensitive layer can be effectively suppressed as well. In this specification, the method for measuring the dissolution rate of the photosensitive layer is based on the method employed in the examples described later.

<< Acid reactive resin >>
The acid-reactive resin is a resin component constituting the photosensitive resin composition, and the dissolution rate in butyl acetate is changed by the action of an acid from a compound that generates an acid upon irradiation with at least one of actinic rays and radiation. The acid-reactive resin used in the present invention is a hydrophobic resin soluble in butyl acetate at 23 ° C.

The acid-reactive resin is a resin component constituting the photosensitive resin composition, and is usually a resin containing a structural unit containing a group dissociated by an acid, and may contain another structural unit.
The acid-reactive resin is soluble in an organic solvent having an sp value (solubility parameter value) of 18.0 (MPa) ^1/2 or less, and has a tetrahydrofuranyl group in a structural unit represented by the following formula (1). A resin that is hardly soluble in an organic solvent having an sp value of 18.0 (MPa) ^1/2 or less when decomposed or dissociated is preferable.
Here, “sp value (solubility parameter value) is 18.0 (MPa) soluble in an organic solvent of ^1/2” or less means that a solution of a compound (resin) is applied on a substrate, and then at 100 ° C. for 1 minute. The dissolution rate of the coating film (thickness 1 μm) of the compound (resin) formed by heating with respect to butyl acetate at 23 ° C. is 20 nm / second or more, and the “sp value is 18.0 (MPa ) “Slightly soluble in ^1/2 or less organic solvent” means that a compound (resin) coating film (thickness) is formed by applying a compound (resin) solution on a substrate and heating at 100 ° C. for 1 minute. 1 μm) at 23 ° C. is less than 0.1 nm / second.

In the present invention, the acid-reactive resin preferably has a dissolution rate that changes due to the action of an acid, and this change is more preferably a decrease in the dissolution rate. The rate of dissolution in an organic solvent (typically butyl acetate) whose sp value of the acid-reactive resin before irradiation with actinic rays or the like is 18.0 (MPa) ^1/2 or less is 40 nm / second or more. Is more preferable. Further, when the acid-decomposable group of the acid-reactive resin is decomposed by irradiation with actinic rays or the like, it is dissolved in an organic solvent (typically butyl acetate) whose sp value is 18.0 (MPa) ^1/2 or less. More preferably, the speed is less than 0.05 nm / second.

The dissolution rate of the photosensitive layer or acid-reactive resin may be changed by a conventional method. For example, the molecular weight of the polymer constituting the acid-reactive resin, the selection of the molecular structure, the selection of the type of the acid protecting group, Depending on the amount of acid and protecting group introduced in the molecule, selection of the type of acid generator, ratio of the amount of acid-reactive resin and acid generator, SP value of the resin, adjustment of the ratio of low-molecular compounds in the solids, etc. The dissolution rate can be adjusted. Specifically, in order to increase the dissolution rate, means such as decreasing the molecular weight of the resin, bringing the SP value of the resin closer to that of butyl acetate, and increasing the low molecular ratio in the solid content are exemplified. On the other hand, to lower it, there are exemplified means such as increasing the molecular weight of the resin, keeping the SP value of the resin away from that of butyl acetate, and reducing the low molecular ratio in the solid content. Further, a resin having a dissolution rate of less than 20 nm / s and a resin having a dissolution rate of more than 200 nm / s may be blended.

<< Protecting group >>
In the present invention, in the acid-reactive resin, 50 mol% to 100 mol% of all the structural units are protected with a hydrophobic protecting group in a group soluble in an alkaline aqueous solution. Here, the group soluble in the alkaline aqueous solution is preferably a structural unit having an acid group. Examples of the acid group include hydroxyl groups (including phenolic hydroxyl groups), carboxyl groups, sulfonic acid groups, sulfinic acid groups, phosphoric acid groups, phosphonic acid groups, phosphoric acid groups, and phosphonic acid groups. A structural unit typically refers to a repeating structural unit of a polymer (sometimes simply referred to as a structural unit), but may mean a substituent or a group of several substituents in the structural unit. Protected by a hydrophobic protecting group is typically a state in which a functional group (usually an acid group) of a group soluble in the alkaline aqueous solution is substituted with a hydrophobic substituent. For example, the phenolic hydroxyl group is substituted with a substituent having an alkyl group to form an ether bond. Alternatively, an example in which a tetrahydropyranyl group is substituted on the carboxyl group to form an ester can be mentioned. The above-mentioned protection by the hydrophobic protective group is based on the ratio of the hydrophobic substituent to the number of functional groups (usually acid groups) of the group soluble in an alkaline aqueous solution present in one molecule. It can be evaluated whether it is a substituent.
When this ratio is shown on a molar ratio basis, in the present invention, it is 50 mol% or more and 100 mol% or less as described above, preferably 55 mol% or more and 100 mol% or less, preferably 60 mol% or more and 100 mol%. The following is more preferable. The alkyl group serving as a protective group may be primary, secondary or tertiary, and may be linear or cyclic, and may be linear or branched. This alkyl group may be via an oxygen atom or a carbonyl group in the chain. It may be cyclic to form an oxazine ring or a tetrahydrofuran ring. An aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms) may be substituted. The intervening oxygen atom is preferably in a ratio of 1 to 1 to 12 carbon atoms. Or the example of the substituent A of postscript Formula (2) is mentioned.
Of these, the acid-reactive resin is preferably an acrylic polymer.

<< Acrylic polymer >>
“Acrylic polymer” is an addition polymerization type resin, which is a polymer containing a structural unit derived from (meth) acrylic acid or an ester thereof, and other than a structural unit derived from (meth) acrylic acid or an ester thereof. These structural units may include, for example, structural units derived from styrenes, structural units derived from vinyl compounds, and the like. The acrylic polymer preferably has a structural 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 structural units in the polymer. Particularly preferred is a polymer consisting only of structural units derived from (meth) acrylic acid or its ester. Such an acrylic polymer is preferably used for negative development.

It is also preferable that the acrylic polymer has a structural unit containing a protected carboxyl group or a protected phenolic hydroxyl group. Examples of the monomer capable of forming a structural unit containing a protected carboxyl group include (meth) acrylic acid protected with an acid dissociable group.

Preferred examples of the monomer having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene. Among these, α-methyl-p-hydroxystyrene is more preferable.

The acrylic polymer preferably has a cyclic ether ester structure, and more preferably has a structure represented by the following formula (1).

In the formula, R ⁸ represents a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3), L ¹ represents a carbonyl group or a phenylene group, and R ¹ R ⁷ each independently represents a hydrogen atom or an alkyl group. R ⁸ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
L ¹ represents a carbonyl group or a phenylene group, and is preferably a carbonyl group.
R ¹ to R ⁷ each independently represents a hydrogen atom or an alkyl group. The alkyl group in R ¹ to R ⁷ has the same meaning as R ⁸ , and the preferred embodiment is also the same. ^Further, among the R 1 ~ ^{R 7,} preferably more than one is a hydrogen ^atom, it is more preferable that all of R 1 ~ ^{R 7} are hydrogen atoms.

As the structural unit (1), (1-1) and (1-2) are particularly preferable.

As the radical polymerizable monomer used for forming the structural 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 be formed by reacting a carboxyl group or a phenolic hydroxyl group with a dihydrofuran compound after polymerization with a precursor monomer.

Examples of the structural unit containing a protected phenolic hydroxyl group include the structural unit represented by the following formula (2).

A represents a hydrogen atom or a group capable of leaving by the action of an acid. Examples of the group capable of leaving by the action of an acid include an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3), and an alkoxyalkyl group (preferably having 2 to 12 carbon atoms and 2 To 6 are more preferred, and 2 to 3 are more preferred), an aryloxyalkyl group (preferably having a total carbon number of 7 to 40, more preferably 7 to 30 and even more preferably 7 to 20), an alkoxycarbonyl group (having 2 carbon atoms). To 12, preferably 2 to 6, more preferably 2 to 3, and an aryloxycarbonyl group (preferably having a carbon number of 7 to 23, more preferably 7 to 19, and still more preferably 7 to 11). A may further have a substituent. R ¹⁰ represents a substituent. R ⁹ represents a group having the same meaning as R ⁸ in Formula (1). nx represents an integer of 0 to 3.

As the group dissociating by an acid, among the compounds described in paragraphs 0039 to 0049 of JP-A-2008-197480, a structural unit having a group dissociating by an acid is preferable, and JP-A-2012-159830 ( The compounds described in paragraph Nos. 0052 to 0056 of Japanese Patent No. 5191567) are also preferable, the contents of which are incorporated herein.

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

In the acrylic polymer, the proportion of the structural unit (1) and the structural unit (2) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and further preferably 10 to 60 mol%. The acrylic polymer may contain only 1 type of structural unit (1), or may contain 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.

The acid-reactive resin may contain a structural unit having a crosslinkable group. Details of the crosslinkable group can be referred to the descriptions in paragraph numbers 0032 to 0046 of JP2011-209692A, the contents of which are incorporated herein.
Although the aspect in which the acid-reactive resin contains the structural unit (structural unit (3)) having a crosslinkable group is also preferable, the acid-reactive resin may have a configuration that does not substantially contain the structural unit (3) having a crosslinkable group. preferable. With such a configuration, the photosensitive layer can be more effectively removed after patterning. Here, “substantially” means, for example, 3 mol% or less, preferably 1 mol% or less of all structural units of the acid-reactive resin.

The acid-reactive resin may contain other structural units (structural unit (4)). Examples of the radical polymerizable monomer used for forming the structural unit (4) include compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623. As a preferred example of the structural unit (4), a structural unit derived from at least one selected from the group consisting of a hydroxyl group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene, and an N-substituted maleimide. Is mentioned. Among these, benzyl (meth) acrylate, (meth) acrylic acid tricyclo [5.2.1.02,6] decan-8-yl, (meth) acrylic acid tricyclo [5.2.1.02,6] (Meth) acrylic acid esters containing alicyclic structures such as decan-8-yloxyethyl, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, or styrene Hydrophobic monomers such as are preferred.
The structural unit (4) can be used alone or in combination of two or more. The content of the monomer unit forming the structural unit (4) in the case where the structural unit (4) is included in all monomer units constituting the acrylic polymer is preferably 1 to 60 mol%, and 5 to 50 mol%. Is more preferable, and 5 to 40 mol% is more preferable. When using 2 or more types, it is preferable that a total amount becomes the said range.

Various methods are known for synthesizing acrylic polymers. For example, radical polymerizable monomers used to form at least the structural unit (1), the structural unit (2), etc. It can be synthesized by polymerizing a radically polymerizable monomer mixture containing a radical polymerization initiator in an organic solvent.
As the acid-reactive resin, 2,3-dihydrofuran is added at room temperature (in the absence of an acid catalyst) to the acid anhydride group in the precursor copolymer obtained by copolymerizing unsaturated polyvalent carboxylic acid anhydrides. A copolymer obtained by addition at a temperature of about 25 ° C. to 100 ° C. is also preferable.
The following resins are also listed as preferred examples of the acid-reactive resin.
BzMA / THFMA / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
BzMA / THFAA / t-BuMA (molar ratio: 20 to 60:35 to 65: 5 to 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, BuMA is butyl methacrylate, THFAA is tetrahydrofuran-2-yl acrylate, and THPMA is tetrahydro-2H-pyran-2. -Yl methacrylate, PEES is p-ethoxyethoxystyrene.

Examples of the acid-reactive resin used for positive development include those described in JP2013-011678A, the contents of which are incorporated herein.

The content of the acid-reactive resin in the photosensitive resin composition is preferably 20 to 99% by mass and more preferably 40 to 99% by mass with respect to the total solid content of the photosensitive resin composition. Preferably, it is 70 to 99% by mass. When the content is within this range, the pattern formability upon development is good. The acid-reactive resin may contain only 1 type, and may contain 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.
The acid-reactive resin preferably accounts for 10% by mass or more of the resin component contained in the photosensitive resin composition, more preferably accounts for 50% by mass or more, and more preferably accounts for 90% by mass or more. .

<< Photoacid generator >>
The photosensitive resin composition may contain a photoacid generator. The photoacid generator is preferably a photoacid generator having absorption at a wavelength of 365 nm.
The photoacid generator is preferably a compound having an oxime sulfonate group (hereinafter also simply referred to as an oxime sulfonate compound).

The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group. However, the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS- It is preferable that it is an oxime sulfonate compound represented by 105).

X ³ represents an alkyl group, an alkoxyl group, or a halogen atom. When a plurality of X ³ are present, they may be the same or different. The alkyl group and alkoxyl group in X ³ may have a substituent. The alkyl group in X ³ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxyl group in X ³ is preferably a linear or branched alkoxyl group having 1 to 4 carbon atoms. The halogen atom in X ³ is preferably a chlorine atom or a fluorine atom.
m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3, the plurality of X ³ may be the same or different.
R ³⁴ represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxyl group having 1 to 5 carbon atoms. And a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W represents 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, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxyl group having 1 to 5 carbon atoms. Group, an aryl group having 6 to 20 carbon atoms, and a halogenated aryl group having 6 to 20 carbon atoms.

In the formula, m3 is 3, X ³ is a methyl group, the substitution position of X ³ is an ortho position, R ³⁴ is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2 A compound which is an -oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the formula (OS-1) include the following compounds described in paragraph numbers 0064 to 0068 of JP2011-209692A, the contents of which are described in the present specification. Incorporated into.

R ¹¹ represents an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ^{12 s} that may be present each independently represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and a plurality of R ^{16 s} that may be present Each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, ns represents 1 or 2, and ms represents 0 to 6 Represents an integer.
The alkyl group, aryl group or heteroaryl group represented by R ¹¹ may have a substituent. The alkyl group represented by R ¹¹ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent. Examples of the substituent that the alkyl group represented by R ¹¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Is mentioned. Examples of the alkyl group represented by R ¹¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, and n-hexyl. Group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group and the like.
In addition, the aryl group represented by R ¹¹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent. Examples of the substituent that the aryl group represented by R ¹¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, Examples thereof include an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group. The aryl group represented by R ¹¹ is preferably a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group. The heteroaryl group represented by R ¹¹ is preferably a heteroaryl group having 4 to 30 carbon atoms which may have a substituent. Examples of the substituent that the heteroaryl group represented by R ¹¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, and an aryloxycarbonyl group. , An aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group. The heteroaryl group represented by R ^{11 only} needs to have at least one heteroaromatic ring. For example, the heteroaromatic ring and the benzene ring may be condensed. Examples of the heteroaryl group represented by R ¹¹ include a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring, which may have a substituent. And a group obtained by removing one hydrogen atom from a ring selected from the group consisting of:

R ¹² is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
Of R ¹² which may be present in the compound in two or more, one or two are preferably an alkyl group, an aryl group or a halogen atom, more preferably one is an alkyl group, an aryl group or a halogen atom. It is particularly preferred that one is an alkyl group and the rest are hydrogen atoms.
The alkyl group or aryl group represented by R ¹² may have a substituent.
Examples of the substituent that the alkyl group or aryl group represented by R ¹² may have include the above W.
The alkyl group represented by R ¹² is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and an alkyl group having 1 to 6 carbon atoms which may have a substituent. More preferably, it is a group.
Examples of the alkyl group represented by R ¹² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, A chloromethyl group, a bromomethyl group, a methoxymethyl group, and a benzyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and an n-hexyl group. A group is more preferable, a methyl group, an ethyl group, an n-propyl group, an n-butyl group and an n-hexyl group are more preferable, and a methyl group is particularly preferable.
The aryl group represented by R ¹² is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
The aryl group represented by R ¹² is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.
Examples of the halogen atom represented by R ¹² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are preferable.
X represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.

ns represents 1 or 2, and when X is O, ns is preferably 1, and when X is S, ns is preferably 2.
The alkyl group and alkyloxy group represented by R ¹⁶ may have a substituent.
The alkyl group represented by R ¹⁶ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyl group represented by R ¹⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Is mentioned.
Examples of the alkyl group represented by R ¹⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, and n-hexyl. Group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group and benzyl group are preferred.
The alkyloxy group represented by R ¹⁶ is preferably an alkyloxy group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyloxy group represented by R ¹⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl. Groups.
The alkyloxy group represented by R ¹⁶ is preferably a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group.
Examples of the aminosulfonyl group for R ¹⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group.
Examples of the alkoxysulfonyl group represented by R ¹⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.
ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

The compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), (OS-110) or (OS-111). The compound represented by 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 represented by the following formula (OS-108). ) Or (OS-109) is particularly preferable.

R ¹¹ represents an alkyl group, an aryl group or a heteroaryl group, R ¹⁷ represents a hydrogen atom or a bromine atom, R ¹⁸ represents 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, a phenyl group or a chlorophenyl group, R ¹⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ²⁰ represents a hydrogen atom or a methyl group.
R ¹⁷ represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R ¹⁸ represents 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, a phenyl group or a chlorophenyl group, and an alkyl group having 1 to 8 carbon atoms, A halogen atom or a phenyl group is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is further preferable, and a methyl group is particularly preferable.
R ¹⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ²⁰ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the oxime sulfonate compound, the oxime steric structure (E, Z) may be either one or a mixture.
Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include the compounds described in paragraph numbers 0088 to 0095 of JP 2011-209692 A, and their contents Are incorporated herein.

Other preferred embodiments of the oxime sulfonate compound having at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

R ¹¹ represents 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, an aryl group or a heteroaryl group. An embodiment in which R ¹¹ is a cyano group or an aryl group is more preferable, and an embodiment in which R ¹¹ is a cyano group, a phenyl group, or a naphthyl group is more preferable.
R ^12a represents an alkyl group or an aryl group.
X is, -O -, - S -, - NH -, - NR 15 -, - CH 2 -, - CR 16 H- or ^-CR 16 ^{R 17} - ^represents, in each of R 15 ^{~ R 17} independently, Represents an alkyl group or an aryl group.
R ²¹ to R ²⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group or aryl. Represents a group. Two of R ²¹ to R ²⁴ may be bonded to each other to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring.
R ²¹ to R ²⁴ are preferably a hydrogen atom, a halogen atom or an alkyl group, and an embodiment in which at least two of R ²¹ to R ²⁴ are bonded to each other to form an aryl group is also preferred. Of these, an embodiment in which R ²¹ to R ²⁴ are all hydrogen atoms is preferred.
Any of the above-described substituents may further have a substituent.
The compound represented by the formula (OS-101) is more preferably a compound represented by the formula (OS-102).
In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
Specific examples of the compound represented by the formula (OS-101) include compounds described in paragraph numbers 0102 to 0106 of JP2011-209692A, the contents of which are incorporated herein.
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 Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Chemical Co., Ltd.), and the like. .

As the photoacid generator sensitive to actinic rays, those which do not contain a 1,2-quinonediazide compound are preferred. The reason is that the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is 1 or less and is less sensitive than the oxime sulfonate compound.
In contrast, the oxime sulfonate compound acts as a catalyst for the deprotection of an acid group protected in response to an actinic ray, so that a large number of acids generated by the action of one photon are present. It contributes to the deprotection reaction, and the quantum yield exceeds 1, for example, a large value such as a power of 10, and it is estimated that high sensitivity is obtained as a result of so-called chemical amplification.
In addition, since the oxime sulfonate compound has a broad π-conjugated system, it has absorption up to the long wavelength side, and not only deep ultraviolet rays (DUV), ArF rays, KrF rays, i rays, It shows very high sensitivity even in the g-line.
By using a tetrahydrofuranyl group as an acid-decomposable group in the acid-reactive resin, an acid-decomposability equivalent to or higher than that of an acetal or ketal can be obtained. Thereby, an acid-decomposable group can be consumed reliably in a shorter post-bake. Furthermore, by using the oxime sulfonate compound that is a photoacid generator in combination, the sulfonic acid generation rate is increased, so that the generation of acid is accelerated and the decomposition of the acid-decomposable group of the resin is accelerated. Moreover, since the acid obtained by decomposing | disassembling an oxime sulfonate compound is a sulfonic acid with a small molecule | numerator, the diffusibility in a cured film is also high, and it can make more highly 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, based on the total solid content of the photosensitive resin composition. It is further preferable to use 10% by mass, more preferably 0.5 to 3% by mass, and still more preferably 0.5 to 1.2% by mass.
A photo-acid generator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Other ingredients >>
The photosensitive resin composition can contain other components.
As other components, an organic solvent is preferably contained from the viewpoint of coatability.
<< Organic solvent >>
The photosensitive resin composition preferably contains an organic solvent, and is preferably prepared as a solution in which an optional component of a photoacid generator and various additives in addition to a reactive resin is dissolved in an organic solvent. .
As the organic solvent used in the photosensitive resin composition, known organic solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether. , Propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetate , Esters, ketones, amides, lactones and the like.
Examples of the organic solvent include (1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; (2) ethylene glycol dimethyl ether, ethylene glycol diethyl Ethylene glycol dialkyl ethers such as ether and ethylene glycol dipropyl ether; (3) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate Acetates; (4) propylene glycol Propylene glycol monoalkyl ethers such as monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 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, propylene glycol monobutyl ether acetate; (7) diethylene glycol dimethyl ether, diethylene glycol diethyl ether, die Diethylene glycol dialkyl ethers such as lenglycol 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, diethylene glycol monobutyl ether acetate; (9) dipropylene Dipropylene glycol monoalkyl ethers such as glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether; (10) dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene (11) Dipropylene such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, 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, isoamyl lactate; (13) n acetate -Butyl, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, Aliphatic carboxylic acid esters such as isopropyl lopionate, n-butyl propionate, isobutyl propionate, 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-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate Acetoacetic acid Other esters such as chill, methyl pyruvate, ethyl pyruvate; (15) such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone Ketones; (16) amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; (17) lactones such as γ-butyrolactone, etc. Can be mentioned.
In addition, these organic solvents may further contain benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-octanol, if necessary. 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.
Of the organic solvents described above, propylene glycol monoalkyl ether acetates and / or diethylene glycol dialkyl ethers are preferred, and diethylene glycol ethyl methyl ether and / or propylene glycol monomethyl ether acetate are particularly preferred.
These organic solvents can be used individually by 1 type or in mixture of 2 or more types.
When using 2 or more types, it is preferable that a total amount becomes the said range.
Furthermore, from the viewpoint of liquid storage stability, the photosensitive resin composition preferably contains a basic compound, and preferably contains a surfactant from the viewpoint of coatability.

<< basic compound >>
It is preferable that the photosensitive resin composition contains a basic compound.
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.
Examples of aliphatic amines 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, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, cyclohexylmorpholinoethylthiourea, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3 .0] Such as 7-undecene 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 carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
When the photosensitive resin composition includes a basic compound, the content of the basic compound is preferably 0.001 to 1 part by mass, and 0.002 to 0 parts per 100 parts by mass of the acid-reactive resin. More preferably, it is 5 parts by mass.
The basic compound may be used singly or in combination of two or more, preferably in combination of two or more, more preferably in combination of two, heterocyclic amine More preferably, two of these are used in combination. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Surfactant >>
It is preferable that the photosensitive resin composition contains a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based and silicone surfactants. .
More preferably, the surfactant contains a fluorine-based surfactant, a silicone-based surfactant, and a combination of both.
Examples of these fluorosurfactants and silicone surfactants include, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, Surfactants described in JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, and JP-A-2001-330953 Commercially available surfactants can also be used.
Examples of commercially available surfactants that can be used include EFTOP EF301, EF303 (above, Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (above, made by Sumitomo 3M Ltd.), MegaFuck F171, F173, F176. , F189, R08 (above, manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.), PF-6320, etc. PolyFox series (OMNOVA) Fluorine-based surfactant or silicone-based surfactant. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

In addition, as a surfactant, it contains a structural unit A and a structural unit B represented by the following formula (41), and is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having (Mw) of 1,000 or more and 10,000 or less.

(In the formula, R ⁴¹ and R ⁴³ each 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 to 4 carbon atoms. represents an alkyl group, L ⁴ represents an alkylene group having 3 to 6 carbon atoms, p4 and q4 is the mass percentage representing the polymerization ratio, p4 represents the following numbers 80 wt% to 10 wt%, q4 represents a numerical value of 20% by mass to 90% by mass, r4 represents an integer of 1 to 18 and n4 represents an integer of 1 to 10.
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 is preferably an alkyl group having 1 to 3 carbon atoms in terms of wettability with respect to the coated surface, and an alkyl group having 2 or 3 carbon atoms. 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 surfactant is included, the addition amount of the surfactant is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the acid-reactive resin. More preferably, the content is 0.01 to 1 part by mass.
Surfactant can be used individually by 1 type or in mixture of 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Moisture content >>
The photosensitive resin composition may contain moisture. It is preferred that the moisture is low or not included, but unavoidable moisture may be included. The moisture content of the photosensitive resin composition is preferably 1% by mass or less, more preferably 0.7% by mass or less, and further preferably 0.4% by mass or less. As a lower limit, it is preferable that it is 0.01 mass% or more, it is more preferable that it is 0.03 mass% or more, and it is more preferable that it is 0.05 mass% or more.

<< metal impurities >>
The photosensitive resin composition usually inevitably contains a trace amount of metal impurities. For example, salts of alkali metals or alkaline earth metals such as sodium, potassium, calcium and the like can be mentioned. In the present invention, the total content of sodium ion, potassium ion and calcium ion in the photosensitive resin composition is, for example, in the range of 1 mass ppt to 1000 mass ppb, and further in the range of 50 mass ppt to 900 mass ppb. It is understood that it exists.
The amount of metal ions is measured by the method described in Examples described later.

<< Other >>
Furthermore, known additions such as antioxidants, plasticizers, thermal radical generators, thermal acid generators, acid multipliers, UV absorbers, thickeners, and organic or inorganic suspending agents are added as necessary. One or more agents can be added, respectively. Details of these can be referred to the description of paragraph numbers 0143 to 0148 of JP2011-209692A, the contents of which are incorporated herein.

<< Static contact angle >>
In this invention, it defines that the static contact angle of the photosensitive resin composition on a water-soluble resin layer is 60 degrees or less. The static contact angle is preferably 50 ° or less, more preferably 40 ° or less, and further preferably 30 ° or less. The lower limit may be 0 °, but is preferably 2 ° or more, more preferably 5 ° or more, and even more preferably 10 ° or more. By setting it to the lower limit value or more, the in-plane film thickness uniformity at the time of spin coating is more effectively achieved, and by setting it to the upper limit value or less, foaming at the time of coating is suppressed.
In addition, in this specification, the measuring method of the static contact angle of the photosensitive resin composition shall be based on the method employ | adopted in the postscript Example.

The static contact angle of the photosensitive resin composition may be changed by a conventional method. For example, the molecular weight of the polymer constituting the acid-reactive resin, the molecular structure, the type and amount of polar groups, and the interface for blending The static contact angle can be adjusted by adjusting the type and amount of the active agent.

<Kit>
The photosensitive resin composition may be combined with a water-soluble resin composition containing a water-soluble resin to form a kit for forming a photosensitive layer and a water-soluble resin layer in this order. Furthermore, it is preferably used as a kit for processing an organic semiconductor layer. At this time, it is preferable to apply each component of the photosensitive resin composition and each component of the water-soluble resin composition described above as specific embodiments. In this invention, it is good also as a kit which combined the composition for organic-semiconductor formation further. As a specific aspect of the composition, it is preferable to apply the above-described organic semiconductor and each component of the composition.

<Organic semiconductor layer patterning method>
Examples of patterning methods that can be suitably employed in the present invention include the following forms. Hereinafter, processing (patterning) of the organic semiconductor layer will be described as an example, but it can also be used for patterning of layers other than the organic semiconductor layer.
The patterning method of the organic semiconductor layer of this embodiment is
(1) forming a water-soluble resin layer on the organic semiconductor layer;
(2) forming a photosensitive layer on the side of the water-soluble resin layer opposite to the organic semiconductor layer;
(3) a step of exposing the photosensitive layer;
(4) a step of developing using a developer containing an organic solvent to produce a mask pattern;
(5) a step of removing at least the non-masked water-soluble resin layer and the organic semiconductor layer by dry etching treatment;
(6) a step of removing the water-soluble resin layer;
including.

<< (1) Step of forming a water-soluble resin layer on the organic semiconductor layer >>
The patterning method of the organic semiconductor layer of this embodiment includes a step of forming a water-soluble resin layer on the organic semiconductor layer. Usually, this process is performed after forming an organic semiconductor layer on a substrate. In this case, the water-soluble resin layer is formed on the surface opposite to the surface of the organic semiconductor on the substrate side. The water-soluble resin layer is usually provided on the surface of the organic semiconductor layer, but other layers may be provided without departing from the spirit of the present invention. Specific examples include a water-soluble undercoat layer. Further, only one water-soluble resin layer may be provided, or two or more layers may be provided. As described above, the water-soluble resin layer is preferably formed using a water-soluble resin composition.

<< (2) Step of forming a photosensitive layer on the side opposite to the organic semiconductor layer of the water-soluble resin layer >>
After the step (1), a photosensitive layer is formed using a photosensitive resin composition on the side opposite to the surface of the water-soluble resin layer on the organic semiconductor layer side. As described above, the photosensitive layer is preferably formed using a photosensitive resin composition, and more preferably formed using a chemically amplified photosensitive resin composition containing an acid-reactive resin and a photoacid generator. Is done.
The chemically amplified photosensitive resin composition contains a photoacid generator. When exposed to light, an acid is generated, and the acid-reactive resin contained in the resist reacts to enable patterning and functions as a photosensitive layer.
The solid content concentration of the photosensitive resin composition is usually 1.0 to 40% by mass, preferably 10 to 35% by mass, and more preferably 16 to 28% by mass. By setting the solid content concentration in the above range, the photosensitive resin composition can be uniformly applied on the water-soluble resin layer, and further, a resist pattern having a high resolution and a rectangular profile can be formed. It becomes possible. The solid content concentration is a percentage of the mass of other resist components excluding the organic solvent with respect to the total mass of the photosensitive resin composition.

<< (3) Step of exposing photosensitive layer >>
(2) After forming the photosensitive layer in the step, the photosensitive layer is exposed. Specifically, the photosensitive layer is irradiated with actinic rays through a mask having a predetermined pattern. Exposure may be performed only once or multiple times.
Specifically, actinic rays are irradiated in a predetermined pattern onto a substrate provided with a dry coating film of the photosensitive resin composition. Exposure may be performed through a mask, or a predetermined pattern may be drawn directly. As the actinic ray, an actinic ray having a wavelength of preferably 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. After this step, a post-exposure heating step (PEB) may be performed as necessary.
For exposure with actinic rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-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, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. In the present invention, it is preferable to use i-line because the effect is suitably exhibited.
In the case of using a laser, wavelengths of 343 nm and 355 nm are preferably used for a solid (YAG) laser, and 193 nm (ArF line), 248 nm (KrF line), and 351 nm (Xe line) are preferably used for an excimer laser. Further, 375 nm and 405 nm are preferably used in the semiconductor laser. Among these, 355 nm and 405 nm are more preferable from the viewpoints of stability and cost. The laser can be applied to the photosensitive layer in one or more times.
The exposure amount is preferably 40 to 120 mJ, and 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 more preferable. To prevent to decompose the coating film by ablation phenomenon, more preferably 1,000 mJ / cm ² or less, 100 mJ / cm ² or less is more preferred.
The pulse width is preferably 0.1 nanosecond (hereinafter referred to as “nsec”) or more and 30,000 nsec or less. In order to prevent the color coating film from being decomposed by the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is more preferable. In order to improve the alignment accuracy at the time of scan exposure, 1,000 nsec or less is more preferable, and 50 nsec or less is further preferable.
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.
Furthermore, in order to shorten the exposure processing time, the frequency of the laser is more preferably 10 Hz or more, further preferably 100 Hz or more. More preferably, it is not more than 1,000 Hz.
The laser is preferable in that it can be easily focused as compared with a mercury lamp, and a mask for forming a pattern in the exposure process is unnecessary and the cost can be reduced.
There are no particular restrictions on the exposure apparatus, but commercially available devices include Calisto (buoy technology), AEGIS (buoy technology), DF2200G (Dainippon Screen Mfg. Co., Ltd.). Etc.) can be used. Further, devices other than those described above are also preferably used.
If necessary, the amount of irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

<< (4) Step of developing mask pattern by developing using developer containing organic solvent >>
In the step (3), the photosensitive layer is exposed through a mask and then developed using a developer containing an organic solvent (hereinafter also referred to as an organic developer). Development is preferably a negative type. Sp value of the solvent contained in the developer is preferably less than ^{19 MPa 1/2,} and more preferably ^{18 MPa 1/2} or less.
As the organic solvent contained in the developer, polar solvents such as ketone solvents, ester solvents, amide solvents, and hydrocarbon solvents can be used.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, Examples include methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of ester solvents 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, diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Can be mentioned.
Examples of amide solvents 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. Moreover, you may mix and use with organic solvents other than the above. However, the water content of the whole developer is preferably less than 10% by mass, and more preferably substantially free of moisture. The term “substantially” as used herein means, for example, that the water content of the entire developing solution is 3% by mass or less, and more preferably the measurement limit or less.
That is, the amount of the organic solvent used relative 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 developer. .
In particular, the organic developer preferably contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, and amide solvents.
The organic developer may contain an appropriate amount of a basic compound as required. Examples of the basic compound include those described in the above basic compound section.
The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and further preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Improves.
Specific examples of the solvent having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 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 Monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, Ester solvents such as butyl acid, propyl formate, ethyl lactate, butyl lactate, propyl lactate, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, xylene And aromatic hydrocarbon solvents such as octane and decane.
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-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, 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, amide solvents such as N- dimethylformamide, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.
An appropriate amount of one or more surfactants can be added to the developer as required.
Although it does not specifically limit as surfactant, For example, surfactant described in the item of said water-soluble resin composition is used preferably.
When a surfactant is blended in the developer, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0, based on the total amount of the developer. 0.01 to 0.5% by mass.
As a development method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.
When the above-mentioned various development 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 (the flow rate per unit area of the discharged developer) is , Preferably 2 mL / sec / mm ² or less, more preferably 1.5 mL / sec / mm ² or less, and even more preferably 1 mL / sec / mm ² or less. There is no particular lower limit of the flow rate, but 0.2 mL / second / mm ² or more is preferable in consideration of throughput. By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure in the above range, the pressure applied to the photosensitive layer by the developer is reduced, and the resist pattern on the photosensitive layer is inadvertently scraped or broken. This is considered to be suppressed.
The developer discharge pressure (mL / second / mm ² ) is a value at the developing nozzle outlet in the developing device.
Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.
Moreover, you may implement the process of stopping image development, after substituting with another organic solvent after the process developed using the developing solution containing the organic solvent.

<< (5) Step of removing at least the non-masked water-soluble resin layer and the organic semiconductor layer by dry etching treatment >>
After developing the photosensitive layer to produce a mask pattern, at least the water-soluble resin layer and the organic semiconductor layer in the non-mask portion are removed by an etching process. The non-mask portion represents a portion where the photosensitive layer has been removed in the development process.
Specifically, in the dry etching, at least the water-soluble resin layer and the organic semiconductor layer are dry etched using the resist pattern as an etching mask. Representative examples of dry etching include Japanese Patent Application Laid-Open Nos. 59-126506, 59-46628, 58-9108, 58-2809, and 57-148706. There are methods described in Japanese Patent Laid-Open No. 61-41102.
The dry etching is preferably performed in the following manner from the viewpoint of forming the pattern cross section closer to a rectangle and reducing damage to the organic semiconductor layer.
A first stage etching using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ) to perform etching up to a region (depth) where the organic semiconductor layer is not exposed, and after this first stage etching, nitrogen gas A second stage etching is performed in which a mixed gas of (N ₂ ) and oxygen gas (O ₂ ) is used, and etching is preferably performed to the vicinity of the region (depth) where the organic semiconductor layer is exposed, and after the organic semiconductor layer is exposed A form including overetching to be performed is preferable. Hereinafter, a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.
Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated. (2) 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 respectively calculated. (3) The first stage etching is performed according to the etching time calculated in (2) above. (4) The second stage etching is performed according to the etching time calculated in (2) 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. (5) Overetching time is calculated with respect to the total time of (3) and (4) above, and overetching is performed.
The mixed gas used in the first stage etching step preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. In the first step, the organic semiconductor layer can be prevented from being damaged by etching the region where the organic semiconductor layer is not exposed. The second-stage etching process and the over-etching process may be performed by performing etching to a region where the organic semiconductor layer is not exposed by a mixed gas of fluorine-based gas and oxygen gas in the first-stage etching process. From the viewpoint of avoiding damage, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.
It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable. The etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.
Etching preferably includes an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

<< (6) Step of removing water-soluble resin layer >>
After the etching, it is preferable to remove the water-soluble resin layer using a solvent (usually water).
Examples of the method for removing the water-soluble resin layer with water include a method for removing the water-soluble resin layer by spraying cleaning water onto the resist pattern from a spray type or shower type spray nozzle. As the washing water, pure water can be preferably used. Examples of the injection nozzle include an injection nozzle in which the entire substrate is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire substrate.
When the spray nozzle is movable, the resist pattern is more effectively removed by spraying the cleaning water by moving from the center of the substrate to the end of the substrate at least twice during the process of removing the water-soluble resin layer. be able to.
It is also preferable to perform a process such as drying after removing water. The drying temperature is preferably 80 to 120 ° C.

<Application>
The photosensitive layer of the present invention can be used for production of an electronic device using an organic semiconductor. Here, the electronic device is a device that contains a semiconductor and has two or more electrodes, and a current flowing between the electrodes and a generated voltage are controlled by electricity, light, magnetism, a chemical substance, or the like, or It is a device that generates light, electric field, magnetic field, etc. by applied voltage or 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, organic field effect transistors, organic photoelectric conversion elements, and organic electroluminescence elements are preferable as applications, more preferably organic field effect transistors and organic photoelectric conversion elements, and particularly preferably organic field effect transistors. .

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “%” and “parts” are based on mass.

<Measurement method of weight average molecular weight (Mw)>
The Mw of the resin was measured by the following method.
<Measurement method of weight average molecular weight (Mw)>
The molecular weight of the water-soluble resin was measured according to the method described in Paragraphs 0067 to 0071 of International Publication No. WO2015 / 098978.
Other resins were measured for molecular weight by gel permeation chromatography (GPC measurement) under the following measurement conditions.
Polystyrene equivalent value Device: HLC-8220 (manufactured by Tosoh Corporation)
Column: Guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation)
Eluent: THF (tetrahydrofuran)
Detector: UV ray (ultraviolet light), wavelength 254nm

Examples 1 to 11 and Comparative Examples 1 to 3
<Preparation of water-soluble resin composition>
In the following formulation, each component was mixed to make a uniform solution, and then filtered using a nylon filter having a pore size of 0.8 μm to prepare a water-soluble resin composition.
<< PVA-1 >>
The following PVA 15.0 parts by mass Surfactant D-1 (described below) 0.008 parts by mass Water 84.9 parts by mass PVA (Kuraray PVA-203 Saponification degree 88.0% Degree of polymerization 300)
<< PVP-1 >>
The following PVP 7.9 parts by mass Surfactant D-1 (described below) 0.008 parts by mass Water 92.1 parts by mass PVP (Mw = 360,000 Polyvinylpyrrolidone K90 manufactured by Tokyo Chemical Industry Co., Ltd.)
<Preparation of water-insoluble resin composition of comparative example>
<< FR-1 >>
In the following formulation, each component was mixed to make a uniform solution, and then filtered using a polypropylene filter having a pore size of 0.6 μm to prepare a water-insoluble resin composition.
CYTOP (registered trademark) CTL-809AP2: Asahi Glass Co., Ltd. 4.0 parts by mass Sumitomo 3M Fluorinert FC77 96.0 parts by mass

<Preparation of photosensitive resin composition>
Each acid-reactive resin was synthesized as follows.
<< Synthesis of Acid Reactive Resin A-1 >>
<Synthesis of Acid Reactive Resin A-1 (Mw = 25,000)>
PGMEA (propylene glycol monomethyl ether acetate) (32.62 g) was placed in a 200 mL three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. Here, BzMA (16.65 g), THFMA (21.08 g), t-BuMA (5.76 g), and V-601 (1.0686 g) dissolved in PGMEA (32.62 g) were taken over 2 hours. And dripped. Thereafter, the reaction solution was stirred for 2 hours to complete the reaction. The white powder produced by reprecipitation of the reaction solution in heptane was collected by filtration to obtain acid-reactive resin A-1. The obtained resin had a protection ratio of 65 mol% of the total THFMA and t-BuMA monomers, a weight average molecular weight of 25,000, and a dissolution rate of 100 nm / s. The amount of the component having Mw of 1,000 or less was 3% by mass.

<< Synthesis of Acid Reactive Resin A-2 >>
<Synthesis of Acid Reactive Resin A-2 (Mw = 57,000)>
PGMEA (32.62 g) was placed in a 200 mL three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. Here, BzMA (16.65 g), THFMA (21.08 g), t-BuMA (5.76 g), and V-601 (0.2157 g) dissolved in PGMEA (32.62 g) were taken over 2 hours. And dripped. Thereafter, the reaction solution was stirred for 2 hours to complete the reaction. The white powder produced by reprecipitation of the reaction solution in heptane was collected by filtration to obtain acid-reactive resin A-2. The obtained resin had a total protection ratio of 65 mol% of THFMA and t-BuMA monomers, a weight average molecular weight of 57,000, and a dissolution rate of 19 nm / s. The amount of the component having Mw of 1,000 or less was 4% by mass.

<< Synthesis of Acid-Reactive Resin A-3 >>
<Synthesis of Acid Reactive Resin A-3 (Mw = 9,000)>
PGMEA (32.62 g) was placed in a 200 mL three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. Here, BzMA (16.65 g), THFMA (21.08 g), t-BuMA (5.76 g), and V-601 (2.2622 g) dissolved in PGMEA (32.62 g) were taken over 2 hours. And dripped. Thereafter, the reaction solution was stirred for 2 hours to complete the reaction. The white powder produced by reprecipitation of the reaction solution in heptane was collected by filtration to obtain acid-reactive resin A-3. The obtained resin had a protection ratio of 65 mol% in total of THFMA and t-BuMA monomers, a weight average molecular weight of 9,000, and a dissolution rate of 432 nm / s. The amount of the component having Mw of 1,000 or less was 3% by mass.

<< Synthesis of Acid Reactive Resin A-4 >>
PGMEA (32.62 g) was placed in a 200 mL three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. Here, BzMA (16.65 g), THFMA (21.08 g), t-BuMA (5.76 g), and V-601 (1.9329 g) dissolved in PGMEA (32.62 g) were taken over 2 hours. And dripped. Thereafter, the reaction solution was stirred for 2 hours to complete the reaction. The white powder produced by reprecipitation of the reaction solution in heptane was collected by filtration to obtain acid-reactive resin A-4. The obtained resin had a cyclic ether ester protection rate of 50 mol%, a weight average molecular weight of 15,000, and a dissolution rate of 200 nm / s. The amount of the component having Mw of 1,000 or less was 3% by mass.

<< Synthesis of Acid Reactive Resin A-5 >>
PGMEA (32.62 g) was placed in a 200 mL three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. Here, BzMA (16.65 g), THFMA (21.08 g), t-BuMA (5.76 g), and V-601 (0.3060 g) dissolved in PGMEA (32.62 g) were taken over 2 hours. And dripped. Thereafter, the reaction solution was stirred for 2 hours to complete the reaction. The white powder produced by reprecipitation of the reaction solution in heptane was collected by filtration to obtain acid-reactive resin A-5. The obtained resin had a protection ratio of 65 mol% of the total THFMA and t-BuMA monomers, a weight average molecular weight of 50,000, and a dissolution rate of 32 nm / s. The amount of the component having Mw of 1,000 or less was 3% by mass.

<< Synthesis of Acid Reactive Resin A-6 >>
PGMEA (propylene glycol monomethyl ether acetate) (32.62 g) was placed in a 200 mL three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. Here, BzMA (21.41 g), THFMA (18.97 g), t-BuMA (3.84 g), and V-601 (1.0686 g) dissolved in PGMEA (32.62 g) were taken over 2 hours. And dripped. Thereafter, the reaction solution was stirred for 2 hours to complete the reaction. The white powder produced by reprecipitation of the reaction solution in heptane was collected by filtration to obtain acid-reactive resin A-6. The obtained resin had a protection ratio of 55 mol% of the total THFMA and t-BuMA monomers, a weight average molecular weight of 25,000, and a dissolution rate of 188 nm / s. The amount of the component having Mw of 1,000 or less was 3% by mass.

<< Synthesis of Acid-Reactive Resin A-7 >>
PGMEA (propylene glycol monomethyl ether acetate) (32.62 g) was placed in a 200 mL three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. Here, BzMA (7.14 g), THFMA (27.41 g), t-BuMA (7.68 g), and V-601 (1.0686 g) dissolved in PGMEA (32.62 g) were taken over 2 hours. And dripped. Thereafter, the reaction solution was stirred for 2 hours to complete the reaction. The white powder produced by reprecipitation of the reaction solution in heptane was collected by filtration to obtain acid-reactive resin A-7. The obtained resin had a protection ratio of 85 mol% for the total THFMA and t-BuMA monomers, a weight average molecular weight of 25,000, and a dissolution rate of 31 nm / s. The amount of the component having Mw of 1,000 or less was 3% by mass.

Each component was mixed with the formulation shown in Table 1 or 2 to make a uniform solution, and then filtered using a nylon filter having a pore diameter of 0.45 μm to prepare a photosensitive resin composition. Details of each component are shown in Table 1 or Table 2.

<Production of organic semiconductor substrate>
An organic semiconductor coating liquid (composition for forming an organic semiconductor) having the following composition was spin-coated on a circular glass substrate and dried at 130 ° C. for 10 minutes to form an organic semiconductor layer. The film thickness was 150 nm.
<< Composition of organic semiconductor coating liquid >>
P3HT (Sigma Aldrich Japan GK) 10% by mass
PCBM (Sigma Aldrich Japan GK) 10% by mass
Chloroform (Wako Pure Chemical Industries, Ltd.) 80% by mass

<Formation of water-soluble resin layer>
A water-soluble resin composition was spin-coated on the surface of the organic semiconductor layer and dried at 100 ° C. for 1 minute to form a water-soluble resin layer having a thickness of 2 μm.

<Evaluation of dissolution rate>
The photosensitive resin composition was applied onto a quartz crystal microbalance (QCM electrode) as a base material and heated at 100 ° C. for 1 minute to form a 2 μm thick film (photosensitive layer). About the dissolution rate with respect to butyl acetate at 23 degreeC, it calculated from the time when the coating film with a film thickness of 2 micrometers melt | dissolves using the QCM method (relative parameter | index).
A: 50 nm or more per second, 150 nm or less per second B: 20 nm or more per second, less than 50 nm, or more than 150 nm per second, 200 nm or less C: less than 20 nm per second, or more than 200 nm per second

<Measurement of metal ion content>
The total content of sodium ion, potassium ion and calcium ion in the photosensitive resin composition is measured by adjusting the metal content in the composition from 1 ppt to 1000 ppb by ICP-MS (inductively coupled plasma mass spectrometry) after preparation. Measured in order.

<Measurement of water content>
After the preparation, the amount of water in the composition was measured using a Karl Fischer moisture meter in the composition.

<Measurement of static contact angle>
The measurement of the static contact angle of the photosensitive resin composition with respect to the water-soluble resin layer was performed as follows. That is, using a static contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.), a droplet having a droplet size of 10 μL was deposited with a syringe, and the contact angle of the droplet was measured.

<Lithography of line pattern>
A photosensitive resin composition (resist) was applied on the water-soluble resin layer prepared above and dried (prebaked) at 100 ° C. for 1 minute to form a photosensitive layer. The film thickness was 2 μm. Next, using a parallel exposure machine, the exposure dose shown in Table 1 or Table 2 is obtained with the light source shown in Table 1 or 2 through a quartz glass binary mask having a mask size of 2 μm and a half pitch of 2 μm. Exposed. Then, it post-baked (PEB) on the conditions shown in Table 1 or Table 2, and developed with the development processing time shown in Table 1 or Table 2 with butyl acetate. After development, the number of lines disappeared by over-development among 4 line and space patterns (L / S) having a width of 2 μm was counted.
The results are shown in Table 1 or Table 2. Here, “no pattern” means that the 2 μm pattern is not resolved due to the low dissolution rate. “No peeling” means no pattern disappearance.

<Over development coefficient>
The over development coefficient in the lithography property of the line pattern was measured.
The over development coefficient was calculated according to the following formula.
Over-development coefficient = [development processing time (s) / [(photosensitive layer thickness (nm) / dissolution rate (nm / sec)]]

<Evaluation of adhesion of island pattern>
A photosensitive resin composition (resist) was applied on the water-soluble resin layer prepared above and dried (prebaked) at 100 ° C. for 1 minute to form a photosensitive layer. The film thickness was 2 μm. Next, it exposed with the light source shown in Table 1 or Table 2 with the exposure amount that 25 patterns of 1 micrometer square were formed using a parallel exposure machine. Then, it post-baked (PEB) on the conditions shown in Table 1 or Table 2, and developed with the development processing time shown in Table 1 or Table 2 with butyl acetate. Of the 25 patterns obtained, the number of peeled patterns was confirmed.

Details in the above table are as follows.
PEB: Post-baking processing conditions Exposure: Describes an exposure light source during development.
Adopted: means that the applicable item was adopted

<Acid generator>
B-1

<Basic compound>
C-1

C-2
2,6-diisopropylaniline (primary amine, manufactured by Tokyo Chemical Industry Co., Ltd.)

<Surfactant>
D-1: OMNOVA, PF6320

D-2
Megafuck F-430, manufactured by DIC Corporation

<Solvent>
E-1: Propylene glycol monomethyl ether acetate (PGMEA)
E-2: Ethyl 3-ethoxypropionate

From the above results, when the photosensitive layer was dissolved too quickly, the pattern collapsed significantly (Comparative Example 1). Further, when the dissolution rate of the photosensitive layer was too low, no pattern was formed (Comparative Example 2). When the static contact angle of the photosensitive resin composition with respect to the water-soluble resin layer was too large, the line itself and the periphery were peeled off after development even if the dissolution rate was within a predetermined range (Comparative Example 3). On the other hand, by setting the dissolution rate of the photosensitive layer in an appropriate range, undercut was reduced, pattern collapse was suppressed, and adhesion was excellent.

Instead of the basic compound C-1 of Example 1, a photosensitive resin composition using C-2 (2,6-diisopropylaniline, manufactured by Tokyo Chemical Industry Co., Ltd.), instead of the surfactant D-1 Photosensitive resin composition using D-2 (Megafac F-430, manufactured by DIC Corporation), instead of solvent E-1, E-1: E-2 (ethyl 3-ethoxypropionate) = 70: Photosensitive resin composition using mixed solvent of 30 (mass ratio), photosensitive resin composition having a mass ratio of resin and acid generator of 25.18: 0.16 (mass ratio), resin and acid generator A photosensitive resin composition having a mass ratio of 24.98: 0.36 (mass ratio) was prepared. A laminate sample was prepared using each photosensitive resin composition. As a result of evaluating the over-development coefficient, lithographic properties, and adhesion of each sample, good results were obtained for all the substrates.

1 Photosensitive layer 2 Water-soluble resin layer 3 Organic semiconductor layer 4 Substrate 5 Removal part

Claims

A photosensitive layer included in a laminate having a water-soluble resin layer and a photosensitive layer,
The photosensitive layer is formed from a photosensitive resin composition containing a compound that generates an acid upon irradiation with actinic rays or radiation, and a resin that changes its dissolution rate with respect to butyl acetate by the action of the acid. The resin in which the dissolution rate changes with respect to the resin has a weight average molecular weight of 10,000 to 50,000, and among all the structural units, 50 mol% to 100 mol% of the group soluble in the alkaline aqueous solution is hydrophobic. A hydrophobic resin soluble in butyl acetate at 23 ° C., protected by a protecting group,
The dissolution rate when the unirradiated photosensitive layer is immersed in butyl acetate at 23 ° C. is 20 nm / s or more and 200 nm / s or less,
The photosensitive layer whose static contact angle of the said photosensitive resin composition on the said water-soluble resin layer is 60 degrees or less.
The photosensitive layer according to claim 1, wherein the photosensitive layer has photosensitivity to i-ray irradiation.
The photosensitive layer according to claim 1 or 2, wherein a content of water in the photosensitive resin composition is 0.01% by mass or more and 1% by mass or less.
4. The photosensitive layer according to claim 1, wherein the change in dissolution rate is a decrease in dissolution rate.
The photosensitive layer according to any one of claims 1 to 4, wherein the resin contained in the photosensitive layer has a structural unit represented by the following formula (1):

In the formula, R 8 represents a hydrogen atom or an alkyl group, L 1 represents a carbonyl group or a phenylene group, and R 1 to R 7 each independently represents a hydrogen atom or an alkyl group.
6. The photosensitive layer according to claim 1, wherein a total content of sodium ion, potassium ion and calcium ion in the photosensitive resin composition is 1 mass ppt to 1000 mass ppb.
The photosensitive layer according to any one of claims 1 to 6, which is used for processing an organic semiconductor layer.
A laminate comprising the photosensitive layer according to any one of claims 1 to 7 and a water-soluble resin layer.
The laminate according to claim 8, further comprising an organic semiconductor layer, wherein the organic semiconductor layer, the water-soluble resin layer, and the photosensitive layer are laminated in this order.
The resin in which the dissolution rate in butyl acetate is changed by the action of the acid is a mixture of a resin having a high dissolution rate in butyl acetate and a resin having a low dissolution rate in butyl acetate. Laminated body.
A photosensitive resin composition for forming a photosensitive layer,
The photosensitive layer is a layer that forms a laminate in combination with a water-soluble resin layer, and the dissolution rate when the unexposed photosensitive layer is immersed in butyl acetate is 20 nm / s or more and 200 nm / second or less,
The photosensitive resin composition contains a compound that generates an acid upon irradiation with actinic rays or radiation, and a resin that causes a change in the dissolution rate in butyl acetate by the action of the acid,
The resin in which the dissolution rate changes in butyl acetate by the action of the acid has a weight average molecular weight of 10,000 to 50,000, and 50 mol% to 100 mol% of all the structural units are groups soluble in an alkaline aqueous solution. Is a hydrophobic resin that is protected by a hydrophobic protecting group and is soluble in butyl acetate, and has a static contact angle of 60 ° or less on the water-soluble resin layer. object.
The photosensitive resin composition according to claim 11, which is used for processing an organic semiconductor layer.
A kit for forming a water-soluble resin layer and a photosensitive layer in this order, the kit comprising the photosensitive resin composition according to claim 11 or 12 and a water-soluble resin composition.
The kit according to claim 13, which is used for processing an organic semiconductor layer.