JP2015087611A - 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 negative photosensitive resin composition that contains a crosslinking agent (A) capable of crosslinking as a result of photodenitrification reaction.

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-mentioned problems, and is a laminate capable of forming a good organic semiconductor pattern, an organic semiconductor manufacturing kit for producing the laminate, and an organic It aims at providing the resist composition for organic-semiconductor manufacture used for the kit for semiconductor manufacture.

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

Specifically, the above problem has been solved by the following means <1>, preferably by <2> to <21>.
<1> Negative photosensitive resin comprising an organic semiconductor film, a protective film on the organic semiconductor film, and a resist film on the protective film, the resist film including a crosslinking agent (A) that can be crosslinked by a photo-denitrogenation reaction A laminate comprising a resin composition.
<2> The laminate according to <1>, wherein the crosslinking agent (A) that can be crosslinked by a photodenitrogenation reaction is a diazonium salt compound and / or an azide compound.
<3> The laminate according to <1> or <2>, wherein the protective film contains a water-soluble resin.
<4> The laminate according to any one of <1> to <3>, wherein the protective film contains at least one of polyvinylpyrrolidone, polyvinyl alcohol, and pullulan.
<5> The laminate according to any one of <1> to <3>, wherein the protective film contains polyvinylpyrrolidone.
<6> The laminate according to any one of <1> to <5>, wherein the crosslinking agent (A) that can be crosslinked by a photo-denitrogenation reaction is substantially insoluble in water.
<7> The laminate according to any one of <1> to <6>, wherein the photosensitive tree composition further includes a sensitizing dye (C) that spectrally sensitizes the photoradical polymerization initiator.
<8> The laminate according to any one of <1> to <7>, wherein the photosensitive tree composition further comprises a binder polymer (C).
<9> The laminate according to <8>, wherein the binder polymer (C) includes a conjugated diene polymer and / or a cyclized product thereof.
<10> A kit for producing an organic semiconductor comprising a resist composition for producing an organic semiconductor containing a crosslinking agent (A) that can be crosslinked by a photodenitrogenation reaction, and a composition for forming a protective film containing a water-soluble resin.
<11> The kit for manufacturing an organic semiconductor according to <10>, wherein the water-soluble resin contains at least one of polyvinylpyrrolidone, polyvinyl alcohol, and pullulan.
<12> The kit for manufacturing an organic semiconductor according to <10>, wherein the water-soluble resin contains polyvinylpyrrolidone.
<13> The kit for producing an organic semiconductor according to any one of <10> to <12>, wherein the crosslinking agent (A) capable of being crosslinked by a photodenitrogenation reaction is substantially insoluble in water.
<14> The organic semiconductor production material according to any one of <10> to <13>, wherein the resist composition for producing an organic semiconductor further contains a sensitizing dye (C) that spectrally sensitizes the photoradical polymerization initiator. kit.
<15> The kit for manufacturing an organic semiconductor according to any one of <10> to <14>, wherein the resist composition for manufacturing an organic semiconductor further contains a binder polymer (C).
<16> The kit for manufacturing an organic semiconductor according to <15>, wherein the binder polymer (C) includes a conjugated diene polymer and / or a cyclized product thereof.
The resist composition for organic-semiconductor manufacture containing the crosslinking agent (A) which can be bridge | crosslinked by <17> photodenitrogenation reaction.
<18> The resist composition for producing an organic semiconductor according to <17>, wherein the crosslinking agent (A) capable of being crosslinked by a photodenitrogenation reaction is substantially insoluble in water.
<19> The resist composition for producing an organic semiconductor according to <17> or <18>, further comprising a sensitizing dye (C) that spectrally sensitizes the photoradical polymerization initiator.
<20> The resist composition for producing an organic semiconductor according to any one of <17> to <19>, further comprising a binder polymer (C).
<21> The resist composition for producing an organic semiconductor according to <20>, wherein the binder polymer (C) includes a conjugated diene polymer and / or a cyclized product thereof.

  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. Furthermore, it is possible to have a configuration in which no mask layer remains even after the patterning is completed.

  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.

  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 has an organic semiconductor film, a protective film on the organic semiconductor film, and a resist film on the protective film on the surface of the organic semiconductor film, and the resist film is subjected to a photodenitrogenation reaction. It consists of a negative photosensitive resin composition containing a crosslinkable crosslinking agent (A). 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.

When an ordinary resist film is formed on the organic semiconductor film formed on the substrate and patterned, the organic semiconductor film is easily dissolved or swollen in the organic solvent contained in the resist film. As a result, the organic semiconductor film is damaged.
On the other hand, in the present invention, a protective film is provided between the organic semiconductor film and the resist film so that the organic semiconductor film is not damaged. In this case, since the resist film and the organic semiconductor film are not in direct contact, it is possible to suppress damage to the organic semiconductor. In particular, it is effective to use a water-soluble resin as the protective film.
Furthermore, since the resist film uses a photosensitive resin composition, high storage stability and fine pattern formability can be achieved.
Further, a crosslinking agent that can be crosslinked by a photo-denitrogenation reaction as a resist film generates nitrogen gas during exposure, so that curing can proceed sufficiently without being affected by oxygen in the air.
Further, the photosensitive resin composition used in the present invention can be easily removed with a solvent that does not dissolve or swell the unexposed portion of the protective film, and the exposed portion can be insolubilized with respect to the solvent that dissolves the protective film. is there. Furthermore, the photosensitive resin composition cured by exposure can be simultaneously removed when the organic semiconductor film is dry-etched.
From the above, Patent Document 1 (Japanese Patent Application Laid-Open No. 2006-41317) has a problem that the protective layer and the resist layer remain even after the patterning is completed. It became possible to produce a patterned organic semiconductor film in which no film and no protective film remained.
Details of the present invention will be described below.

<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 opposite to the side on which the protective film of the organic semiconductor 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, methanol, propanol, 1-methoxy-2-propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol Alcohol solvents such as alcohol; for example, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole; and the like; Examples thereof include polar solvents such as methyl-2-imidazolidinone and dimethyl 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 used in 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.

  The protective film may contain a dye. By including the dye, the absorption wavelength can be adjusted in accordance with the wavelength of the exposure light source, and therefore 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.
Dyes may be used alone or in combination of two or more.

<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.
In a preferred embodiment of the photosensitive resin composition used in the present invention, the photosensitive resin composition is crosslinked by a crosslinking agent that can be crosslinked by a photo-denitrogenation reaction, and the dissolution rate in an organic solvent having an sp value of less than 19 (MPa) ^1/2 Is preferably a composition that is hardly soluble in an organic solvent of 18.5 (MPa) ^1/2 or less, and 18.0 (MPa) ^1/2 or less. More preferably, the composition has a lower dissolution rate in the organic solvent.
The photosensitive resin composition used in the present invention is preferably a negative resist composition because a particularly high effect can be obtained because a finer trench / hole pattern can be formed.

The photosensitive resin composition according to the present invention can form a resist film having a surface with suppressed generation of residues during development and excellent smoothness.
Here, in the present invention, the “residue” means a residual film present on the periphery of the edge of the patterned resist film when a patterned resist film is formed using the photosensitive resin composition.

<Crosslinking agent (A) capable of crosslinking by photodenitrogenation reaction>
The crosslinking agent (A) that can be crosslinked by the photodenitrogenation reaction can be appropriately selected from known crosslinking agents. For example, a diazonium salt compound and an azide compound are mentioned. For example, a diazonium salt compound and an azide compound are described in detail below.
The term “crosslinkable by photodenitrogenation” refers to a compound that can be crosslinked by active species (carbon radical, nitrogen radical, carbene, nitrene, etc.) generated by the elimination of nitrogen molecules by irradiation with actinic rays.
Although the quantity of the crosslinking agent in this invention can be suitably defined in the kind of crosslinking agent, it is 0.1-50 mass% with respect to the total solid of the photosensitive resin composition, for example.

<< diazonium salt compound >>
As the negative photosensitive diazo compound, any known diazo compound that can be cured by exposure can be selected and used, but contains a diazonium salt and a reactive carbonyl salt such as aldol or acetal. A typical reaction product with an organic condensing agent is exemplified. Specifically, an organic condensation containing a diazonium salt and a reactive carbonyl salt such as aldol or acetal disclosed in US Pat. Nos. 2,063,631 and 2,667,415. A condensation product (so-called photosensitive diazo resin) obtained by further condensing diphenylamine-p-diazonium salt, which is a reaction product with an agent, with formaldehyde. Other useful condensed diazo compounds are disclosed in JP-B Nos. 49-48001, 49-45322, 49-45323, etc., and these are also incorporated in the photosensitive resin composition of the present invention. be able to. These types of photosensitive diazo compounds are usually obtained in the form of water-soluble inorganic salts. Therefore, the coating solution (photosensitive resin composition) for forming a resist film is an aqueous solution or a coating solution prepared by an aqueous solvent. It can be.

Further, these water-soluble diazo compounds are reacted with an aromatic or aliphatic compound having one or more phenolic hydroxyl groups, sulfonic acid groups, or both by the method disclosed in Japanese Patent Publication No. 47-1167. Thus, a substantially water-insoluble photosensitive diazo resin can be used to form a resist film. Further, as described in JP-A-56-121031, a photosensitive diazo resin that has been made water-insoluble by reacting with hexafluorophosphate or tetrafluoroborate can also be used. The diazonium salt compound used in the present invention is preferably substantially insoluble in water from the viewpoint of sensitivity.
The “substantially insoluble in water” as used in the present invention is obtained by dissolving only a target compound in a solvent such as butyl acetate and applying a composition having a solid content of 3.5% by mass on a silicon wafer. When the coating film (film thickness 100 nm) was formed, the film was immersed for 1000 seconds in ion-exchanged water at room temperature (25 ° C.) measured using a QCM (quartz crystal microbalance) sensor or the like. The average dissolution rate (thickness reduction rate) is 1 nm / s or less, preferably 0.1 nm / s or less.

  Examples of compounds having phenolic hydroxyl groups that are reacted with water-soluble diazo compounds to obtain water-insoluble diazo resins include hydroxybenzophenone, 4,4-bis (4′-hydroxyphenyl) pentanoic acid, resorcinol, or diresorcinol And these may further have a substituent such as an alkyl group, an alkoxy group, a halogen atom, or a cyano group. Here, hydroxybenzophenone means 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone or 2,2 ', 4,4'-. It includes derivatives such as tetrahydroxybenzophenone.

  Preferred compounds having a sulfonic acid group to be reacted with a water-soluble diazo compound in order to obtain a water-insoluble diazo resin (hereinafter, appropriately referred to as a sulfonic acid group-containing compound) include, for example, benzene, toluene, xylene, naphthalene, phenol , Aromatic sulfonic acid compounds in which a sulfonic acid group is introduced into an aromatic compound such as naphthol and benzophenone, and soluble salts thereof are exemplified. Examples of the soluble salts include ammonium salts and alkali metal salts of the above compounds. it can. Such a sulfonic acid group-containing compound may be further substituted with a lower alkyl group, a nitro group, a halo group, and / or another sulfonic acid group.

  Preferable specific examples of such sulfonic acid group-containing compounds include benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, sodium benzenesulfonate, naphthalene-2-sulfonic acid, 1- Naphthol-2 (or 4) -sulfonic acid, 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, m- (p'-anilinophenylazo) ) Benzenesulfonic acid, alizarin sulfonic acid, o-toluidine-m-sulfonic acid, ethanesulfonic acid and the like. As the aliphatic compound having a sulfonic acid group, sulfonic acid esters of alcohol and salts thereof are also useful. Such compounds are usually readily available as anionic surfactants. Examples thereof include lauryl sulfate, alkylaryl sulfate, p-nonylphenyl sulfate, 2-phenylethyl sulfate, isooctylenoxydiethoxyethyl sulfate and the like, and ammonium salts or alkali metal salts thereof.

  The substantially water-insoluble photosensitive diazo resin preferably has approximately the same amount of the water-soluble photosensitive diazo resin and the aqueous solution of the aromatic or aliphatic compound having the phenolic hydroxyl group or sulfonic acid group. It can be prepared by isolating as a precipitate by mixing and reacting in amounts.

  Moreover, as a negative photosensitive diazo compound contained in the photosensitive resin composition used by this invention, the diazo resin described in British Patent 1,312,925 is also preferable. Further, a diazo resin containing an oxygen acid group of phosphorus described in JP-A-3-253857, and a diazo resin condensed with a carboxyl group-containing aldehyde or an acetal compound thereof described in JP-A-4-18559. Also preferred are copolymerized diazo resins with carboxy group-containing aromatic compounds such as phenoxyacetic acid described in Japanese Patent Application No. 3-23031.

  Negative photosensitive diazo compounds particularly suitable for the photosensitive resin composition according to the present invention include dodecylbenzenesulfonate salt of 4-diazodiphenylamine and formaldehyde condensate, condensate of 4-diazodiphenylamine and formaldehyde, 4 Examples include a condensate of -diazodiphenylamine and formaldehyde, and examples thereof include 2-mechito-4-hydroxy-5-benzoylbenzenesulfonate, which is a condensate of 4-diazodiphenylamine and formaldehyde.

The diazonium compound used in the present invention is preferably a compound having a molecular weight of 1,000 to 100,000.
The content of the photosensitive diazo compound is suitably 5 to 50% by mass in terms of solid content in the photosensitive resin composition. When the amount of the diazo compound is reduced, the photosensitivity is naturally increased, but the stability with time is lowered. The content of the diazo compound is preferably 8 to 30% by mass, and more preferably 8 to 20% by mass.
You may use the diazo compound used for this invention in combination of 2 or more type as needed. When using 2 or more types together, it is preferable that the total amount is the said range.

<< Azide Compound >>
As the azide compound, a diazide compound (bisazide compound) is more preferable, and an aromatic azide compound is more preferable.
Specific examples of the aromatic azide compound include azidobenzene, 4,4′-diazidodiphenyl (also called p-phenylene-bisazide), azidoanisole, azidonitrobenzene, azidodimethylaniline, diazidebenzophenone (for example, 4,4 ′ -Diazidobenzophenone), diazide diphenylmethane (eg, 4,4′-diazidodiphenylmethane), diazide diphenyl ether, diazide diphenylsulfone, diazide diphenyl sulfide, diazidostilbene (eg, 4,4′-diazidostilbene) ), Azido chalcone, diazide chalcone (for example, 4,4′-diazido chalcone), diazidobenzalacetone, 2,6-di (paraazidobenzal) -4-cyclohexanone, 2,6-di (para Azidobenzal) -4-methylcyclohe Sanon, 3- (4- (p-1- azide) -1,3-butadienyl) -5,5-dimethyl-2-cyclohexane-1-one, and the like.
Examples of the azide compound include compounds described in US Pat. No. 2,940,853.
The azide compound used in the present invention is preferably a compound having a molecular weight of 200 to 10,000.

The content of the azide compound is preferably 0.01 to 205% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.5 to 5% by mass with respect to the total solid content of the photosensitive resin composition. preferable.
You may use the azide compound used for this invention in combination of 2 or more type as needed. When using 2 or more types together, it is preferable that the total amount is the said range.

<Sensitizing dye (B)>
The photosensitive resin composition used in the present invention can contain a sensitizing dye in order to promote its decomposition in combination with a radical photopolymerization initiator.
A sensitizing dye absorbs actinic rays or radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with the photo radical polymerization initiator, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the photoradical polymerization initiator undergoes a chemical change and decomposes to generate radicals.
Examples of preferable sensitizing dyes include compounds belonging to the following compounds and having an absorption wavelength in any of 350 nm to 450 nm.

  Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squariums (eg, squalium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine-11-non).

  Among these sensitizing dyes, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

  The blending amount of the sensitizing dye is preferably such that the mass ratio of the sensitizing dye / photoradical polymerization initiator is 0.1 / 1.0 to 10 / 1.0, and 0.2 / 1.0 to 5.0 / 1. 0.0 is more preferable. Only one kind of sensitizing dye may be used, or two or more kinds thereof may be used. When using 2 or more types, the total amount becomes the said range.

<Binder polymer (C)>
The photosensitive resin composition used in the present invention may contain a binder polymer (C) in order to improve the sensitivity, developability, and resistance to dry etching in a balanced manner.
Examples of the binder polymer that can be used in the present invention include (meth) acrylic polymers, polyurethane resins, polyvinyl alcohol resins, polyvinyl acetal resins (preferably polyvinyl butyral resins), polyvinyl formal resins, polyamide resins, polyester resins, and epoxies. Resin and novolac resin are exemplified.

In the present invention, “(meth) acrylic polymer” means (meth) acrylic acid, (meth) acrylic acid ester (alkyl ester, aryl ester, allyl ester, etc.), (meth) acrylamide and (meth) acrylamide derivatives. It refers to a copolymer having a (meth) acrylic acid derivative such as
Here, the “polyurethane resin” refers to a polymer produced by a condensation reaction of a compound having two or more isocyanate groups and a compound having two or more hydroxyl groups. An example is 2-hydroxyethyl methacrylate / acrylonitrile / ethyl methacrylate / methacrylic acid copolymer.

  “Polyvinyl butyral resin” refers to a polymer synthesized by reacting polyvinyl alcohol and butyraldehyde obtained by saponifying part or all of polyvinyl acetate under an acidic condition (acetalization reaction). A polymer having an acid group or the like introduced by a method of reacting a compound having a remaining hydroxy group and an acid group or the like is also included.

“Novolak resin” refers to a polymer produced by a condensation reaction of phenols (such as phenol and cresol) and aldehydes (such as formaldehyde). Furthermore, the polymer which introduce | transduced the substituent by the method of making another compound react with the remaining hydroxy group etc. is also contained.
Preferable examples of the novolak resin include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, or m- / p -Any of mixing) Novolak resin such as mixed formaldehyde resin may be mentioned. A novolak resin having a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 10,000 is preferred. Moreover, the compound which made it react with another compound with respect to the hydroxyl group in a novolak resin and introduce | transduced the substituent can also be used preferably.

  The binder polymer that can be used in the present invention is exemplified by a polymer compound to be blended in order to adjust the coating property. The applicability here means the uniformity of the film thickness after application and the film formability after application. Therefore, the binder polymer has various repeating structural units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required properties such as resolution, heat resistance, and sensitivity. be able to.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
Thereby, the performance required for the resin used for the photosensitive resin used in the present invention, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Fine adjustment such as dry etching resistance can be performed.

As such a monomer, for example, addition polymerization selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters, etc. Examples include compounds having one unsaturated bond.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

In the binder polymer (C), the molar ratio of each repeating structural unit is the dry etching resistance of the photosensitive resin composition, the standard developer suitability, the substrate adhesion, the resist profile, and the general required performance of the resist. It is set as appropriate to adjust the resolution, heat resistance, sensitivity, and the like.
The form of the binder polymer (C) may be any of random type, block type, comb type, and star type. The binder polymer (C) can be synthesized, for example, by radical, cation, or anionic polymerization of an unsaturated monomer corresponding to each structure. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.

  The binder polymer (C) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the photosensitive resin composition used by this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, it is preferable to perform polymerization using the same solvent as that used in the photosensitive resin composition. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, the polymerization is started using a commercially available radical initiator (azo initiator, peroxide, etc.). As the radical initiator, an azo-based initiator is preferable, and an azo-based initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.

  After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

  The solvent used for the precipitation or reprecipitation operation from the polymer solution (precipitation or reprecipitation solvent) may be a poor solvent for this polymer. Depending on the type of polymer, hydrocarbon, halogenated hydrocarbon, nitro A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use.

The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but is generally 100 to 10,000 parts by mass, preferably 200 to 2, based on 100 parts by mass of the polymer solution. 000 parts by mass, more preferably 300 to 1,000 parts by mass.
The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.
The precipitated or re-precipitated polymer is usually subjected to common solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).
In addition, after depositing and separating the resin once, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is contacted, the resin is precipitated (step a), the resin is separated from the solution (step b), and the resin solution A is dissolved again in the solvent. Preparation (step c), and then contacting the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably a volume amount not more than 5 times). Alternatively, a method including precipitating a resin solid (step d) and separating the precipitated resin (step e) may be used.

  In order to prevent the resin from aggregating after the preparation of the composition, for example, as described in JP-A-2009-037108, the synthesized resin is dissolved in a solvent to form a solution. A step of heating at about 30 ° C. to 90 ° C. for about 30 minutes to 4 hours may be added.

Examples of the binder polymer that can be used in the present invention include conjugated diene polymers and cyclized products thereof. The conjugated diene polymer may be a polymer composed only of conjugated diene or a copolymer with other monomers. Examples of the monomer that forms the copolymer include the monomers described above.
In this invention, when using an azide compound as a crosslinking agent (A), it can use especially preferably. This is probably because nitrene generated by exposure is added to the double bond and the crosslinking proceeds effectively.

The conjugated diene polymer or the cyclized product thereof is preferably a cyclized product of a conjugated diene polymer.
The conjugated diene polymer cyclized product used in the present invention is preferably a polymer or copolymer cyclized product having a repeating unit represented by the following general formula in the polymer chain.

In the above general formula,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group (eg, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group or a propyl group), or aryl Represents a group (eg, phenyl, naphthyl, etc.).
Specific examples include cis-1,4-butadiene units, trans-1,4-butadiene units, cis-1,4-isoprene units, trans-1,4-isoprene units, cis-1,4-pentadiene units, trans A polymer having -1,4-pentadiene unit, 1,4-diphenylbutadiene unit, 1,2-butadiene unit, 3,4-isoprene unit, 1,2-pentadiene unit, 3,4-diphenylbutadiene unit, etc. Alternatively, these conjugated diene units and unsaturated compound units, for example, vinyl aromatic compound units such as styrene units, α-methylstyrene units, paramethylstyrene units, and olefin compound units such as ethereno units, propylene units, and isobutylene units. The cyclized product of the copolymer which has can be mentioned. Of course, natural rubber cyclized products can also be used. In the present invention, cyclized isoprene rubber is particularly preferred.
The method for producing the cyclized product of the conjugated diene polymer used in the present invention is not particularly limited. For example, as described in JP-B-60-57584, JP-B-57-44682, etc. A conjugated diene polymer in an inert solvent and having the general formula CF _n H _3-n SO ₃ R
(Wherein R is a hydrogen atom, an alkyl group or CF _n H _3-n SO ₂ , n is 1, 2 or 3) and is cyclized by contact with the fluorine-containing substituted sulfonic acid compound represented by Can be obtained by:
As the fluorine-containing substituted sulfonic acid compound, trifluoromethanesulfonic acid, or an anhydride thereof, methyl ester, ethyl ester or acid chloride is preferable, and trifluoromethanesulfonic acid is particularly preferable.
The conjugated diene polymer is first dissolved in an inert solvent and then cyclized by contacting with a fluorine-containing substituted sulfonic acid compound. As the solvent used in the production of the cyclized product, an inert hydrocarbon (for example, pentane, Suitable examples include hexane, heptanone, benzene, toluene, xylene, and the like) and inert halogenated hydrocarbons (for example, methylene dichloride, chlorobenzene, and the like).
A form in which two or more of these solvents are mixed is also preferable from the viewpoint of applicability and the like.
The amount of the fluorine-containing substituted sulfonic acid compound used in the production of the cyclized product is preferably 1/6000 to 1/10 in molar ratio per repeating unit of the conjugated diene polymer, and is 1/5000 to 1/20. More preferably.
The cyclization reaction is usually performed in a temperature range of 40 ° C. to the boiling point of the solvent under normal pressure, but may be performed under pressure. For example, when the solvent is xylene, the reaction is usually performed at a temperature of 60 to 120 ° C. under normal pressure. This cyclization reaction is a very fast reaction, and it is considered that the reaction is almost completed immediately after the addition of the catalyst. The cyclization rate is usually almost the same as that after 10 minutes and that after 1 hour. Absent.

The cyclization rate of the cyclized product of the conjugated diene polymer used in the present invention is not particularly limited, but is preferably 50% or more, more preferably 50 to 95%, and 60 to 75%. More preferably it is.
The cyclization rate was determined by measuring the peak area of protons derived from double bonds before and after the cyclization reaction of the conjugated diene polymer used as a raw material by ¹ H-NMR analysis. The ratio of the double bond remaining in the cyclized product after the cyclization reaction is calculated, and is a value (%) represented by the calculation formula = (100−the ratio of the double bond remaining in the cyclized product).

The lower limit of the weight average molecular weight of the binder polymer (C) used in the present invention is preferably 10,000 or more, 2,000 or more, 3,000 or more, 5,000 or more, and 10,000 or more in order, and the upper limit is 300,000 or less, 250,000 or less, 200,000 or less, 100,000 or less, 50,000 or less, 20,000 or less, or 10,000 or less.
Further, the number average molecular weight is preferably 1,000 or more, and more preferably 2,000 to 250,000.
The polydispersity (weight average molecular weight / number average molecular weight) is usually 1.0 to 10.0, preferably 1.0 to 3.0, more preferably 1.1 to 2.6, and still more preferably. It is 1.2 to 2.4, particularly preferably 1.4 to 2.2. When the molecular weight distribution satisfies the above range, the resolution and resist shape are excellent, the side wall of the resist pattern is smooth, and the roughness is excellent.
In the photosensitive resin composition used in the present invention, the lower limit of the blending ratio of the binder polymer (C) in the entire composition is 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% in the total solid content. It is preferable in the order of mass% or more, 60 mass% or more, and 70 mass% or more, and the upper limit is preferably 99 mass% or less, 90 mass% or less, and 80 mass% or less.
In the present invention, the binder polymer (C) may be used alone or in combination of two or more.

<Other ingredients>
The photosensitive resin composition in the present invention can contain other components.

<< Photoradical polymerization initiator >>
The negative photosensitive resin composition used in the present invention may contain a polymerization initiator. Thereby, the crosslinking reaction of a photosensitive crosslinking agent can be accelerated | stimulated. The following radical photopolymerization initiators can be used as the polymerization initiator.
The photo radical initiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) in a radical polymerizable compound described later, and can be appropriately selected from known polymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Moreover, the activator which produces | generates an active radical by producing a certain effect | action with the photosensitized sensitizing dye may be sufficient.
The radical photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (preferably 330 nm to 500 nm).

  As the radical photopolymerization initiator, known compounds can be used. For example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group), Acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo series Examples thereof include compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, and the like.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the compounds described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro Methyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl)- 1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl)- , 3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3 4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4-oxadi Azole etc.).

  In addition, as photo radical polymerization initiators other than the above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, 9-phenylacridine, etc.) , Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuranoyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- ( 1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonyl Bis (5,7-di-n-propoxycoumarin), 3,3 -Carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy -3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc.), acylphosphine oxides (for example, bis (2 , 4,6-Trimethylbenzoyl) -pheni Phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) And compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. No. 3,615,455.

Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bisdicyclohexyl) Amino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzof Non, 4,4′-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoy Propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.
Kayacure DETX (manufactured by Nippon Kayaku) is also suitably used as a commercial product.

As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used. As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  More preferred examples of the photo radical polymerization initiator include oxime compounds. Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

  Examples of oxime compounds such as oxime derivatives that are preferably used as photo radical polymerization initiators include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimibutane. 2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4- Toluenesulfonyloxy) iminobutan-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) p. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used as commercial products.

  Further, as oxime ester compounds other than those described above, compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of carbazole, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye site, a ketoxime compound described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are identical A compound described in US Pat. No. 7,556,910 contained in the molecule, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used. .

Preferably, it can also be suitably used for the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A. Among the cyclic oxime compounds, the cyclic oxime compounds fused to the carbazole dyes described in JP2010-32985A and JP2010-185072A in particular have high light absorptivity from the viewpoint of high sensitivity. preferable.
Further, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because it can achieve high sensitivity by regenerating active radicals from polymerization inert radicals. it can.
Particularly preferred are oxime compounds having a specific substituent as disclosed in JP-A-2007-2699779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061.

  As the azo compound, an azobenzene compound is preferable, and a diazoaminobenzene compound is more preferable.

  A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

The photoradical polymerization initiator may be ionic or nonionic, but is preferably a nonionic photoradical initiator in view of exposure sensitivity and avoiding mixing with a protective film.
Nonionic photo radical initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, benzothiazoles Compounds selected from the group consisting of compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3-aryl-substituted coumarin compounds, and azobenzene compounds are preferred.

  More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, α-aminoketone compounds, oximes. At least one compound selected from the group consisting of a compound, a triarylimidazole dimer, a benzophenone compound, and an azobenzene compound is more preferable, and an oxime compound is more preferable.

The content of the photo radical polymerization initiator in the photosensitive resin composition is preferably 0.1% by mass or more and 50% by mass or less, and preferably 0.1% by mass or more and 30% by mass with respect to the total solid content of the photosensitive resin composition. The following is more preferable, 0.1% by mass or more and 20% by mass or less is further preferable, and 1% by mass or more and 10% by mass or less is particularly preferable.
Only one type of radical photopolymerization initiator may be used alone, or two or more types may be used in combination. When two or more types of radical photopolymerization initiators are used in combination, the total amount is preferably in the above range.

<< Radically polymerizable compound >>
The photosensitive resin composition used in the present invention may contain a radical polymerizable compound. The radically polymerizable compound can be arbitrarily selected from among radically polymerizable compounds described below.

  The number of functional groups of the radical polymerizable compound means the number of radical polymerizable groups in one molecule. The radically polymerizable group is typically a group that can be polymerized by irradiation with actinic rays or radiation, or by the action of radicals.

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

The radical polymerizable compound may be in any chemical form such as, for example, a monomer or a prepolymer, that is, a dimer, a trimer and an oligomer, a polymer, or a mixture thereof and a multimer thereof. Monomers and / or oligomers are preferred, and monomers are more preferred.
The monomer is typically a low molecular compound, preferably has a molecular weight of 2000 or less, more preferably 1500 or less, and still more preferably a molecular weight of 900 or less. In addition, the minimum of molecular weight is 100 or more normally.
The oligomer is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 monomers are bonded. The weight average molecular weight is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and still more preferably 2,000 to 10,000.
The polymer is a high molecular weight polymer and preferably has a weight average molecular weight of 20,000 or more.

In order to avoid mixing with the protective film, the radically polymerizable compound is preferably substantially insoluble in water. “Substantially insoluble in water” means a coating film (film) obtained by dissolving only a radical polymerizable compound in a solvent such as butyl acetate and applying a composition having a solid content of 3.5% by mass on a silicon wafer. The average dissolution when the coating film was immersed for 1000 seconds in ion-exchanged water at room temperature (25 ° C.) measured using a QCM (quartz crystal microbalance) sensor or the like. It indicates that the speed (thickness reduction rate) is 1 nm / s or less, preferably 0.1 nm / s or less.
The radically polymerizable compound used in the present invention preferably has a water solubility at 25 ° C. of 1.0 g / 100 g or less, more preferably 0.1 g / 100 g or less of water. By adopting such a configuration, even when a water-soluble resin is used for the protective film, the radical polymerizable compound is less likely to penetrate into the protective film, and the effects of the present invention are more effectively exhibited.

  The polymerizable group equivalent (mmol / g) of the radical polymerizable compound in the photosensitive resin composition is preferably 0.1 to 7.0, more preferably 1.0 to 6.0, and 2.0 to 5. 0 is more preferable. If the polymerizable group equivalent of the radical polymerizable compound becomes too high, the resist layer may crack due to curing shrinkage during curing. On the other hand, if the polymerizable group equivalent of the radical polymerizable compound is too low, the curability may be insufficient. In addition, polymeric group equivalent (mmol / g) represents the number of (mmol) of the polymeric group contained per total solid content mass of the photosensitive resin composition.

Examples of the case where the radical polymerizable compound is a monomer or an oligomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, amides of unsaturated carboxylic acids and polyhydric amine compounds, and multimers thereof.
Further, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group and the like with monofunctional or polyfunctional isocyanates or epoxies, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substituted reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.

  Specific examples of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate. , Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetra Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, di Intererythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, isocyanuric acid ethylene oxide (EO) modified tri Examples include acrylates and polyester acrylate oligomers.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.

  Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

  Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

  Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. Gazettes, those having an aromatic skeleton described in JP-A-59-5241, JP-A-2-226149, those containing an amino group described in JP-A-1-165613, and the like are preferably used. These contents are incorporated herein.

  Specific examples of amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic. Examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

  Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726, the contents of which are incorporated herein.

In addition, urethane-based addition polymerizable monomers produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Etc.
^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (A)
(However, R ⁴ and R ⁵ represent H or CH _3. )
Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable, and the contents thereof are incorporated in the present specification.

  Further, as the radically polymerizable monomer, compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can be preferably used in the present invention, and the contents thereof are described in the present specification. Incorporated.

Further, as the radically polymerizable monomer, a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso Polyfunctional alcohols such as anurate, glycerin and trimethylolethane, which are added with ethylene oxide or propylene oxide and then (meth) acrylated, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Publication No. 51- Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
Further, as other preferable radical polymerizable monomers, those having a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, Japanese Patent No. 4364216, etc., and having 2 ethylenic polymerizable groups. It is also possible to use a compound having a functionality or higher, a cardo resin, the contents of which are incorporated herein.
Further, other examples of the radical polymerizable monomer include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. And vinyl phosphonic acid-based compounds described in the Japanese Patent Publication. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984) can also be used as photocurable monomers and oligomers, the contents of which are incorporated herein.

  Further, as a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one ethylenically unsaturated group capable of addition polymerization, compounds described in paragraph numbers 0254 to 0257 of JP-A-2008-292970 are also included. These contents are preferred and are incorporated herein.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the above general formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. A plurality of R and T present in one molecule may be the same or different.
In each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH ₂ , or represents an -OC (= O) C (CH 3) = groups represented by CH _2.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include the compounds described in paragraphs 0248 to 0251 of JP-A-2007-26979. It can be used suitably also in invention, These contents are integrated in this specification.

  In addition, compounds that are (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof are also included. Can be used as a radical polymerizable monomer.

  Among these, as the radical polymerizable monomer, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku) Dipentaerythritol penta (meth) acrylate (manufactured by K.K.) and dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues. These oligomer types can also be used.

  The radically polymerizable monomer is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  The monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. The polyfunctional monomer provided is preferred, and particularly preferably in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

In this invention, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel tends to be inferior. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.
Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a radically polymerizable monomer.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Especially, the polyfunctional monomer which has a caprolactone structure represented with the following general formula (B) is preferable.

General formula (B)

(In the formula, all six Rs are groups represented by the following general formula (C), or 1 to 5 of the six Rs are groups represented by the following general formula (C). And the remainder is a group represented by the following general formula (D).)

General formula (C)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

Formula (D)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.)
Polyfunctional monomers having such a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, for example, and DPCA-20 (m = 1, the number of groups represented by the general formula (C) = 2, a compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, the group represented by the general formula (C) Number = 3, compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by general formula (C) = 6, compound in which R ¹ is all hydrogen atoms ), DPCA-120 (a compound in which m = 2 in the formula, the number of groups represented by the general formula (C) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

  In addition, the polyfunctional monomer is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

In the general formulas (i) and (ii), each E independently represents — ((CH ₂ ) yCH ₂ O) —, or — ((CH ₂ ) yCH (CH ₃ ) O) —, and y Each independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (i), the total number of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group.
In the general formula (ii), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

In general formula (i) or formula (ii) in the _{- ((CH 2) yCH 2} O) - or _{- ((CH 2) yCH (} CH 3) O) - , the terminal oxygen atom side X The form which couple | bonds with is preferable.

  In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

  The compound represented by the general formula (i) or (ii) is a ring-opening skeleton obtained by ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. And a step of reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available radical polymerizable monomers represented by general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.

Examples of the radical polymerizable monomer include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 as polymerizable monomers. Monomers can also be used.
Commercially available products of radical polymerizable monomers include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200, A-TMMT, A-9300, AD-TMP, A-DPH, A-TMM. -3, A-TMPT, A-TMPT-9EO, U-4HA, U-15HA, A-BPE-4, A-BPE-20 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, light acrylate TMP-A (manufactured by Kyoeisha) and the like.

  The radical polymerizable monomer in the present invention may be used singly or in combination of two or more types for the bifunctional or lower radical polymerizable monomer and the trifunctional or higher functional radical polymerizable monomer, From the viewpoint of having a three-dimensional cross-linking structure, it is preferable to include at least one kind of tri- or higher functional radical polymerizable monomer.

Only one type of radical polymerizable monomer may be used, or two or more types may be used in combination.
From the viewpoint of good sensitivity, the content of the radical polymerizable monomer is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and more preferably 20 to 80% by mass with respect to the total solid content of the photosensitive resin composition. % Is more preferable.

  When the radical polymerizable compound is a polymer, examples of the radical polymerizable polymer include (meth) acrylic polymer, styrene polymer, polyurethane resin, polyvinyl alcohol resin, polyvinyl acetal resin (preferably polyvinyl butyral resin), A polyvinyl formal resin, a polyamide resin, a polyester resin, an epoxy resin, a novolac resin, or the like can be used, and has a radical polymerizable group in the side chain of the polymer.

  The radical polymerizable polymer is generally synthesized by polymerizing a monomer having a partial structure to be polymerized by radical polymerization or the like, and has a repeating unit derived from the monomer having a partial structure to be polymerized. Examples of the partial structure to be polymerized include an ethylenically polymerizable partial structure.

  From the viewpoint of a method for producing a polymer compound having a radical polymerizable group in the side chain, a (meth) acrylic polymer and a polyurethane resin can be preferably used.

  The radical polymerizable group is preferably, for example, a functional group that can undergo an addition polymerization reaction, and examples of the functional group that can undergo an addition polymerization reaction include an ethylenically unsaturated group. As the ethylenically unsaturated bond group, a styryl group, an allyl group, a (meth) acryloyl group, a vinyl group, a vinyloxy group, and an alkynyl group are preferable. Among these, it is particularly preferable to have a (meth) acryloyl group from the viewpoint of sensitivity.

  In the radical polymerizable polymer, for example, free radicals (polymerization initiating radicals or growth radicals in the polymerization process of a polymerizable compound) are added to the polymerizable group, and the polymer is directly or via a polymerization chain of polymerizable monomers. As a result of the addition polymerization, a cross-link is formed between the molecules of the polymer compound and cured. Alternatively, atoms in the polymer compound (for example, a hydrogen atom on a carbon atom adjacent to the functional bridging group) are extracted by free radicals to form radicals, which are bonded to each other, thereby forming a molecule of the polymer compound. Crosslinks are formed between them and harden.

  Specifically, the polymer compound is represented by a group represented by the following general formula (1), a group represented by the following general formula (2), and the following general formula (3) as a radical polymerizable group. It is preferable to have one or more groups selected from the group consisting of the following groups, and more preferable to have a group represented by the following general formula (1).

(In the formula, X and Y each independently represent an oxygen atom, a sulfur atom or —N (R ¹² ) —. Z represents an oxygen atom, a sulfur atom, —N (R ¹² ) — or a phenylene group. R ^{1 to} R ¹² each independently represents a hydrogen atom or a monovalent substituent.)

In the general formula (1), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent substituent. For example, R ¹ has a hydrogen atom or a monovalent organic group, for example, a substituent. And an alkyl group which may be used. Among them, a hydrogen atom, a methyl group, a methylalkoxy group and a methyl ester group are preferable. R ² and R ³ may each independently have a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or a substituent. Alkyl group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituted An arylamino group that may have a group, an alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable. Here, examples of the substituent that can be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group. X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, and examples of R ¹² include a hydrogen atom and an alkyl group which may have a substituent.

In the general formula (2), R ^{4 to} R ⁸ each independently represent a hydrogen atom or a monovalent substituent, such as a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, or an alkoxycarbonyl group. , A sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. A good aryloxy group, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an aryl which may have a substituent Examples thereof include a sulfonyl group, and among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable. Examples of the substituent that can be introduced include those listed in the general formula (1). Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Examples of R ¹² include those listed in general formula (1).

In the general formula (3), R ^{9 to} R ¹¹ each independently represent a hydrogen atom or a monovalent substituent, such as a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, or an alkoxycarbonyl group. , A sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. A good aryloxy group, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an aryl which may have a substituent Examples thereof include a sulfonyl group, and among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable. Here, as a substituent, what was mentioned in General formula (1) is illustrated similarly. Z represents an oxygen atom, a sulfur atom, —N (R ¹² ) — or a phenylene group. Examples of R ¹² include those listed in general formula (1). Among these, a radical polymerizable group having a methacryloyl group represented by the general formula (1) is preferable.

In the case of introducing a structural unit having a radical polymerizable group (for example, an ethylenically unsaturated group as described above) in the radical polymerizable polymer, the content thereof is iodine titration (content of radical polymerizable group per 1 g of polymer). The measurement is preferably 0.1 to 10.0 mmol, more preferably 1.0 to 7.0 mmol, and most preferably 2.0 to 5.5 mmol. Within this range, good sensitivity and good storage stability can be obtained.
The radical polymerizable polymer typically has a repeating unit having a radical polymerizable group, and in this case, the content of the repeating unit having a radical polymerizable group is the total number of repeating units of the radical polymerizable polymer. 1 to 70 mol% is preferable, 2 to 60 mol% is more preferable, and 5 to 50 mol% is more preferable.

  The radical polymerizable group includes (a) a urethanization reaction using a hydroxyl group on the polymer side chain and an isocyanate having a radical polymerization reactive group, and (b) a hydroxyl group on the polymer side chain, and a radical polymerization reactive group. Esterification reaction using carboxylic acid, carboxylic acid halide, sulfonic acid halide, or carboxylic acid anhydride, (c) carboxy group of the polymer side chain or a salt thereof, and isocyanate having a radical polymerization reactive group Reaction, (d) esterification reaction using a carbonyl halide, carboxy group or a salt thereof on the polymer side chain and an alcohol having a radical polymerization reactive group, (e) a carbonyl halide group on the polymer side chain, carboxy An amidation reaction using a group or a salt thereof and an amine having a radical polymerization reactive group, (f) An amidation reaction using a carboxylic acid having a radical polymerization reactive group, a carboxylic acid halide, a sulfonic acid halide, or a carboxylic anhydride, and (g) an epoxy group on the polymer side chain. , A ring-opening reaction with various nucleophilic compounds having a radical polymerization reactive group, and (h) an etherification reaction between a haloalkyl group on the polymer side chain and an alcohol having a radical polymerization reactive group. .

  The radical polymerizable polymer preferably has a repeating unit having at least one group represented by the general formulas (1) to (3). As such a repeating unit, specifically, a repeating unit represented by the following general formula (4) is more preferable.

In General Formula (4), R ^{101 to} R ¹⁰³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. T represents a radical polymerizable group represented by any one of the above general formulas (1) to (3), and a preferred embodiment is the same as that described in the above radical polymerizable group.

In general formula (4), A is selected from the group consisting of a single bond, or —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. Represents a divalent linking group. Specific examples L ^{1 to} L ¹⁸ of A composed of combinations are listed below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to the radical polymerizable group represented by any one of the general formulas (1) to (3).

L ¹ : -CO-NH-2 valent aliphatic group -O-CO-NH-2 valent aliphatic group-
L ^{2: -CO-NH-2} divalent aliphatic group -
L ³ : —CO-2 valent aliphatic group—
L ^4: -CO-O-2 divalent aliphatic group -
L ⁵ : a divalent aliphatic group
L ^6: -CO-NH-2-valent aromatic group -
L ⁷ : —CO-2 valent aromatic group—
L ⁸ : -valent aromatic group-
L ⁹ : -CO-O-2 valent aliphatic group -CO-O-2 valent aliphatic group-
L ¹⁰ : -CO-O-2 valent aliphatic group -O-CO-2 valent aliphatic group-
L ¹¹ : -CO-O-2 valent aromatic group -CO-O-2 valent aliphatic group-
L ^12: -CO-O-2-valent aromatic group -O-CO-2 divalent aliphatic group -
L ^13: -CO-O-2 divalent aliphatic group -CO-O-2-valent aromatic group -
L ¹⁴ : -CO-O-2 valent aliphatic group -O-CO-2 valent aromatic group-
L ^15: -CO-O-2-valent aromatic group -CO-O-2-valent aromatic group -
L ^16: -CO-O-2-valent aromatic group -O-CO-2-valent aromatic group -
L ^17: -CO-O-2-valent aromatic group -O-CO-NH-2 divalent aliphatic group -
L ¹⁸ : -CO-O-2 valent aliphatic group -O-CO-NH-2 valent aliphatic group-

Here, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group. Of these, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
The divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure. The number of carbon atoms of the divalent aliphatic group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 12, and further preferably 1 to 10. 1 to 8 is more preferable, and 1 to 4 is particularly preferable.
Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.

Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.

  The radical polymerizable polymer preferably has other repeating units in addition to the repeating unit having a radical polymerizable group, as long as the effects of the present invention are not impaired. In the case of a polymer compound that can be synthesized by radical polymerization such as a (meth) acrylic polymer, it is preferable to copolymerize a radical polymerizable monomer in order to add another repeating unit. Examples of monomers that can be copolymerized include acrylic esters, methacrylic esters, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides, styrenes, acrylonitriles, and methacrylonitrile. And monomers selected from among the above.

  Specifically, for example, acrylic esters such as alkyl acrylate (alkyl group having 1 to 20 carbon atoms is preferable), (specifically, for example, methyl acrylate, ethyl acrylate, acrylic acid) Propyl, butyl acrylate, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, Pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (eg , Phenyl acrylate, etc.), methacrylic acid esters (eg, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate) such as alkyl methacrylate (the alkyl group preferably has 1 to 20 carbon atoms). , Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane Monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, Sulfyl methacrylate, tetrahydrofurfuryl methacrylate, etc.), aryl methacrylate (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.), styrene such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, Diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (eg methoxy styrene, 4-methoxy -3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (for example, black Rostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, promstyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3 -Trifluoromethylstyrene etc.), acrylonitrile, methacrylonitrile and the like.

  Since the polymerizable polymer is preferably substantially insoluble in water, the polymerizable polymer may or may not have a hydrophilic group, but it is preferably not.

Examples of the hydrophilic group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol substituted with an electron-withdrawing group at the α-position (for example, hexafluoroisopropanol group, —C (CF ₃ ) ₂ OH), OH groups, and the like.

  The weight average molecular weight (Mw) of the radical polymerizable polymer is preferably 2,500 or more, more preferably 2,500 to 1,000,000, and even more preferably 5,000 to 1,000,000. The dispersity (weight average molecular weight / number average molecular weight) of the polymer compound (A) is preferably 1.1 to 10.

You may use a radically polymerizable polymer in combination of 2 or more type as needed.
From the viewpoint of good sensitivity, the content of the radical polymerizable polymer is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and more preferably 20 to 80% by mass with respect to the total solid content of the photosensitive resin composition. % Is more preferable.

  Specific examples of the radical polymerizable polymer are shown below, but the present invention is not limited thereto. The composition ratio of the polymer structure represents a mole percentage.

<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, 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 ethers. Alkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, Examples include lactones.

  Examples of the solvent 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 dimethyl ether and ethylene glycol diethyl ether. Ethylene glycol dialkyl ethers such as ethylene glycol dipropyl ether; (3) ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate (4) Propylene glycol Propylene glycol monoalkyl ethers such as methyl 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 ether, diethylene glycol monoethyl ether, etc. Propylene glycol dialkyl ethers;

(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 contains a solvent, the content of the solvent is preferably 1 to 3,000 parts by mass, more preferably 5 to 2,000 parts by mass per 100 parts by mass of the solid content. More preferably, it is 10 to 1,500 parts by mass.
Moreover, when the photosensitive resin composition contains a solvent, the amount of the solvent in the composition is preferably 10 to 95% by mass, more preferably 60 to 95% by mass, and 70 to 90% by mass. Is more preferable.

<< Surfactant >>
The photosensitive resin composition used in the present invention preferably contains a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based and silicone surfactants. .

The photosensitive resin composition 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.

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 used by 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 solid content, and 0.01-10 mass Part is more preferable, and 0.01 to 1 part by mass is even more preferable.

  Furthermore, if necessary, the photosensitive resin composition in the present invention includes an antioxidant, a chain transfer agent, a polymerization inhibitor, a coloring material, a plasticizer, a thermal radical generator, a thermal acid generator, an acid multiplier, Known additives such as ultraviolet absorbers, thickeners, and organic or inorganic suspending agents 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.

<< Antioxidant >>
The photosensitive resin composition used in the present invention preferably contains an antioxidant. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a quinone-based antioxidant, a nitrogen-based antioxidant, a phosphite-based antioxidant, and the like can be used.

Examples of phenolic antioxidants include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol (4,4′-butylidene-bis (6-tert-butyl-m-cresol)), Examples include “Irganox 1010”, “Irganox 1330”, “Irganox 3114”, “Irganox 1035” manufactured by BASF Corporation, “Sumizer MDP-S”, “Sumilizer GA-80” manufactured by Sumitomo Chemical Co., Ltd., and the like.
Examples of the sulfur-based antioxidant include 3,3′-thiodipropionate distearyl, “Sumilizer TPM”, “Sumilizer TPS”, “Sumilizer TP-D” manufactured by Sumitomo Chemical Co., Ltd., and the like.
Examples of the quinone antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone.
As the nitrogen-based antioxidant, an amine-based antioxidant is preferable, and examples thereof include dimethylaniline and phenothiazine.
Examples of the hofphite-based antioxidant include tris (2,4-ditert-butylphenyl) phosphite sold by BASF under the name Irgafos 168).
Among the above antioxidants, Irganox 1010, Irganox 1330, Irganox 1726, and 3,3′-thiodipropionate distearyl are preferred, Irganox 1010 and Irganox 1330 are more preferred, and Irganox 1330 is particularly preferred.
4,4'-Butylidene-bis (6-tert-butyl-m-cresol)
Only one type of antioxidant may be used, or two or more types may be combined.

  From the viewpoint of preventing sublimation during heating, the molecular weight of the antioxidant is 250 ° C. or more when the mass is reduced by 1% by mass when measured under a nitrogen stream under a constant temperature raising condition of 20 ° C./min. Preferably, 270 ° C. or higher is more preferable, and 300 ° C. or higher is particularly preferable. The upper limit is not particularly defined, but can be, for example, 500 ° C. or less.

The content of the antioxidant is preferably 0.1 to 6% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good. Further, as additives other than antioxidants, various ultraviolet absorbers described in "New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)", metal deactivators, and the like can be used. You may add to a resin composition.

<< Chain transfer agent >>
The photosensitive resin composition used in the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by Polymer Society, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used.

When the photosensitive resin composition contains a chain transfer agent, the amount of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. -10 parts by mass, particularly preferably 1-5 parts by mass.
Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably within the above range.

<< Polymerization inhibitor >>
The photosensitive resin composition used in the present invention contains a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the radical photopolymerization initiator and the radical polymerizable compound during the production or storage of the photosensitive resin composition. It is preferable to add.
Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol). 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt is preferable.
When the photosensitive resin composition contains a polymerization inhibitor, the blending amount of the polymerization inhibitor is preferably 0.005 to 5% by mass with respect to the total solid content of the photosensitive resin composition.
Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more polymerization inhibitors, the total is preferably in the above range.

<< Color material >>
The photosensitive resin composition used in the present invention may contain a color material. Examples of the color material include dyes and pigments, and dyes are preferable from the viewpoint of effects.
Color materials such as dyes and pigments may function as sensitizing dyes. The sensitizing dye can improve the crosslinking reaction of the photosensitive crosslinking agent.

As coloring materials such as dyes and pigments, naphthalazine (1,2-bis (1-naphthylmethylene) hydrazine), p-hydroxy-p-dimethylaminoazobenzene, Paris First Yellow (manufactured by Orient Chemical), Sumiplast Yellow (Sumitomo) Chemical), Macroletus Yellow (Bayer), Seres Blue GN01 (Bayer), Clariant's product name “Hostalux KCB”, Eastman's product name “OB-1”, Ciba Specialty Chemicals' “OB” "Product name" TBO "from Sumitomo Seika Co., Ltd., product name" Kay Coal "from Nippon Soda Co., Ltd., product names" Kayalite "," Kayaset Yellow "and" Kayakril Rhodamine FB "from BASF Product name "Lumogen F Ywllow083", "Lum Gen F Ywllow 170 "," Lumogen F Orange240 "," Lumogen F Pink285 "," Lumogen F Red305 "," Lumogen F Violet 570 "," Lumogen F Blue 650 "and" Lumogen F Blue 650 " 2801 "," FZ-2802 "," FZ-2803 "," FZ-2817 "," FZ-2808 "," FZ-SB "," FZ-5209 "," FX-301 "," FX-303 " , “FX-307” and “FX-327”, trade names “ZQ-19”, “ZQ-18”, “ZQ-19”, “IPO-13”, “IPO-18”, “IPO” -19 "," NX-13 "," GPL-11 "," GPL- 3 "," Z-11 "and" Z-13 ", trade name Inagawa pigment Inc." Rhodamine B lake ", is commercially available at Keikoru C (manufactured by Nippon Soda).
Examples of the oil colorant include oil red SST extra, oil red 5B, color mate blue, blue SS, oil yellow, yellow SS (all manufactured by Silado Chemical), oil blue # 603 (manufactured by Orient Kogyo Co., Ltd.), and the like. However, it is not limited to these. Other examples include azo dye compounds, azo metal-containing dye compounds, and fluorescent whitening agents for general fibers.

A color material may be used individually by 1 type, or may use 2 or more types together.
The actinic ray-sensitive or radiation-sensitive resin composition (II) may or may not contain a color material, but when it is contained, the content of the color material is the total amount of the photosensitive resin composition. 0.01-10 mass% is preferable with respect to solid content, 0.05-5 mass% is more preferable, and it is still more preferable that it is 0.1-1 mass%.

The thickness of the resist film is preferably 100 to 2000 nm, more preferably 100 to 1000 nm, still more preferably 300 to 1500 nm, and particularly preferably 300 to 850 nm, from the viewpoint of improving resolution. Is preferred. 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.
If the film thickness becomes too high, the resist layer may crack due to curing shrinkage of the polymerizable compound. On the other hand, if the film thickness is too low, there is a possibility that sufficient masking properties cannot be ensured when the protective film and the organic semiconductor film are removed by the dry etching process described later.

<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 using the protective film forming composition;
(2) forming a resist film made of a photosensitive resin composition on the side of the protective film opposite to the organic semiconductor film;
(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 the non-masked protective film and the organic semiconductor film by dry etching,
(6) a step of dissolving the protective film,
It is characterized by including.

<< (1) Step of Forming Protective Film on 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. The protective film is provided by applying a composition for forming a protective film on the organic semiconductor film. The method for applying the protective film is preferably coating. The protective film is preferably a film mainly composed of a water-soluble resin. 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 usually formed by applying a photosensitive resin composition to the surface of the protective film, but it may be through a film such as an undercoat layer. For the method of applying the photosensitive resin composition, the description of the protective film forming composition can be referred to.

  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 in the above range, the resist solution can be uniformly applied on the protective film, and further, a resist pattern having 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 the resist film is formed 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. The photosensitive resin composition used by this invention contains the crosslinking agent which can be bridge | crosslinked by photodenitrogenation reaction. By including such a cross-linking agent, when exposed, a cross-linked structure is formed in the exposed portion, and patterning becomes possible and functions as a resist film.
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. To prevent the coating film from being decomposed by an ablation phenomenon, 1,000 mJ / cm ² is preferable. cm ² or less is more preferable, and 500 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.

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, the surfactant described in the column of the said composition for protective film formation 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 form a mask pattern, and at least the non-mask portion of the protective film and the organic semiconductor are removed by etching. 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. As typical examples of dry etching, Japanese Patent Laid-Open Nos. 59-126506, 59-46628, 58-9108, 58-2809, 57-148706, 57-148706, There are methods described in publications such as 61-41102.

The dry etching is preferably performed in the following manner from the viewpoint of forming the pattern cross section closer to a rectangle and reducing damage to the organic semiconductor.
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, the second stage etching, and the overetching 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) above. (4) The second stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time. (5) Overetching time is calculated with respect to the total time of (3) and (4) above, and overetching is performed.

The mixed gas used in the first stage etching step preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. In 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. Further, the second etching step and the over-etching step are performed by etching the region where the organic semiconductor is not exposed by the 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>
After etching, the protective film is dissolved and removed. In the present invention, it is preferable to remove the protective film using water.

Examples of the method of removing the protective film with water include a method of 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 is more effectively removed by spraying the cleaning water by moving from the support center to the support end more than twice during the process of removing the protective film. be able to.
It is also preferable to perform a process such as drying after removing water. The drying temperature is preferably 80 to 120 ° C.

<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.

<Example 1>
(1) Preparation of composition for forming protective film and photosensitive resin composition After mixing the components shown in the table below to obtain a uniform solution, a polytetrafluoroethylene filter having a pore size of 0.1 μm was used. The composition for protective film formation of Example 1 and the photosensitive resin composition were prepared by filtering, respectively.

<< Protective film forming composition 1 >>
・ Polyvinylpyrrolidone (Pitzkor K-30, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
99.9g
・ Surfinol 440 (manufactured by Nissin Chemical Industry Co., Ltd.)
0.1g
・ Water 90g

<< Photosensitive resin composition 1 >>
・ Dodecylbenzenesulfonate 1.2g of condensate of 4-diazodiphenylamine and formaldehyde
-Copolymer of 2-hydroxyethyl methacrylate / acrylonitrile / ethyl methacrylate / methacrylic acid = 35/25/35/5 (molar ratio) 5 g
・ Oil Blue # 603 (Orient Kogyo Co., Ltd.) 0.18g
・ 30 g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 50g
・ Methanol 20g

<Example 2>
A protective film-forming composition 2 was prepared in the same manner as in Example 1, except that the polyvinyl pyrrolidone of Example 1 was changed to polyvinyl alcohol (PXP-05, manufactured by Nippon Vinegar Poval Co., Ltd.).

<Example 3>
A protective film forming composition 3 was prepared in the same manner as in Example 1, except that the polyvinyl pyrrolidone of Example 1 was changed to Pullulan (manufactured by Hayashibara Co., Ltd.).

<Example 4>
A protective film-forming composition 4 was prepared in the same manner as in Example 1, except that the polyvinyl pyrrolidone of Example 1 was changed to methyl cellulose (Metroses SM-4 manufactured by Shin-Etsu Chemical Co., Ltd.).

<Example 5>
The dodecylbenzenesulfonate salt of 4-diazodiphenylamine and formaldehyde condensate of Example 1 is changed to 2-mechitosi-4-hydroxy-5-benzoylbenzenesulfonate, which is a condensate of 4-diazodiphenylamine and formaldehyde. Except for the above, a photosensitive resin composition 2 was obtained in the same manner as in Example 1.

<Example 6>
In the same manner as in Example 1, except that the dodecylbenzenesulfonate salt of the condensate of 4-diazodiphenylamine and formaldehyde in Example 1 is changed to a sulfate salt that is a condensate of 4-diazodiphenylamine and formaldehyde. A resin composition 3 was obtained.

[Evaluation]
<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 a spin coater (on a 4-inch bare silicon substrate). And dried at 140 ° C. for 15 minutes on a hot plate 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 protective film forming composition shown in Table 1 on the wafer 1 with a spin coater (1200 rpm, 30 seconds), baking was performed at 100 ° C. for 60 seconds to provide a protective film having a thickness of 700 nm on the organic semiconductor film. The obtained wafer 2 was formed.

<Pattern formation and shape evaluation using photosensitive resin composition>
The photosensitive resin composition shown in the following table was applied to the 4-inch wafer 2 described above using a spin coater (1200 rpm, 30 seconds), then baked at 110 ° C. for 60 seconds, and a resist film having a thickness of 500 nm 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 (exposure 120 mJ / cm ² ), and the line width is 10 μm. Exposure was through a binary mask with a 1: 1 line and space pattern. 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. By performing cross-sectional observation using a scanning electron microscope, the pattern shape of the photosensitive resin composition and the residue on the substrate (non-pattern part) were evaluated.
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 2 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

As is clear from the above results, the laminate of the present invention was excellent in the pattern forming property of the photosensitive resin composition and also in the post-processing line width evaluation of the organic semiconductor pattern. In contrast, when the protective film was not provided (Comparative Example 1), the post-processing line width evaluation of the organic semiconductor pattern was inferior.
In particular, it was found that the use of polyvinylpyrrolidone as the main component of the protective film and the use of a sulfonate salt of a diazonium salt compound as a crosslinking agent of the photosensitive resin composition proved more effective.
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.

<Example 7>
Preparation of photosensitive resin composition After mixing each component shown in the following table to obtain a uniform solution, the mixture was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain a photosensitive resin composition. Each was prepared.
(Photosensitive resin composition 12-20)

The components and abbreviations in the above table are as follows.
<Cyclized product of conjugated diene polymer>
Cyclized isoprene rubber: weight average molecular weight 49,000, dispersity (weight average molecular weight / number average molecular weight) 1.7, cyclization rate 65%.
<Azide compound>
2,6-di (paraazidobenzal) -4-methylcyclohexanone,
p-phenylene-bisazide,
4,4′-diazidodiphenylmethane,
2,6-di (paraazidobenzal) -4-cyclohexanone <polymerization initiator>
Diazoaminobenzene <Antioxidant>
4,4'-Butylidene-bis (6-tert-butyl-m-cresol)
[Color material]
Naphthalazine Oil Yellow SS special (manufactured by Silado Chemical)
Keikoru C (made by Nippon Soda)
[solvent]
Xylene

[Evaluation]
Evaluation was performed in the same manner as in Example 1. The results are shown in the table below.

  As is clear from the above results, the laminate of the present invention was excellent in the pattern forming property of the photosensitive resin composition and also in the post-processing line width evaluation of the organic semiconductor pattern. In contrast, when the protective film was not provided (Comparative Example 2), the post-processing line width evaluation of the organic semiconductor pattern was inferior.

From the above table, the laminate of the present invention is excellent in pattern shape, and also has a high linearity between the resist pattern line width and the organic semiconductor line width before and after etching, and is a useful technique for forming fine patterns of organic semiconductors. It was recognized that there was.
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 (21)

Negative photosensitive resin comprising an organic semiconductor film, a protective film on the organic semiconductor film, and a resist film on the protective film, wherein the resist film contains a crosslinking agent (A) that can be crosslinked by a photo-denitrogenation reaction A laminate comprising a resin composition. The laminated body of Claim 1 whose crosslinking agent (A) which can be bridge | crosslinked by photodenitrogenation reaction is a diazonium salt compound and / or an azide compound. The laminate according to claim 1 or 2, wherein the protective film contains a water-soluble resin. The laminated body of any one of Claims 1-3 in which a protective film contains at least 1 sort (s) of polyvinylpyrrolidone, polyvinyl alcohol, and a pullulan. The laminated body of any one of Claims 1-3 in which a protective film contains polyvinylpyrrolidone. The laminate according to any one of claims 1 to 5, wherein the crosslinking agent (A) that can be crosslinked by a photo-denitrogenation reaction is substantially insoluble in water. The laminate according to any one of claims 1 to 6, wherein the photosensitive tree composition further comprises a sensitizing dye (C) for spectrally sensitizing the photoradical polymerization initiator. The laminate according to any one of claims 1 to 7, wherein the photosensitive tree composition further comprises a binder polymer (C). The laminate according to claim 8, wherein the binder polymer (C) comprises a conjugated diene polymer and / or a cyclized product thereof. A kit for producing an organic semiconductor comprising a resist composition for producing an organic semiconductor containing a crosslinking agent (A) that can be crosslinked by a photodenitrogenation reaction, and a composition for forming a protective film comprising a water-soluble resin. The kit for manufacturing an organic semiconductor according to claim 10, 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 10, wherein the water-soluble resin contains polyvinylpyrrolidone. The kit for manufacturing an organic semiconductor according to any one of claims 10 to 12, wherein the crosslinking agent (A) that can be crosslinked by a photodenitrogenation reaction is substantially insoluble in water. The organic semiconductor manufacturing kit according to any one of claims 10 to 13, wherein the resist composition for manufacturing an organic semiconductor further contains a sensitizing dye (C) for spectrally sensitizing the photoradical polymerization initiator. The organic semiconductor manufacturing kit according to any one of claims 10 to 14, wherein the organic semiconductor manufacturing resist composition further comprises a binder polymer (C). The kit for manufacturing an organic semiconductor according to claim 15, wherein the binder polymer (C) contains a conjugated diene polymer and / or a cyclized product thereof. A resist composition for producing an organic semiconductor comprising a crosslinking agent (A) that can be crosslinked by a photo-denitrogenation reaction. The resist composition for manufacturing an organic semiconductor according to claim 17, wherein the crosslinking agent (A) that can be crosslinked by a photodenitrogenation reaction is substantially insoluble in water. Furthermore, the resist composition for organic-semiconductor manufacture of Claim 17 or 18 containing the sensitizing dye (C) which carries out the spectral sensitization of radical photopolymerization initiator. Furthermore, the resist composition for organic-semiconductor manufacture of any one of Claims 17-19 containing a binder polymer (C). The resist composition for manufacturing an organic semiconductor according to claim 20, wherein the binder polymer (C) contains a conjugated diene polymer and / or a cyclized product thereof.