WO2019167914A1

WO2019167914A1 - Multilayer body, water-soluble resin composition, and kit

Info

Publication number: WO2019167914A1
Application number: PCT/JP2019/007194
Authority: WO
Inventors: 誠也増田
Original assignee: 富士フイルム株式会社
Priority date: 2018-03-01
Filing date: 2019-02-26
Publication date: 2019-09-06
Also published as: JPWO2019167914A1; KR20200115609A; CN111788527A; TW201936768A

Abstract

The present invention provides a multilayer body which has a member and a water-soluble resin layer that is on the surface of the member, and which is configured such that: the water-soluble resin layer is dissolved at a rate of 0.1-3.0 μm/second if immersed in water at 25°C; the water-soluble resin layer is formed from a water-soluble resin composition that contains a water-soluble resin and a surfactant that contains an acetylene group; and the water-soluble resin composition has a static contact angle of 69° or less with respect to the member. The present invention also provides a water-soluble resin composition and a kit.

Description

Laminate, water-soluble resin composition, kit

The present invention relates to a laminate, a water-soluble resin composition, and a kit.

In recent years, semiconductor 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 properties by changing the molecular structure. In addition, there are a wide variety of materials, and it is thought that functions and elements that could not be achieved with inorganic semiconductors can be realized. Organic semiconductors can be applied to electronic devices such as organic solar cells, organic electroluminescence displays, organic photodetectors, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifying elements, organic inverters, information recording elements, etc. There is sex.

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

Therefore, a semiconductor patterning method using a water-soluble resin as a protective film has been studied. For example, Patent Document 1 discloses a hydrophilic composition containing a hydrophilic polymer (I) having a specific structure and an additive having an antibacterial or antifungal action in an amount exceeding 10% based on the total solid content of the hydrophilic composition. Have proposed to use. Accordingly, it is described that a hydrophilic composition and a hydrophilic member having high hydrophilicity, excellent durability, and high antifungal effect can be provided. Patent Document 2 includes an organic semiconductor film, a protective film on the organic semiconductor film, and a resist film on the protective film, and the resist film generates an organic acid having a pKa of generated acid of −1 or less. Disclosed is a laminate comprising a photoacid generator (A) and a photosensitive resin composition comprising a resin (B) that reacts with an acid generated from the photoacid generator to reduce the dissolution rate in a developer containing an organic solvent. ing. Thereby, it is described that a good pattern can be formed on the organic semiconductor.

JP 2010-095655 A Japanese Patent Laying-Open No. 2015-087609

When using a laminate in which a water-soluble resin layer is formed on a member such as an organic semiconductor, the wettability of the water-soluble resin composition to the member such as the organic semiconductor layer is ensured in order to obtain a good coated surface. It is desirable to do. For that purpose, it is desirable that the solid content in the composition is more hydrophobic. However, if the solid content is made hydrophobic, the solubility in an aqueous solvent is inferior, and cannot be completely removed in the step of removing the water-soluble resin layer, and a residue may remain on the surface.
The present invention aims to achieve both improvement of the coated surface and suppression of residue, and in a laminate having a water-soluble resin layer on the surface of the member, a laminate having an improved coated surface of the water-soluble resin layer, An object is to provide a water-soluble resin composition and a kit.

Based on the above problems, the present inventors have conducted a study, and as a result, the solubility of the water-soluble resin layer is within a specific range, a surfactant containing an acetylene group is used, and the water-soluble resin layer is further formed. It has been found that the above problem can be solved by setting the static contact angle of the resin composition to be within a predetermined range. Specifically, the above problem has been solved by the following means <1>, preferably <2> to <15>.
<1> A laminate having a member and a water-soluble resin layer in contact with the surface of the member, wherein the water-soluble resin layer has a speed of 0.1 to 3.0 μm / second when immersed in water at 25 ° C. The water-soluble resin layer is formed from a water-soluble resin composition containing a water-soluble resin and a surfactant containing an acetylene group, and the static contact angle of the water-soluble resin composition with respect to the member Is a laminate having an angle of 69 ° or less.
<2> The laminate according to <1>, wherein the surfactant includes a compound represented by the following formula (9);

In the formula, each of R ⁹¹ and R ⁹² independently represents an alkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, or an aromatic heterocyclic group having 4 to 15 carbon atoms. .
<3> The laminate according to <1>, wherein the surfactant includes a compound represented by the following formula (91);

R ⁹³ to R ⁹⁶ are each independently a hydrocarbon group having 1 to 24 carbon atoms, n9 is an integer of 1 to 6, m9 is an integer twice as large as n9, and n10 is an integer of 1 to 6. M10 is an integer twice as large as n10, and l9 and l10 are each independently a number of 0 or more and 12 or less.
<4> The laminate according to <1>, wherein the surfactant includes a compound represented by the following formula (92);

R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ are each independently a hydrocarbon group having 1 to 24 carbon atoms, and l11 and l12 are each independently a number of 0 or more and 12 or less.
<5> The laminate according to any one of <1> to <4>, wherein the surface tension of the 0.1% by mass aqueous solution of the surfactant at 23 ° C. is 45 mN / m or less.
<6> The laminate according to any one of <1> to <5>, wherein the in-plane uniformity of the water-soluble resin layer is 5% or less.
<7> The water-soluble resin constituting the water-soluble resin layer includes at least one structural unit of a structural unit represented by the following formula (P1-1) and a structural unit represented by the formula (P1-2) , <1> to <6> the laminate according to any one of the above;

In formulas (P1-1) and (P1-2), R ^P1 is independently a hydrogen atom or a methyl group, and np and mp are positive integers.
<8> The laminate according to any one of <1> to <7>, having a photosensitive layer on the water-soluble resin layer.
<9> The laminate according to <8>, having the photosensitive layer on the surface of the water-soluble resin layer.
<10> The laminate according to <8> or <9>, wherein the photosensitive layer is exposed and developed using a developer containing an organic solvent to form a pattern on the photosensitive layer.
<11> The laminate according to any one of <8> to <10>, wherein the photosensitive layer contains a photoacid generator and a photosensitive resin.
<12> The laminate according to any one of <1> to <11>, wherein the member is an organic semiconductor layer.
<13> A water-soluble resin composition for forming a water-soluble resin layer possessed by the laminate according to any one of <1> to <12>, comprising a surfactant containing an acetylene group and a water-soluble resin composition A water-soluble resin composition comprising a resin and an aqueous solvent.
<14> The water-soluble resin layer according to <13>, wherein the water-soluble resin layer formed from the water-soluble resin composition dissolves at a rate of 0.1 to 3.0 μm / second when immersed in water at 25 ° C. Resin composition.
<15> A kit of a resin composition for producing a laminate having a member, a water-soluble resin layer, and a photosensitive layer in the above order, and the water-soluble resin composition according to <13> or <14>, A kit comprising a photosensitive resin composition.

According to the present invention, it is possible to provide a laminate, a water-soluble resin composition, and a kit in which the surface of the water-soluble resin layer is improved in a laminate having a water-soluble resin layer on a member surface.

It is sectional drawing which shows typically the process of the laminated body which concerns on preferable embodiment of this invention. It is a side view which shows typically the measurement state of a stationary contact angle.

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

The laminate of the present invention has a member and a water-soluble resin layer on the surface of the member, and the water-soluble resin layer dissolves at a rate of 0.1 to 3.0 μm / second when immersed in water at 25 ° C. The composition for forming a water-soluble resin layer includes a water-soluble resin and a surfactant containing an acetylene group, and the static contact angle of the composition for forming a water-soluble resin layer with respect to a member is 69 °. It is characterized by the following.
It is presumed that the above-described configuration has solved the problems of the present invention for the following reason. That is, normally, in order to ensure wettability to a hydrophobic member typified by an organic semiconductor, the solid content in the composition is required to be hydrophobic. However, if the solid content in the composition is made hydrophobic, when the soluble resin layer is dissolved and removed with an aqueous solvent, the water-soluble resin layer cannot be sufficiently dissolved and remains in the member as a residue. In the present invention, a surfactant having an acetylene group is used, and by adjusting the dissolution rate of the water-soluble resin layer, both the improvement of the coating surface state of the water-soluble resin layer and the suppression of residues have been successfully achieved. did. That is, when the dissolution rate is 0.1 μm / second or more, when the water-soluble resin layer is dissolved and removed with an aqueous solvent, the water-soluble resin can be washed away with the surfactant involved. By setting the dissolution rate to 3.0 μm / second or less, it is possible to maintain the affinity between the hydrophobic component and the hydrophilicity of the composition. As a result, a laminate having a water-soluble resin layer excellent in coating surface shape and dissolution / removability can be obtained.

FIG. 1 is a cross-sectional view schematically showing a process of processing a laminate according to a preferred embodiment of the present invention. In one embodiment of the present invention, the organic semiconductor layer 3 is disposed on the substrate 4 as in the example shown in FIG. Furthermore, the water-soluble resin layer 2 that protects the organic semiconductor layer 3 is disposed on the surface thereof in contact therewith. However, another layer may be provided between the organic semiconductor layer 3 and the water-soluble resin layer 2. Next, the photosensitive layer 1 is disposed on the water-soluble resin layer, preferably on the surface of the water-soluble resin layer. In the example shown in FIG. 1B, the photosensitive layer 1 is exposed and developed. That is, the photosensitive layer 1a after exposure and development is formed in which the photosensitive layer 1 is exposed with a predetermined mask and developed with an organic solvent to remove the resin in the removal portion 5. At this time, the water-soluble resin layer 2 is insoluble in the organic solvent and remains as it is, and the organic semiconductor layer 3 is protected without being damaged. Next, the water-soluble resin layer 2 and the organic semiconductor layer 3 in the removed portion 5 without the developed photosensitive layer (resist) 1a are removed by dry etching (FIG. 1C). Thereby, the patterning which removes the organic-semiconductor layer 3 in the removal part 5a after an etching can be performed. After the patterning, the developed photosensitive layer 1a and the water-soluble resin layer 2 that are no longer necessary are washed with an aqueous removal solution (FIG. 1D). As described above, according to a preferred embodiment of the present invention, a desired pattern is formed on the organic semiconductor layer 3, and the photosensitive layer 1 serving as a resist and the water-soluble resin layer 2 serving as a protective film are gently and accurately removed. be able to. Details of these steps will be described later.

<Member>
The member used in the present invention is not particularly defined, and widely known members can be employed. For example, a layer having a semiconductor layer on the surface is exemplified. Examples of the member in a preferred embodiment of the present invention include a member having an organic semiconductor layer on a substrate. However, the present invention is not construed as being limited thereto.

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

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

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

The n-type semiconductor material that can be used for the organic semiconductor layer may be any organic semiconductor material as long as it includes an electron transporting property, but is preferably a fullerene compound, an electron-deficient phthalocyanine compound, or a naphthalene tetracarbonyl compound. Perylene tetracarbonyl compound, TCNQ compound (tetracyanoquinodimethane compound), n-type π-conjugated polymer, more preferably fullerene compound, electron-deficient phthalocyanine compound, naphthalene tetracarbonyl compound, perylene tetracarbonyl compound, n-type π-conjugated polymers, particularly preferably fullerene compounds and n-type π-conjugated polymers. In the present invention, the fullerene compound refers to a substituted or unsubstituted fullerene, and the fullerene is C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₀ , C ₈₂ , C ₈₄ , C ₈₆ , C ₈₈ , C _90. , C ₉₆ , C ₁₁₆ , C ₁₈₀ , C ₂₄₀ , C ₅₄₀ fullerene and the like may be used, preferably substituted or unsubstituted C ₆₀ , C ₇₀ , C ₈₆ fullerene, and particularly preferably PCBM ([6, 6] -Phenyl-C61-butyric acid methyl ester, Sigma-Aldrich Japan GK, etc.) and analogs thereof (substitute the C ₆₀ moiety with C ₇₀ , C _86, etc., the benzene ring of the substituent being another aromatic ring or Substituted with a heterocyclic ring, and methyl ester substituted with n-butyl ester, i-butyl ester, etc.). Electron-deficient phthalocyanines are phthalocyanines of various central metals (F ₁₆ MPc, FPc-S8, etc., in which four or more electron withdrawing groups are bonded, where M is a central metal, Pc is phthalocyanine, and S8 is ( n-octylsulfonyl group)), naphthalocyanine, anthracocyanine, substituted or unsubstituted tetrapyrazinoporphyrazine and the like. Any naphthalene tetracarbonyl compound may be used, but naphthalene tetracarboxylic anhydride (NTCDA), naphthalene bisimide compound (NTCDI), and perinone pigment (Pigment Orange 43, Pigment Red 194, etc.) are preferable. Any perylene tetracarbonyl compound may be used, but perylene tetracarboxylic acid anhydride (PTCDA), perylene bisimide compound (PTCDI), and benzimidazole condensed ring (PV) are preferable. The TCNQ compound is a substituted or unsubstituted TCNQ and a benzene ring portion of TCNQ replaced with another aromatic ring or a hetero ring. For example, TCNQ (tetracyanoquinodimethane), TCNAQ (tetracyanoanthraquino) Dimethane), TCN3T (2,2 ′-((2E, 2 ″ E) -3 ′, 4′-Alkyl substituted-5H, 5 ″ H- [2,2 ′: 5 ′, 2 ″- tertiophene] -5,5 ″ -diylidene) dimalonitol derivatives)) and the like. In addition, graphene is also included. Particularly preferred examples of the n-type organic semiconductor material are shown below.

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

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

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

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

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

<Water-soluble resin layer (water-soluble resin composition)>
The water-soluble resin layer contains a water-soluble resin. The water-soluble resin refers to a resin in which the amount of the resin dissolved in 100 g of water at 23 ° C. is 1 g or more, preferably 5 g or more, more preferably 10 g or more, and 30 g or more. Is more preferable. There is no upper limit, but it is practical to be 100 g.

In the present invention, an alcohol-soluble resin can also be used as the water-soluble resin. Examples of the alcohol-soluble resin include polyvinyl acetal. Although what is normally used should just be selected as alcohol which can be utilized as a solvent, For example, isopropyl alcohol is mentioned. The alcohol-soluble resin means a resin having a solubility of 1 g or more with respect to 100 g of alcohol (for example) at 23 ° C., preferably 10 g or more, and more preferably 20 g or more. Although there is no upper limit, it is practical that it is 30 g or less. Unless otherwise specified, in the present invention, the alcohol-soluble resin is defined to be included in the water-soluble resin.

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

Specific examples of the water-soluble resin include polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), water-soluble polysaccharides (water-soluble cellulose (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, etc. ), Pullulan or pullulan derivatives, starch, hydroxypropyl starch, carboxymethyl starch, chitosan, cyclodextrin), polyethylene oxide, polyethyloxazoline and the like. Moreover, 2 or more types may be selected and used from these, and you may use as a copolymer.

Specifically, in the present invention, the water-soluble resin contains at least one structural unit of the structural unit represented by the formula (P1-1) and the structural unit represented by the formula (P1-2). And a water-soluble resin containing a structural unit represented by the following formula (P1) or a structural unit represented by the formula (P2) is more preferable.

In formulas (P1-1) and (P1-2), R ^P1 is independently a hydrogen atom or a methyl group. np and mp are positive integers. The polymer may be composed of only these structural units, but may be a copolymer of the structural unit represented by the formula (P1-1) or (P1-2) and another structural unit. .

The structural units represented by the formulas (P1) and (P2) are shown considering that they are copolymers. ^{R P1} in these formulas has the same meaning as ^{R P} in formula (P1-1) and (P1-2).
The R ^P2, include groups ^-L P -T ^P. L ^P is a single bond or the following linking group L. ^TP is a substituent, and examples of the following substituent T are given. Among them, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, 2 to 3 carbon atoms). Is more preferable), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, To 10 are more preferable), or a hydrocarbon group such as an arylalkyl group (preferably having a carbon number of 7 to 23, more preferably 7 to 19, and further preferably 7 to 11). These alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and arylalkyl groups may further have a group defined by the substituent T within the range where the effects of the present invention are exhibited.
Formulas (P1) and (P2) represent a copolymer. In the formula, np1 and np2 and mp1 and mp2 are constituent ratios in the molecule on a mass basis, and are each independently 10% by mass or more and less than 100% by mass. However, np1 + np2 and mp1 + mp2 do not exceed 100% by mass, respectively. When np1 + np2 and mp1 + mp2 are each less than 100% by mass, it means a copolymer containing other structural units.

Examples of the water-soluble resin include cellulose containing a structure represented by the following formula (C1) and pullulan containing a structure represented by the formula (C2).

na and nb are positive integers. R ^a is (CH ₂ CH ₂ O) _ma H, CH ₂ COONa, or a hydrogen atom. ma is an integer of 1 to 2. The hydroxyl group in the formulas (C1) and (C2) may be optionally substituted with a substituent T or a group combining the linking group L with the substituent T. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to a ring in the formula through or without a linking group L to form a ring.

Examples of the substituent T include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms), and an arylalkyl group (preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms). 7 to 11 are more preferable), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an alkynyl group (preferably 2 to 12 carbon atoms are preferable and 2 to 6 carbon atoms are preferable). More preferably 2 to 3), hydroxyl group, amino group (preferably having 0 to 24 carbon atoms, more preferably 0 to 12 and further preferably 0 to 6), thiol group, carboxyl group, aryl group (carbon A number of 6 to 22, preferably 6 to 18, more preferably 6 to 10, and an alkoxyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, To 3 are more preferable), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms and more preferably 2 to 6 carbon atoms). Preferably 2 to 3), acyloxy groups (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), aryloyl groups (preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms). More preferably, 7 to 11 are more preferable), aryloyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 11 carbon atoms), carbamoyl group (preferably 1 to 12 carbon atoms are preferable). 1 to 6 are more preferable, and 1 to 3 are more preferable.) A sulfamoyl group (having 0 to 12 carbon atoms is preferable, 0 to 6 is more preferable, and 0 to 3 is more preferable). ), A sulfo group, an alkylsulfonyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an arylsulfonyl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms). 6 to 10 are more preferable), a heterocyclic group (preferably having a carbon number of 1 to 12, preferably 1 to 8, more preferably 2 to 5, and preferably including a 5-membered or 6-membered ring), ( (Meth) acryloyl group, (meth) acryloyloxy group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), oxo group (= O), imino group (= NR ^N ), alkylidene group (= C (R ^N ) ₂ ) and the like. ^RN is a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 3), and is preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group. The alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be linear or cyclic, and may be linear or branched. When the substituent T is a group that can take a substituent, the substituent T may further have a substituent T. For example, the alkyl group may be a halogenated alkyl group, or may be a (meth) acryloyloxyalkyl group, an aminoalkyl group, or a carboxyalkyl group. When the substituent is a group capable of forming a salt such as a carboxyl group or an amino group, the group may form a salt.

As the linking group L, an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) 2 to 3 are more preferable), an alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 and further preferably 2 to 3), an (oligo) alkyleneoxy group (of the alkylene group in one structural unit) The number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and the arylene group ( Preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), oxygen atom, sulfur atom, sulfonyl group, carbonyl group, thiocarbonyl group, NR N ^-, and the linking group according to a combination thereof. The alkylene group may have the following substituent T. For example, the alkylene group may have a hydroxyl group. The number of atoms contained in the linking group L is preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30, excluding hydrogen atoms. The number of connected atoms means the number of atoms located in the shortest path among the atomic groups involved in the connection. For example, in the case of —CH ₂ — (C═O) —O—, there are 6 atoms involved in the connection, and 4 atoms excluding hydrogen atoms. On the other hand, the shortest atom involved in the connection is —C—C—O—, which is three. The number of connecting atoms is preferably 1 to 24, more preferably 1 to 12, and still more preferably 1 to 6. The alkylene group, alkenylene group, alkynylene group, and (oligo) alkyleneoxy group may be linear or cyclic, and may be linear or branched. When the linking group is a group capable of forming a salt such as —NR ^N —, the group may form a salt.

The water-soluble resin is incorporated herein by reference to the resin described in International Publication No. 2016/175220.

The weight average molecular weight of the water-soluble resin is preferably 50,000 to 400,000 when it is polyvinyl pyrrolidone, and preferably 15,000 to 100,000 when it is polyvinyl alcohol. In the case, it is preferably within the range of 10,000 to 300,000.
Further, the molecular weight dispersity of the water-soluble resin used in the present invention is preferably 1.0 to 5.0, more preferably 2.0 to 4.0.

The content of the water-soluble resin in the water-soluble resin composition may be appropriately adjusted as necessary, but is preferably 30% by mass or less, more preferably 25% by mass or less in the solid content, and 20 More preferably, it is at most mass%. As a minimum, it is preferred that it is 1 mass% or more, it is more preferred that it is 2 mass% or more, and it is still more preferred that it is 4 mass% or more.
The water-soluble resin composition may contain only one type of water-soluble resin, or may contain two or more types. When 2 or more types are included, the total amount is preferably within the above range.

The solvent for dissolving the water-soluble resin is typically water, but may be a mixed solvent of water and a water-soluble solvent such as alcohol. In the present specification, such a solvent may be referred to as an aqueous solvent. When the aqueous solvent is a mixed solvent, it is preferably a mixed solvent of an organic solvent and water having a solubility in water at 23 ° C. of 1 g or more. The solubility of the organic solvent in water at 23 ° C. is more preferably 10 g or more, and further preferably 30 g or more.
The water-soluble resin composition may contain only 1 type of solvent, and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.

<< Surfactant containing acetylene group >>
In the present invention, the water-soluble resin composition contains a surfactant containing an acetylene group.
A surfactant capable of maintaining appropriate wettability without generating bubbles on the organic semiconductor layer, which is often hydrophobic, requires a certain degree of hydrophobicity. On the other hand, when the hydrophobicity is strong, the surfactant remains on the organic semiconductor layer during cleaning. In order to avoid this, a form of washing with a water-soluble resin while entraining a surfactant is preferable. On the other hand, if the water-soluble resin on the entraining side is too water-soluble, the water-soluble resin is likely to agglomerate, and for example, streaks are likely to occur during spin coating. That is, there is a region where the hydrophobicity of the surfactant and the hydrophilicity of the water-soluble resin are well balanced. Through such a mechanism, the interaction by adopting a combination of a surfactant containing an acetylene group and a water-soluble resin layer whose dissolution rate is specified in a specific range is exhibited, and the effects of the present invention are exhibited. It is understood that.
The surfactant containing an acetylene group only needs to contain an acetylene group in the molecule. The number of acetylene groups in the molecule is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and still more preferably 1 to 2.

The molecular weight of the surfactant containing an acetylene group is preferably relatively small, preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. Although there is no particular lower limit, it is practical that it is 200 or more.

The surfactant containing an acetylene group is preferably a compound represented by the following formula (9).

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

The compound of formula (9) is preferably represented by the following formula (91).

R ⁹³ to R ⁹⁶ are each independently a hydrocarbon group having 1 to 24 carbon atoms, n9 is an integer of 1 to 6, m9 is an integer twice as large as n9, and n10 is an integer of 1 to 6. M10 is an integer twice as large as n10, and l9 and l10 are each independently a number of 0 or more and 12 or less. R ⁹³ to R ⁹⁶ are hydrocarbon groups, and among them, an alkyl group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, more preferably 1 to 3), and an alkenyl group (having 2 to 12 carbon atoms). Preferably 2 to 6, more preferably 2 to 3, more preferably an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms), aryl group (having 6 to 6 carbon atoms). 22 is preferable, 6 to 18 is more preferable, and 6 to 10 is more preferable, and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 and further preferably 7 to 11) is preferable. . The alkyl group, alkenyl group and alkynyl group may be linear or cyclic, and may be linear or branched. R ⁹³ to R ⁹⁶ may have a substituent T as long as the effects of the present invention are exhibited. R ⁹³ to R ⁹⁶ may be bonded to each other or form a ring via the linking group L. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to a hydrocarbon group in the formula through or without a linking group L to form a ring.
R ⁹³ and R ⁹⁴ are each preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 3). Of these, a methyl group is preferable.
R ⁹⁵ and R ⁹⁶ are preferably alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 3 to 6 carbon atoms). Of these, — (C _n11 R ⁹⁸ _m11 ) —R ⁹⁷ is preferable. Here, R ⁹⁷ and R ⁹⁸ are each independently a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms). n11 is an integer of 1 to 6, preferably an integer of 1 to 3. m11 is twice as many as n11.
R ⁹⁵ and R ⁹⁶ are particularly preferably isobutyl groups.
n9 is an integer of 1 to 6, and an integer of 1 to 3 is preferable. m9 is an integer twice as large as n9.
n10 is an integer of 1 to 6, and an integer of 1 to 3 is preferable. m10 is an integer twice as large as n10.
l9 and l10 are each independently a number from 0 to 12. However, l9 + l10 is preferably a number from 0 to 12, more preferably from 0 to 8, more preferably from 0 to 6, more preferably from 0 to less than 6, and more than 0 to 3 or less. Is more preferred. For l9 and l10, the compound of the formula (91) may be a mixture of compounds different in number, and in this case, the number of l9 and l10, or l9 + l10 is a number including a decimal point. May be.

The surfactant represented by the formula (91) is preferably a surfactant represented by the following formula (92).

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

Surfactants containing acetylene groups include the following Surfynol 104 series (trade name, Nissin Chemical Industry Co., Ltd.), the following acetylenol E00, E40, E13T, and 60 (all of which are the same). Trade name, manufactured by Kawaken Finechem Co., Ltd.), among which Surfinol 104 series, acetylenol E00, E40, and E13T are preferred, and acetylenol E40 and E13T are more preferred. Surfynol 104 series and acetylenol E00 are surfactants having the same structure.

In the water-soluble resin composition, the content of the surfactant containing an acetylene group is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and further preferably 0.1% by mass in the solid content. That's it. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less. As the surfactant containing an acetylene group, one kind or a plurality of kinds may be used. When using a plurality of items, the total amount is within the above range.

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

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

When the water-soluble resin composition contains another surfactant, the total amount of the surfactant containing the acetylene group and the other surfactant, and the addition amount of the surfactant is preferably 0.05 in the solid content. It is an amount contained in a ratio of ˜20% by mass, more preferably 0.07-15% by mass, still more preferably 0.1-10% by mass. These surfactants may be used alone or in combination. When using a plurality of items, the total amount is within the above range.
Moreover, in this invention, it can also be set as the structure which does not contain other surfactant substantially. “Substantially free” means that the content of other surfactant is 5% by mass or less of the content of the surfactant containing an acetylene group, preferably 3% by mass or less, and preferably 1% by mass or less. Is more preferable.

<<< Preservatives and mold inhibitors (preservatives, etc.) >>>
It is also preferable to contain a preservative or fungicide in the water-soluble resin composition.
As the antiseptic / antifungal agent (hereinafter referred to as preservative), the additive having antibacterial or antifungal action preferably contains at least one selected from water-soluble or water-dispersible organic compounds. Examples of the antibacterial or antifungal additive such as antiseptics include organic antibacterial and antifungal agents, inorganic antibacterial and antifungal agents, and natural antibacterial and antifungal agents. For example, as the antibacterial or antifungal agent, those described in “Antimicrobial / antifungal technology” published by Toray Research Center, Inc. can be used.
In the present invention, by adding a preservative or the like to the water-soluble resin layer, the effect of suppressing an increase in coating defects due to bacterial growth inside the solution after long-term storage at room temperature is more effectively exhibited.

Examples of preservatives include phenol ether compounds, imidazole compounds, sulfone compounds, N-haloalkylthio compounds, anilide compounds, pyrrole compounds, quaternary ammonium salts, arsine compounds, pyridine compounds, triazine compounds. , Benzoisothiazoline compounds, isothiazoline compounds and the like. Specifically, for example, 2 (4thiocyanomethyl) benzimidazole, 1,2benzothiazolone, 1,2-benzisothiazolin-3-one, N-fluorodichloromethylthio-phthalimide, 2,3,5,6-tetrachloro Isophthalonitrile, N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide, copper 8-quinolinate, bis (tributyltin) oxide, 2- (4-thiazolyl) benzimidazole, 2-benzimidazolecarbamic acid Methyl, 10,10′-oxybisphenoxyarsine, 2,3,5,6-tetrachloro-4- (methylsulfone) pyridine, bis (2-pyridylthio-1-oxide) zinc, N, N-dimethyl-N '-(Fluorodichloromethylthio) -N'-phenylsulfamide, poly- (hexamethyl) Lenvguanide) hydrochloride, dithio-2-2'-bis, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 2-bromo-2-nitro-1,3-propanediol, hexahydro- Examples include 1,3-tris- (2-hydroxyethyl) -S-triazine, p-chloro-m-xylenol, 1,2-benzisothiazolin-3-one, and methylphenol.

Natural antibacterial / antifungal agents include chitosan, a basic polysaccharide obtained by hydrolyzing chitin contained in crab and shrimp shells. Nikko's “trade name Holon Killer Bees Sera” made of amino metal in which metal is compounded on both sides of amino acid is preferable.

The content of the preservative and the like in the water-soluble resin composition is preferably 0.005 to 5% by mass, more preferably 0.01 to 3% by mass in the total solid content, and 0.05 to The content is more preferably 2% by mass, and further preferably 0.1 to 1% by mass. One kind or a plurality of preservatives may be used. When using a plurality of items, the total amount is within the above range.
Antibacterial effects such as preservatives can be evaluated according to JIS Z 2801 (antibacterial processed product-antibacterial test method / antibacterial effect). Further, the antifungal effect can be evaluated in accordance with JIS Z 2911 (mold resistance test).

<< Light-shielding agent >>
The water-soluble resin composition preferably contains a light shielding agent. By blending a light-shielding agent, damage to the organic semiconductor layer or the like due to light can be further suppressed.
The blending amount of the light-shielding agent is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and further preferably 5 to 25% by mass in the solid content of the water-soluble resin composition. As the light shielding agent, one kind or a plurality of kinds may be used. When using a plurality of items, the total amount is within the above range.

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

The thickness of the water-soluble resin layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1.0 μm or more, and further preferably 2.0 μm or more. As an upper limit of the thickness of a water-soluble resin layer, 10 micrometers or less are preferable, 5.0 micrometers or less are more preferable, and 3.0 micrometers or less are further more preferable.
The water-soluble resin layer can be formed, for example, by applying the water-soluble resin composition on the organic semiconductor layer and drying it.
The in-plane uniformity of the thickness of the water-soluble resin layer is preferably 5% or less, preferably 3% or less, more preferably 1% or less, and 0.5% or less. More preferably. The lower limit is practically 0.1% or more. For the in-plane uniformity of the film thickness, a value measured based on the method described in Examples described later is adopted.

The solid content concentration of the water-soluble resin composition is preferably 0.5 to 30% by mass, more preferably 1.0 to 20% by mass, and further preferably 2.0 to 14% by mass. preferable. It can apply | coat more uniformly by making solid content concentration into the said range.

In the present invention, the water-soluble resin layer is set so that it can be dissolved at a rate of 0.1 to 3.0 μm / sec when immersed in water at 25 ° C. By having such a dissolution rate, it interacts with the surfactant or supplements the function of the surfactant, realizing good protection of the organic semiconductor layer, etc. Can be achieved, and quick and reliable detergency at the time of washing can be imparted. The upper limit of the dissolution rate is as described above, but is preferably 2.5 μm / second or less, more preferably 2.2 μm / second or less, and further preferably 2 μm / second or less. preferable. The lower limit is preferably 0.05 μm / second or more, more preferably 0.1 μm / second or more, and further preferably 0.2 μm / second or more. The method for measuring the dissolution rate of the water-soluble resin layer is based on the method employed in the examples described later. A method for adjusting the dissolution rate of the water-soluble resin layer may be a conventional method in this technical field. For example, it can be adjusted by increasing or decreasing the molecular weight of the water-soluble resin composition, or adjusting the blend ratio of the low molecular weight resin and the high molecular weight resin.

The static contact angle with respect to the member of the water-soluble resin composition is preferably 69 ° or less, more preferably 50 ° or less, and further preferably 40 ° or less. The lower limit may be 0 °, but is practically 2 ° or more. By setting the static contact angle to be equal to or less than the above upper limit value, it is possible to suppress coating unevenness and obtain an effect of good coating uniformity. The method for measuring the static contact angle is based on the method employed in the examples described later. The method for adjusting the static contact angle of the water-soluble resin composition may be a conventional method in this technical field. For example, the blend ratio of a water-soluble resin and a surfactant containing an acetylene group in the water-soluble resin composition is adjusted, a surfactant not containing an acetylene group is further blended, or the alkyloxy chain of the surfactant side chain By increasing the length, the contact angle increases.

<Photosensitive layer (photosensitive resin composition)>
The photosensitive layer contains a photosensitive resin, and a material commonly used in this technical field can be appropriately used. The photosensitive layer is preferably a layer formed from a photosensitive resin composition further containing an acid generator. That is, an embodiment in which the photosensitive layer includes a photoacid generator and a photosensitive resin is exemplified.

The weight average molecular weight of the photosensitive resin is preferably 10,000 or more, more preferably 20,000 or more, and further preferably 35,000 or more. The upper limit is not particularly defined, but is preferably 100,000 or less, may be 70,000 or less, and may be 50,000 or less.
In addition, the amount of the component having a weight average molecular weight of 1,000 or less contained in the photosensitive resin is preferably 10% by mass or less, more preferably 5% by mass or less of the total photosensitive resin component.
The molecular weight dispersity (weight average molecular weight / number average molecular weight) of the photosensitive resin is preferably 1.0 to 4.0, and more preferably 1.1 to 2.5.

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

The content of the photosensitive resin in the photosensitive layer is preferably 20 to 99.9% by mass, more preferably 40 to 99% by mass, and further preferably 70 to 99% by mass. 1 type or 2 or more types of photosensitive resin may be contained. When using 2 or more types, it is preferable that a total amount becomes the said range.

The photosensitive layer is preferably hardly soluble in a developing solution containing an organic solvent in the exposed portion. Slightly soluble means that the exposed portion is hardly soluble in the developer, and specifically, 50 mJ / cm at least one of a wavelength of 365 nm (i-line), a wavelength of 248 nm (KrF line) and a wavelength of 193 nm (ArF line). ^The polarity is changed by exposure at an irradiation dose of ² or more, and it is preferably hardly soluble in a solvent having an sp value (solubility parameter value) of less than 19 (MPa) ^1/2 , and 18.5 (MPa). It is more preferable that it is hardly soluble in a solvent of ^1/2 or less, and it is more preferable that it is hardly soluble in a solvent of 18.0 (MPa) ^1/2 or less. Furthermore, the polarity changes as described above by exposing at a dose of 50 to 250 mJ / cm ² at at least one of a wavelength of 365 nm (i-line), a wavelength of 248 nm (KrF line) and a wavelength of 193 nm (ArF line). Is more preferable.

The photosensitive layer may be a negative photosensitive layer or a positive photosensitive layer.
The thickness of the photosensitive layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 0.75 μm or more, and particularly preferably 0.8 μm or more from the viewpoint of improving the resolution. The upper limit of the thickness of the photosensitive layer is preferably 10 μm or less, more preferably 5.0 μm or less, and further preferably 2.0 μm or less.
Furthermore, the total thickness of the photosensitive layer and the water-soluble resin layer is preferably 0.2 μm or more, more preferably 1.0 μm or more, and further preferably 2.0 μm or more. The upper limit is preferably 20.0 μm or less, more preferably 10.0 μm or less, and even more preferably 5.0 μm or less.

The photosensitive layer preferably has photosensitivity to i-ray irradiation. Photosensitivity refers to the rate of dissolution in an organic solvent (preferably butyl acetate) due to irradiation with at least one of actinic rays and radiation (i-line irradiation if it has photosensitivity to i-line irradiation). To do.

The photosensitive layer is usually formed using a photosensitive resin composition. The photosensitive resin composition is preferably a chemically amplified photosensitive resin composition containing at least a photosensitive resin and a photoacid generator.

The photosensitive resin preferably has a compound that generates an acid upon irradiation with at least one of actinic rays and radiation, and a dissolution rate in the developer that changes due to the action of the acid.
The photosensitive resin in the present invention is usually a resin containing a structural unit containing a group that is dissociated by an acid, and may contain another structural unit.

In the present invention, the photosensitive resin is a resin whose dissolution rate in the developer (preferably butyl acetate) is changed by the action of an acid, and this change is more preferably a decrease in the dissolution rate.
The dissolution rate of the photosensitive resin in an organic solvent having an sp value of 18.0 (MPa) ^1/2 or less is more preferably 40 nm / second or more. Further, when the acid-decomposable group of the photosensitive resin is decomposed, the dissolution rate in an organic solvent having an sp value of 18.0 (MPa) ^1/2 or less is more preferably less than 1 nm / second.
The photosensitive resin is also soluble in an organic solvent having an sp value (solubility parameter value) of 18.0 (MPa) ^1/2 or less, and has a tetrahydrofuranyl group in the structural unit represented by the formula (1). A resin that is hardly soluble in an organic solvent having an sp value of 18.0 (MPa) ^1/2 or less when decomposed or dissociated is preferable.
Here, “sp value (solubility parameter value) is 18.0 (MPa) soluble in an organic solvent of ^1/2” or less means that a solution of a compound (resin) is applied on a substrate, and then at 100 ° C. for 1 minute. The dissolution rate of the coating film (thickness 1 μm) of the compound (resin) formed by heating with respect to the developer at 23 ° C. is 20 nm / second or more, and the “sp value is 18.0 (MPa ) “Slightly soluble in ^1/2 or less organic solvent” means that a compound (resin) coating film (thickness) is formed by applying a compound (resin) solution on a substrate and heating at 100 ° C. for 1 minute. 1 μm) at 23 ° C. is less than 10 nm / second.

<< Acrylic polymer >>
The photosensitive resin is preferably an acrylic polymer.
“Acrylic polymer” is an addition polymerization type resin, which is a polymer containing a structural unit derived from (meth) acrylic acid or an ester thereof, and other than a structural unit derived from (meth) acrylic acid or an ester thereof. These structural units may include, for example, structural units derived from styrenes, structural units derived from vinyl compounds, and the like. The acrylic polymer preferably contains 50 mol% or more, more preferably 80 mol% or more of the structural unit derived from (meth) acrylic acid or its ester, based on the total structural units in the polymer. Particularly preferred is a polymer consisting only of structural units derived from (meth) acrylic acid or its ester.

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

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

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

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

It is also preferable that the acrylic polymer contains a structural unit containing a protected carboxyl group or a protected phenolic hydroxyl group. As the carboxylic acid monomer capable of forming this structural unit, those capable of forming a structural unit by protecting the carboxyl group can be used, and examples thereof include acrylic acid and methacrylic acid. Moreover, as a structural unit, the structural unit derived from the carboxylic acid by which these carboxyl groups were protected can be mentioned as a preferable thing. Preferred examples of the monomer containing a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene. Among these, α-methyl-p-hydroxystyrene is more preferable.

Examples of the structural unit containing a protected carboxyl group or a protected phenolic hydroxyl group include structural units of the following formula (2).

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

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

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

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

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

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

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

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

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

<< Photoacid generator >>
The photosensitive resin composition may contain a photoacid generator. The photoacid generator is preferably a photoacid generator that decomposes by 80 mol% or more when exposed to 100 mJ / cm ² or more at a wavelength of 365 nm.
The degree of decomposition of the photoacid generator can be determined by the following method.
A chemically amplified photosensitive resin composition having a film thickness of 700 nm is formed on a silicon wafer, heated at 100 ° C. for 1 minute, then exposed to 100 mJ / cm ^{2 at} 365 nm, and heated at 100 ° C. for 1 minute. Immerse in methanol / THF = 50/50 solution for 10 minutes while applying ultrasonic waves. By analyzing the extract by HPLC (high performance liquid chromatography), the decomposition rate of the photoacid generator is calculated from the following formula.
Decomposition rate (%) = decomposition amount (mol) / charge amount (mol) × 100
The photoacid generator is preferably one that decomposes by 85 mol% or more when exposed to 100 to 250 mJ / cm ² at a wavelength of 365 nm.
The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter also simply referred to as an oxime sulfonate compound).

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

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

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

Specific examples of the oxime sulfonate compound represented by the formula (OS-1) are described in paragraph numbers 0064 to 0068 of JP2011-209692A and paragraph numbers 0158 to 0167 of JP2015-194664A. The following compounds are exemplified and their contents are incorporated herein.

R ^s1 represents an alkyl group, an aryl group, or a heteroaryl group, and R ^s2 , which may be present in plural, independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and R ^s6 that may exist in plural Each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents 0 to 6 Represents an integer.
The alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by R ^s1 has a substituent T. It may be.

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

ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2.
The alkyl group represented by R ^s6 (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) may have a substituent.
ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

The compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), (OS-110) or (OS-111). The compound represented by OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is represented by the following formula (OS-108). ) Or (OS-109) is particularly preferable.

R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl A group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ^t2 represents a hydrogen atom or a methyl group.
R ^t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, and an alkyl group having 1 to 8 carbon atoms, A halogen atom or a phenyl group is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is further preferable, and a methyl group is particularly preferable.
R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ^t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the oxime sulfonate compound, the oxime steric structure (E, Z) may be either one or a mixture.
Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 0088 to 0095 in JP2011-209692A and paragraph numbers in JP2015-194673A. The compounds described in 0168 to 0194 are exemplified, the contents of which are incorporated herein.

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

R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group. An embodiment in which R ^u9 is a cyano group or an aryl group is more preferable, and an embodiment in which R ^u9 is a cyano group, a phenyl group, or a naphthyl group is more preferable.
R ^u2a represents an alkyl group or an aryl group.
Xu is, -O -, - S -, - NH -, - NR u5 -, - CH 2 -, - CR u6 H- or ^-CR u6 ^{R u7} - ^represents, in each of R u5 ^{~ R u7} independently, Represents an alkyl group or an aryl group.
R ^u1 to R ^u4 are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group or aryl. Represents a group. 2 in turn, each may be bonded to each other to form a ring of the ^R ^u1 ~ R ^u4. At this time, the ring may be condensed to form a condensed ring together with the benzene ring.
R ^u1 to R ^u4 are preferably a hydrogen atom, a halogen atom or an alkyl group, and an embodiment in which at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group is also preferred. In particular, an embodiment in which R ^u1 to R ^u4 are all hydrogen atoms is preferable.
Any of the above-described substituents may further have a substituent.
The compound represented by the formula (OS-101) is more preferably a compound represented by the formula (OS-102).
In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
Specific examples of the compound represented by the formula (OS-101) include compounds described in paragraph numbers 0102 to 0106 of JP2011-209692A and paragraph numbers 0195 to 0207 of JP2015-194664A. The contents of which are incorporated herein.
Among the above compounds, b-9, b-16, b-31 and b-33 are preferable.
Examples of commercially available products include WPAG-336 (manufactured by Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Chemical Co., Ltd.), and the like. it can.

As the photoacid generator sensitive to actinic rays, those which do not contain a 1,2-quinonediazide compound are preferred. The reason is that the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is 1 or less and is less sensitive than the oxime sulfonate compound.
In contrast, the oxime sulfonate compound acts as a catalyst for the deprotection of an acid group protected in response to an actinic ray, so that a large number of acids generated by the action of one photon are present. It contributes to the deprotection reaction, and the quantum yield exceeds 1, for example, a large value such as a power of 10, and it is estimated that high sensitivity is obtained as a result of so-called chemical amplification.
In addition, since the oxime sulfonate compound has a broad π-conjugated system, it has absorption up to the long wavelength side, and not only deep ultraviolet rays (DUV), ArF rays, KrF rays, i rays, It shows very high sensitivity even in the g-line.
By using a tetrahydrofuranyl group as an acid-decomposable group in the photosensitive resin, an acid-decomposability equivalent to or higher than that of an acetal or ketal can be obtained. Thereby, an acid-decomposable group can be consumed reliably in a shorter post-bake. Furthermore, by using the oxime sulfonate compound that is a photoacid generator in combination, the sulfonic acid generation rate is increased, so that the generation of acid is accelerated and the decomposition of the acid-decomposable group of the resin is accelerated. Moreover, since the acid obtained by decomposing | disassembling an oxime sulfonate compound is a sulfonic acid with a small molecule | numerator, the diffusibility in a cured film is also high, and it can make more highly sensitive.
The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, based on the total solid content of the photosensitive resin composition. It is further preferable to use 10% by mass, more preferably 0.5 to 3% by mass, and still more preferably 0.5 to 1.2% by mass.
A photo-acid generator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Other ingredients >>
The photosensitive resin composition may also contain other components.
<< Organic solvent >>
The photosensitive resin composition preferably contains an organic solvent.
In addition to the photosensitive resin, the photoacid generator and optional components of various additives are preferably prepared as a solution dissolved in an organic solvent.
As the organic solvent used in the photosensitive resin composition, known organic solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether. , Propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetate , Esters, ketones, amides, lactones and the like.
Examples of the organic solvent include (1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; (2) ethylene glycol dimethyl ether, ethylene glycol diethyl Ethylene glycol dialkyl ethers such as ether and ethylene glycol dipropyl ether; (3) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate Acetates; (4) propylene glycol Propylene glycol monoalkyl ethers such as monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; (5) Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether and propylene glycol diethyl ether; (6) Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; (7) diethylene glycol dimethyl ether, diethylene glycol diethyl ether, die Diethylene glycol dialkyl ethers such as lenglycol ethyl methyl ether; (8) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate; (9) dipropylene Dipropylene glycol monoalkyl ethers such as glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether; (10) dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene (11) Dipropylene such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate (12) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate; (13) n acetate -Butyl, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, Aliphatic carboxylic acid esters such as isopropyl lopionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate; (14) ethyl hydroxyacetate , Ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate Acetoacetic acid Other esters such as chill, methyl pyruvate, ethyl pyruvate; (15) such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone Ketones; (16) amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; (17) lactones such as γ-butyrolactone, etc. Can be mentioned.
In addition, these organic solvents may further contain benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-octanol, if necessary. Organic solvents such as nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate can also be added.
Of the organic solvents described above, propylene glycol monoalkyl ether acetates or diethylene glycol dialkyl ethers are preferable, and diethylene glycol ethyl methyl ether or propylene glycol monomethyl ether acetate is particularly preferable.
When the photosensitive resin composition contains an organic solvent, the content of the organic solvent is preferably 1 to 3,000 parts by mass per 100 parts by mass of the photosensitive resin, and is 5 to 2,000 parts by mass. More preferred is 10 to 1,500 parts by mass.
These organic solvents can be used individually by 1 type or in mixture of 2 or more types.
When using 2 or more types, it is preferable that a total amount becomes the said range.
Furthermore, from the viewpoint of liquid storage stability, the photosensitive resin composition preferably contains a basic compound, and preferably contains a surfactant from the viewpoint of coatability.

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

<< Surfactant >>
It is preferable that the photosensitive resin composition contains a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based and silicone surfactants. .
More preferably, the surfactant includes a fluorine-based surfactant or a silicone-based surfactant.
As these fluorosurfactants or silicone surfactants, for example, JP-A-62-036663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950 are disclosed. The interfaces described in JP-A-63-03540, JP-A-07-230165, JP-A-08-062834, JP-A-09-054432, JP-A-09-005988, and JP-A-2001-330953. An activator can be mentioned and a commercially available surfactant can also be used.
Examples of commercially available surfactants that can be used include EFTOP EF301, EF303 (above, Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (above, made by Sumitomo 3M Ltd.), MegaFuck F171, F173, F176. , F189, R08 (above, manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.), PF-6320, etc. PolyFox series (OMNOVA) Fluorine-based surfactant or silicone-based surfactant. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

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

(In the formula, R ⁴¹ and R ⁴³ each independently represent a hydrogen atom or a methyl group, R ⁴² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁴ represents a hydrogen atom or 1 to 4 carbon atoms. represents an alkyl group, L ⁴ represents an alkylene group having 3 to 6 carbon atoms, p4 and q4 is the mass percentage representing the polymerization ratio, p4 represents the following numbers 80 wt% to 10 wt%, q4 represents a numerical value of 20% by mass to 90% by mass, r4 represents an integer of 1 to 18 and n4 represents an integer of 1 to 10.
L ⁴ is preferably a branched alkylene group represented by the following formula (42). R ⁴⁵ in the formula (42) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of wettability with respect to the coated surface, and an alkyl group having 2 or 3 carbon atoms. Groups are more preferred.
—CH ₂ —CH (R ⁴⁵ ) — (42)
The weight average molecular weight of the copolymer is more preferably 1,500 or more and 5,000 or less.
When a surfactant is included, the addition amount of the surfactant is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the photosensitive resin. More preferably, the content is 0.01 to 1 part by mass.
Surfactant can be used individually by 1 type or in mixture of 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.

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

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

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

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

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

<< (3) Step of exposing photosensitive layer >>
After forming the photosensitive layer in the step (2), the photosensitive layer is exposed. Specifically, the photosensitive layer is irradiated with actinic rays through a mask including a predetermined pattern. Exposure may be performed only once or multiple times.
Specifically, actinic rays are irradiated so that it may become a predetermined pattern to the board | substrate which provided the dry coating film of the photosensitive resin composition. Exposure may be performed through a mask, or a predetermined pattern may be drawn directly. As the actinic ray, an actinic ray having a wavelength of preferably 180 nm or more and 450 nm or less, more preferably 365 nm (i line), 248 nm (KrF line) or 193 nm (ArF line) can be used. After this step, a post-exposure heating step (PEB) may be performed as necessary.
For exposure with actinic rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a laser generator, a light emitting diode (LED) light source, or the like can be used.
When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. In the present invention, it is preferable to use i-line because the effect is suitably exhibited.
When a laser is used, wavelengths of 343 nm and 355 nm are preferably used for a solid (YAG) laser, and 193 nm (ArF line), 248 nm (KrF line), and 351 nm (Xe line) are preferably used for an excimer laser. Further, 375 nm and 405 nm are preferably used in the semiconductor laser. Among these, 355 nm and 405 nm are more preferable from the viewpoints of stability and cost. The laser can be applied to the photosensitive layer in one or more times.
The exposure amount is preferably 40 to 120 mJ, and more preferably 60 to 100 mJ.
The energy density per pulse of the laser is preferably 0.1 mJ / cm ² or more and 10,000 mJ / cm ² or less. In order to sufficiently cure the coating film, 0.3 mJ / cm ² or more is more preferable, and 0.5 mJ / cm ² or more is more preferable. To prevent to decompose the coating film by ablation phenomenon, more preferably 1,000 mJ / cm ² or less, 100 mJ / cm ² or less is more preferred.
The pulse width is preferably 0.1 nanosecond (hereinafter referred to as “nsec”) or more and 30,000 nsec or less. In order to prevent the color coating film from being decomposed by the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is more preferable. In order to improve the alignment accuracy at the time of scan exposure, 1,000 nsec or less is more preferable, and 50 nsec or less is further preferable.
The frequency of the laser is preferably 1 Hz or more and 50,000 Hz or less, and more preferably 10 Hz or more and 1,000 Hz or less.
Furthermore, in order to shorten the exposure processing time, the frequency of the laser is more preferably 10 Hz or more, further preferably 100 Hz or more, and in order to improve the alignment accuracy during the scan exposure, it is more preferably 10,000 Hz or less. More preferably, it is not more than 1,000 Hz.
The laser is preferable in that it can be easily focused as compared with a mercury lamp, and a mask for forming a pattern in the exposure process is unnecessary and the cost can be reduced.
There are no particular restrictions on the exposure apparatus, but commercially available devices include Callisto (buoy technology), AEGIS (buoy technology), DF2200G (Dainippon Screen Mfg. Co., Ltd.). Etc.) can be used. Further, devices other than those described above are also preferably used.
If necessary, the amount of irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

<< (4) Step of developing mask pattern by developing using developer containing organic solvent >>
In the step (3), the photosensitive layer is exposed through a mask, and then developed using a developer containing an organic solvent (hereinafter sometimes referred to as an organic developer). Development is preferably a negative type. Sp value of the solvent contained in the developer is preferably less than ^{19 MPa 1/2,} and more preferably ^{18 MPa 1/2} or less.
As the organic solvent contained in the developer, polar solvents such as ketone solvents, ester solvents, amide solvents, and hydrocarbon solvents can be used.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, Examples include methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Can be mentioned.
Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone, and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
The organic solvent may be used alone or in combination of two or more. Moreover, you may mix and use with organic solvents other than the above. However, the water content of the whole developer is preferably less than 10% by mass, and more preferably substantially free of moisture. The term “substantially” as used herein means, for example, that the water content of the entire developing solution is 3% by mass or less, and more preferably the measurement limit or less.
That is, the amount of the organic solvent used relative to the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.
In particular, the organic developer preferably contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, and amide solvents.
The organic developer may contain an appropriate amount of a basic compound as required. Examples of the basic compound include those described in the above basic compound section.
The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and further preferably 2 kPa or less at 23 ° 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, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface. Will improve.
Specific examples of the solvent having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone and diisobutyl. Ketone solvents such as ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylisobutylketone, butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol Monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, Ester solvents such as butyl acid, propyl formate, ethyl lactate, butyl lactate, propyl lactate, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, xylene And aromatic hydrocarbon solvents such as octane and decane.
Specific examples of the solvent having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, Ketone solvents such as methylcyclohexanone and phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, Ester solvents such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, N-methyl-2- Pyrrolidone, N, N- dimethylacetamide, N, amide solvents such as N- dimethylformamide, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.
An appropriate amount of one or more surfactants can be added to the developer as required.
Although it does not specifically limit as surfactant, For example, surfactant described in the item of said water-soluble resin composition is used preferably.
When a surfactant is blended in the developer, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0, based on the total amount of the developer. 0.01 to 0.5% by mass.
As a development method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.
When the above-mentioned various development methods include a step of discharging the developer from the developing nozzle of the developing device toward the photosensitive layer, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is , Preferably 2 mL / sec / mm ² or less, more preferably 1.5 mL / sec / mm ² or less, and even more preferably 1 mL / sec / mm ² or less. Although there is no particular lower limit of the discharge pressure, 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 in the above range, the pressure applied to the photosensitive layer by the developer is reduced, and the resist pattern on the photosensitive layer is inadvertently scraped or broken. This is considered to be suppressed.
The developer discharge pressure (mL / second / mm ² ) is a value at the developing nozzle outlet in the developing device.
Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.
Moreover, you may implement the process of stopping image development, after substituting with another organic solvent after the process developed using the developing solution containing the organic solvent.

<< (5) Step of removing at least the non-masked water-soluble resin layer and the organic semiconductor layer by dry etching treatment >>
After developing the photosensitive layer to produce a mask pattern, at least the water-soluble resin layer and the organic semiconductor layer in the non-mask portion are removed by an etching process. A non-mask part represents the location which is not exposed with the mask at the time of exposing a photosensitive layer and producing a mask pattern.
Specifically, in the dry etching, at least the water-soluble resin layer and the organic semiconductor layer are dry etched using the resist pattern as an etching mask. Representative examples of dry etching include Japanese Patent Application Laid-Open Nos. 59-126506, 59-046628, 58-009108, 58-002809, and 57-148706. There is a method described in Japanese Patent Laid-Open No. 61-0410102.
The dry etching is preferably performed in the following manner from the viewpoint of forming the pattern cross section closer to a rectangle and reducing damage to the organic semiconductor layer.
A first stage etching using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ) to perform etching up to a region (depth) where the organic semiconductor layer is not exposed, and after this first stage etching, nitrogen gas The second stage etching, in which etching is performed to the vicinity of the region (depth) after the organic semiconductor layer is exposed, using a mixed gas of (N ₂ ) and oxygen gas (O ₂ ), and the organic semiconductor layer is exposed A mode including over-etching performed later is preferable. Hereinafter, a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.
Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated. (2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated. (3) The first stage etching is performed according to the etching time calculated in (2) above. (4) The second stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time. (5) Overetching time is calculated with respect to the total time of (3) and (4) above, and overetching is performed.
The mixed gas used in the first stage etching step preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. In the first step, the organic semiconductor layer can be prevented from being damaged by etching the region where the organic semiconductor layer is not exposed. The second-stage etching process and the over-etching process may be performed by performing etching to a region where the organic semiconductor layer is not exposed by a mixed gas of fluorine-based gas and oxygen gas in the first-stage etching process. From the viewpoint of avoiding damage, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.
It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable. The etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.
Etching preferably includes an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

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

<Application>
The laminated body of this invention can be used for manufacture of the electronic device using an organic semiconductor. Here, the electronic device is a device that contains a semiconductor and has two or more electrodes, and a current flowing between the electrodes and a generated voltage are controlled by electricity, light, magnetism, a chemical substance, or the like, or It is a device that generates light, electric field, magnetic field, etc. by applied voltage or current. Examples include organic photoelectric conversion elements, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifying elements, organic inverters, information recording elements, and the like. The organic photoelectric conversion element can be used for both optical sensor applications and energy conversion applications (solar cells). Among these, organic field effect transistors, organic photoelectric conversion elements, and organic electroluminescence elements are preferable as applications, more preferably organic field effect transistors and organic photoelectric conversion elements, and particularly preferably organic field effect transistors. .

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

<Water-soluble resin composition>
The water-soluble resin shown in Table 1 (below), surfactant, and preservative are blended in the proportions (parts by mass) shown in Table 1, and the water-soluble resin is blended so that the solid content concentration is 15% by mass, Each component was mixed to make a uniform 2 L solution, and then filtered using a 3M ZetaPlusEC8PI-150GN depth filter (equivalent to 0.8 μm) to prepare a water-soluble resin composition.
Polyvinyl alcohol (PVA): manufacturer Kuraray, product number PVA-203, polymerization degree 300
Polyvinylpyrrolidone (PVP): Tokyo Kasei Polyvinylpyrrolidone K90, Mw 360,000

Surfactant:
Acetylenol E00: Kawaken Finechem

Acetylenol E13T: manufactured by Kawaken Finechem Co. (m + n is 4)

Acetylenol E60: manufactured by Kawaken Finechem Co. (m + n is 6)

Surfynol 440: manufactured by Nissin Chemical Industry Co., Ltd. (m + n is 3.5)

Surfynol 82: Nissin Chemical Industry Co., Ltd. (m + n is 4)

MegaFuck F-556: DIC, fluorine group / hydrophilic group / lipophilic group-containing oligomer, nonionic surfactant

Megafac F-444: DIC, fluorinated / hydrophilic group-containing oligomer orphine E1020: Nissin Chemical Industry Preservative X-1: 1,2-Benzisothiazoline-3-one

<Photosensitive resin composition>
Each photosensitive resin was synthesized as follows.
<< Synthesis Example Synthesis of Photosensitive Resin A-1 >>
PGMEA (propylene glycol monomethyl ether acetate) (32.62 g) was placed in a 200 mL three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. Here, BzMA (16.65 g), THFMA (21.08 g), t-BuMA (5.76 g), and V-601 (0.4663 g) dissolved in PGMEA (32.62 g) were taken over 2 hours. And dripped. Thereafter, the reaction solution was stirred for 2 hours to complete the reaction. The white powder produced by reprecipitation of the reaction solution in heptane was collected by filtration to obtain acid-reactive resin A-2. The weight average molecular weight (Mw) was 45,000.
The amount of the component having Mw of 1,000 or less was 3% by mass.

In the following formulation, each component was mixed to make a uniform solution, and then filtered using a nylon filter having a pore diameter of 0.45 μm to prepare a photosensitive resin composition.
<Combination>
Photosensitive resin A-1 25.091 parts by mass Acid generator B-1 0.255 parts by mass Base generator C-1 0.077 parts by mass Surfactant D-1 0.077 parts by mass Solvent E-1 74. 500 parts by mass

Acid generator B-1

Basic compound C-1

Surfactant D-1: OMNOVA, part number PF6320

Solvent E-1: Propylene glycol monomethyl ether acetate

<Production of organic semiconductor substrate>
An organic semiconductor coating solution (composition for forming an organic semiconductor) having the following composition is spin-coated on a glass substrate of a disk-shaped glass substrate having a diameter of 8 inches (1 inch is 2.54 cm), and 10 at 130 ° C. An organic semiconductor layer was formed by partial drying. The film thickness was 150 nm.
Composition of organic semiconductor coating solution P3HT (Sigma Aldrich Japan GK) 10% by mass
PCBM (Sigma Aldrich Japan GK) 10% by mass
Chloroform (Wako Pure Chemical Industries, Ltd.) 80% by mass

<Formation of photosensitive layer>
A photosensitive resin composition was spin-coated on the surface of the water-soluble resin layer thus formed, and dried (prebaked) at 100 ° C. for 1 minute to form a photosensitive layer. The film thickness was 2 μm.

<Dissolution rate>
A water-soluble resin composition was spin coated on the surface of the organic semiconductor layer and dried at 100 ° C. for 1 minute to form a water-soluble resin layer having a thickness of 2 μm.
The dissolution rate of the water-soluble resin layer in water was calculated from the time during which the coating film having a thickness of 2 μm was dissolved using a quartz crystal microbalance (QCM) method. The measurement was performed 3 times for each sample, and the arithmetic average value was adopted.

<In-plane uniformity of film thickness (in-plane variation)>
The in-plane uniformity (in-plane variation) of the water-soluble resin layer was measured as follows.
A water-soluble resin composition was spin coated on the surface of the organic semiconductor layer and dried at 100 ° C. for 1 minute to form a water-soluble resin layer having a thickness of 2 μm. 121 points of the film thickness of the entire surface of the substrate were measured with an F-50 film thickness meter manufactured by FILMETRIX. When the arithmetic average value of the film thickness at 121 points in the plane is M and the standard deviation is σ, the value obtained by the following equation is the film thickness in-plane uniformity.
In-plane uniformity of film thickness = 3σ ÷ M × 100 [%]

<Measurement of static contact angle>
Using a static contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) on the surface of the organic semiconductor layer, a water droplet having a droplet size of 10 μL is deposited with a syringe. It was measured. The measurement was performed 3 times for each sample, and the arithmetic average value was adopted.
Other conditions were based on JIS R3257: 1999.

<Measurement of surface tension>
The surface tension was measured at 23 ° C. using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. using a glass plate. The unit is mN / m. Regarding the surface tension (γUL) of the surfactant containing an acetylene group, measurement was carried out as a 0.1% by mass dilution using ultrapure water as the solvent. The measurement was performed 3 times for each sample, and the arithmetic average value was adopted.

<Applied surface>
A water-soluble resin composition was spin coated on the surface of the organic semiconductor layer and dried at 100 ° C. for 1 minute to form a water-soluble resin layer having a thickness of 2 μm. The wet-spreading of the water-soluble resin layer, coating unevenness, and coating defects were visually observed during spin coating onto the organic semiconductor layer.

<Applied surface>
A: Wetting spread was good and no coating unevenness or coating defect was observed. B: One of an area where wet spreading was insufficient, coating unevenness in a wet spreading part, and coating defect in a wet spreading part was present. C : There were two or more of the areas where the wet spread was insufficient, the coating unevenness in the wet spread area, and the coating defect in the wet spread area.

<Cleanability of pattern opening>
A water-soluble resin composition was spin coated on the surface of the organic semiconductor layer and dried at 100 ° C. for 1 minute to form a water-soluble resin layer having a thickness of 2 μm. On top of this, a photosensitive resin composition (resist) was applied to a thickness of 2 μm using a spin coater. Using an i-line parallel exposure machine, i-line was irradiated through a predetermined mask so as to be 200 mJ / cm ² and exposed to an exposure amount of 80 mJ. Thereafter, post-baking (PEB) was performed at 80 ° C. for 60 seconds, and development was performed with butyl acetate for 80 seconds to obtain a rectangular hole opening in which a 5 mm square water-soluble resin layer was exposed.
The substrate after the development was further filled with 30 ml of ultrapure water and held for 15 seconds. The water-soluble resin was removed only at the opening and spin drying was performed. A 5 mm square organic semiconductor layer was exposed, and the residue of the water-soluble resin layer remaining in the portion was counted with an optical microscope. The arithmetic average of three measurements was adopted.
A: No residue B: 1 residue C: 2 or more residues

From the above results, a surfactant containing an acetylene group is included in the water-soluble resin layer, the water-soluble resin layer has a water dissolution rate of 0.1 to 3.0 μm / second, and a contact angle of 69 ° or less. According to the laminate of the example, it was found that a good coated surface shape of the water-soluble resin layer on the organic semiconductor layer can be obtained. On the other hand, in the laminate using the water-soluble resin layer having a contact angle exceeding 69 ° (Comparative Examples 1 to 5), it was found that the coating surface shape of the water-soluble resin layer and the cleanability of the pattern opening were inferior. Furthermore, among the examples, it was found that particularly good coated surface condition (Evaluation of A) was obtained when acetylenol E00 and E13T (both trade names) were used as surfactants containing an acetylene group. It was.

DESCRIPTION OF SYMBOLS 1 Photosensitive layer 1a Exposed and developed photosensitive layer 2 Water-soluble resin layer 3 Organic semiconductor layer 3a Processed organic semiconductor layer 4 Substrate 5 Removal part 5a Etching removal part 22 Test object (substrate)
21 Sample droplet Θ Static contact angle

Claims

A laminate having a member and a water-soluble resin layer in contact with the surface of the member,
The water-soluble resin layer is a layer that dissolves at a rate of 0.1 to 3.0 μm / second when immersed in water at 25 ° C., and the water-soluble resin layer has a surface activity containing a water-soluble resin and an acetylene group. Formed from a water-soluble resin composition containing an agent,
The static contact angle of the water-soluble resin composition with respect to the member is 69 ° or less,
Laminated body.
The laminated body of Claim 1 in which the said surfactant contains the compound represented by following formula (9);

In the formula, each of R 91 and R 92 independently represents an alkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, or an aromatic heterocyclic group having 4 to 15 carbon atoms. .
The laminate according to claim 1, wherein the surfactant comprises a compound represented by the following formula (91);

R 93 to R 96 are each independently a hydrocarbon group having 1 to 24 carbon atoms, n9 is an integer of 1 to 6, m9 is an integer twice as large as n9, and n10 is an integer of 1 to 6. M10 is an integer twice as large as n10, and l9 and l10 are each independently a number of 0 or more and 12 or less.
The laminate according to claim 1, wherein the surfactant comprises a compound represented by the following formula (92);

R 93 , R 94 , R 97 to R 100 are each independently a hydrocarbon group having 1 to 24 carbon atoms, and l11 and l12 are each independently a number of 0 or more and 12 or less.
The laminate according to any one of claims 1 to 4, wherein the surface tension of a 0.1% by mass aqueous solution of the surfactant at 23 ° C is 45 mN / m or less.
The laminate according to any one of claims 1 to 5, wherein the in-plane uniformity of the film thickness of the water-soluble resin layer is 5% or less.
The water-soluble resin constituting the water-soluble resin layer includes at least one structural unit of a structural unit represented by the following formula (P1-1) and a structural unit represented by the formula (P1-2). The laminate according to any one of 1 to 6;

In formulas (P1-1) and (P1-2), R P1 is independently a hydrogen atom or a methyl group, and np and mp are positive integers.
The laminate according to any one of claims 1 to 7, further comprising a photosensitive layer on the water-soluble resin layer.
The laminate according to claim 8, which has the photosensitive layer on the surface of the water-soluble resin layer.
The laminate according to claim 8 or 9, wherein the photosensitive layer is exposed and developed using a developer containing an organic solvent to form a pattern on the photosensitive layer.
The laminate according to any one of claims 8 to 10, wherein the photosensitive layer comprises a photoacid generator and a photosensitive resin.
The laminate according to any one of claims 1 to 11, wherein the member is an organic semiconductor layer.
A water-soluble resin composition for forming a water-soluble resin layer of the laminate according to any one of claims 1 to 12, comprising a surfactant containing an acetylene group, a water-soluble resin, and an aqueous solvent. A water-soluble resin composition comprising:
The water-soluble resin composition according to claim 13, wherein the water-soluble resin layer formed from the water-soluble resin composition dissolves at a rate of 0.1 to 3.0 µm / sec when immersed in water at 25 ° C. .
It is a kit of the resin composition for producing the laminated body which has a member, a water-soluble resin layer, and a photosensitive layer in the said order, Comprising: The water-soluble resin composition of Claim 13 or 14, and the photosensitive resin composition And a kit containing.