JP2015087612A - Laminate, organic-semiconductor manufacturing kit, and resist composition for manufacturing organic semiconductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a laminate that allows the formation of a good organic semiconductor pattern; an organic-semiconductor manufacturing kit for manufacturing the laminate; and a resist composition for manufacturing an organic semiconductor, the resist composition being used in the organic-semiconductor manufacturing kit.SOLUTION: This laminate comprises an organic semiconductor film, a protective film on top of the organic semiconductor film, and a resist film on top of the protective film. The resist film comprises a photosensitive resin composition that contains the followings (1) and/or (2): (1) a compound (A1) of which the main chain is broken down by means of light irradiation at wavelengths of 100-600 nm; and (2) an activating agent (B) that generates an active species by means of light irradiation at wavelengths of 100-600 nm and a compound (A2) of which the main chain is broken down by means of the activating agent (B).

Description

  The present invention relates to a laminate, an organic semiconductor manufacturing kit, and an organic semiconductor manufacturing resist composition. Specifically, in the production of an organic semiconductor, a laminate of an organic semiconductor film, a protective film and a resist film, an organic semiconductor production kit for producing such a laminate, and an organic semiconductor production used for the organic semiconductor production kit The present invention relates to a resist composition.

In recent years, electronic devices using organic semiconductors have been widely used. 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, it is possible to easily change the material characteristics by changing the molecular structure, and there are a wide variety of materials, making it possible to realize functions and elements that could not be achieved with inorganic semiconductors. It is thought to be. 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.
Patterning of an organic semiconductor has been performed by a printing technique so far, but there is a limit to fine processing in the patterning by the printing technique. Organic semiconductors are also susceptible to damage.

  Here, Patent Document 1 includes a step of forming an organic semiconductor layer, a step of forming a protective layer for protecting the organic semiconductor layer from a mask layer on the organic semiconductor layer, and the predetermined pattern. Patterning an organic semiconductor layer, comprising: forming a mask layer on the protective layer; and patterning the protective layer and further the organic semiconductor layer in the same shape by etching using the mask layer as a mask. Disclosed is a method for patterning an organic semiconductor layer, characterized in that the protective layer is formed of an organic polymer compound or an insulating inorganic compound that is different in material from the mask layer and has hydrophilicity. Yes.

JP 2006-41317 A

Here, when Patent Document 1 (Japanese Patent Laid-Open No. 2006-41317) was examined, it was found that with this method, the mask layer remained as a protective film even after the patterning was completed.
The present invention has been made to solve the above problems, and is a laminate capable of forming a good organic semiconductor pattern, an organic semiconductor production kit for producing such a laminate, and organic semiconductor production An object of the present invention is to provide a resist composition for producing an organic semiconductor used in a kit for use.

  As a result of detailed investigations, the inventors have formed a protective film and a resist film made of a photosensitive resin composition in this order on one surface of the organic semiconductor film, and organic etching is performed by performing dry etching after patterning the resist film. The inventors have found that patterning can be performed without damaging the semiconductor, and the present invention has been completed.

Specifically, the above-mentioned problem has been solved by the following means <1>, preferably <2> to <20>.
<1> An organic semiconductor film, a protective film on the organic semiconductor film, and a resist film on the protective film, and the resist film is made of a photosensitive resin composition containing the following (1) and / or (2) , Laminates;
(1) including a compound (A1) whose main chain is decomposed by irradiation with light having a wavelength of 100 to 600 nm;
(2) The active agent (B) which generate | occur | produces an active species by light irradiation with a wavelength of 100-600 nm and the compound (A2) which a main chain decomposes | disassembles by an active agent (B) are included.
<2> The laminate according to <1>, wherein the protective film contains a water-soluble resin.
<3> The laminate according to <1>, wherein the protective film contains at least one of polyvinylpyrrolidone, polyvinyl alcohol, and pullulan.
<4> The laminate according to <1>, wherein the protective film contains polyvinylpyrrolidone.
<5> The laminate according to any one of <1> to <4>, wherein the activator (B) is a photoacid generator or a photobase generator.
<6> (A1) The laminate according to any one of <1> to <5>, wherein the compound includes a vinyl resin having a carbonyl group directly bonded to the main chain.
The <7> (A2) compound is selected from a polyester resin, a polyurethane resin, a polyamide resin, a polyimide resin, a polycarbonate resin, a polyether resin, and a copolymer of anhydrous (meth) acrylic acid and poly (meth) acrylic acid. The laminated body in any one of <1>-<6> containing at least 1 sort.
<8> The laminate according to any one of <1> to <7>, wherein the photosensitive resin composition contains a sensitizing dye (C).
<9> A kit for producing an organic semiconductor comprising a resist composition for producing an organic semiconductor comprising the following (1) and / or (2) and a composition for forming a protective film comprising a water-soluble resin;
(1) including a compound (A1) whose main chain is decomposed by irradiation with light having a wavelength of 100 to 600 nm;
(2) The active agent (B) which generate | occur | produces an active species by light irradiation with a wavelength of 100-600 nm and the compound (A2) which a main chain decomposes | disassembles by an active agent (B) are included.
<10> The kit for producing an organic semiconductor according to <9>, wherein the water-soluble resin contains at least one of polyvinylpyrrolidone, polyvinyl alcohol, and pullulan.
<11> The kit for manufacturing an organic semiconductor according to <9>, wherein the water-soluble resin contains polyvinylpyrrolidone.
<12> The kit for manufacturing an organic semiconductor according to any one of <9> to <11>, wherein the activator (B) is a photoacid generator or a photobase generator.
<13> The kit for manufacturing an organic semiconductor according to any one of <9> to <12>, in which the compound (A1) includes a vinyl resin having a carbonyl group directly bonded to the main chain.
The <14> (A2) compound is selected from a polyester resin, a polyurethane resin, a polyamide resin, a polyimide resin, a polycarbonate resin, a polyether resin, and a copolymer of anhydrous (meth) acrylic acid and poly (meth) acrylic acid. The kit for manufacturing an organic semiconductor according to any one of <9> to <13>, comprising at least one kind.
<15> The kit for manufacturing an organic semiconductor according to any one of <9> to <14>, wherein the photosensitive resin composition contains a sensitizing dye (C).
<16> A resist composition for producing an organic semiconductor, comprising the following (1) and / or (2);
(1) including a compound (A1) whose main chain is decomposed by irradiation with light having a wavelength of 100 to 600 nm;
(2) The active agent (B) which generate | occur | produces an active species by light irradiation with a wavelength of 100-600 nm and the compound (A2) which a main chain decomposes | disassembles by an active agent (B) are included.
<17> The resist composition for producing an organic semiconductor according to <16>, wherein the activator (B) is a photoacid generator or a photobase generator.
<18> The resist composition for producing an organic semiconductor according to <16> or <17>, wherein the compound (A1) comprises a vinyl resin having a carbonyl group directly bonded to the main chain.
The <19> (A2) compound is selected from polyester resins, polyurethane resins, polyamide resins, polyimide resins, polycarbonate resins, polyether resins, and copolymers of anhydrous (meth) acrylic acid and poly (meth) acrylic acid. The resist composition for producing an organic semiconductor according to any one of <16> to <18>, comprising at least one kind.
<20> The resist composition for producing an organic semiconductor according to any one of <16> to <19>, wherein the photosensitive resin composition contains a sensitizing dye (C).

  According to the present invention, there are provided a laminate capable of forming a good organic semiconductor pattern, an organic semiconductor production kit for producing such a laminate, and an organic semiconductor production resist composition for use in the organic semiconductor production kit. It became possible.

  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 unsubstituted includes the thing which has a substituent with the thing which does not have 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 excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.

 In the present 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” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .

In this specification, solid content concentration is the mass percentage of the mass of the other component except a solvent with respect to the gross mass of a composition. Moreover, solid content concentration says the density | concentration in 25 degreeC unless there is particular mention.
The main component in the present invention refers to a component having the largest blending amount in a specific composition / component, and usually refers to a component occupying 70% by mass or more in the specific composition / component.

  In this specification, a weight average molecular weight is defined as a polystyrene conversion value by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation) and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. Unless otherwise stated, the eluent shall be measured using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution.

<Laminate>
The laminate of the present invention includes an organic semiconductor film, a protective film on the organic semiconductor film, and a resist film on the protective film, and the resist film includes the following (1) and / or (2): It consists of a photosensitive resin composition.
(1) including a compound (A1) whose main chain is decomposed by irradiation with light having a wavelength of 100 to 600 nm;
(2) An active agent (B) that generates active species by irradiation with light having a wavelength of 100 to 600 nm, and a compound (A2) whose main chain is decomposed by the active agent (B) are included.
Further, an undercoat layer may be provided between the organic semiconductor film and the protective film and / or between the protective film and the resist film.
In the compound (A1), the main chain is decomposed by irradiation with active energy rays, the dissolution rate with respect to the developer containing the organic solvent is increased, the exposed portion is easily dissolved in the developer, and the mask pattern is formed by the non-exposed portion. It can be formed and can be used as a mask for dry etching after the mask pattern is formed. Similarly, compound (A2) also generates active species by (B) activator upon irradiation with active energy rays.
In the compound (A1), the main chain is decomposed by irradiation with active energy rays, the dissolution rate with respect to the developer containing the organic solvent is increased, the exposed portion is easily dissolved in the developer, and the mask pattern is formed by the non-exposed portion. It can be formed and can be used as a mask for dry etching after the mask pattern is formed.

When an ordinary resist film is formed on the organic semiconductor film and patterned, the organic semiconductor is easily dissolved in an organic solvent contained in the resist, and the organic semiconductor film is damaged.
In contrast, in the present invention, a protective film is formed on the organic semiconductor, and a resist film is formed thereon. In this case, since the resist film and the organic semiconductor film are not in direct contact with each other, damage to the organic semiconductor film can be suppressed. Furthermore, since the resist film uses a photosensitive resin composition, high storage stability and fine pattern formability can be achieved.
Hereinafter, the present invention will be described in detail.

<Organic semiconductor film>
The organic semiconductor film used in the present invention is a film 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 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.

  In general, the organic semiconductor film 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 film opposite to the side where the water-soluble resin film is laminated. As a substrate that can be used in the present invention, for example, various materials such as silicon, quartz, ceramic, polyester film such as glass polyethylene naphthalate (PEN), polyethylene terephthalate (PET), and polyimide film may be used as the substrate. Any substrate may be selected according to the application. For example, a flexible substrate can be used in the case of use of a flexible element. Further, the thickness of the substrate is not particularly limited.

  As a p-type semiconductor material that can be used, any material of organic semiconductor material and inorganic semiconductor material may be used as long as it exhibits a hole transport property. Preferably, a p-type π-conjugated polymer (for example, substituted or substituted) is used. Unsubstituted polythiophene (eg, poly (3-hexylthiophene) (P3HT)), 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, 2-TNATA, NPD, TPD, mCP, CBP, etc.), hetero 5-membered ring compounds (For example, substituted or unsubstituted options Gothiophene, TTF, etc.), phthalocyanine compounds (substituted or unsubstituted central metal phthalocyanines, naphthalocyanines, anthracocyanines, tetrapyrazinoporphyrazine), porphyrin compounds (substituted or unsubstituted central metal porphyrins), carbon nanotubes Any one of carbon nanotubes and graphene modified with a semiconductor polymer, more preferably any of p-type π-conjugated polymers, condensed polycyclic compounds, triarylamine compounds, hetero 5-membered ring compounds, phthalocyanine compounds, and porphyrin compounds More preferably, it is a p-type π-conjugated polymer.

As an n-type semiconductor material that can be used as a semiconductor material, any organic semiconductor material or inorganic semiconductor material may be used as long as it has a hole transporting property. Tetracarbonyl compound, perylene tetracarbonyl compound, TCNQ compound, n-type π-conjugated polymer, n-type inorganic semiconductor, more preferably fullerene compound, electron-deficient phthalocyanine compound, naphthalene tetracarbonyl compound, perylene tetracarbonyl compound, π-conjugated Polymers, particularly preferably fullerene compounds and π-conjugated polymers. In the present invention, the fullerene compound refers to a substituted or unsubstituted fullerene. As the fullerene, C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₀ , C ₈₂ , C ₈₄ , C ₈₆ , C ₈₈ , C _{90 are used.} , C ₉₆ , C ₁₁₆ , C ₁₈₀ , C ₂₄₀ , C _{540 and the} like may be used, but substituted or unsubstituted C ₆₀ , C ₇₀ , C ₈₆ are preferable, and PCBM ([6, 6] is particularly preferable. - phenyl -C ₆₁ - those butyric acid methyl ester) and its analogs and (C ₆₀ moiety is substituted with C _70, C _86, etc., those with substitution of the benzene ring substituent in other aromatic ring or heterocyclic ring, methyl ester Is substituted with n-butyl ester, i-butyl ester or the like. Electron-deficient phthalocyanines are phthalocyanines (F ₁₆ MPc, FPc-S8, etc.), naphthalocyanines, anthracyanines, substituted or unsubstituted tetrapyrazinoporphyrazines of various central metals to which 4 or more electron withdrawing groups are bonded. Etc. 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 substituted or unsubstituted TCNQ and a compound in which the benzene ring portion of TCNQ is replaced with another aromatic ring or a heterocyclic ring, and examples thereof include TCNQ, TCAQ, TCN3T, and the like. In addition, graphene is also included. Particularly preferred examples of the type organic semiconductor material are shown below.

  In the formula, R may be any group, but may be a hydrogen atom, a substituent or an unsubstituted branched or straight chain alkyl group (preferably having 1 to 18 carbon atoms, more preferably 1 to 12, more preferably Is preferably 1 to 8), or a substituted or unsubstituted aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms).

The above materials are usually blended in a solvent, applied in layers and dried to form a film. As an application method, description of a protective film described later can be referred to.
Solvents include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, and 1,2-dichlorobenzene; for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene and chlorotoluene; ester solvents such as ethyl acetate, butyl acetate and amyl acetate; For example, alcohol solvents such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol; Ether solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, dimethyl Examples include polar solvents such as sulfoxide. 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 film (composition for forming an organic semiconductor) is preferably 0.1 to 80% by mass, more preferably 0.1 to 10% by mass. A film having a thickness can be formed.

Moreover, you may mix | blend a resin binder with the composition for organic-semiconductor formation. 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. Examples of the resin binder include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, and polypropylene, and copolymers thereof. , Photoconductive polymers such as 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. Considering the mechanical strength of the thin film, a resin binder having a high glass transition temperature is preferable, and considering the charge mobility, a resin binder, a photoconductive polymer, or a conductive polymer having a structure not containing a 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 film.

  Depending on the application, a single layer or a mixed solution to which various semiconductor materials and additives are added may be applied 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 the 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. Although there is no restriction | limiting in particular as temperature of a board | substrate, Preferably it is -200 to 400 degreeC, More preferably, it is -100 to 300 degreeC, More preferably, it is 0 to 200 degreeC.

  The characteristics of the formed organic semiconductor film can be adjusted by post-processing. For example, characteristics can be improved by changing the film morphology and molecular packing in the film by heat treatment or exposure to solvent vapor. 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 film 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.

<Protective film>
The protective film of the present invention is formed on the organic semiconductor film, and is preferably formed on the surface of the organic semiconductor film. There may be an undercoat layer or the like between the organic semiconductor film and the protective film.
The protective film is preferably one that does not damage the organic semiconductor when it is formed on the organic semiconductor, and that does not cause intermixing (interlayer mixing) when a resist film is applied on the protective film. The protective film is preferably a film containing a water-soluble resin, and more preferably a film containing a fat-soluble resin as a main component. The main component means the largest component among the components constituting the protective film, and preferably 80% by mass or more is a water-soluble resin.
The water-soluble resin in the present invention refers to a resin having a solubility in water at 20 ° C. of 1% or more.

The protective film is difficult to dissolve in a developer containing an organic solvent and is preferably dissolved in water. For this reason, when using water-soluble resin for a protective film, it is preferable that the sp value (solubility parameter) is 18 (MPa) ^1/2 or more and less than 25 (MPa) ^1/2 , 20-24 (MPa) More preferably, it is ^1/2 , and it is more preferable that it is 21-24 (MPa) ^1/2 . The sp value is a value calculated by the Hoy method, and the Hoy method is described in POLYMER HANDBOOK FOURTH EDITION.
Moreover, although the composition for protective film formation may contain 2 or more types of resin, it is preferable in this case that 2 or more types of resin each satisfy | fills the said range.

Water-soluble resins used in the present invention include polyvinylpyrrolidone, water-soluble polysaccharides (water-soluble cellulose (such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose), pullulan or pullulan derivatives, starch, hydroxypropyl. Starch, carboxymethyl starch, chitosan, cyclodextrin), polyvinyl alcohol, polyethylene oxide, polyethyloxazoline, and the like. Polyvinyl pyrrolidone, polyvinyl alcohol, and pullulan are preferable. Among these, polyvinyl pyrrolidone is preferable because it has a good coated surface and is easily dissolved and removed with water.
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 resin forming the protective film used in the present invention is preferably from 500 to 400,000, more preferably from 2,000 to 300,000, still more preferably 3, as a polystyrene-converted value by the GPC method. 000-200,000.
The degree of dispersion (molecular weight distribution) of the protective film resin is usually from 1.0 to 3.0, and preferably in the range of from 1.0 to 2.6.

In the present invention, the protective film is formed, for example, by applying a protective film forming composition on the organic semiconductor film and drying it.
As an application method, coating is preferable. Examples of application methods include casting method, blade coating method, wire bar coating method, spray coating method, dipping (dipping) coating method, bead coating method, air knife coating method, curtain coating method, inkjet method, spin coating method, The Langmuir-Blodgett (LB) method can be used. In the present invention, it is more preferable to use a casting method, a spin coating method, and an ink jet method. By such a process, a film such as an organic semiconductor film having a smooth surface and a large area can be produced at low cost.

  The solid content concentration of the composition for forming a protective film is preferably 0.5 to 30% by mass, more preferably 1.0 to 20% by mass, and 2.0 to 14% by mass. Further preferred. It can apply | coat more uniformly by making solid content concentration into the said range.

  It is preferable that the composition for forming a protective film 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 allyl 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 silicon or silicon, acetylene glycol, ethylene oxide adducts of acetylene glycol, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, sodium butyl naphthalene sulfonate, sodium pentyl naphthalene sulfonate, hexyl Alkyl naphthalene sulfonates such as sodium naphthalene sulfonate and sodium octyl naphthalene sulfonate, alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium dodecyl sulfonate, sulfosuccinate esters such as sodium dilauryl sulfosuccinate, etc. Anionic surfactants; alkylbetaines such as lauryl betaine and stearyl betaine, and amphoteric boundaries such as amino acids An activator can be used, but particularly preferred is an acetylene skeleton represented by the following formula (1), which has a low content of metal ions that affect the electrical characteristics of the organic semiconductor and has excellent antifoaming properties. It has a nonionic surfactant.

式（１）中、Ｒ¹、Ｒ²はお互い独立に、置換基を有してもよい炭素数３〜１５のアルキル基、置換基を有してもよい炭素数６〜１５の芳香族炭化水素基、または置換基を有してもよい炭素数４〜１５の複素芳香族環基（置換基としては炭素数１〜２０のアルキル基、炭素数６〜１５の芳香族炭化水素基、炭素数７〜１７のアラルキル基、炭素数１〜２０のアルコキシ基、炭素数２〜２０のアルコキシ−カルボニル基、炭素数２〜１５のアシル基が挙げられる。）を示す。
上記界面活性剤の例として、日信化学工業（株）製、サーフィノールシリーズが例示される。
保護膜形成用組成物が界面活性剤を含む場合、界面活性剤の添加量は、保護膜としたときに、好ましくは０．０５〜８質量％、さらに好ましくは０．０７〜５質量％、特に好ましくは０．１〜３質量％の割合で含まれていることが好ましい。
これら界面活性剤は、１種のみ用いてもよいし、２種類以上用いてもよい。

In formula (1), R ¹ and R ² are each independently an alkyl group having 3 to 15 carbon atoms which may have a substituent, or an aromatic carbon atom having 6 to 15 carbon atoms which may have a substituent. A hydrogen group, or a heteroaromatic cyclic group having 4 to 15 carbon atoms which may have a substituent (the substituent is an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, carbon And an aralkyl group having 7 to 17 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy-carbonyl group having 2 to 20 carbon atoms, and an acyl group having 2 to 15 carbon atoms.
As an example of the surfactant, the Surfinol series manufactured by Nissin Chemical Industry Co., Ltd. is exemplified.
When the composition for forming a protective film contains a surfactant, the amount of the surfactant added is preferably 0.05 to 8% by mass, more preferably 0.07 to 5% by mass, when the protective film is formed. Particularly preferably, it is contained in a proportion of 0.1 to 3% by mass.
These surfactants may be used alone or in combination of two or more.

  The protective film preferably has a thickness of 20 nm to 5 μm, and more preferably has a thickness of 100 nm to 1 μm. By setting the solid content concentration in the protective composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property, the film thickness as described above can be obtained.

  You may mix | blend dye with a protective film. By blending the dye, it is possible to adjust the absorption wavelength in accordance with the wavelength of the exposure light source, so that damage due to exposure of the organic semiconductor material can be effectively prevented.

As dyes, azo dyes, nitro dyes, nitrosolo dyes, stilbene azo dyes, ketoimine dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine / polymethine dyes, thiazole dyes, indamine / indophenol dyes, azine dyes Oxazine dye, thiazine dye, sulfur dye, aminoketone dye, oxyketone dye, anthraquinone dye, indigoid dye, phthalocyanine dye, and the like.
When mix | blending dye, it can be 0.1-10 mass% of a protective film.
The dye may be used alone or in combination.

<Photosensitive resin composition>
The photosensitive resin composition used in the present invention plays a role as a resist composition for producing an organic semiconductor, and is used for forming a resist film on a protective film.
The photosensitive resin composition used in the present invention increases the dissolution rate in a developer containing an organic solvent due to the main chain decomposition reaction of the compound (A1) and / or the compound (A2) after light irradiation, and has an sp value of 19 preferably the dissolution rate is increased relative to the organic solvent (MPa) of less than ^1/2, more preferably in a readily soluble against 18.5 (MPa) ^1/2 or less of the organic solvent, 18.0 (MPa) It is more preferable that the dissolution rate increases with respect to an organic solvent of ^1/2 or less.
In the present invention, one of (A1) compound and compound (A2) may be used, or both may be used. When both are used, the total amount is preferably in the range of 10 to 100% by mass in the solid content of the photosensitive resin composition, and more preferably in the range of 30 to 100% by mass.

<< (A1) Compound >>
The compound (A1) is a compound whose main chain is decomposed by light irradiation with a wavelength of 100 to 600 nm. In such a compound, the main chain is decomposed by light irradiation, and the dissolution rate in a developer containing an organic solvent is increased. The compound (A1) is usually a resin. The molecular weight reduction rate is preferably, for example, 50% or more.
As the compound (A1), known compounds such as those described in Japanese Patent Application Laid-Open Nos. 2006-7675 and 2006-44238 can be arbitrarily used. Specifically, a resin whose main component is a structural unit that includes a bond in its structure that is cleaved by irradiation with light having a wavelength of 100 to 600 nm. When the resin containing such a structural unit as a main component is exposed, the bond in the structural unit is cleaved by the exposure, whereby the resin component itself is decomposed and the solubility in the developer increases.
Preferable resins include vinyl resins having a carbonyl group directly bonded to the main chain. Examples of such a resin include structural units constituted by cleavage of an ethylenic double bond of a vinyl compound having a carbonyl group.
More specifically, examples include acrylic polymers mainly composed of structural units derived from (meth) acrylic acid esters, and vinyl ketone polymers mainly composed of structural units derived from vinyl ketones such as isopropenyl ketone. It is done.
The light irradiation light is preferably ultraviolet light (for example, light in a wavelength band selected from a wavelength of 100 to 400 nm, more preferably far ultraviolet light to medium ultraviolet light (for example, 200 nm to 350 nm). When irradiated, one or both bonds on both sides of the carbonyl group are broken and the resin component itself is decomposed, thereby increasing the solubility in the developer.
Particularly preferred compound (A1) is a compound in which a tertiary carbon atom is bonded to one or both of both sides of a structural unit constituted by cleavage of an ethylenic double bond of a vinyl compound having a carbonyl group from the viewpoint of sensitivity or the like. The structural unit is included, and further, the structural unit is the main component.

 The compound (A1) is mainly composed of a repeating unit selected from the group consisting of a structural unit represented by the following general formula (a-1) and a structural unit represented by the following general formula (a-2). Are preferred.

In the general formula (a-1), R is a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of sensitivity.
R ¹¹ is an optionally substituted alkyl group or aryl group.
Examples of the alkyl group for R ¹¹ include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a cycloalkyl group having 4 to 23 carbon atoms such as a cyclopentyl group and a cyclohexyl group; a cyclopentenyl group and a cyclohexenyl group. A cycloalkenyl group having 4 to 23 carbon atoms such as a group; an aryloxyalkyl group having 7 to 26 carbon atoms (-ROAr group) such as a phenoxymethyl group, a 2-phenoxyethyl group and a 4-phenoxybutyl group; a benzyl group, 3 -Aralkyl groups having 7 to 20 carbon atoms such as phenylpropyl group.
As the aryl group of R ^11, an aryl group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and a tolyl group, an electron donating group, and / or an electron withdrawing group is substituted. An aryl group etc. are mentioned.
R ¹¹ is preferably a linear or branched lower alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 15 carbon atoms. Among them, a methyl group, a tert-butyl group, a phenyl group, or a naphthyl group is preferable. Of these, a methyl group and a phenyl group are preferable.
As the structural unit (a1), one type may be used alone, or two or more types may be used in combination.

In the general formula (a-2), R is a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of sensitivity.
R ¹² is an optionally substituted alkyl group or aryl group.
Examples of the alkyl group for R ¹² include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group and a propyl group; a cycloalkyl group having 4 to 23 carbon atoms such as a cyclopentyl group and a cyclohexyl group; a cyclopentenyl group and a cyclohexenyl group A cycloalkenyl group having 4 to 23 carbon atoms such as a group; an aryloxyalkyl group having 7 to 26 carbon atoms (-ROAr group) such as a phenoxymethyl group, a 2-phenoxyethyl group and a 4-phenoxybutyl group; a benzyl group, 3 -Aralkyl groups having 7 to 20 carbon atoms such as phenylpropyl group.
As the aryl group for R ^12, an aryl group having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, and a tolyl group, an electron donating group, and / or an electron withdrawing group is substituted. An aryl group etc. are mentioned.
R ¹² is preferably a linear or branched lower alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 15 carbon atoms, and among them, a methyl group, an ethyl group, a propyl group, a phenyl group, and a naphthyl group are preferable. Among them, a methyl group, an ethyl group, a propyl group, and a phenyl group are preferable.
As the structural unit (a2), one type may be used alone, or two or more types may be used in combination.

In the compound (A1), either one of the structural units (a1) and (a2) may be used, or both may be used in combination. In view of excellent effects of the present invention, at least the structural unit (a1) is preferably used.
In the compound (A1), the total proportion of the structural units (a1) and (a2) is preferably 60 mol% or more, more preferably 70 mol% or more with respect to the total of all the structural units constituting the compound (A1). 80 mol% or more is more preferable, 90 mol% or more is further more preferable, and 100 mol% is particularly preferable.

In the present invention, since the effect, sensitivity, etc. of the present invention are particularly excellent, in the compound (A1), R in the general formula (a-1) is a methyl group, and R ¹¹ has 1 to 5 carbon atoms. It is preferably an isopropenyl ketone polymer mainly composed of a structural unit which is a lower alkyl group or a phenyl group.
As the isopropenyl ketone-based polymer, those in which R is a methyl group, R ¹¹ is a lower alkyl group or a phenyl group, and those in which R ¹¹ is a methyl group are particularly preferable.

The compound (A1) may have other repeating units in addition to the structural unit. Here, examples of other repeating units include repeating units derived from various known monomers.
Preferred examples include known monomers such as acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide and the like. Examples include derived repeating units.
Specific examples of acrylic esters include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, Dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chloro Benzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl Acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenyl carbonyloxy) ethyl acrylate, polyalkylene glycol acrylate. Among these, alkyl acrylate and aryl acrylate are preferable, alkyl acrylate is more preferable, and methyl acrylate, ethyl acrylate, and propyl acrylate are more preferable.
Specific examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chloro Benzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphene Examples include til methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenylcarbonyloxy) ethyl methacrylate, and polyalkylene glycol methacrylate. It is done. Among these, alkyl methacrylate and aryl methacrylate are preferable, alkyl methacrylate is more preferable, and methyl methacrylate, ethyl methacrylate, and propyl methacrylate are more preferable.
Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, and N-tolylacrylamide. N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-phenylacrylamide , N-hydroxyethyl-N-methylacrylamide, polyalkylene glycol acrylamide and the like.
Specific examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, N-hydroxyethylmethacrylamide, N -Phenylmethacrylamide, N-tolylmethacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide, N , N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide, polyalkylene glycol methacrylamide and the like.
Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like. Specific examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

The weight average molecular weight (Mw) of the compound (A1) before decomposition is not particularly limited, but is preferably in the range of 1,000 to 1,000,000, and 10,000 to 100,000. Is more preferable, and 30,000 to 80,000 is particularly preferable. When the amount is not more than the upper limit of the above range, the solubility of the exposed area in the developer tends to be further improved. When it is at least the lower limit of the above range, film loss in the unexposed area is less likely to occur.
The weight average molecular weight (Mw) after main chain decomposition of the compound (A1) is not particularly limited, but is preferably in the range of 0.1% to 90% before main chain decomposition. 5% to 70% is more preferable, and 1% to 50% is particularly preferable. When the amount is not more than the upper limit of the above range, the difference in solubility in the developing solution between the exposed portion and the unexposed portion is remarkable, and a good pattern is easily obtained.

  In addition to the above, as the compound (A1), compounds described in JP-A-2006-11181 can also be preferably employed, and these documents are incorporated in the present specification.

  Although the specific example of a compound (A1) is given to the following, it cannot be overemphasized that this invention is not limited to these. In addition, a weight average molecular weight (Mw) is an example and can be adjusted suitably. Moreover, when two or more types of repeating units are included, the ratio of each repeating unit indicates mol%. The ratio of these repeating units can also be adjusted as appropriate.

A compound (A1) can be used 1 type or in mixture of 2 or more types.
In the photosensitive resin composition used in the present invention, the concentration of the compound (A1) is not particularly limited as long as the photosensitive resin composition can be applied to a substrate or the like, and depends on the resist film thickness to be formed. What is necessary is just to set suitably. As a density | concentration of the compound (A1) in solid content of the photosensitive resin composition, it is preferable to exist in the range of 10-100 mass%, and the inside of the range of 30-100 mass% is more preferable.

<< (A2) Compound >>
The compound (A2) is a compound in which the main chain is decomposed by the activator (B) that generates active species when irradiated with light having a wavelength of 100 to 600 nm. In such a compound, the main chain is decomposed by light irradiation, and the dissolution rate in a developer containing an organic solvent is increased. The compound (A2) is usually a resin.
As the compound (A2), a compound in which the main chain is decomposed by heating in the presence of an acid or a base to reduce the molecular weight can be particularly preferably used. The molecular weight reduction rate is preferably, for example, 50% or more. Such a resin is not particularly limited. For example, vinyl resins, polycarbonate resins, polyester resins, polyamide resins, polyimide resins, polyether resins, polyurethane resins, (meth) acrylates. Based resins, etc., and one or more of these can be used in combination. Among these, polycarbonate resins, vinyl resins and (meth) acrylic resins are preferable, and polycarbonate resins are particularly preferable. These are more suitably selected as the resin component because their molecular weight is more significantly reduced by heating in the presence of an acid or base.

<<< Vinyl resin >>>
Although it does not restrict | limit especially as vinyl resin, For example, polyvinyl ethers, such as a polymer of styrene derivatives, such as polystyrene and poly-alpha-methylstyrene, poly (ethyl vinyl ether), poly (butyl vinyl ether), polyvinyl formal And derivatives thereof, etc., and one or more of them can be used in combination. Among these, poly-α-methylstyrene is preferable. Such a resin component is particularly preferably used from the viewpoint of excellent workability.

<<< Polycarbonate resin >>>
Furthermore, the polycarbonate-based resin is not particularly limited, but includes a linear chemical structure such as polypropylene carbonate, polyethylene carbonate, and polybutylene carbonate in a carbonate constituent unit, or a cyclic chemical structure in a carbonate structural unit. Among them, among them, it is preferable that a cyclic chemical structure is contained in the carbonate structural unit. Such a resin component is particularly preferably used from the viewpoint of excellent workability.

 Hereinafter, the polycarbonate resin comprising the cyclic chemical structure in the carbonate structural unit will be described in detail.

 The polycarbonate-based resin containing a cyclic chemical structure may have any structure as long as the structural unit has a cyclic chemical structure (hereinafter also referred to as “cyclic body”). It is preferable to have at least two annular bodies. By appropriately selecting the number and type of cyclic bodies in such a polycarbonate resin, it is possible to easily reduce the molecular weight of the product by heating in the presence of an acid or base generated from the active agent by irradiation with active energy rays. It becomes.

 The number of cyclic bodies is preferably 2 to 5, more preferably 2 or 3, and still more preferably 2. By including such a number of cyclic bodies as the carbonate structural unit, the temporary fixing agent obtains excellent etching resistance before irradiation with active energy rays.

 The plurality of cyclic bodies may have a linked polycyclic structure formed by connecting the vertices to each other, but the condensed polycycle formed by condensing each side of each ring A system structure is preferred. Thereby, since the planarity of the carbonate structural unit is improved, it becomes possible to set a larger difference in the dissolution rate in the developer before and after irradiation with the active energy ray.

 Furthermore, it is preferable that each of the plurality of cyclic bodies is a 5-membered ring or a 6-membered ring. As a result, the planarity of the carbonate structural unit is further maintained, so that the difference in the dissolution rate in the developer before and after irradiation with the active energy ray can be set to be larger and the solubility in the solvent can be increased. It can be made more stable.

 Such a plurality of cyclic bodies are preferably alicyclic compounds. When each cyclic body is an alicyclic compound, the effects as described above are more remarkably exhibited.

 In consideration of these, in the polycarbonate (resin component), as the carbonate structural unit, for example, a structure represented by the following chemical formula (1) is a particularly preferable structure.

 In addition, the polycarbonate which has a carbonate structural unit represented by the said Chemical formula (1) can be obtained by the polycondensation reaction of decalin diol and carbonic acid diester like diphenyl carbonate.

 Moreover, in the carbonate structural unit represented by the chemical formula (1), the carbon atoms derived from the hydroxyl group of decalin diol are carbon atoms constituting decalin (that is, two cyclic bodies forming a condensed polycyclic structure), respectively. And three or more atoms are preferably interposed between these carbon atoms.

 As a result, the linearity of the polycarbonate is maintained, and as a result, the difference in the dissolution rate in the developer before and after irradiation with the active energy ray can be set more reliably and large. Furthermore, the solubility with respect to a solvent can be stabilized more.

 Examples of such a carbonate structural unit include those represented by the following chemical formulas (1A) and (1B).

 Further, the plurality of cyclic bodies may be alicyclic compounds or may be heteroalicyclic compounds. Even when each cyclic body is a heteroalicyclic compound, the effects as described above are more remarkably exhibited.

 In this case, in the polycarbonate (resin component), as the carbonate structural unit, for example, a structure represented by the following chemical formula (2) is a particularly preferable structure.

 In addition, the polycarbonate which has a carbonate structural unit represented by the said Chemical formula (2) can be obtained by the polycondensation reaction of ether diol represented by following Chemical formula (2a), and carbonic acid diester like diphenyl carbonate.

 In the carbonate structural unit represented by the chemical formula (2), the carbon atom derived from the hydroxyl group of the cyclic ether diol represented by the chemical formula (2a) forms the cyclic ether (that is, a condensed polycyclic structure). It is preferable that three or more atoms are interposed between these carbon atoms and bonded to the carbon atoms constituting the two cyclic bodies. As a result, the linearity of the polycarbonate is maintained, and as a result, the difference in the dissolution rate in the developer before and after irradiation with the active energy ray can be set more reliably and large. Furthermore, the solubility with respect to a solvent can be stabilized more.

 Examples of such a carbonate structural unit include those of the 1,4: 3,6-dianhydro-D-sorbitol (isosorbide) type represented by the following chemical formula (2A), and those represented by the following chemical formula (2B). 4: 3,6-dianhydro-D-mannitol (isomannide) type.

The polycarbonate resin may have a repeating unit in addition to the structural unit. Here, examples of other repeating units include repeating units derived from various known hydroxy compounds.
Preferable examples include structural units derived from aliphatic dihydroxy compounds and structural units derived from alicyclic dihydroxy compounds. Specific examples of the aliphatic dihydroxy compound and the alicyclic dihydroxy compound include the following.

Examples of the aliphatic dihydroxy compound include 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and 2-ethyl. -1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol and the like.

In addition, the said exemplary compound is an example of the aliphatic dihydroxy compound which can be used for this invention, Comprising: It is not limited to these at all. These aliphatic dihydroxy compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

Although it does not specifically limit as an alicyclic dihydroxy compound, Usually, the compound containing a 5-membered ring structure or a 6-membered ring structure is mentioned. When the alicyclic dihydroxy compound has a 5-membered ring structure or a 6-membered ring structure, the heat resistance of the obtained polycarbonate resin tends to increase. The six-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond. Carbon number contained in an alicyclic dihydroxy compound is 70 or less normally, Preferably it is 50 or less, More preferably, it is 30 or less. An alicyclic dihydroxy compound having 70 or less carbon atoms is preferable because it is easy to synthesize and purify, and is inexpensive and easily available.

Specific examples of the alicyclic dihydroxy compound containing a 5-membered ring structure or a 6-membered ring structure include alicyclic dihydroxy compounds represented by the following general formula (I) or (II).
_{HOCH 2 -R 9 -CH 2 OH (} I)
HO—R ₁₀ —OH (II)
However, in formula (I) and formula (II), R ₉ and R ₁₀ each independently represents a substituted or unsubstituted divalent group containing a cycloalkyl structure having 4 to 20 carbon atoms. )

As cyclohexanedimethanol which is an alicyclic dihydroxy compound represented by the above general formula (I), in general formula (I), R ₉ is the following general formula (Ia) (wherein R ₁₁ is a hydrogen atom, or Represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.). Specific examples thereof include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and the like.

Examples of tricyclodecane dimethanol and pentacyclopentadecane dimethanol, which are alicyclic dihydroxy compounds represented by the above general formula (I), include, in general formula (I), R ₉ represents the following general formula (Ib) (in the formula: , N represents 0 or 1).

As decalin dimethanol or tricyclotetradecane dimethanol, which is an alicyclic dihydroxy compound represented by the general formula (I), in general formula (I), R ₉ is represented by the following general formula (Ic) (wherein m represents 0 or 1). Specific examples thereof include 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, and the like.

Moreover, as norbornane dimethanol which is an alicyclic dihydroxy compound represented by the general formula (I), various isomers in which R ₉ is represented by the following general formula (Id) in the general formula (I) Include. Specific examples thereof include 2,3-norbornane dimethanol, 2,5-norbornane dimethanol and the like.

The adamantane dimethanol, which is an alicyclic dihydroxy compound represented by the general formula (I), includes various isomers in which R ₉ is represented by the following general formula (Ie) in the general formula (I). Specific examples of such a material include 1,3-adamantane dimethanol.

Further, cyclohexanediol, which is an alicyclic dihydroxy compound represented by the general formula (II), in the general formula (II), R ₁₀ is represented by the following general formula (IIa) (wherein R ₁₁ is a hydrogen atom, substituted Or an unsubstituted alkyl group having 1 to 12 carbon atoms). Specific examples thereof include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and the like.

As tricyclodecanediol and pentacyclopentadecanediol, which are alicyclic dihydroxy compounds represented by the general formula (II), in general formula (II), R ₁₀ is represented by the following general formula (IIb) (wherein n Represents 0 or 1).

As decalin diol or tricyclotetradecane diol, which is an alicyclic dihydroxy compound represented by the general formula (II), in general formula (II), R ₁₀ is represented by the following general formula (IIc) (where m is It represents 0 or 1). Specifically, 2,6-decalindiol, 1,5-decalindiol, 2,3-decalindiol and the like are used as such.

The norbornanediol, which is an alicyclic dihydroxy compound represented by the general formula (II), includes various isomers in which R ₁₀ is represented by the following general formula (IId) in the general formula (II). Specifically, 2,3-norbornanediol, 2,5-norbornanediol, and the like are used as such.

The adamantanediol which is an alicyclic dihydroxy compound represented by the general formula (II) includes various isomers in which R ₁₀ is represented by the following general formula (IIe) in the general formula (II). Specifically, 1,3-adamantanediol etc. are used as such.

Among the specific examples of the alicyclic dihydroxy compounds described above, cyclohexane dimethanols, tricyclodecane dimethanols, adamantane diols, and pentacyclopentadecane dimethanols are preferable, and are easily available and easy to handle. From the viewpoint, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and tricyclodecane dimethanol are particularly preferable.

In addition, the said exemplary compound is an example of the alicyclic dihydroxy compound which can be used for this invention, Comprising: It is not limited to these at all. These alicyclic dihydroxy compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The weight average molecular weight (Mw) before decomposition of the compound (A2) is slightly different depending on the kind of the resin component and the like, but is preferably 1,000 to 1,000,000, and 10,000 to 80,000. It is more preferable that If it is below the upper limit of the above range, the solubility of the exposed area in the developer tends to be further improved. When it is at least the lower limit of the above range, film loss in the unexposed area is less likely to occur.
The weight average molecular weight (Mw) of the component (A2) after main chain decomposition is not particularly limited, but is preferably in the range of 0.1% to 90% before main chain decomposition. 5% to 70% is more preferable, and 1% to 50% is particularly preferable. When the amount is not more than the upper limit of the above range, the difference in solubility in the developing solution between the exposed portion and the unexposed portion is remarkable, and a good pattern is easily obtained.

Although the preferable example of a polycarbonate-type resin is given to the following, it cannot be overemphasized that this invention is not limited to these.

<<< (Meth) acrylate-based resin >>>
The (meth) acrylic resin is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Copolymers selected from various (meth) acrylic monomers such as acrylic acid and 2-hydroxyethyl (meth) acrylate. Among these, polymethyl methacrylate or polyethyl methacrylate is preferable. Such a resin component is particularly preferably used from the viewpoint of excellent workability.

A compound (A2) can be used 1 type or in mixture of 2 or more types.
In the photosensitive resin composition used in the present invention, the concentration of the compound (A2) is not particularly limited as long as the photosensitive resin composition can be applied to a substrate or the like, and depends on the resist film thickness to be formed. What is necessary is just to set suitably. As a density | concentration of the compound (A2) in solid content of the photosensitive resin composition, it is preferable to exist in the range of 10-100 mass%, and the inside of the range of 30-100 mass% is more preferable.

<< Activator (B) >>
The activator is an activator that generates active species upon irradiation with light having a wavelength of 100 to 600 nm, and the active species may be an acid or a base. It has a function of reducing the molecular weight of the compound (A2) by heating in the presence of this active species.
That is, examples of the activator in the present invention include a photoacid generator that generates an acid upon irradiation with light having a wavelength of 100 to 600 nm and a photobase generator that generates a base. In the present invention, an acid generator is more preferable.

<<< acid generator >>>
As the acid generator, any one that generates an organic acid and one that generates an inorganic acid can be preferably used.

The organic acid is preferably at least one selected from sulfonic acid, trialkylsulfonylmethide acid and dialkylsulfonylimide acid.
The photoacid generator that generates an organic acid used in the present invention is:
(I) a compound having an oxime sulfonate group (hereinafter also referred to as oxime sulfonate compound) and a compound having an imide sulfonate group (hereinafter also referred to as imide sulfonate group),
(Ii) Compound having sulfonium cation (hereinafter also referred to as sulfonium salt) and compound having iodonium cation (hereinafter also referred to as iodonium salt)
(Iii) Diazodisulfone compound and disulfone compound (more preferably, diazodisulfone compound)
Those corresponding to any of the group consisting of:

(I) Compound having oxime sulfonate group, compound having imide sulfonate group The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (2), formula (OS-103) described later And an oxime sulfonate compound represented by the formula (OS-104) or the formula (OS-105).

式（２）におけるＸはそれぞれ独立に、アルキル基、アルコキシ基、または、ハロゲン原子を表す。
前記Ｘにおけるアルキル基およびアルコキシ基は、置換基を有していてもよい。前記Ｘにおけるアルキル基としては、炭素数１〜４の、直鎖状または分岐状アルキル基が好ましい。前記Ｘにおけるアルコキシ基としては、炭素数１〜４の直鎖状または分岐状アルコキシ基が好ましい。前記Ｘにおけるハロゲン原子としては、塩素原子またはフッ素原子が好ましい。
式（２）におけるｍは、０〜３の整数を表し、０または１が好ましい。ｍが２または３であるとき、複数のＸは同一でも異なっていてもよい。

X in Formula (2) represents an alkyl group, an alkoxy group, or a halogen atom each independently.
The alkyl group and alkoxy group in X may have a substituent. The alkyl group for X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group for X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in X is preferably a chlorine atom or a fluorine atom.
M in Formula (2) represents an integer of 0 to 3, and 0 or 1 is preferable. When m is 2 or 3, the plurality of X may be the same or different.

R ⁴ in Formula (2) represents an alkyl group or an aryl group, and is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 is preferably a halogenated alkoxy group, 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 is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or an alkoxy halide having 1 to 5 carbon atoms. Represents a group.
Specific examples of the alkyl group having 1 to 10 carbon atoms in R ⁴ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert. -Butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like can be mentioned.
Specific examples of the alkoxy group having 1 to 10 carbon atoms in R ⁴ include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group, n-octyloxy group, An n-decyloxy group etc. are mentioned.
Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms in R ⁴ include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro-n. -An amyl group etc. are mentioned.
Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms in R ⁴ include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, and a perfluoro-n. -An amyloxy group etc. are mentioned.

Specific examples of the phenyl group optionally substituted by W in R ⁴ include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethyl. Phenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s-butyl) Phenyl group, p- (tert-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (tert-amyl) phenyl group, o-methoxyphenyl group, m -Methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenol Group, p- (n-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (tert-butoxy) phenyl group, p- (n-amyloxy) Phenyl group, p- (i-amyloxy) phenyl group, p- (tert-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4 -Dibromophenyl group, 2,4-difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl group, pentachlorophenyl group, pentabromo A phenyl group, a pentafluorophenyl group, a p-biphenylyl group, etc. are mentioned.

Specific examples of the naphthyl group which may be substituted with W in R ⁴ include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, and 5-methyl. -1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group and the like.

Specific examples of the anthranyl group optionally substituted with W in R ⁴ include 2-methyl-1-anthranyl group, 3-methyl-1-anthranyl group, 4-methyl-1-anthranyl group, 5-methyl -1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1-anthranyl group 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7-methyl- Examples include 2-anthranyl group, 8-methyl-2-anthranyl group, 9-methyl-2-anthranyl group, 10-methyl-2-anthranyl group, and the like.

In the formula (2), m is 1, X is a methyl group, the substitution position of X is an ortho position, R ⁴ is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- A compound having a 2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.
Specific examples of the oxime sulfonate compound represented by the formula (2) include the following compound (i), compound (ii), compound (iii), compound (iv) and the like. May be used in combination, or two or more types may be used in combination. Compounds (i) to (iv) can be obtained as commercial products. Specific examples of the oxime sulfonate compound represented by the other formula (2) are given below.

（式（ＯＳ−１０３）〜（ＯＳ−１０５）中、Ｒ¹¹はアルキル基、アリール基またはヘテロアリール基を表し、複数存在するＲ¹²はそれぞれ独立に、水素原子、アルキル基、アリール基またはハロゲン原子を表し、複数存在するＲ¹⁶はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基またはアルコキシスルホニル基を表し、ＸはＯまたはＳを表し、ｎは１または２を表し、ｍは０〜６の整数を表す。）

(In the formulas (OS-103) to (OS-105), R ¹¹ represents an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ¹² are each independently a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. A plurality of R ¹⁶ independently represent 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, and n represents 1 or 2 and m represents an integer of 0 to 6.)

In the formulas (OS-103) to (OS-105), the alkyl group, aryl group or heteroaryl group represented by R ¹¹ may have a substituent.
In the formulas (OS-103) to (OS-105), 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.

In the formulas (OS-103) to (OS-105), examples of the alkyl group represented by R ¹¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, and s-butyl. Group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, etc. Is mentioned.

In the formulas (OS-103) to (OS-105), the aryl group represented by R ¹¹ is preferably an aryl group having 6 to 30 carbon atoms in total 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.

Examples of the aryl group represented by R ¹¹ include phenyl group, p-methylphenyl group, trimethylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group. preferable.

In the formulas (OS-103) to (OS-105), the heteroaryl group represented by R ¹¹ is preferably a heteroaryl group having 4 to 30 carbon atoms in total 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.

In the formulas (OS-103) to (OS-105), 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 include It 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:

In Formulas (OS-103) to (OS-105), R ¹² is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.
In the formulas (OS-103) to (OS-105), it is preferable that one or two of R ¹² present in the compound is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. More preferably an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the rest is a hydrogen atom.
In the formulas (OS-103) to (OS-105), 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 same groups as the substituent that the alkyl group or aryl group in R ¹ may have.

In the formulas (OS-103) to (OS-105), the alkyl group represented by R ¹² is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent. It is more preferable that it is a C1-C6 alkyl group which may have 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. Group is more preferable, methyl group, ethyl group, n-propyl group, n-butyl group and n-hexyl group are more preferable, and methyl group is particularly preferable.

In the formulas (OS-103) to (OS-105), the aryl group represented by R ¹² is preferably an aryl group having 6 to 30 carbon atoms in total 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.

In the formulas (OS-103) to (OS-105), X represents O or S, and is preferably O. In the formulas (OS-103) to (OS-105), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.
In the formulas (OS-103) to (OS-105), n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is 2 is preferable.

In the formulas (OS-103) to (OS-105), the alkyl group and alkyloxy group represented by R ¹⁶ may have a substituent.
In the formulas (OS-103) to (OS-105), 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.

In the formulas (OS-103) to (OS-105), examples of the alkyl group represented by R ¹⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, and s-butyl. Group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group preferable.

In the formulas (OS-103) to (OS-105), 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, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, aminocarbonyl Groups.

In the formulas (OS-103) to (OS-105), examples of the alkyloxy group represented by R ¹⁶ include a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, and a trichloromethyloxy group. Or an ethoxyethyloxy group is preferred.
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.

  In the formulas (OS-103) to (OS-105), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. It is particularly preferred.

  The compound represented by the 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 formula (OS-105) is represented by the following formula (OS-108). ) Or (OS-109) is particularly preferable.

（式（ＯＳ−１０６）〜（ＯＳ−１１１）中、Ｒ¹¹はアルキル基、アリール基またはヘテロアリール基を表し、Ｒ¹⁷は、水素原子または臭素原子を表し、Ｒ¹⁸は水素原子、炭素数１〜８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基またはクロロフェニル基を表し、Ｒ¹⁹は水素原子、ハロゲン原子、メチル基またはメトキシ基を表し、Ｒ²⁰は水素原子またはメチル基を表す。）

(In the formulas (OS-106) to (OS-111), 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, 1 to 8 represents an alkyl group, 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; ²⁰ represents a hydrogen atom or a methyl group.)

R ¹¹ in the formulas (OS-106) to (OS-111) has the same meaning as R ¹¹ in the formulas (OS-103) to (OS-105), and preferred embodiments thereof are also the same.
R ¹⁷ in the formula (OS-106) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R ¹⁸ in the above formulas (OS-106) to (OS-111) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or Represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. More preferred is a methyl group.
R ¹⁹ in the formulas (OS-108) and (OS-109) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ²⁰ in the formulas (OS-108) to (OS-111) 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 formulas (OS-103) to (OS-105) include the following exemplary compounds, but the present invention is not limited thereto.

  As another preferred embodiment of the oxime sulfonate compound having at least one oxime sulfonate group, a compound represented by the following formula (OS-101) can be mentioned.

In the formula (OS-101), R ¹¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy 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. Represents. R ¹² 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 - represent, respectively the R ¹⁵ to R ¹⁷ independently represent an alkyl Represents a group or an aryl group.
R ^{21 to} R ²⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy 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.
As R ^{21 to} R ²⁴ , a hydrogen atom, a halogen atom or an alkyl group is preferable, 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 preferable. Among these, an embodiment in which R ^{21 to} R ²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
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 following formula (OS-102).

In the formula (OS-102), R ^11, R ¹² and R ²¹ to R ²⁴ has the same meaning as R ^11, R ¹² and R ²¹ to R ²⁴ in each formula (OS-101), preferred examples also It is the same.
Among these, an embodiment in which R ¹¹ in the formula (OS-101) and the formula (OS-102) is a cyano group or an aryl group is more preferable, represented by the formula (OS-102), in which R ¹¹ is a cyano group, phenyl The embodiment which is a group or a naphthyl group is most preferred.

  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 (exemplary compounds b-1 to b-34) of the compound represented by the formula (OS-101) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto. In specific examples, Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

Among the above compounds, b-9, b-16, b-31, and b-33 are preferable from the viewpoint of achieving both sensitivity and stability.
Commercially available products include WPAG-336 (manufactured by Wako Pure Chemical Industries, Ltd.), WPAG-443 (the following structure, manufactured by Wako Pure Chemical Industries, Ltd.), MBZ-101 (the following structure, manufactured by Midori Chemical Co., Ltd.). Etc.

Examples of the imidosulfonate compound include compounds represented by general formula (ZV).

In General Formula (ZV), R ²⁰⁸ represents an alkyl group or an aryl group. A represents an alkylene group, an alkenylene group or an arylene group. When the alkyl group is a cyclic alkyl group, a ring may be formed via a carbonyl group.
The alkyl group for R ²⁰⁸ is preferably a linear alkyl group or a cyclic alkyl group. R ²⁰⁸ is preferably a linear or branched alkyl group or an aryl group. These groups may be substituted or unsubstituted. When the alkyl group is a cyclic alkyl group, a ring may be formed via a carbonyl group, and the cyclic alkyl group may be polycyclic. Preferably, a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, or pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group). Or a norbornyl group). The alkyl group for R ²⁰⁸ may be further substituted with, for example, a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, and / or a nitro group.

The aryl group for R ²⁰⁸ is preferably a phenyl group or a naphthyl group.
R ²⁰ 8 Noariru groups are, for example, a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, but be further substituted by a cyano group and / or nitro group, preferably a carbon number from 1 to 10 Linear or branched alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group or pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group or norbornyl group). Can be mentioned.

The alkylene group of A is an alkylene group having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 carbon atoms. ˜12 alkenylene groups (for example, ethenylene group, propenylene group, butenylene group, etc.), and as the arylene group of A, C 6-10 arylene groups (for example, phenylene group, tolylene group, naphthylene group, etc.) Each can be mentioned. Among these, a naphthylene group is a preferable example when i-line is used as an exposure wavelength.
Although the example of an imide sulfonate compound is given to the following, this invention is not limited to these.

(Ii) sulfonium salt, iodonium salt sulfonium salt or iodonium salt (ii) sulfonium salt, iodonium salt sulfonium salt or iodonium salt has an anion that is non-nucleophilic and photodecomposes an organic acid having a pKa of −1 or less. Although it will not be restrict | limited especially if it is a compound to generate | occur | produce, The thing which has a sulfonate anion, a sulfonyl imide anion, a bis (alkyl sulfonyl) imide anion, and a tris (alkyl sulfonyl) methyl anion as an anion is suitable.
More preferred examples include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the general formula (ZI),
R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represents an organic group.
The carbon number of the organic group as R ²⁰¹ , R ²⁰² and R ²⁰³ is generally 1-30, preferably 1-20.
Two of R ^{201 to} R ²⁰³ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ²⁰¹ to R ^203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Z ⁻ represents a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion, etc.), Examples include a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methide anion.

  The aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. 3-30 cycloalkyl groups are mentioned.

  The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), an aryloxysulfonyl group (preferably carbon) Number 6-20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

  Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
The alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.
Z ⁻ represents a carbon number in the cation from the viewpoint of suppressing intermixing (mixing of sulfonium salt and iodonium salt into the protective film) when the photosensitive resin composition is applied on the protective film layer. It preferably contains an aromatic ring group having three or more alkyl groups as substituents. The alkyl group preferably has 6 or more carbon atoms, more preferably 8 or more. The alkyl group may be linear, branched or cyclic, and specifically includes n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-amyl, i-amyl. , Tert-amyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, n-octyl, 2-ethylhexyl, and the like.
Similarly, the anion is preferably a sulfonate containing an alkyl group having 6 or more carbon atoms or a sulfonate containing an aromatic ring having an alkyl group having 3 or more carbon atoms as a substituent.

Z ⁻ is particularly preferably an anion represented by the following general formula (AN1). By adopting such a configuration, when a film containing a water-soluble resin is used as the protective film, the photoacid generator is less likely to enter the protective film, which is preferable. This is particularly effective when a resist film is provided on the surface of the protective film.

Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R ¹ and R ² , R ¹ and R ² may be the same or different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents a cyclic organic group.
x represents an integer of 0 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) will be described in more detail.
The alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , and CH ₂ CH ₂ C ₄ F ₉ are mentioned, among which a fluorine atom and CF ₃ are preferable. In particular, it is preferable that both Xf are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specific examples of the alkyl group having a substituent for R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C ₇ F _15. C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ can be mentioned, among which CF ₃ is preferable.
R ¹ and R ² are preferably a fluorine atom or CF ₃ .

x is preferably 0 to 10, and more preferably 0 to 2.
y is preferably from 0 to 8, and more preferably from 0 to 6.
z is preferably 0 to 5, and more preferably 0 to 3.
The divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, Examples thereof include an alkenylene group or a linking group in which a plurality of these are linked, and a linking group having a total carbon number of 12 or less is preferred. Among these, —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromaticity but also aromaticity). And the like).
The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group. A polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like is present in the film in the post-exposure heating step. Diffusivity can be suppressed, which is preferable from the viewpoint of improving MEEF.
Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.

  Moreover, a lactone structure can also be mentioned as a cyclic | annular organic group.

  The cyclic organic group may have a substituent, and the substituent may be a linear or branched alkyl group (which may be linear, branched or cyclic, and has 1 to 12 carbon atoms. Is preferable), a cycloalkyl group (which may be any of monocyclic, polycyclic, and spiro rings, preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxy group, and an alkoxy group. Ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

^Examples of the organic group for R ²⁰¹ , R ²⁰² and R ²⁰³ include an aryl group, an alkyl group, and a cycloalkyl group.
Of R ²⁰¹ , R ²⁰² and R ²⁰³ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used. The alkyl group and cycloalkyl groups R ²⁰¹ to R ^203, preferably, may be mentioned linear or branched alkyl group having 1 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms. More preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. More preferable examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. These groups may further have a substituent. Examples of the substituent include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

In the case of forming the two members ring structure of R ²⁰¹ to R ^203, it is preferably a structure represented by the following general formula (A1).

In general formula (A1),
R ^{1a to} R ^13a each independently represents a hydrogen atom or a substituent.
It is preferable that 1-3 are not a hydrogen atom among R ^{< 1a} > -R < ^13a >, and it is more preferable that any one of R ^{< 9a} > -R < ^13a > is not a hydrogen atom.
Za is a single bond or a divalent linking group.
X ⁻ has the same meaning as Z ⁻ in formula (ZI).

Specific examples in the case where R ^{1a to} R ^13a are not hydrogen atoms include halogen atoms, straight chain, branched and cyclic alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, nitro groups and carboxyl groups. , Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, amino Carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl group Yo Arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinyl groups Amino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—OSO ₃ H), and other known ones Examples of the substituent are as follows.
When R ^{1a to} R ^13a are not a hydrogen atom, a linear, branched or cyclic alkyl group substituted with a hydroxyl group is preferable.

Examples of the divalent linking group for Za include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether bond, a thioether bond, an amino group, a disulfide group, and — (CH _{2 ) n -CO -, - (CH} 2) n -SO 2 -, - CH = CH-, an aminocarbonylamino group, and an amino sulfonylamino group (n is an integer of 1 to 3).

In addition, as a preferable structure when at least one of R ²⁰¹ , R ²⁰² and R ²⁰³ is not an aryl group, paragraphs 0046 to 0048 of JP-A-2004-233661, paragraphs 0040 to 340 of JP-A-2003-35948 are disclosed. Compounds exemplified as formulas (I-1) to (I-70) in U.S. Patent Application Publication No. 2003 / 0224288A1, and formula (IA-1) in U.S. Patent Application Publication No. 2003 / 0077540A1. ) To (IA-54) and cation structures such as compounds exemplified as formulas (IB-1) to (IB-24).

In formula (ZII), R ²⁰⁴ ~R ²⁰⁵ represents an aryl group.
The aryl group for R ^{204 to} R ²⁰⁵ is the same as the aryl group described as the aryl group for R ^{201 to} R ²⁰³ in the aforementioned compound (ZI).
Aryl group R ²⁰⁴ to R ²⁰⁵ may have a substituent. Examples of the substituent include those that the aryl group of R ^{201 to} R ²⁰³ in the compound (ZI) may have.

Hereinafter, preferred examples of the sulfonium salt, iodonium sulfonyl salt, or iodonium salt will be described. Needless to say, the present invention is not limited to these examples. Moreover, the compounds described in JP 2013-214053 A can also be preferably used.

(Iii) Diazodisulfone compound, disulfone compound Examples of the diazodisulfone compound include compounds represented by the following general formula (ZIII).

In general formula (ZIII),
R ^{206 to} R ²⁰⁷ each independently represents an aryl group or an alkyl group.
The aryl group and alkyl group of R ^{206 to} R ²⁰⁷ are the same as the aryl group and alkyl group described as the aryl group and alkyl group of R ^{201 to} R ²⁰³ in the aforementioned compound (ZI).
The aryl group and alkyl group of R ^{206 to} R ²⁰⁷ may have a substituent. Examples of this substituent include those which the aryl group and alkyl group of R ^{201 to} R ²⁰³ in the above-mentioned compound (ZI) may have.
Examples of the disulfone compound include compounds represented by the following general formula (ZIV).

In general formulas (ZIV) to (ZVI), Ar ³ and Ar ⁴ each independently represents an aryl group.
Specific examples of the aryl group of Ar ³ and Ar ⁴ include the same examples as the specific examples of the aryl group as R ²⁰¹ , R ²⁰² and R ²⁰³ in the general formula (ZI).

  The acid generator for generating an inorganic acid used in the present invention is not particularly limited, and examples thereof include tetrakis (pentafluorophenyl) borate-4-methylphenyl [4- (1-methylethyl) phenyl] iodonium (DPI-TPFPB). , Tris (4-tert-butylphenyl) sulfonium tetrakis- (pentafluorophenyl) borate (TTBPS-TPFPB), tris (4-tert-butylphenyl) sulfonium hexafluorophosphate (TTBPS-HFP), triphenylsulfonium triflate ( TPS-Tf), bis (4-tert-butylphenyl) iodonium triflate (DTBPI-Tf), triazine (TAZ-101), triphenylsulfonium hexafluoroantimonate (TPS-103) Triphenylsulfonium bis (perfluoromethanesulfonyl) imide (TPS-N1), di- (p-tert-butyl) phenyliodonium, bis (perfluoromethanesulfonyl) imide (DTBPI-N1), triphenylsulfonium, tris (per Fluoromethanesulfonyl) methide (TPS-C1), di- (p-tert-butylphenyl) iodonium tris (perfluoromethanesulfonyl) methide (DTBPI-C1), and the like. Among these, one kind or two or more kinds Can be used in combination. Among these, tetrakis (pentafluorophenyl) borate-4-methylphenyl [4- (1-methylethyl) phenyl] iodonium (DPI-TPFPB), in particular, from the viewpoint that the molecular weight of the resin component can be efficiently reduced. ) Is preferred.

<<< Photobase generator >>>
The photobase generator is not particularly limited, and examples thereof include 5-benzyl-1,5-diazabicyclo (4.3.0) nonane and 1- (2-nitrobenzoylcarbamoyl) imidazole. One kind or a combination of two or more kinds can be used. Among these, 5-benzyl-1,5-diazabicyclo (4.3.0) nonane and derivatives thereof are particularly preferable from the viewpoint that the molecular weight of the resin component can be efficiently lowered.

 Moreover, in this invention, a well-known thing can be used as a photobase generator. For example, M. Shirai, and M Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Tsunooka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J Photopolym. Sci. Technol., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006), Ionicity neutralized by salt formation of the base component, such as transition metal compound complexes, ammonium salts and other structures that have been latentized by salt formation of the amidine moiety with carboxylic acid , Urethane bonds such as carbamate derivatives, oxime ester derivatives, acyl compounds Base component due oxime bond can be exemplified nonionic compounds latent.

 As a photobase generator, it can be used individually by 1 type or in combination of 2 or more types. Specific examples of the ionic compound used as the photobase generator include those represented by the following structural formulas. Needless to say, the present invention is not limited to these examples.

 Moreover, as an oxime ester derivative as a photobase generator, what is shown by the following structural formula can be mentioned, for example.

As an acyl compound, what is shown by the following structural formula can be mentioned, for example.

Moreover, the following compound is mentioned as a carbamate compound as a photobase generator.

（式（５）中、Ｒ^Cは、それぞれ独立に、水素又は１価の有機基であり、同一であっても異なっていても良い。Ｒ^Cは、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。但し、Ｒ^Cの少なくとも１つは１価の有機基である。また、化１７における、Ｒ⁵、Ｒ⁶、Ｒ⁷及びＲ⁸は、それぞれ独立に、水素、ハロゲン、水酸基、ニトロ基、ニトロソ基、メルカプト基、シリル基、シラノール基又は１価の有機基であり、同一であっても異なっていても良い。Ｒ⁵、Ｒ⁶、Ｒ⁷及びＲ⁸は、それらの２つ以上が結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。） Moreover, as a photobase generator used suitably in this invention, a compound as shown to following formula (5) is mentioned.

(In Formula (5), R ^C each independently represents hydrogen or a monovalent organic group, and may be the same or different. R ^C is bonded to form a cyclic structure. And may contain a heteroatom bond, provided that at least one of R ^C is a monovalent organic group, and R ⁵ , R ⁶ , R ⁷ and R ⁸ in Chemical Formula 17 are each independently hydrogen, halogen, hydroxyl, nitro, nitroso group, a mercapto group, a silyl group, a silanol group or a monovalent organic group, it may be different even in the same .R ^5, R ⁶ , R ^7, and R ⁸ may be bonded to each other to form a cyclic structure, and may include a hetero atom bond.

（Ｒ^Cは、それぞれ独立に、水素原子又は１価の有機基であり、同一であっても異なっていても良い。Ｒ^Cは、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。但し、Ｒ^Cの少なくとも１つは１価の有機基である。また、Ｒ^dは、それぞれ独立に、水素原子又は１価の有機基であり、同一であっても異なっていても良い。Ｒ^dは、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。） Examples of the basic substance generated in the photobase generator according to the present invention include amines represented by the following formula (A) and amidines represented by the following formula (B).

(R ^C each independently represents a hydrogen atom or a monovalent organic group, and may be the same or different. R ^C may combine to form a cyclic structure, It may contain a heteroatom bond, provided that at least one of R ^C is a monovalent organic group, and R ^d is independently a hydrogen atom or a monovalent organic group, and R ^d may be bonded to form a cyclic structure or may contain a hetero atom bond.)

In addition, when R ^C in the formula (A) has an amidine structure as contained in the formula (B), the generated base is not the amine of the formula (A) but the formula (B ) Belonging to amidine.

 In view of the large effect of the generated basic substance such as the catalytic effect as described above, it is preferable that the generated basic substance is an aliphatic amine or amidine because it is a highly basic amine. Among these, from the viewpoint of basicity, secondary or tertiary aliphatic amines or amidines are preferable.

In the present invention, the aliphatic amine is generated to achieve high sensitivity, and further, from the viewpoint of increasing the solubility contrast of the unexposed portion of the exposed portion, the nitrogen atom of R ^c in the formula (A), etc. , All the atoms directly bonded to the nitrogen atom constituting the amino group of the generated amine are hydrogen atoms or carbon atoms having SP3 orbitals (except when all of R ^c are hydrogen atoms). Is preferred.
Examples of the substituent in which the atom directly bonded to the nitrogen atom is a carbon atom having an SP3 orbital include a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon. An aliphatic hydrocarbon group composed of a group or a combination thereof. In addition, the said aliphatic hydrocarbon group may have substituents, such as an aromatic group, or may contain bonds other than hydrocarbons, such as a hetero atom, in a hydrocarbon chain. Preferable examples include a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a phenoxyalkyl group having 7 to 26 carbon atoms, and an aryl having 7 to 26 carbon atoms. An alkyl group and a C1-C20 hydroxyalkyl group are mentioned.
Here, when R ^c has the above cyclic aliphatic hydrocarbon group or the above cycloalkyl group, a heterocyclic structure containing a nitrogen atom to which two of R ^c are linked to form a ring and R ^c is bonded Including the case of forming.

Specific examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a cyclohexyl group, an isobornyl group, a norbornyl group, and an adamantyl group. , A benzyl group and the like, but are not limited thereto.
Further, it becomes annularly two of R ^c linked, the heterocyclic structure when forming a heterocyclic structure containing a nitrogen atom to which R ^c is attached, for example, aziridine (three-membered ring) Azetidine (4-membered ring), pyrrolidine (5-membered ring), piperidine (6-membered ring), azepane (7-membered ring), azocane (8-membered ring) and the like. These heterocyclic structures may have a substituent such as a linear or branched alkyl group. For example, as an alkyl substituent, a monoalkylaziridine such as methylaziridine, a dialkylaziridine such as dimethylaziridine, and methylazetidine Monoalkyl azetidine such as dialkyl azetidine such as dimethyl azetidine, trialkyl azetidine such as trimethyl azetidine, monoalkyl pyrrolidine such as methyl pyrrolidine, dialkyl pyrrolidine such as dimethyl pyrrolidine, trialkyl pyrrolidine such as trimethyl pyrrolidine, tetra Tetraalkylpyrrolidines such as methylpyrrolidine, monoalkylpiperidines such as methylpiperidine, dialkylpiperidines such as dimethylpiperidine, and trialkylpiperidines such as trimethylpiperidine Lysine, a tetraalkyl piperidine, such as tetramethylpiperidine, penta-alkyl piperidines such as such as pentamethyl piperidine.

Examples of the compound represented by the formula (A) include the following compounds. In addition, a photobase generator described in JP-A-2008-247747 is also preferably used, the contents of which are incorporated herein.

 Specific examples of amines generated during the decomposition of the photobase generator according to the present invention include primary amines such as n-butylamine, amylamine, hexylamine, cyclohexylamine, octylamine, and benzylamine, diethylamine, and diamine. Linear secondary amines such as propylamine, diisopropylamine and dibutylamine, secondary amines such as aziridine, azetidine, pyrrolidine, piperidine, azepane and azocan and secondary amines such as these alkyl substituents , Aromatic tertiary amines such as dimethylaniline, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, 1,4-diazabicyclo [2.2.2] octane, quinuclidine and 3-quinuclidinol Tribe Tertiary amines, and isoquinoline, pyridine, collidine, and heterocyclic tertiary amines such as beta-picoline and the like.

 Specific examples of amidine generated upon decomposition of the photobase generator according to the present invention include secondary amidines such as imidazole, purine, triazole, guanidine and derivatives thereof, pyrimidine, triazine, 1,8-diazabicyclo [5]. .4.0] undec-7-ene (DBU) and 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) and other tertiary amidines and derivatives thereof.

The base generator represented by the above formula (5) generates a base only by being irradiated with electromagnetic waves, but generation of the base is promoted by heating appropriately. Therefore, by combining electromagnetic wave irradiation and heating, it is possible to efficiently generate a base with a small amount of electromagnetic wave irradiation, and it has higher sensitivity than conventional so-called photobase generators.
Since the base generator represented by the above formula (5) has the above-mentioned specific structure, as shown by the following formula when irradiated with electromagnetic waves, (—CH═CH—C) in the formula (5) The (= O)-) moiety isomerizes to the cis isomer and is further cyclized by heating to produce the base (NHR ^c R ^c ). By the catalytic action of the amine, the temperature at which the reaction when the polyimide precursor becomes the final product is lowered, or the curing reaction where the polyimide precursor becomes the final product can be started.

 When the base generator represented by the formula (5) is cyclized, the phenolic hydroxyl group disappears, the solubility changes, and in the case of a basic aqueous solution, the solubility decreases. Thereby, it has the function of further assisting the decrease in solubility due to the reaction of the polyimide precursor to the final product, and it becomes possible to increase the solubility contrast between the exposed portion and the unexposed portion.

In the formula (5), Rc may be the same as Rc in the above formula (A), and the description thereof is omitted here. Examples of the generated base (NHR ^c R ^c ) include primary and secondary amines containing NH groups and amidines containing NH groups among the above-mentioned bases.
Especially, when the base to generate | occur | produce is a secondary amine and / or amidine, it is preferable from the point that the sensitivity as a base generator becomes high. It is presumed that this is because the use of secondary amine or amidine eliminates active hydrogen at the amide bond site, thereby changing the electron density and improving the sensitivity of isomerization.

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, A phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or a monovalent organic group, which may be the same or different. Two or more of R ⁵ , R ⁶ , R ^7, and R ⁸ may be bonded to form a cyclic structure, and may include a hetero atom bond.
Examples of the halogen include fluorine, chlorine, bromine and the like.
The monovalent organic group is not particularly limited, and may be a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group, a cyano group, an isocyano group, Examples include cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, carboxyl group, carboxylate group, acyl group, acyloxy group, and hydroxyimino group. These organic groups may contain bonds and substituents other than hydrocarbon groups such as heteroatoms in the organic group, and these may be linear or branched.

The bond other than the hydrocarbon group in the organic group of R ^{5 to} R ⁸ is not particularly limited as long as the effect of the present invention is not impaired, and an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, and an ester bond. Amide bond, urethane bond, carbonate bond, sulfonyl bond, sulfinyl bond, azo bond and the like.
From the viewpoint of heat resistance, the bond other than the hydrocarbon group in the organic group includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C (— R)-, -C (= NR)-: where R is a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.

The substituent other than the hydrocarbon group in the organic group of R ^{5 to} R ⁸ is not particularly limited as long as the effect of the present invention is not impaired, and includes a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, Isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group Acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, saturated or unsaturated alkyl ether group, saturated or unsaturated alkyl thioether group, aryl ether group, and Arylthioether group, amino (-NH2, -NHR, -NRR ': wherein, R and R' are each independently a hydrocarbon group), such as an ammonio group. The hydrogen contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be any of linear, branched, and cyclic.
Among them, examples of the substituent other than the hydrocarbon group in the organic group represented by R ^{5 to} R ⁸ include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, and an isothiocyanato group. , Silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino A group, a phosphinyl group, a phosphono group, a phosphonato group, a hydroxyimino group, a saturated or unsaturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, and an aryl thioether group are preferred.

Examples of the monovalent organic group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, and a propyl group; cycloalkyl groups having 4 to 23 carbon atoms such as a cyclopentyl group and a cyclohexyl group; a cyclopentenyl group and a cyclohexenyl group. A cycloalkenyl group having 4 to 23 carbon atoms such as a group; an aryloxyalkyl group having 7 to 26 carbon atoms (-ROAr group) such as a phenoxymethyl group, a 2-phenoxyethyl group and a 4-phenoxybutyl group; a benzyl group, 3 An aralkyl group having 7 to 20 carbon atoms such as phenylpropyl group; an alkyl group having 2 to 21 carbon atoms having a cyano group such as cyanomethyl group and β-cyanoethyl group; 1 to 20 carbon atoms having a hydroxyl group such as hydroxymethyl group Alkyl group, methoxy group, ethoxy group, etc., C1-C20 alkoxy group, acetamide group, benzenesulfonamide group _{C 6 H 5 SO 2 NH 2} -) amide group having a carbon number of 2 to 21, such as a methylthio group, an alkylthio group (-SR group having 1 to 20 carbon atoms such as an ethylthio group), an acetyl group, carbon atoms such as benzoyl group 6 to 20 carbon atoms such as an acyl group having 1 to 20 carbon atoms, a methoxycarbonyl group, an acetoxy group and the like, an ester group having 2 to 21 carbon atoms (-COOR group and -OCOR group), a phenyl group, a naphthyl group, a biphenyl group, a tolyl group ˜20 aryl group, electron donating group and / or electron withdrawing group substituted aryl group having 6 to 20 carbon atoms, electron donating group and / or electron withdrawing group substituted benzyl group, cyano group, and It is preferably a methylthio group (—SCH ₃ ). The alkyl moiety may be linear, branched or cyclic.

Moreover, two or more of R ^{5 to} R ⁸ may be bonded to form a cyclic structure.
The cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings. The structure which becomes may be sufficient. For example, R ⁵ to R ⁸ are formed by combining two or more of them, naphthalene share atoms of the benzene ring of R ⁵ to R ⁸ are attached, anthracene, phenanthrene, and fused ring indene In this case, the absorption wavelength is preferable from the viewpoint of increasing the wavelength.

In the present invention, at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is a hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, A phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, or an ammonio group is desirable. By introducing at least one of the above substituents into the substituents R ^{5 to} R ⁸ , it is possible to adjust the wavelength of the light to be absorbed. By introducing the substituent, the desired wavelength is absorbed. It can also be made to do. It is also possible to improve the solubility and compatibility with the polymer precursor to be combined. Thereby, it is possible to improve the sensitivity in consideration of the absorption wavelength of the polyimide precursor to be combined.

 As a guideline of what substituents should be introduced to shift the absorption wavelength with respect to a desired wavelength, the Interspection of the Ultraviolet Products (AI Scott 1964) and the spectrum of organic compounds The table described in the identification method 5th edition (RM Silverstein 1993) can be referred to.

Among them, compared the base generator in the present invention, R ^5, when at least one of R ^6, R ⁷ and R ⁸ is a hydroxyl group, and R ^5, R ^6, does not contain a hydroxyl group at R ⁷ and R ⁸ compound, This is preferable from the viewpoint of improving the solubility in a basic aqueous solution and the like and increasing the absorption wavelength. In particular, when R ⁸ is a phenolic hydroxyl group, a reaction site for cyclization of a compound isomerized to a cis isomer increases, which is preferable from the viewpoint of easy cyclization.

 The structure represented by the chemical formula (5) has a geometric isomer at the (—CH═CH—C (═O) —) moiety, but it is preferable to use only the trans isomer. However, cis isomers that are geometric isomers may be mixed during synthesis and purification steps and storage, and in this case, a mixture of trans isomer and cis isomer may be used. It is preferable that the ratio of cis-isomer is less than 10%.

In the photosensitive resin composition used in the present invention, the activator (B) is preferably 0.01 to 50% by mass and more preferably 0.1 to 30% by mass of the solid content of the photosensitive resin composition. Is more preferable. By setting it within this range, the molecular weight of the compound (A2) can be stably lowered within the target range.
By adding such an active agent, active species such as acid or base are generated by irradiating active energy rays, and heating in the presence of this active species decomposes the main chain of the resin component. It is assumed that the molecular weight decreases.

このような増感色素は、樹脂の光熱反応に直接影響を与えない範囲で加えられる。増感色素の含有量は、配合する場合、光酸発生剤の活性剤の総量１００質量部に対して、１００質量部以下であるのが好ましく、７５質量部以下であることが好ましい。下限値としては、２０質量部以上が好ましい。 << Sensitizing dye (C) >>
The photosensitive resin composition may contain a sensitizing dye (C) that is a component having a function of developing or increasing the reactivity of the activator (B). The sensitizing dye (C) can broaden the wavelength range in which the activator (B) can be activated, and the optimum sensitizing dye has a maximum extinction coefficient near the light source used, It is a compound that can efficiently pass the absorbed energy to the activator.
Although it does not specifically limit as a sensitizing dye, When a photoacid generator is included, for example, polynuclear aromatics (for example, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9, 10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosin, rhodamine B, rose bengal), xanthones (for example, xanthone, Thioxanthone, dimethylthioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg Merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), acridones (eg, acridone, 10- Butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), styryls, base styryls (eg, 2- [2- [4- (dimethylamino) phenyl] ethenyl] Benzoxazole), coumarins (eg, 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H- [1] benzopyrano [ 6, 7, -Ij] quinolizine-11-non, the following compounds) or combinations thereof.

Such a sensitizing dye is added in a range that does not directly affect the photothermal reaction of the resin. When blended, the content of the sensitizing dye is preferably 100 parts by mass or less, more preferably 75 parts by mass or less, based on 100 parts by mass of the total amount of the photoacid generator activator. As a lower limit, 20 mass parts or more are preferable.

<< Binder polymer >>
In order to improve the sensitivity, developability and dry etching resistance in a balanced manner, a binder polymer may be added. Examples of such a binder polymer include semiconductor resist materials described in paragraph Nos. 0012 to 0027 of JP2010-169810A, the contents of which are incorporated herein (provided that the compound (A1)). And those corresponding to the compound (A2) are excluded).
When blended, the blending amount of the binder polymer is preferably blended at a ratio of 1 to 40% by mass of the solid content of the photosensitive resin composition.

<< Solvent >>
The photosensitive resin composition in the present invention preferably contains a solvent.
The photosensitive resin composition in the present invention is preferably prepared as a solution in which optional components of the specific resin and the specific photoacid generator, which are essential components, and various additives are dissolved in a solvent.

  As the solvent used in the photosensitive resin composition in the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl. Ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like.

  Examples of the solvent used in the photosensitive resin composition in the present invention include (1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. (2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether; (3) ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene Ethylene glycol monoalkyl ethers such as glycol monobutyl ether acetate (4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; (5) propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl Propylene glycol dialkyl ethers such as ether and diethylene glycol monoethyl 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, diethylene glycol ethyl Diethylene glycol dialkyl ethers such as methyl ether; (8) diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, etc. (9) Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether; (10) Dipropylene glycol dimethyl ether Dipropylene glycol dialkyl ethers such as dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether;

(11) Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate; (12) methyl lactate, lactic acid Lactic acid esters such as ethyl, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate; (13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, N-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate , Ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate and the like; (14) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl Acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate Other esters such as;

(15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; (16) N-methylformamide, N, N-dimethyl Examples include amides such as formamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; and (17) lactones such as γ-butyrolactone.
In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added.
Of the 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 solvents can be used alone or in combination of two or more.

When the photosensitive resin composition in this invention contains a solvent, it is preferable that content of a solvent is 1-3000 mass parts per 100 mass parts of resin (B), and is 5-2,000 mass parts. More preferably, it is 10 to 1,500 parts by mass.
Only one type of solvent may be used, or two or more types of solvents may be used. When two or more types are used, the total amount falls within the above range.

<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 the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-photosensitive resin composition used in the present invention, ( Component I) It preferably contains a basic compound.
(Component I) 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 the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 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, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. It is preferable to use two kinds of heterocyclic amines in combination.
When the photosensitive resin composition in this invention contains a basic compound, it is preferable that content of a basic compound is 0.001-1 mass part with respect to 100 mass parts of specific resin, 0.002- More preferably, it is 0.2 parts by mass.

<Surfactant>
It is preferable that the photosensitive resin composition used by this invention contains surfactant from a viewpoint of improving applicability | paintability more.
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. .

The photosensitive resin composition in the present invention more preferably contains a fluorine-based surfactant and / or a silicone-based surfactant as the surfactant.
As these fluorosurfactants and silicone surfactants, 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 are listed. 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, Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, PolyFox series (OMNOVA) such as 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. Fluorine-based surfactants or silicone-based surfactants, etc.). 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 (1), 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.

（式（１）中、Ｒ¹およびＲ³はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ²は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴は水素原子または炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐおよびｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｎは１以上１０以下の整数を表す。）

(In the formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is a numerical value of 10 mass% to 80 mass%. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and n represents an integer of 1 to 10.

The L is preferably a branched alkylene group represented by the following formula (2). R ⁵ in the formula (2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. More preferred is an alkyl group of 3.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.
When the photosensitive resin composition in this invention contains surfactant, it is preferable that the addition amount of surfactant is 10 mass parts or less with respect to 100 mass parts of specific resin, 0.01-10 mass parts It is more preferable that it is 0.01-1 mass part.

  Further, if necessary, the photosensitive resin composition of the present invention includes an antioxidant, a plasticizer, a thermal radical generator, a thermal acid generator, an acid multiplier, an ultraviolet absorber, a thickener, and an organic material. Or well-known additives, such as an inorganic precipitation inhibitor, can be added. Details of these can be referred to the descriptions in paragraph numbers 0143 to 0148 of JP2011-209692A, and the contents thereof are incorporated in the present specification.

  The thickness of the resist film is preferably 100 to 1000 nm, more preferably 300 to 850 nm, from the viewpoint of improving resolution. Such a film thickness can be obtained by setting the solid content concentration in the photosensitive resin composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.

Hereinafter, a method for patterning an organic semiconductor film using the present invention will be described.
<Organic semiconductor film patterning method>
The patterning method of the organic semiconductor film in the present invention is:
(1) forming a protective film on the organic semiconductor film;
(2) A step of forming a resist film made of a photosensitive resin composition containing the following (1) and / or (2) on the side of the protective film opposite to the organic semiconductor film;
(1) including a compound (A1) whose main chain is decomposed by irradiation with light having a wavelength of 100 to 600 nm;
(2) including an active agent (B) that generates active species upon irradiation with light having a wavelength of 100 to 600 nm, and a compound (A2) whose main chain is decomposed by the active agent (B);
(3) a step of exposing the resist film;
(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 protective film and the organic semiconductor film in the non-mask portion by dry etching treatment;
(6) a step of dissolving the protective film with water;
It is characterized by including.

<(1) Step of forming a protective film on the organic semiconductor film>
The organic semiconductor film patterning method of the present invention includes a step of forming a protective film on the organic semiconductor film. Usually, this process is performed after forming an organic semiconductor film on a substrate. In this case, the protective film is formed on the surface opposite to the surface of the organic semiconductor on the substrate side. The protective film is usually provided on the surface of the organic semiconductor film, 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 protective film may be provided, or two or more protective films may be provided.

<(2) Step of forming a resist film made of a photosensitive resin composition on the side of the protective film opposite to the organic semiconductor film>
After the step (1), (2) a resist film made of a photosensitive resin composition is formed on the side of the protective film opposite to the surface on the organic semiconductor side. The resist film is preferably formed by applying a photosensitive resin composition to the surface of the protective film, but may be interposed through a film such as an undercoat layer. The description of the protective film can be referred to for the method of applying the photosensitive resin composition.

  The solid content concentration of the photosensitive resin composition is usually 1.0 to 20% by mass, preferably 1.5 to 17% by mass, and more preferably 2.0 to 15% by mass. By setting the solid content concentration within the above range, the resist solution can be uniformly applied on the water-soluble resin film, and further, a resist pattern having a high resolution and a rectangular profile can be formed. . The solid content concentration is the mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the resin composition.

<(3) Step of exposing resist film>
(2) After forming the resist film in the step, the resist film is exposed. Specifically, actinic rays are irradiated to the resist film through a mask having a predetermined pattern. Exposure may be performed only once or multiple times.
Specifically, an actinic ray having a predetermined pattern is irradiated 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. Actinic rays having a wavelength of 300 nm to 450 nm, preferably 365 nm, can be preferably used. After this step, a post-exposure heating step (PEB) may be performed as necessary.

For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a laser generator, an 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. Mercury lamps are preferred in that they are suitable for large area exposure compared to lasers.

  When a laser is used, 343 nm and 355 nm are preferably used for a solid (YAG) laser, 351 nm (XeF) is preferably used for an excimer laser, and 375 nm and 405 nm are preferably used for a semiconductor laser. Among these, 355 nm and 405 nm are more preferable from the viewpoints of stability and cost. The coating can be irradiated with the laser once or a plurality of times.

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 most preferable. cm ² or less is more preferable, and 100 mJ / cm ² or less is most preferable.
The pulse width is preferably 0.1 nsec or more and 30,000 nsec or less. In order not to decompose the color coating film due to the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is most preferable, and in order to improve the alignment accuracy at the time of scanning exposure, 1,000 nsec or less is more preferable, Most preferred is 50 nsec or less.
Furthermore, the frequency of the laser is preferably 1 Hz to 50,000 Hz, more preferably 10 Hz to 1,000 Hz.
Furthermore, the frequency of the laser is more preferably 10 Hz or more, most preferably 100 Hz or more for shortening the exposure processing time, and more preferably 10,000 Hz or less for improving the alignment accuracy during the scan exposure. 000 Hz or less is most preferable.

Compared with a mercury lamp, a laser is preferable in that the focus can be easily reduced and a mask for forming a pattern in the exposure process is not necessary and the cost can be reduced.
The exposure apparatus that can be used in the present invention is not particularly limited, but commercially available exposure apparatuses include Callisto (buoy technology), AEGIS (buoy technology) and DF2200G (Dainippon). Screen Manufacturing Co., Ltd.) can be used. Further, devices other than those described above are also preferably used.
Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.

<(4) Step of developing using a developer containing an organic solvent to produce a mask pattern>
(3) After the resist film is exposed in the step, it is developed using a developer containing an organic solvent. 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 used in the present invention, polar solvents such as ketone solvents, ester solvents, amide solvents, and hydrocarbon solvents can be used.
Examples of ketone solvents 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 the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
The above solvents may be used alone or in combination of two or more. Moreover, you may mix and use with solvents other than the above. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole 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 in 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 is preferably a developer containing 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. As an example of a basic compound, what was mentioned above in the term of a basic compound can be mentioned.

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly 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. Sexuality improves.
Specific examples 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, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, 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, formate , Ester solvents such as propyl formate, ethyl lactate, butyl lactate, propyl lactate, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, xylene, etc. Examples thereof include aromatic hydrocarbon solvents, and aliphatic hydrocarbon solvents such as octane and decane.
Specific examples 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, and methylcyclohexanone. , Ketone solvents such as 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, 3- Ester solvents such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, N-methyl-2-pyrrole Emissions, N, N- dimethylacetamide, N, N-dimethylformamide amide solvents, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.

An appropriate amount of a surfactant can be added to the developer as necessary.
Although it does not specifically limit as surfactant, For example, surfactant described in the column of the said water-soluble resin composition is used preferably.
When the interfacial chemical is added to the developer, the amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0%, based on the total amount of the developer. 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 various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is preferably 2mL / sec / mm ² or less, more preferably 1.5mL / sec / mm ² or less, more preferably 1mL / sec / mm ² or less. Although there is no particular lower limit of the flow rate, 0.2 mL / sec / 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 within the above range, the pressure applied by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / 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, substituting with another solvent after the process developed using the developing solution containing an organic solvent.

<(5) Step of removing at least protective film and organic semiconductor of non-mask part by dry etching process>
The resist film is developed to produce a mask pattern, and at least the water-soluble resin film and the organic semiconductor in the non-mask portion are removed by an etching process. A non-mask part represents the location which is not exposed by the mask at the time of producing a mask pattern by exposing a resist film.

  Specifically, in the dry etching, at least the protective film and the organic semiconductor are dry etched using the resist pattern as an etching mask. Representative examples of dry etching include JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102, and the like. There is a method described in this publication.

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.
Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), the first stage etching is performed to the region (depth) where the organic semiconductor is not exposed, and after this first stage etching, nitrogen gas ( N ₂₎ and using a mixed gas of oxygen gas (O _2), over-etching preferably performed and the etching of the second step of performing etching to the vicinity area (depth) to expose the organic semiconductor, after the organic semiconductor is exposed The form containing these 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 respectively. (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). (4) The second stage etching is performed according to the etching time calculated in (2). 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), 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 addition, the first step etching process can avoid damage to the organic semiconductor by performing etching to a region where the organic semiconductor is not exposed. Also, the second etching step and the over-etching step may be performed by etching the organic semiconductor to a region where the organic semiconductor is not exposed by a mixed gas of fluorine-based gas and oxygen gas in the first etching step, and then damaging the organic semiconductor. From the viewpoint of avoidance, 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 5 to 25% in terms of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

<(6) Step of dissolving and removing the protective film with water>
After the etching, the protective film is removed using a solvent or water. In the case of a water-soluble resin, water is preferred.
Examples of the method for removing the water-soluble resin film with water include a method for removing the protective film 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. Further, examples of the injection nozzle include an injection nozzle in which the entire support 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 support. When the spray nozzle is movable, the resist pattern can be more effectively moved by spraying cleaning water by moving from the center of the support to the end of the support at least twice during the process of removing the water-soluble resin film. Can be removed.
It is also preferable to perform a process such as drying after removing water. The drying temperature is preferably 80 to 120 ° C.

<Industrial applicability>
The present invention can be used for manufacturing an electronic device using an organic semiconductor. Here, an electronic device is a device that contains a semiconductor and has two or more electrodes, and the current flowing between the electrodes and the generated voltage are controlled by electricity, light, magnetism, chemical substances, or the like. It is a device that generates light, electric field, magnetic field, etc. by the applied voltage 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, an organic field effect transistor, an organic photoelectric conversion element, and an organic electroluminescence element are preferable, an organic field effect transistor and an organic photoelectric conversion element are more preferable, and an organic field effect transistor is particularly preferable.

  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.

Preparation of Protective Film Forming Composition and Photosensitive Resin Composition Each component shown in the table below is mixed with solvent F1 (PGMEA) to obtain a uniform solution, and then a polytetrafluoroethylene filter having a pore size of 0.1 μm The composition for protective film formation of the Example and the comparative example and the photosensitive resin composition were prepared, respectively. The solid content concentration was 15% by mass.

Abbreviations in the table are as follows.
X1: Polyvinylpyrrolidone (Pitzkor K-30, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
X2: Polyvinyl alcohol (PXP-05, manufactured by Nippon Vinegar Poval Co., Ltd.)
X3: Pullulan (manufactured by Hayashibara Co., Ltd. X4: methylcellulose (Metroles SM-4, manufactured by Shin-Etsu Chemical Co., Ltd.) Y1: Surfynol 440 (manufactured by Nissin Chemical Industry Co., Ltd.)
A1: the following structure, synthetic product A2: the following structure, synthetic product A3: the following structure, synthetic product A4: the following structure, synthetic product A5: the following structure, synthetic product A6: the following structure, synthetic product A7: the following structure, synthetic product A8 : Structure and synthetic product AC1: Ultrason E6020 (manufactured by BASF, Polytersulfone resin)
AC2: TOPAS 5013 (polyplastic, cycloolefin copolymer)
B1: The following structure, Rhodorsil Speed 2074 (manufactured by Rhodia)
B2: The following structure, Irgacure 250 (made by BASF)
B3: The following structure, CPI-101A (manufactured by San Apro)
B4: The following structure, Aldrich B5: The following structure, synthesized by the method described in Patent Document WO 03/033500 C1: The following structure, ITX (manufactured by LAMBSON)
C2: The following structure, anthracure UVS-1331 (manufactured by Kawasaki Chemical Industries)
C3: The following structure, DETX-S (Nippon Kayaku)
E1: PF-6320 (manufactured by OMNOVA Solutions Inc.)
F1: PGMEA methoxypropyl acetate (manufactured by Daicel Chemical Industries, Ltd.)

Ａ２：Ｍｗ＝６０，０００

Ａ３：Ｍｗ＝４０，０００

Ｅｔはエチル基である。
Ａ４：Ｍｗ＝１００，０００

Ｍｅはメチル基である。
Ａ５：Ｍｗ＝４０，０００

Ａ６：Ｍｗ＝６０，０００

Ａ７：Ｍｗ＝５５，０００

Ａ８：Ｍｗ＝７０，０００

Ｂ１：光酸発生剤

Ｂ２：光酸発生剤

Ｂ３：光酸発生剤

Ｂ４：光酸発生剤

Ｂ５：光塩基発生剤

Hereinafter, the numbers in parentheses are molar ratios.
A1: Mw = 50,000

A2: Mw = 60,000

A3: Mw = 40,000

Et is an ethyl group.
A4: Mw = 100,000

Me is a methyl group.
A5: Mw = 40,000

A6: Mw = 60,000

A7: Mw = 55,000

A8: Mw = 70,000

B1: Photoacid generator

B2: Photoacid generator

B3: Photoacid generator

B4: Photoacid generator

B5: Photobase generator

Ｃ２：増感色素

Ｃ３：増感色素

C1: Sensitizing dye

C2: sensitizing dye

C3: Sensitizing dye

<Synthesis example of A1 to A4 and A8>
In a three-necked flask equipped with a nitrogen-substituted stirrer / reflux tube, a total of 40 parts by mass of each monomer mixture, 60 parts by mass of 1-methoxy-2-propanol, and 1 part by mass of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) Mixed and heated to 80 ° C. After finishing heating in 3 hours and cooling to room temperature, the reaction product was added dropwise to 500 parts by mass of pure water while stirring. The obtained white powder was taken out by filtration and blown and dried to obtain a polymer.

<Synthesis example of A5 to A7>
A total of 40 parts by mass of each monomer diol mixture, 60 parts by mass of diethyl carbonate, and 60 parts by mass of a 20% sodium ethoxide ethanol solution were mixed in a three-necked flask equipped with a stirrer and a reflux tube purged with nitrogen, and the temperature was raised to 120 ° C. did. Thereafter, the inside of the reactor was decompressed by about 30 kPa and further stirred for 1 hour. Thereafter, the mixture was stirred for 3 hours under a vacuum of 0.1 kPa. After cooling to room temperature, the reaction product was added dropwise to 500 parts by mass of pure water while stirring. The obtained white powder was taken out by filtration and blown and dried to obtain a polymer.

<Formation of protective film on organic semiconductor film>
As an organic semiconductor, 10 mL of a P3HT (Merck) chlorobenzene solution having a concentration of 20 g / L and 10 mL of a [60] PCBM (Solenne) chlorobenzene solution having a concentration of 14 g / L are mixed and spin coated on a 4-inch bare silicon substrate. The coating was carried out at (1200 rpm, 30 seconds) and dried on a hot plate at 140 ° C. for 15 minutes to form an organic semiconductor film having a thickness of 100 nm. A wafer having the organic semiconductor film formed on the substrate was designated as wafer 1. After applying the resin composition described in Table 1 on the wafer 1 by a spin coater (1200 rpm, 30 seconds), the wafer was baked at 100 ° C. for 60 seconds, and a protective film having a thickness of 700 nm was provided on the organic semiconductor film. 2 was formed.

<Pattern formation and shape evaluation using photosensitive resin composition>
The photosensitive composition shown in Table 1 below was applied to the 4-inch wafer 2 described above using a spin coater (1200 rpm, 30 seconds), and then baked at 110 ° C. for 60 seconds to form a 500 nm thick resist film on the wafer 2. A wafer 3 on which was formed was formed.
Next, the wafer 3 is exposed with an i-line projection exposure apparatus NSR2005i9C (manufactured by Nikon Corporation) under the optical conditions of NA: 0.57 and sigma: 0.60 (for Examples and Comparative Examples not using an activator) exposure 3000 mJ / cm ^2, exposure dose 500 mJ / cm ²⁾ subjected to for examples and comparative examples using the active agents, a line width of 10 [mu] m 1: were exposed through a line-and-space pattern binary mask. Thereafter, the film was heated at 110 ° C. for 60 seconds, developed with butyl acetate for 15 seconds, and spin-dried to obtain a 1: 1 line and space resist pattern having a line width of 10 μm. The pattern shape of the photosensitive composition was evaluated by performing cross-sectional observation using a scanning electron microscope.
A: There is no undercut of the bottom part of the photosensitive resin composition, and the taper angle of the pattern is in the range of 85 ° to 95 °.
Rectangle profile B: The bottom portion of the photosensitive resin composition has an undercut of 0.5 μm or less, and the pattern taper angle is in the range of 85 ° to 95 °.
Although slightly recognized, rectangular profile C: the bottom portion of the photosensitive resin composition has an undercut of 0.5 μm or less, and the pattern taper angle is in the range of 95 ° to 105 ° (reverse taper).
D: Pattern shape is poor or no pattern is formed.

<Removal of non-masked protective film and organic semiconductor by dry etching>
The substrate was dry-etched under the following conditions to remove the protective film in the non-mask pattern portion and the organic semiconductor 1 in the non-mask pattern portion.
Gas: CF ₄ (flow rate 200 ml / min), Ar (flow rate 800 ml / min), O ₂ (flow rate 50 ml / min)
Source power: 800W
Wafer bias: 600W
Antenna bias: 100W
ESC voltage: 400V
Time: 60sec

<Dissolving and removing the remaining protective film resin>
The substrate obtained is washed with water, the pattern made of the protective film is removed, and then heated at 100 ° C. for 10 minutes to remove the water remaining in the organic semiconductor 1 and to repair the damage in the process by drying. A substrate with a patterned film was obtained.

<Evaluation of organic semiconductor film pattern>
The line width of the organic semiconductor was evaluated by observing the pattern of the organic semiconductor after dry etching and removal of the protective film using a scanning electron microscope.
A: The line width of the organic semiconductor under 10 μm (L / S pattern) of the photosensitive resin composition is 9 μm to 10 μm.
B: The line width of the organic semiconductor under the 1 μm L / S pattern of the photosensitive resin composition is 8 μm or more and less than 9 μm C: The line width of the organic semiconductor under the 1 μm L / S pattern of the photosensitive resin composition Less than 8μm

From the said table | surface, it was recognized that the laminated body of this invention is excellent in a resist pattern shape, and is a technique useful for fine pattern formation of an organic semiconductor.
Moreover, about the line | wire width evaluation after the process of an organic-semiconductor pattern, even if it changed the kind of dry etching gas into chlorine / Ar, it confirmed that the same tendency was acquired.
By using the present invention, the display device shown in FIG. 2 of JP2012-216501A can be easily manufactured.

Claims (20)

It has an organic semiconductor film, a protective film on the organic semiconductor film, and a resist film on the protective film, and the resist film is made of a photosensitive resin composition containing the following (1) and / or (2) , Laminates;
(1) including a compound (A1) whose main chain is decomposed by irradiation with light having a wavelength of 100 to 600 nm;
(2) An active agent (B) that generates active species by irradiation with light having a wavelength of 100 to 600 nm, and a compound (A2) whose main chain is decomposed by the active agent (B) are included. The laminate according to claim 1, wherein the protective film contains a water-soluble resin. The laminate according to claim 1, wherein the protective film contains at least one of polyvinyl pyrrolidone, polyvinyl alcohol, and pullulan. The laminate according to claim 1, wherein the protective film contains polyvinylpyrrolidone. The laminate according to any one of claims 1 to 4, wherein the activator (B) is a photoacid generator or a photobase generator. The laminate according to any one of claims 1 to 5, wherein the compound (A1) includes a vinyl resin having a carbonyl group directly bonded to the main chain. The (A2) compound is at least one selected from polyester resin, polyurethane resin, polyamide resin, polyimide resin, polycarbonate resin, polyether resin, and a copolymer of anhydrous (meth) acrylic acid and poly (meth) acrylic acid. The laminated body of any one of Claims 1-6 containing a seed | species. The laminated body of any one of Claims 1-7 in which the said photosensitive resin composition contains a sensitizing dye (C). A kit for producing an organic semiconductor comprising a resist composition for producing an organic semiconductor comprising the following (1) and / or (2) and a composition for forming a protective film comprising a water-soluble resin;
(1) including a compound (A1) whose main chain is decomposed by irradiation with light having a wavelength of 100 to 600 nm;
(2) An active agent (B) that generates active species by irradiation with light having a wavelength of 100 to 600 nm, and a compound (A2) whose main chain is decomposed by the active agent (B) are included. The kit for manufacturing an organic semiconductor according to claim 9, wherein the water-soluble resin contains at least one of polyvinyl pyrrolidone, polyvinyl alcohol, and pullulan. The kit for manufacturing an organic semiconductor according to claim 9, wherein the water-soluble resin contains polyvinylpyrrolidone. The kit for manufacturing an organic semiconductor according to any one of claims 9 to 11, wherein the activator (B) is a photoacid generator or a photobase generator. The kit for manufacturing an organic semiconductor according to any one of claims 9 to 12, wherein the compound (A1) contains a vinyl resin having a carbonyl group directly bonded to the main chain. The (A2) compound is at least one selected from polyester resin, polyurethane resin, polyamide resin, polyimide resin, polycarbonate resin, polyether resin, and a copolymer of anhydrous (meth) acrylic acid and poly (meth) acrylic acid. The kit for organic-semiconductor manufacture of any one of Claims 9-13 containing a seed | species. The kit for manufacturing an organic semiconductor according to any one of claims 9 to 14, wherein the photosensitive resin composition contains a sensitizing dye (C). A resist composition for producing an organic semiconductor, comprising the following (1) and / or (2):
(1) including a compound (A1) whose main chain is decomposed by irradiation with light having a wavelength of 100 to 600 nm;
(2) An active agent (B) that generates active species by irradiation with light having a wavelength of 100 to 600 nm, and a compound (A2) whose main chain is decomposed by the active agent (B) are included. The resist composition for manufacturing an organic semiconductor according to claim 16, wherein the activator (B) is a photoacid generator or a photobase generator. The resist composition for producing an organic semiconductor according to claim 16 or 17, wherein the compound (A1) comprises a vinyl resin having a carbonyl group directly bonded to the main chain. The (A2) compound is at least one selected from polyester resin, polyurethane resin, polyamide resin, polyimide resin, polycarbonate resin, polyether resin, and a copolymer of anhydrous (meth) acrylic acid and poly (meth) acrylic acid. The resist composition for organic-semiconductor manufacture of any one of Claims 16-18 containing a seed | species. The resist composition for manufacturing an organic semiconductor according to any one of claims 16 to 19, wherein the photosensitive resin composition contains a sensitizing dye (C).