KR20200110425A - Photosensitive layer, laminate, photosensitive resin composition, kit - Google Patents

Abstract

As a photosensitive layer included in a laminate having a water-soluble resin layer and a photosensitive layer, the photosensitive layer changes the dissolution rate of butyl acetate by the action of an acid-generating compound and an acid by irradiation with actinic rays or radiation. A resin formed of a photosensitive resin composition containing a resin and in which a change in dissolution rate for butyl acetate occurs due to the action of the acid has a weight average molecular weight of 10,000 to 50,000, and in the total structural unit, from 50 mol% to Dissolution rate when 100 mol% is a hydrophobic resin soluble in butyl acetate at 23°C in which a group soluble in an alkaline aqueous solution is protected by a hydrophobic protecting group, and the unirradiated photosensitive layer is immersed in butyl acetate at 23°C Is 20 nm/s or more and 200 nm/s or less, and a stop contact angle of the photosensitive resin composition on the aqueous solution resin layer is 60° or less.

Description

Photosensitive layer, laminate, photosensitive resin composition, kit

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

Recently, electronic devices using organic semiconductors have been widely used. A device using an organic semiconductor has the advantage that it can be manufactured by a simple process compared to a device using an inorganic semiconductor such as silicon. Further, the organic semiconductor can easily change material properties by changing its molecular structure. In addition, there is a wide variety of material variations, and it is thought that it becomes possible to realize functions and devices that could not be achieved with inorganic semiconductors. Organic semiconductors are used in electronic devices such as organic solar cells, organic electroluminescence displays, organic photodetectors, organic field effect transistors, organic electroluminescent devices, gas sensors, organic rectifying devices, organic inverters, and information recording devices. It may be applied.

Patterning of organic semiconductors has been performed so far by printing techniques. However, there is a limit to fine processing by patterning by printing technology. In addition, there is a problem that organic semiconductors are easily damaged.

Therefore, a method for patterning an organic semiconductor using a water-soluble resin as a protective film is being studied. For example, Patent Document 1 discloses a laminate in which a specific water-soluble resin layer and a photosensitive layer are included in this order on an organic semiconductor layer, and a water-soluble resin layer and a photosensitive layer are in contact with each other. Thereby, it is described that a fine pattern by exposure phenomenon of the photosensitive layer can be realized, and cracks in the laminate can be suppressed. Patent Documents 2 and 3 disclose a laminate having a water-soluble resin layer and a photosensitive layer on the surface of an organic semiconductor layer, in which a photosensitive resin composition is mixed with a specific photoacid generator and a specific resin. Thereby, it is described that a good pattern can be formed on an organic semiconductor.

Patent Document 1: International Publication No. 2016/175220 Patent Document 2: Japanese Laid-Open Patent Publication No. 2015-194674 Patent Document 3: Japanese Laid-Open Patent Publication No. 2015-087609

By means of the above-described technique, by interposing a water-soluble resin layer between the organic semiconductor layer and the photosensitive layer, the protection of the organic semiconductor layer is realized.

Here, in the case of producing a photosensitive layer having a thick thickness, it is required to use a resin having a large molecular weight for the photosensitive layer. This is to suppress the occurrence of cracks. Further, in the case of performing patterning a plurality of times, a thick photosensitive layer is required in order to suppress the influence of the step difference.

However, for a resin having a large molecular weight, the dissolution rate in a hydrophobic developer becomes significantly slower. For this reason, it is required to increase the dissolution rate from the viewpoint of production efficiency. In order to increase the dissolution rate, it is conceivable to increase the hydrophobicity of the resin in the photosensitive layer, but if so, the adhesion between the photosensitive layer and the water-soluble resin layer is lowered, resulting in pattern peeling or the like. The present invention aims to solve these problems, and to provide a photosensitive layer, a laminate, a photosensitive resin composition, and a kit capable of appropriately forming a pattern even when a resin having a large molecular weight is used for the photosensitive layer. do.

In order to solve the above problems, the inventors have repeatedly studied, improved and tested various materials and structures. As a result, by designing a balance between the dissolution rate of the photosensitive layer and the static contact angle of the photosensitive resin composition with respect to the water-soluble resin layer, it was found that even if a resin having a large molecular weight is used for the photosensitive layer, a pattern can be appropriately formed. It came to the completion of the invention. That is, the present invention provides the following means.

<1> As a photosensitive layer contained in a laminate having a water-soluble resin layer and a photosensitive layer,

The photosensitive layer is formed of a photosensitive resin composition comprising a compound that generates an acid by irradiation with actinic rays or radiation and a resin in which a change in dissolution rate for butyl acetate occurs due to the action of the acid. As a result, the resin in which the dissolution rate for butyl acetate is changed has a weight average molecular weight of 10,000 to 50,000, and a group soluble in an aqueous alkali solution of 50 to 100 mol% of the total structural units is protected by a hydrophobic protecting group. It is a hydrophobic resin soluble in butyl acetate at 23°C,

The dissolution rate when the unirradiated photosensitive layer is immersed in butyl acetate at 23° C. is 20 nm/s or more and 200 nm/s or less,

The photosensitive layer on the aqueous solution resin layer, wherein the stop contact angle of the photosensitive resin composition is 60° or less.

<2> The photosensitive layer according to <1>, wherein the photosensitive layer has a photosensitive ability against i-ray irradiation.

<3> The photosensitive layer according to <1> or <2>, wherein the content of water in the photosensitive resin composition is 0.01% by mass or more and 1% by mass or less.

<4> The photosensitive layer according to any one of <1> to <3>, wherein the change in the dissolution rate is a decrease in the dissolution rate.

<5> The photosensitive layer according to any one of <1> to <4>, in which the resin contained in the photosensitive layer has a structural unit represented by the following formula (1);

[Formula 1]

In the formula, R ⁸ represents a hydrogen atom or an alkyl group, L ¹ represents a carbonyl group or a phenylene group, and R ¹ to R ⁷ each independently represent a hydrogen atom or an alkyl group.

<6> The photosensitive layer according to any one of <1> to <5>, wherein the total content of sodium ions, potassium ions, and calcium ions of the photosensitive resin composition is 1 mass ppt to 1000 mass ppb.

The photosensitive layer in any one of <1> to <6> which is for <7> organic semiconductor layer processing.

<8> A laminate having the photosensitive layer and water-soluble resin layer in any one of <1> to <7>.

The laminate according to <8>, further comprising an <9> organic semiconductor layer, wherein the organic semiconductor layer, the water-soluble resin layer, and the photosensitive layer are laminated in this order.

<10> The resin in which the change in dissolution rate in butyl acetate occurs due to the action of the acid is a mixture of a resin having a high dissolution rate in butyl acetate and a resin having a low dissolution rate in butyl acetate. The laminate according to> or <9>.

As a photosensitive resin composition for forming a <11> photosensitive layer,

The photosensitive layer is a layer that forms a laminate in combination with a water-soluble resin layer, and the dissolution rate when the unexposed photosensitive layer is immersed in butyl acetate is 20 nm/s or more and 200 nm/second or less,

The photosensitive resin composition contains a compound that generates an acid by irradiation with actinic rays or radiation and a resin in which a change in dissolution rate for butyl acetate occurs by the action of the acid,

The resin having a change in the dissolution rate for butyl acetate by the action of the acid has a weight average molecular weight of 10,000 to 50,000, and a group soluble in an aqueous alkali solution in which 50 to 100 mol% of the total constituent units is a hydrophobic protecting group. A photosensitive resin composition, which is a hydrophobic resin that is protected by and is soluble in butyl acetate, and is a resin in which a static contact angle on the water-soluble resin layer is 60° or less.

The photosensitive resin composition as described in <11> which is for <12> organic semiconductor layer processing.

As a kit for forming a <13> water-soluble resin layer and a photosensitive layer in this order, a kit comprising the photosensitive resin composition and water-soluble resin composition according to <11> or <12>.

<14> The kit according to <13>, which is for processing an organic semiconductor layer.

According to the present invention, even if a resin having a large molecular weight is used for the photosensitive layer, it has become possible to provide a photosensitive layer laminate, a photosensitive resin composition, and a kit capable of appropriately forming a pattern.

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

The description of the constituent elements 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 notation of the group (atomic group) in the present specification, the notation that does not describe substituted or unsubstituted includes not only having no substituent but also having a substituent. For example, the term "alkyl group" includes not only an alkyl group not having a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In addition, "actinic ray" in this specification means a bright ray spectrum of a mercury lamp, far ultraviolet ray typified by excimer laser, extreme ultraviolet ray (EUV light), X ray, electron ray, etc., for example. In addition, in the present invention, light means actinic ray or radiation. The term "exposure" in the present specification includes not only exposure by far ultraviolet rays, X-rays, EUV light, etc. typified by mercury lamps and excimer lasers, but also drawing by particle rays such as electron beams and ion beams, unless otherwise specified. .

In the present specification, the numerical range indicated by using "~" means a range including a numerical value described before and after "~" as a lower limit value and an upper limit value.

In addition, in this specification, "(meth)acrylate" represents both or any one of acrylate and methacrylate, and "(meth)acrylic" represents both or any one of acrylic and methacrylate, "(Meth)acryloyl" represents both or any one of acryloyl and methacryloyl.

In the present specification, the term "step" does not mean only an independent step, and even if it cannot be clearly distinguished from another step, if the desired action of the step is achieved, the step is included in the term.

In the present specification, the solid content concentration is a percentage of the mass of other components excluding the solvent with respect to the total mass of the composition.

In the present specification, when describing "upper" and "lower", the upper or lower side of the structure may be sufficient. That is, other structures may be interposed, and there is no need to be in contact. In addition, unless specifically described, the photosensitive layer side is called an image, and a substrate to an organic semiconductor layer side is called "lower."

The photosensitive layer of the present invention is a photosensitive layer included in a laminate having a water-soluble resin layer and a photosensitive layer, and the photosensitive layer is a compound that generates an acid by irradiation with actinic ray or radiation (this compound is referred to as "acid It is a resin (acid-reactive resin) in which a change in the dissolution rate for butyl acetate occurs due to the action of an acid and an acid, and has a weight average molecular weight of 10,000 to 50,000, and among all structural units, 50 to 100 mol% is formed of a photosensitive resin composition containing a hydrophobic resin soluble in butyl acetate, in which a group soluble in an aqueous alkali solution is protected with a hydrophobic protecting group, and the unexposed photosensitive layer is formed of butyl acetate at 23°C. The dissolution rate when immersed in is 20 nm/sec or more and 200 nm/sec or less, and the composition for forming a photosensitive layer is characterized in that the static contact angle on the water-soluble resin layer is 60° or less.

By setting it as such a structure, even if a resin with a large molecular weight is used for a photosensitive layer, a pattern can be formed suitably.

That is, for a resin having a large molecular weight, the dissolution rate in a hydrophobic developer becomes significantly slower. In order to increase the dissolution rate, it is conceivable to increase the hydrophobicity of the resin, but when doing so, the adhesion with the water-soluble resin layer decreases, causing pattern peeling and the like. Here, in order to suppress pattern peeling, it is conceivable to adjust so as not to contain bubbles etc. which tend to trigger pattern peeling. Therefore, by adjusting the contact angle of the photosensitive resin composition with respect to the water-soluble resin layer to a predetermined range, even if a resin having a large molecular weight is used, it has succeeded in forming a pattern appropriately.

It is preferable to use the photosensitive layer of this invention in combination with a water-soluble resin layer, and to arrange both in a contact state. When an embodiment of the present invention is shown, an organic semiconductor layer 3 is disposed on a substrate 4 as in the example shown in Fig. 1A. Further, a water-soluble resin layer 2 protecting the organic semiconductor layer 3 is disposed thereon in a contact manner. Next, a photosensitive layer 1 is disposed thereon in a manner in contact with the water-soluble resin layer. In the example shown in Fig. 1B, the improved photosensitive layer 1 is formed, and even if it is exposed and developed with a predetermined mask, no defect occurs in the removal unit 5. In this way, the photosensitive layer of the present invention exhibits a particularly high effect in the state of being laminated on the water-soluble resin layer.

In Fig. 1, the form provided on the organic semiconductor layer is illustrated as an example, but a water-soluble resin layer and a photosensitive layer may be used in combination on the surface of another material. In the present invention, it is preferable that it is for processing an organic semiconductor layer.

The laminate of the present invention is a laminate having a photosensitive layer and a water-soluble resin layer of the present invention, and preferably further has an organic semiconductor layer, and the organic semiconductor layer, the water-soluble resin layer, and the photosensitive layer are sequentially laminated. It is a laminated body. And, it is preferable that these layers are in contact with each other.

Hereinafter, the characteristics of each layer and the material constituting the same will be described.

<Organic semiconductor layer>

The organic semiconductor layer is a layer containing an organic material exhibiting semiconductor properties. Organic semiconductors include a p-type organic semiconductor that conducts with holes as carriers and an n-type organic semiconductor that conducts electrons as carriers, as in the case of a semiconductor made of an inorganic material. The ease of flow of carriers in the organic semiconductor layer is indicated by the carrier mobility μ. According to the application it is also different, but, in general, mobility may shift higher, 10 ^-7 cm ² / Vs or more, and preferably, 10 ^-6 cm ² / Vs or more, and more preferably, 10 ^-5 cm ² / Vs is more than desirable. The mobility can be determined by the characteristics when the field effect transistor (FET) element is manufactured or by a time of flight measurement (TOF) method.

It is preferable to use the organic semiconductor layer by forming a film on the substrate as described above. That is, it is preferable to have the substrate on the surface of the organic semiconductor layer on the side far from the water-soluble resin layer. Examples of the substrate include a variety of materials such as silicon, quartz, ceramic, glass, polyester film such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET), and polyimide film. You may choose For example, when used for a flexible element, a flexible substrate can be used. In addition, the thickness of the substrate is not particularly limited.

As the p-type semiconductor material that can be used for the organic semiconductor layer, any material among organic semiconductor materials may be used as long as it exhibits hole (hole) transport properties, but preferably a p-type π-conjugated polymer (e.g., substituted or unsubstituted Polythiophene (e.g., poly(3-hexylthiophene) (P3HT, manufactured by Sigma-Aldrich Japan joint company), etc.), polyselenophene, polypyrrole, polyparaphenylene, polyparaphenylene vinylene, polythiophene Offenvinylene, polyaniline, etc.), condensed polycyclic compounds (e.g., substituted or unsubstituted anthracene, tetracene, pentacene, anthradiothiophene, hexabenzocoronene, etc.), triarylamine compounds (e.g. , m-MTDATA(4,4',4''-Tris[(3-methylphenyl)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'-diamine), 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. ), 5-membered heterocyclic compounds (e.g., substituted or unsubstituted oligothiophene, TTF (Tetrathiafulvalene), etc.), phthalocyanine compounds (substituted or unsubstituted phthalocyanine of various central metals, naphthalocyanine In other words, anthracyanine, tetrapyrazinopopyrazine), porphyrin compounds (substituted or unsubstituted porphyrins of various central metals), carbon nanotubes, carbon nanotubes modified with semiconductor polymers, graphene, and more preferred Preferably, it is any one of a p-type π conjugated polymer, a condensed polycyclic compound, a triarylamine compound, a hetero 5-membered cyclic compound, a phthalocyanine compound, and a porphyrin compound, and more preferably a p-type π conjugated polymer.

As the n-type semiconductor material that can be used for the organic semiconductor layer, any organic semiconductor material may be used as long as it has electron transport properties. Preferably, a fullerene compound, an electron-deficient phthalocyanine compound, a naphthalene tetracarbonyl compound, or a p Rylene tetracarbonyl compound, TCNQ compound (tetracyanoquinodimethane compound), n-type π conjugated polymer, more preferably fullerene compound, electron deficient phthalocyanine compound, naphthalene tetracarbonyl compound, perylene They are tetracarbonyl compounds and n-type pi conjugated polymers, and particularly preferably fullerene compounds and n-type pi 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 , Any of C ₉₆ , C ₁₁₆ , C ₁₈₀ , C ₂₄₀ , C ₅₄₀ fullerene may be used, but preferably substituted or unsubstituted C ₆₀ , C ₇₀ , C ₈₆ fullerene, and particularly preferably PCBM ([6, 6-phenyl-butyric acid methyl ester -C61-, said Sigma-Aldrich Japan Co., Ltd. joint meeting, etc.) and their analogous compounds (for C ₆₀ part C _70, C ₈₆ will be in a substituted, such as a benzene ring of the substituent other aromatic ring or heterocyclic Substituted by a ring, methyl ester substituted with n-butyl ester, i-butyl ester, etc.). The 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 the central metal and Pc is the phthalocyanine. , S8 represents (n-octylsulfonyl group)), naphthalocyanine, anthracyanine, substituted or unsubstituted tetrapyrazinofopyrazine, and the like. The naphthalene tetracarbonyl compound may be any, but preferably naphthalene tetracarboxylic anhydride (NTCDA), a naphthalene bisimide compound (NTCDI), and a perinone pigment (Pigment Orange 43, Pigment Red 194, etc.). Any of the perylene tetracarbonyl compounds may be used, but preferred are perylene tetracarboxylic anhydride (PTCDA), perylene bisimide compounds (PTCDI), and benzimidazole condensed compounds (PV). The TCNQ compound is a substituted or unsubstituted TCNQ and a benzene ring moiety of TCNQ substituted with another aromatic ring or a hetero ring, such as TCNQ, TCAQ (tetracyanoquinodimethane), TCN3T(2,2 '-((2E,2''E)-3',4'-Alkyl substituted-5H,5''H-[2,2':5',2''-terthiophene]-5,5''- diylidene)dimalononitrile derivatives). It also includes graphene. A particularly preferable example of the n-type organic semiconductor material is shown below.

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

[Formula 2]

The number of organic materials that exhibit the characteristics of the semiconductor contained in the organic semiconductor layer may be one or two or more.

The material is usually blended in a solvent, applied in a layered form on a substrate, dried, and formed into a film. As an application method, the description of a water-soluble resin layer mentioned later can be referred.

Examples of the solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, and 1-methylnaphthalene; For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; For example, halogenated hydrocarbon-based solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene; For example, ester solvents such as ethyl acetate, butyl acetate, and amyl acetate; For example, alcohol-based solvents such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, and ethylene glycol; For example, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, and anisole; For example, polarity of N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, dimethyl sulfoxide, etc. Solvents, etc. are mentioned. These solvents may be used alone or in combination of two or more.

The proportion 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, thereby forming a film having an arbitrary thickness. can do.

Moreover, you may mix|blend a resin binder with the composition for organic semiconductor formation. In this case, a film-forming material and a binder resin are dissolved or dispersed in the above-described suitable solvent to form a coating liquid, and a thin film can be formed by various coating methods. As a resin binder, polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, polypropylene Insulating polymers such as, and copolymers thereof, photoconductive polymers such as polyvinylcarbazole and polysilane, and conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyparaphenylene vinylene. A resin binder may be used individually or may be used in combination of a plurality. Considering the mechanical strength of the thin film, a resin binder having a high glass transition temperature is preferable, and considering the charge mobility, a photoconductive polymer having a structure not including a polar group or a resin binder composed of a conductive polymer is preferable.

When blending a resin binder, the blending amount is preferably used in an amount of 0.1 to 30 mass% in the organic semiconductor layer. Only one type of resin binder may be used, and two or more types may be used. When using two or more types, it is preferable that the total amount falls within the above range.

Depending on the application, a blended film made of a plurality of material types may be obtained by applying a single or a mixed solution to which various semiconductor materials or additives are added onto a substrate or the like. For example, when producing a photoelectric conversion layer, it is possible to use a mixed solution with another semiconductor material.

Further, during film formation, the substrate may be heated or cooled, and the film quality or 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 still more preferably 0°C to 200°C.

The formed organic semiconductor layer can be adjusted in properties by post-treatment. For example, it is possible to improve properties by changing the morphology of the film or packing of molecules in the film by heat treatment or exposing the vaporized solvent. Further, by exposing to an oxidizing or reducing gas, a solvent, or a substance, or by mixing them, an oxidation or reduction reaction is caused, and the carrier density in the film can be adjusted.

The film thickness of the organic semiconductor layer is not particularly limited and varies depending on the type of electronic device to be used, and the like, 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)>

It is preferable that the water-soluble resin layer contains a water-soluble resin and is formed from a water-soluble resin composition. The water-soluble resin refers to a resin in which the amount of the resin soluble in 100 g of water at 20°C is 1 g or more, preferably 5 g or more, more preferably 10 g or more, and still more preferably 30 g or more. There is no upper limit, but 20g is practical.

As a water-soluble resin, specifically, polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), water-soluble polysaccharides (water-soluble cellulose (methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxy) Oxypropylmethylcellulose, etc.), pullulan or pullulan derivatives, starch, hydroxypropyl starch, carboxymethyl starch, chitosan, cyclodextrin), polyethylene oxide, polyethyloxazoline, etc., and PVP and PVA are preferred. And PVA is more preferable. In addition, among these, two or more types having different main chain structures may be selected and used, or may be used as a copolymer.

The weight average molecular weight of the water-soluble resin is not particularly limited, but the weight average molecular weight of the polyvinylpyrrolidone used in the present invention is preferably 50,000 to 400,000. It is preferable that the weight average molecular weight of the polyvinyl alcohol used by this invention is 15000-100,000. In other resins, it is preferable to exist in the range of 10,000 to 300,000.

Moreover, 1.0-5.0 are preferable and, as for the dispersion degree (weight average molecular weight/number average molecular weight) of the water-soluble resin (the said PVP, PVA) used by this invention, 2.0-4.0 are more preferable.

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

The thickness of the water-soluble resin layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1.0 μm or more, and even more preferably 2.0 μm or more. As the upper limit of the thickness of the water-soluble resin layer, 10 μm or less is preferable, 5.0 μm or less is more preferable, and 3.0 μm or less is still more preferable.

The water-soluble resin layer can be formed by, for example, applying a water-soluble resin composition containing one or two or more water-soluble resins on the organic semiconductor layer and drying. Usually, the water-soluble resin composition contains water as a solvent, and may further contain other additives.

It is preferable that it is 0.5-30 mass %, as for the solid content concentration of a water-soluble resin composition, it is more preferable that it is 1.0-20 mass %, and it is still more preferable that it is 2.0-14 mass %. By setting the solid content concentration in the above range, it can be applied more uniformly.

As an application method, application is preferable. Examples of application methods include slit coating method, cast method, blade coating method, wire bar coating method, spray coating method, dipping (dipping) coating method, bead coating method, air knife coating method, curtain coating method, inkjet method, spin coating The method, Langmuir-Blodgett (LB) method, etc. are mentioned. It is more preferable to use a cast method, a spin coat method, and an ink jet method. By such a process, it becomes possible to produce a water-soluble resin layer having a smooth surface and a large area at low cost.

It is preferable to further contain a surfactant for improving coatability in the water-soluble resin composition.

As the surfactant, any one such as nonionic, anionic, or amphoteric fluorine may be used as long as it lowers the surface tension. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene nonyl. Polyoxyethylene alkyl aryl ethers such as phenyl ether, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, Sorbitan alkyl esters such as sorbitan sesquioleate and sorbitan trioleate; monoglyceride alkyl esters such as glycerol monostearate and glycerol monooleate; oligomers containing fluorine or silicon; acetylene glycerides Nonionic surfactants such as chol and ethylene oxide adducts of acetylene glycol; Alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, sodium pentylnaphthalenesulfonate, sodium hexylnaphthalenesulfonate, alkyl naphthalenesulfonates such as sodium octylnaphthalenesulfonate, sodium lauryl sulfate, etc. Anionic surfactants such as alkyl sulfates, alkyl sulfonates such as sodium dodecylsulfonic acid, and sulfosuccinic acid ester salts such as sodium dilaurylsulfosuccinate; Amphoteric surfactants, such as alkyl betaines, such as lauryl betaine and stearyl betaine, and amino acids, can be used.

When the water-soluble resin composition contains a surfactant, the amount of surfactant added is preferably 0.001 to 20% by mass, more preferably 0.001 to 5% by mass, and still more preferably 0.01 to 1% by mass in the solid content. It is the amount included as. These surfactants may be used alone or in combination of two or more. When using two or more types, it is preferable that the total amount falls within the above range.

<Photosensitive layer (photosensitive resin composition)>

The photosensitive layer is formed of a composition for forming a photosensitive layer containing an acid generator and a resin. The weight average molecular weight of the acid-reactive resin in the photosensitive layer is 10,000 or more, preferably 15,000 or more, and more preferably 20,000 or more. As an upper limit, it is 50,000 or less, and it is preferable that it is 45,000 or less. In the present invention, even if a resin having such a large molecular weight is used, the value is high in that a pattern can be appropriately formed.

Moreover, it is preferable that it is 10 mass% or less of all acid-reactive resin components, and it is more preferable that it is 5 mass% or less of the amount of the component contained in the acid-reactive resin. By setting it as such a structure, the sensitivity fluctuation between resin production lots can be reduced.

As for the dispersion degree (weight average molecular weight/number average molecular weight) of an acid-reactive resin, 1.0-4.0 are preferable, and 1.1-2.5 are more preferable.

In addition, in the present invention, the weight molecular weight is a value measured by the method shown in Examples.

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

The content of the acid-reactive resin in the photosensitive layer is preferably 20 to 99.9 mass%, more preferably 40 to 99 mass%, and still more preferably 70 to 99 mass%. One type or two or more types of acid-reactive resins may be contained. When using two or more types, it is preferable that the total amount falls within the above range.

In the present invention, the acid-reactive resin may be a mixture of a resin having a high dissolution rate in butyl acetate and a resin having a low dissolution rate in butyl acetate. For example, a mixture of an acid-reactive resin having a dissolution rate of less than 20 nm/s and a resin having a dissolution rate of more than 200 nm/s is exemplified. The dissolution rate in this case refers to the dissolution rate measured by the method described in Examples below for a composition obtained by substituting the acid-reactive resin for the acid-reactive resin in Example 1 described later.

It is preferable that the exposed portion of the photosensitive layer is poorly soluble in a developer containing an organic solvent. Poorly soluble means that the exposed part is difficult to dissolve in the developer, specifically, polarity by exposure with an irradiation dose of 50 mJ/cm ² or more in at least one of a wavelength of 365 nm (i-line), a wavelength of 248 nm (KrF line) and a wavelength of 193 nm (ArF line) Is changed, and the sp value (dissolution parameter value) is preferably poorly soluble for a solvent of less than 19 (MPa) ^1/2 , more preferably poorly soluble for a solvent of 18.5 (MPa) ^1/2 or less. , It is more preferable to be poorly soluble in a solvent of 18.0 (MPa) ^1/2 or less. In addition, it is more preferable that the polarity changes as described above by exposure with an irradiation dose of 50 to 250 mJ/cm ² 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 photosensitive layer may be a negative photosensitive layer or a positive photosensitive layer, but the negative photosensitive layer is preferable because it becomes possible to form finer trenches and hole patterns.

From the viewpoint of improving the resolution, the thickness of the photosensitive layer is preferably 0.5 μm or more, may exceed 1.0 μm, 1.5 μm or more, or 1.8 μm or more. The upper limit of the thickness of the photosensitive layer is preferably 10 μm or less, more preferably 5.0 μm or less, and may be 3.0 μm or less.

Further, it is preferable that the total thickness of the photosensitive layer and the water-soluble resin layer is 2.0 μm or more. As the upper limit, it is preferably 20.0 μm or less, more preferably 10.0 μm or less, and still more preferably 5.0 μm or less.

It is preferable that the photosensitive layer has a photosensitive ability against irradiation of i-rays. Photosensitivity refers to a property in which a material is deteriorated by irradiation of at least one of actinic rays and radiation (in the case of irradiation with i-rays, in the case of irradiation with i-rays), and in the present invention, the deterioration of the material is It is accompanied by a change in dissolution rate for

1.0-4.0 are preferable and, as for the over development coefficient of a photosensitive layer, 1.1-1.9 are more preferable. By setting it as such a range, the effect of suppressing the footing and undercut of a pattern can be exhibited effectively. The over-development coefficient is measured and calculated according to the description of Examples to be described later.

It is preferable that the photosensitive resin composition is a chemically amplified photosensitive resin composition containing at least an acid-reactive resin and a photoacid generator.

<<melting rate>>

In the present invention, the dissolution rate when the unirradiated photosensitive layer is immersed in butyl acetate at 23°C is defined as 20 nm/sec or more and 200 nm/sec or less. This dissolution rate is preferably 180 nm/second or less, more preferably 150 nm/second or less, and further preferably 120 nm/second or less. As a lower limit, it is preferable that it is 25 nm/second or more, it is more preferable that it is 40 nm/second or more, and it is more preferable that it is 70 nm/second or more. By setting this dissolution rate in the above range, in addition to defining the static contact angle of the photosensitive resin composition below, the occurrence of undercut in the photosensitive layer is suppressed or prevented, and collapse of the pattern resulting from this is prevented. In addition, peeling of the photosensitive layer can be effectively suppressed. In addition, in the present specification, the method of measuring the dissolution rate of the photosensitive layer is based on the method adopted in the following examples.

<<acid reactive resin>>

The acid-reactive resin is a resin component constituting the photosensitive resin composition, and the dissolution rate in butyl acetate changes due to the action of an acid from a compound that generates an acid by irradiation of at least one of active light and radiation. The acid-reactive resin used in the present invention is a hydrophobic resin soluble in butyl acetate at 23°C.

The acid-reactive resin is a resin component constituting the photosensitive resin composition, is usually a resin containing a structural unit containing a group dissociated by an acid, and may contain other structural units.

The acid-reactive resin is soluble in an organic solvent having an sp value (dissolution parameter value) of 18.0 (MPa) ^1/2 or less, and when the tetrahydrofuranyl group in the structural unit represented by the following formula (1) is decomposed or dissociated It is preferable that it is a resin which is poorly soluble in an organic solvent having an sp value of 18.0 (MPa) ^1/2 or less.

Here, "soluble in an organic solvent having a sp value (dissolution parameter value) of 18.0 (MPa) ^1/2 or less" means a compound formed by applying a solution of a compound (resin) on a substrate and heating it at 100°C for 1 minute The dissolution rate of the coating film (thickness 1 μm) of (resin) in butyl acetate at 23° C. is at least 20 nm/sec, and “slightly soluble in organic solvents with a sp value of 18.0 (MPa) ^1/2 or less” , The dissolution rate of the coating film (thickness 1 μm) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating at 100° C. for 1 minute at 23° C. in butyl acetate is 0.1 nm. It is less than /second.

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

Changing the dissolution rate of the photosensitive layer or the acid-reactive resin can be done according to a conventional method. For example, the molecular weight of the polymer constituting the acid-reactive resin, the molecular structure selection, the selection of the type of the protecting group of the acid, the acid in the molecule and The dissolution rate can be controlled by the introduction amount of the protecting group, the selection of the type of the acid generator, the ratio of the amount of the acid-reactive resin and the acid generator, the SP value of the resin, and the ratio of the low molecular weight compound in the solid content. Specifically, in order to increase the dissolution rate, means such as lowering the molecular weight of the resin, making the SP value of the resin close to that of butyl acetate, or increasing the low molecular weight ratio in the solid content are exemplified. Conversely, in order to lower it, a means such as increasing the molecular weight of the resin, making the SP value of the resin away from that of butyl acetate, or reducing the low molecular weight ratio in the solid content are exemplified. Further, a resin having a dissolution rate of less than 20 nm/s and a resin having a dissolution rate of more than 200 nm/s may be blended.

<<protector>>

In the present invention, in the acid-reactive resin, a group in which 50 to 100 mol% is soluble in an aqueous alkali solution is protected by a hydrophobic protecting group among the total structural units. Here, it is preferable that a group soluble in an aqueous alkali solution is a structural unit having an acid group. Examples of the acid group include a hydroxyl group (including a phenolic hydroxyl group), a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphonic acid group, a phosphoric acid group, and a phosphonic acid group. The structural unit typically refers to a repeating structural unit of a polymer (it may be simply referred to as a structural unit), but may also mean a substituent in a structural unit or a set of several substituents. Protection by a hydrophobic protecting group is a typical example in which a functional group (usually an acidic group) possessed by a soluble group in the aqueous alkali solution is substituted by a hydrophobic substituent. For example, an aspect in which a substituent having an alkyl group is substituted on a phenolic hydroxyl group to form an ether bond can be mentioned. Alternatively, an example in which a tetrahydropyranyl group is substituted with a carboxyl group to form an ester is exemplified. The protection by the hydrophobic protecting group can be evaluated by what proportion of the hydrophobic substituent is substituted with respect to the number of functional groups (usually acidic groups) possessed by a group soluble in an aqueous alkali solution present in one molecule.

When this ratio is expressed in terms of a molar ratio, in the present invention, as described above, it is 50 mol% or more and 100 mol% or less, preferably 55 mol% or more and 100 mol% or less, and more preferably 60 mol% or more and 100 mol% or less. Do. As the alkyl group serving as a protecting group, it may be of primary, secondary, tertiary, chain or cyclic, and may be linear or branched. This alkyl group may have an oxygen atom or a carbonyl group interposed in the chain. It becomes cyclic and may be an oxazine ring or a tetrahydrofuran ring. Moreover, an aryl group (carbon number 6-22 is preferable, 6-18 are more preferable, and 6-10 are more preferable) may be substituted. It is preferable that the intervening oxygen atom is a ratio of 1 to 1 to 12 carbon atoms. Or, the example of the substituent A of following formula (2) is mentioned.

Among them, it is preferable that the acid-reactive resin is an acrylic polymer.

<<acrylic polymer>>

"Acrylic polymer" is an addition polymerization type resin, is a polymer containing a structural unit derived from (meth)acrylic acid or its ester, and structural units other than the structural unit derived from (meth)acrylic acid or its ester, For example, a structural unit derived from styrene, a structural unit derived from a vinyl compound, or the like may be included. The acrylic polymer preferably has a structural unit derived from (meth)acrylic acid or its ester, relative to the total structural units in the polymer, 50 mol% or more, more preferably 80 mol% or more, and (meth) It is particularly preferable that it is a polymer consisting only of structural units derived from acrylic acid or its ester. Such an acrylic polymer is preferably used for negative development.

It is also preferable that the acrylic polymer has a structural unit containing a protected carboxyl group or a protected phenolic hydroxyl group. As a monomer capable of forming a structural unit containing a protected carboxyl group, for example, (meth)acrylic acid protected by an acid dissociable group may be mentioned.

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

It is preferable that an acrylic polymer has a cyclic ether ester structure, and it is more preferable that it has a structure represented by following formula (1).

[Formula 3]

In the formula, R ⁸ represents a hydrogen atom or an alkyl group (carbon number 1 to 12 is preferable, 1 to 6 are more preferable, and 1 to 3 are more preferable), L ¹ represents a carbonyl group or a phenylene group, R ¹ to R ⁷ each independently represent 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 represent a hydrogen atom or an alkyl group. The alkyl group for R ¹ to R ⁷ has the same definition as R ^8, and the preferred aspect is also the same. In addition, R ¹ ~ R ⁷ wherein it is more preferable to have at least one hydrogen atom is preferred, and R ¹ ~ R ⁷ are both hydrogen atoms.

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

[Formula 4]

As the radically polymerizable monomer used to form 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, after polymerization with a precursor monomer, it can also be formed by reacting a carboxyl group or a phenolic hydroxyl group with a dihydrofuran compound.

As a structural unit containing a protected phenolic hydroxyl group, the structural unit of following formula (2) is mentioned.

[Formula 5]

A represents a hydrogen atom or a group that is desorbed by the action of an acid. As a group to be desorbed by the action of an acid, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6, more preferably 1 to 3), an alkoxyalkyl group (2 to 12 carbon atoms is preferable, and 2 to 6 is more preferable, 2 to 3 are more preferable), aryloxyalkyl group (7 to 40 carbon atoms are preferable, 7 to 30 are more preferable, 7 to 20 are more preferable), alkoxycarbonyl group (carbon number 2-12 are preferable, 2-6 are more preferable, 2-3 are more preferable), aryloxycarbonyl group (carbon number 7-23 is preferable, 7-19 are more preferable, and 7-11 are more Preferred) is preferred. A may further have a substituent. R ¹⁰ represents a substituent. R ⁹ represents a group having the same meaning as R ⁸ in formula (1). nx represents the integer of 0-3.

As a group dissociating by an acid, among the compounds described in paragraphs 0039 to 0049 of JP 2008-197480 A, a structural unit having a group dissociating by an acid is also preferable, and JP 2012-159830 A (Japanese The compounds described in paragraphs 0052 to 0056 of Patent Publication No. 591567) are also preferable, and these contents are incorporated herein by reference.

Although a specific example of the structural unit (2) is shown, this invention is limited by this and is not interpreted.

[Formula 6]

[Formula 7]

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

The acid-reactive resin may contain a structural unit having a crosslinkable group. For details of the crosslinkable group, description of paragraphs 0032 to 0046 of JP2011-209692A can be referred to, and these contents are incorporated herein by reference.

The acid-reactive resin is also preferably a configuration including a structural unit having a crosslinkable group (constituent unit (3)), but it is preferable to have a configuration substantially not including the structural unit (3) having a crosslinkable group. By setting it as such a structure, it becomes possible to remove a photosensitive layer more effectively after patterning. Here, "substantially" means 3 mol% or less of the total structural units of the acid-reactive resin, and preferably 1 mol% or less.

The acid-reactive resin may contain other structural units (constituent units (4)). Examples of the radical polymerizable monomer used to form the structural unit (4) include compounds described in paragraphs 0021 to 0024 of JP 2004-264623A. Preferred examples of the structural unit (4) include 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 N-substituted maleimide. Among these, benzyl (meth)acrylate, (meth)acrylic acid tricyclo[5.2.1.02,6]decane-8-yl, (meth)acrylic acid tricyclo[5.2.1.02,6]decane-8-yloxy (Meth)acrylic acid esters containing alicyclic structures such as ethyl, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, or hydrophobic monomers such as styrene are preferred. .

The structural unit (4) can be used alone or in combination of two or more. In the case of containing the structural unit (4) among all the monomer units constituting the acrylic polymer, the content rate of the monomer unit forming the structural unit (4) is preferably 1 to 60 mol%, and 5 to 50 mol% Is more preferable, and 5 to 40 mol% is more preferable. When using two or more types, it is preferable that the total amount falls within the above range.

Various methods are known for the synthesis method of the acrylic polymer, but for example, a radical polymerizable monomer mixture containing at least a radical polymerizable monomer used to form a structural unit (1), a structural unit (2), etc. In a solvent, it can be synthesized by polymerization using a radical polymerization initiator.

As an acid-reactive resin, it is obtained by adding 2,3-dihydrofuran to an acid anhydride group in a precursor copolymer copolymerized with an unsaturated polyhydric carboxylic acid anhydride at a temperature of about room temperature (25°C) to 100°C in the absence of an acid catalyst. Copolymers are also preferred.

The following resin is also mentioned as a preferable example of an acid-reactive resin.

BzMA/THFMA/t-BuMA (molar ratio: 20~60:35~65:5~30)

BzMA/THFAA/t-BuMA (molar ratio: 20~60:35~65:5~30)

BzMA/THPMA/t-BuMA (molar ratio: 20~60:35~65:5~30)

BzMA/PEES/t-BuMA (molar ratio: 20~60:35~65:5~30)

BzMA is benzyl methacrylate, THFMA is tetrahydrofuran-2-yl methacrylate, BuMA is butyl methacrylate, THFAA is tetrahydrofuran-2-yl acrylate, and THPMA is, It is tetrahydro-2H-pyran-2-yl methacrylate, and PEES is p-ethoxyethoxystyrene.

As the acid-reactive resin used for positive-type development, those described in Japanese Unexamined Patent Publication No. 2013-011678 are exemplified, and these contents are incorporated herein by reference.

The content of the acid-reactive resin in the photosensitive resin composition is preferably 20 to 99% by mass, more preferably 40 to 99% by mass, and more preferably 70 to 99% by mass, based on the total solid content of the photosensitive resin composition. Do. When the content is in this range, the pattern formability when developed is good. The acid-reactive resin may contain only 1 type, and may contain 2 or more types. When using two or more types, it is preferable that the total amount falls within the above range.

In addition, the acid-reactive resin preferably occupies 10 mass% or more of the resin component contained in the photosensitive resin composition, more preferably 50 mass% or more, and still more preferably 90 mass% or more.

<<mine generator>>

The photosensitive resin composition may contain a photoacid generator. It is preferable that the photoacid generator is a photoacid generator having absorption at a wavelength of 365 nm.

The photoacid generator is preferably a compound having an oxime sulfonate group (hereinafter, also simply referred to as an oxime sulfonate compound).

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

[Formula 8]

X ³ represents an alkyl group, an alkoxyl group, or a halogen atom. When multiple X ³ exist, each may be the same or different. The alkyl group and the alkoxyl group for X ³ may have a substituent. As the alkyl group for X ³ , a linear or branched alkyl group having 1 to 4 carbon atoms is preferable. The alkoxyl group for X ³ is preferably a linear or branched alkoxyl group having 1 to 4 carbon atoms. The halogen atom for X ³ is preferably a chlorine atom or a fluorine atom.

m3 represents the integer of 0-3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X ³ may be the same or different.

R ³⁴ represents an alkyl group or an aryl group, and is substituted with 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, a halogenated alkoxyl group having 1 to 5 carbon atoms, and W It is preferable that it is a phenyl group which may exist, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an 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 , A C6-C20 aryl group and a C6-C20 halogenated aryl group.

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 C1-C10 linear alkyl group, a 7,7-dimethyl-2-oxonobornylmethyl group, Or a compound which is a p-toluyl group is particularly preferable.

As a specific example of the oxime sulfonate compound represented by formula (OS-1), the following compounds described in paragraph numbers 0064 to 0068 of JP2011-209692A are illustrated, and these contents are used in this specification.

[Formula 9]

R ¹¹ represents an alkyl group, an aryl group, or a heteroaryl group, and R ¹² that may be present in plural each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ¹⁶ that may be present in a plurality are each independently As a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, ns represents 1 or 2, and ms represents an integer of 0-6.

The alkyl group, aryl group, or heteroaryl group represented by R ¹¹ may have a substituent. The alkyl group represented by R ¹¹ is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent. Examples of the substituent which the alkyl group represented by R ¹¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Examples of the alkyl group represented by R ¹¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group , n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, and the like.

Moreover, as the aryl group represented by R ¹¹ , an aryl group having 6 to 30 total carbon atoms which may have a substituent is preferable. Examples of the substituent that the aryl group represented by R ¹¹ may have include halogen atom, alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group, sulfonic acid group , An aminosulfonyl group, and an alkoxysulfonyl group. As the aryl group represented by R ¹¹ , a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable. Moreover, as the heteroaryl group represented by R ¹¹ , a heteroaryl group having 4 to 30 carbon atoms in total which may have a substituent is preferable. Examples of the substituent that the heteroaryl group represented by R ¹¹ may have include halogen atom, alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group, sulfone An acid group, an aminosulfonyl group, and an alkoxysulfonyl group are mentioned. The heteroaryl group represented by R ¹¹ should just have at least one heteroaromatic ring, and for example, the heteroaromatic ring and the benzene ring may be condensed. As the heteroaryl group represented by R ¹¹ , which may have a substituent, consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring And groups in which one hydrogen atom has been removed from the ring selected from the group.

R ¹² is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.

Of R ¹² which may be present in two or more compounds, one or two is 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, and one is an alkyl group And it is particularly preferred that the remainder is a hydrogen atom.

The alkyl group or aryl group represented by R ¹² may have a substituent.

As the substituent which the alkyl group or the aryl group represented by R ¹² may have, the W can be illustrated.

The alkyl group represented by R ¹² is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and more preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent.

Examples of the alkyl group represented by R ¹² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, chloromethyl group, bromomethyl group , A methoxymethyl group, a benzyl group is preferable, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a s-butyl group, an n-hexyl group are more preferable, and a methyl group, An ethyl group, n-propyl group, n-butyl group, and n-hexyl group are more preferable, and a methyl group is particularly preferable.

The aryl group represented by R ¹² is preferably an aryl group having 6 to 30 carbon atoms in total which may have a substituent.

As the aryl group represented by R ¹² , a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.

Examples of the halogen atom represented by R ¹² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are preferable.

X represents O or S, and is preferably O. In the formulas (OS-103) to (OS-105), the ring containing X as a reduction is a 5-membered ring or a 6-membered ring.

ns represents 1 or 2, when X is O, ns is preferably 1, and when X is S, ns is preferably 2.

The alkyl group and the alkyloxy group represented by R ¹⁶ may have a substituent.

The alkyl group represented by R ¹⁶ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

Examples of the substituent that the alkyl group represented by R ¹⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.

Examples of the alkyl group represented by R ¹⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group , n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group are preferable.

The alkyloxy group represented by R ¹⁶ is preferably an alkyloxy group having 1 to 30 carbon atoms in total that may have a substituent.

Examples of the substituent that the alkyloxy group represented by R ¹⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .

As the alkyloxy group represented by R ¹⁶ , a methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, or ethoxyethyloxy group is preferable.

Examples of the aminosulfonyl group for R ¹⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group.

Examples of the alkoxysulfonyl group represented by R ¹⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

ms represents the integer of 0-6, it is preferable that it is an integer of 0-2, it is more preferable that it is 0 or 1, and it is especially preferable that it is 0.

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

[Formula 10]

R ¹¹ represents an alkyl group, an aryl group or a heteroaryl group, R ¹⁷ represents a hydrogen atom or a bromine atom, and R ¹⁸ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, Represents a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ¹⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ²⁰ represents a hydrogen atom or a methyl group.

R ¹⁷ represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

R ¹⁸ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, and an alkyl group having 1 to 8 carbon atoms, a halogen atom Or it is preferable that it is a phenyl group, it is more preferable that it is a C1-C8 alkyl group, it is more preferable that it is a C1-C6 alkyl group, and it is especially preferable that it is a methyl group.

R ¹⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

R ²⁰ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

Moreover, in the said oxime sulfonate compound, about the three-dimensional structure (E, Z) of oxime, either one may be sufficient and a mixture may be sufficient.

As a specific example of the oxime sulfonate compound represented by the above formulas (OS-103) to (OS-105), the compounds described in paragraphs 0088 to 0095 of Japanese Unexamined Patent Application Publication No. 2011-209692 are illustrated, and these contents are incorporated herein by reference. do.

As another suitable aspect of the oxime sulfonate compound which has at least one oxime sulfonate group, a compound represented by the following formula (OS-101) and (OS-102) is mentioned.

[Formula 11]

R ¹¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group. The aspect in which R ¹¹ is a cyano group or an aryl group is more preferable, and the aspect in which R ¹¹ is a cyano group, a phenyl group or a naphthyl group is more preferable.

R ^12a represents an alkyl group or an aryl group.

X represents -O-, -S-, -NH-, -NR ^15- , -CH _2- , -CR ¹⁶ H- or -CR ¹⁶ R ^17- , and R ¹⁵ to R ¹⁷ are each independently an alkyl group Or an aryl group.

R ²¹ to R ²⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group. Show. Two of R ²¹ to R ^{24 may} each be bonded to each other to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring.

As R ²¹ to R ²⁴ , a hydrogen atom, a halogen atom or an alkyl group is preferable, and an aspect in which at least two of R ²¹ to R ²⁴ are bonded to each other to form an aryl group is also preferable. Among them, an aspect in which all of R ²¹ to R ²⁴ are hydrogen atoms is preferable.

All 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).

Moreover, in the said oxime sulfonate compound, about the three-dimensional structure (E, Z, etc.) of an oxime and a benzothiazole ring, either one may be sufficient, and a mixture may be sufficient.

As a specific example of the compound represented by formula (OS-101), the compound described in paragraph number 0102-0106 of Unexamined-Japanese-Patent No. 2011-209692 is illustrated, and these contents are incorporated in this specification.

Among the above compounds, b-9, b-16, b-31, and b-33 are preferable.

As a commercial item, WPAG-336 (made by Wako Junyaku Kogyo Co., Ltd.), WPAG-443 (made by Wako Junyaku Kogyo Co., Ltd.), MBZ-101 (made by Midori Chemical Co., Ltd.), etc. are mentioned.

It is preferable not to contain a 1,2-quinone diazide compound as a photoacid generator that is sensitive to actinic rays. The reason is that the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but the quantum yield is 1 or less, and the sensitivity is lower than that of the oxime sulfonate compound.

In contrast, the oxime sulfonate compound acts as a catalyst for the deprotection of the protected acid groups by the acid generated in response to the actinic ray, so that the acid generated by the action of one photon contributes to a number of deprotection reactions, The yield exceeds 1, and becomes a large value such as a power of ten, and it is assumed that high sensitivity is obtained as a result of so-called chemical amplification.

In addition, since the oxime sulfonate compound has a π-conjugated system with diffusion, it has absorption to the long wavelength side, and is very high not only in deep ultraviolet (DUV), ArF, KrF, i-rays, but also g-rays. Indicates sensitivity.

By using a tetrahydrofuranyl group as the acid-decomposable group in the acid-reactive resin, acid decomposability equal to or higher than that of acetal or ketal can be obtained. Thereby, the acid-decomposable group can be reliably consumed by post-baking in a shorter time. Further, by using a photoacid generator in combination with an oxime sulfonate compound, the rate of generation of sulfonic acid increases, so that the generation of acid is accelerated, and the decomposition of the acid-decomposable group of the resin is accelerated. In addition, since the acid obtained by decomposition of the oxime sulfonate compound is a sulfonic acid having a small molecule, the diffusibility in the cured film is also high, and the sensitivity can be further increased.

The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and more preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive resin composition. It is more preferable to use -3 mass%, and it is especially preferable to use 0.5-1.2 mass%.

Photo-acid generators may be used individually by 1 type, and may use 2 or more types together. When using two or more types, it is preferable that the total amount falls within the above range.

<<other ingredients>>

The photosensitive resin composition can contain other components.

It is preferable to contain an organic solvent from the viewpoint of coatability as another component.

<<organic solvent>>

It is preferable that the photosensitive resin composition contains an organic solvent, and it is preferable to prepare as a solution in which optional components of a photoacid generator and various additives other than the reactive resin are dissolved in an organic solvent.

As the organic solvent used in the photosensitive resin composition, a known organic solvent can be used, and ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, and propylene glycol Lycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, die Propylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like can be exemplified.

As an organic solvent, for example, (1) ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc. Colmonoalkyl ethers; (2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether; (3) Ethylene glycol monoalkyl such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, etc. Ether acetates; (4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; (5) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether and propylene glycol diethyl ether; (6) Propylene glycol monoalkyl such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate Ether acetates; (7) Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether; (8) Diethylene, such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monobutyl ether acetate Glycol monoalkyl ether acetates; (9) Dipropylene glycol mono, such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether Alkyl ethers; (10) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether; (11) Dipropylene such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate Glycol monoalkyl ether acetates; (12) lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, and isoamyl lactate; (13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, propionic acid Aliphatic carboxylic acid esters such as isobutyl, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, and isobutyl butyrate; (14) Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, Other esters such as 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, and ethyl pyruvate; (15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; (16) amides such as N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; (17) Lactones, such as γ-butyrolactone, etc. are mentioned.

In addition, if necessary for these organic solvents, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Organic solvents such as isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate You can also add.

Among the above organic solvents, propylene glycol monoalkyl ether acetates, and/or diethylene glycol dialkyl ethers are preferred, and diethylene glycol ethyl methyl ether, and/or propylene glycol Monomethyl ether acetate is particularly preferred.

These organic solvents can be used singly or in combination of two or more.

When using two or more types, it is preferable that the total amount falls within the above range.

Moreover, from a viewpoint of liquid storage stability, it is preferable that the photosensitive resin composition contains a basic compound, and it is preferable that it contains a surfactant from a viewpoint of coatability.

<<basic compound>>

It is preferable that the photosensitive resin composition contains a basic compound.

As the basic compound, it can be arbitrarily selected and used from those used for chemically amplified resists. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, and a quaternary ammonium salt of a carboxylic acid, etc. are mentioned.

As the aliphatic amine, for example, trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine , Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

As an aromatic amine, aniline, benzylamine, N,N-dimethylaniline, diphenylamine, etc. are mentioned, for example.

As the heterocyclic amine, for example, 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, nicotinic acid amide, 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]-7-undecene, etc. are mentioned.

Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide. .

Examples of the quaternary ammonium salt of the carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

When the photosensitive resin composition contains a basic compound, the content of the basic compound is preferably 0.001 to 1 parts by mass, more preferably 0.002 to 0.5 parts by mass, based on 100 parts by mass of the acid-reactive resin.

The basic compound may be used alone or in combination of two or more, but it is preferable to use two or more types, more preferably, two or more types, and two or more types of heterocyclic amines are used in combination. More preferable. When using two or more types, it is preferable that the total amount falls within the above range.

<<surfactant>>

It is preferable that the photosensitive resin composition contains a surfactant.

As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based and silicone-based surfactants.

As the surfactant, it is more preferable to contain a fluorine-based surfactant, a silicone-based surfactant, and a combination of both.

As these fluorine-based surfactants and silicone-based surfactants, for example, Japanese Unexamined Patent Publication No. 62-036663, Japanese Unexamined Patent Publication No. 61-226746, Japanese Unexamined Patent Publication No. 61-226745, and Japanese Unexamined Patent Publication No. 62- 170950, JP-A-63-034540, JP-A-07-230165, JP-A08-062834, JP-A-09-054432, JP-A09- The surfactant described in each publication of JP 2001-330953 A and 005988 can be mentioned, and a commercially available surfactant can also be used.

As commercially available surfactants that can be used, for example, Ftop EF301, EF303 (above, manufactured by Shin Akita Kasei Co., Ltd.), Fluorad FC430, 431 (above, manufactured by Sumitomo 3M Corporation), Megapac F171, F173 , F176, F189, R08 (above, manufactured by DIC Corporation), Surfron S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Corporation), PolyFox such as PF-6320 Fluorine-based surfactants such as series (manufactured by OMNOVA) or silicone-based surfactants are mentioned. Further, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Industries, Ltd.) can also be used as a silicone-based surfactant.

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

[Formula 12]

(In the formula, R ⁴¹ and R ⁴³ each independently represent a hydrogen atom or a methyl group, R ⁴² represents a straight chain alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴⁴ represents a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms. , L ⁴ represents an alkylene group having 3 or more and 6 or less carbon atoms, p4 and q4 are mass percentages representing the polymerization ratio, p4 represents a numerical value of 10 mass% or more and 80 mass% or less, and q4 is 20 mass% or more and 90 mass% % Or less, r4 represents an integer of 1 or more and 18 or less, and n4 represents an integer of 1 or more and 10 or less.)

It is preferable that said L ⁴ is a branched alkylene group represented by following formula (42). R ⁴⁵ in formula (42) represents an alkyl group having 1 or more and 4 or less carbon atoms, and from the viewpoint of wettability to the surface to be coated, an alkyl group having 1 or more and 3 or less carbon atoms is preferable, and an alkyl group having 2 or 3 carbon atoms is more preferable. Do.

-CH _2- CH(R ⁴⁵ )- (42)

It is more preferable that the weight average molecular weight of the said copolymer is 1,500 or more and 5,000 or less.

When a surfactant is included, the amount of surfactant added is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass, and still more preferably 0.01 to 1 parts by mass, based on 100 parts by mass of the acid-reactive resin.

Surfactants can be used alone or in combination of two or more. When using two or more types, it is preferable that the total amount falls within the above range.

<<Moisture amount>>

The photosensitive resin composition may contain moisture. Moisture is preferably small or not included, but inevitable moisture may be included. The moisture content of the photosensitive resin composition is preferably 1% by mass or less, more preferably 0.7% by mass or less, and still more preferably 0.4% by mass or less. As a lower limit, it is preferable that it is 0.01 mass% or more, it is more preferable that it is 0.03 mass% or more, and it is still more preferable that it is 0.05 mass% or more.

<<metal impurities>>

The photosensitive resin composition usually inevitably contains a trace amount of metal impurities. For example, salts of alkali metals or alkaline earth metals such as sodium, potassium, and calcium may be mentioned. In the present invention, the total content of sodium ions, potassium ions, and calcium ions in the photosensitive resin composition is present in the range of, for example, 1 mass ppt to 1000 mass ppb, and further 50 mass ppt to 900 mass ppb. Is interpreted.

The amount of metal ions is measured by the method described in Examples to be described later.

<<other>>

In addition, one or two or more of known additives, such as antioxidants, plasticizers, thermal radical generators, thermal acid generators, acid proliferators, ultraviolet absorbers, thickeners, and organic or inorganic precipitation inhibitors, are added as needed. can do. For these details, reference can be made to the description of paragraphs 0143 to 0148 of JP2011-209692A, and these contents are incorporated in this specification.

<<Stop contact angle>>

In the present invention, it is defined that the static contact angle of the photosensitive resin composition on the water-soluble resin layer is 60° or less. The static contact angle is preferably 50° or less, more preferably 40° or less, and still more preferably 30° or less. As the lower limit, 0° may be sufficient, but it is preferably 2° or more, more preferably 5° or more, and still more preferably 10° or more. By setting it as the lower limit or more, the film thickness in-plane uniformity at the time of spin coating is achieved more effectively, and by setting it as the upper limit or less, foaming at the time of coating is suppressed.

In addition, in the present specification, the method of measuring the static contact angle of the photosensitive resin composition is based on the method employed in the following examples.

Changing the static contact angle of the photosensitive resin composition can be done according to a conventional method. For example, the molecular weight of the polymer constituting the acid-reactive resin, the molecular structure, control of the type or amount of polar groups, and the type or amount of surfactant to be mixed The stop contact angle may be adjusted by adjustment or the like.

<kit>

The photosensitive resin composition may be combined with a water-soluble resin composition containing a water-soluble resin, and may be used as a kit for forming a photosensitive layer and a water-soluble resin layer in this order, respectively. Furthermore, it is preferable to use it as a kit for processing an organic semiconductor layer. At this time, as a specific embodiment, it is preferable to apply each component of the photosensitive resin composition and each component of the water-soluble resin composition described above. In the present invention, it is good also as a kit in which the composition for forming an organic semiconductor is combined. As a specific aspect of the composition, it is preferable to apply the aforementioned organic semiconductor and each component of the composition.

<Organic semiconductor layer patterning method>

The following forms are mentioned as a patterning method which can be suitably adopted in this invention. Hereinafter, the processing (patterning) of the organic semiconductor layer is exemplified, but it can also be used for patterning of layers other than the organic semiconductor layer.

The organic semiconductor layer patterning method of this embodiment,

(1) the step of forming a water-soluble resin layer on the organic semiconductor layer,

(2) the step of forming a photosensitive layer on the side opposite to the organic semiconductor layer of the water-soluble resin layer,

(3) the step of exposing the photosensitive layer,

(4) a process of developing and producing a mask pattern using a developer containing an organic solvent,

(5) a step of removing at least the water-soluble resin layer and the organic semiconductor layer of the non-mask portion by dry etching treatment,

(6) A step of removing the water-soluble resin layer is included.

<<(1) Process of forming a water-soluble resin layer into a film on the organic semiconductor layer>>

The organic semiconductor layer patterning method of the present embodiment includes a step of forming a water-soluble resin layer on the organic semiconductor layer. Usually, this step is performed after forming an organic semiconductor layer on the substrate. In this case, the water-soluble resin layer is formed on the surface of the organic semiconductor on the side opposite to the surface 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 scope of the present invention. Specifically, a water-soluble undercoat layer, etc. are mentioned. Moreover, only 1 layer may be provided, and 2 or more layers may be provided as for a water-soluble resin layer. As described above, the water-soluble resin layer is preferably formed using a water-soluble resin composition.

<<(2) Process of forming a photosensitive layer into a film on the side opposite to the organic semiconductor layer of the water-soluble resin layer>>

After the step (1) above, a photosensitive layer is formed using a photosensitive resin composition on the side opposite to the surface of the (2) water-soluble resin layer on the organic semiconductor layer side. As described above, the photosensitive layer is preferably formed using a photosensitive resin composition, and more preferably formed using a chemically amplified photosensitive resin composition containing an acid-reactive resin and a photoacid generator.

The chemically amplified photosensitive resin composition contains a photoacid generator, generates an acid upon exposure, and reacts with the acid-reactive resin contained in the resist, thereby enabling patterning to function 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, it becomes possible to form a resist pattern having a high resolution and a rectangular profile. The solid content concentration is a percentage of the mass of the resist components other than the organic solvent with respect to the total mass of the photosensitive resin composition.

<<(3) Process of exposing the 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 having a predetermined pattern. Exposure may be performed only once or may be performed multiple times.

Specifically, the substrate on which the dry coating film of the photosensitive resin composition is provided is irradiated with actinic rays in a predetermined pattern. 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-ray), 248 nm (KrF ray) or 193 nm (ArF ray) may be used. After this step, if necessary, a post-exposure heating step (PEB) may be performed.

For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a laser generator, a light emitting diode (LED) light source, or the like can be used.

When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), h-line (405 nm), or the like can be preferably used. In the present invention, it is preferable to use i-line because the effect is suitably exhibited.

In the case of using a laser, wavelengths of 343 nm and 355 nm are suitably used for solid-state (YAG) lasers, and 193 nm (ArF line), 248 nm (KrF line), and 351 nm (Xe ray) are suitably used for excimer lasers, In addition, 375nm and 405nm are suitably used for semiconductor lasers. Among these, 355 nm and 405 nm are more preferable in terms of stability and cost. The laser can be divided once or multiple times, and irradiated to the photosensitive layer.

The exposure amount is preferably 40 to 120 mJ, more preferably 60 to 100 mJ.

Energy density per one pulse of the laser, it is 0.1mJ / cm ² or more 10,000mJ / 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 still more preferable. In order not to decompose the coating film by the ablation phenomenon, 1,000 mJ/cm ² or less is more preferable, and 100 mJ/cm ² or less is still more preferable.

Further, the pulse width is preferably 0.1 nanoseconds (hereinafter referred to as "nsec") or more and 30,000 nsec or less. In order not to decompose the color film due to the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is more preferable. In order to improve the accuracy according to the scan exposure, 1,000 nsec or less is more preferable, and 50 nsec or less is more 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.

In addition, in order to shorten the exposure processing time, the frequency of the laser is more preferably 10 Hz or more, more preferably 100 Hz or more, and in order to improve the accuracy according to the scan exposure, 10,000 Hz or less is more preferable, and 1,000 Hz. The following are more preferable.

Compared with a mercury lamp, the laser is preferable in that it is easier to focus, and a mask for pattern formation in the exposure step is unnecessary, and the cost can be reduced.

The exposure apparatus is not particularly limited, but commercially available ones include Callisto (manufactured by V Technology Co., Ltd.), AEGIS (manufactured by V Technology Co., Ltd.), DF2200G (manufactured by Dai Nippon Screen Seizo Co., Ltd.), etc. It is possible to use Further, devices other than the above are also suitably used.

Further, if necessary, the amount of irradiated light may be adjusted through a spectral filter such as a long wavelength cutoff filter, a short wavelength cutoff filter, and a band pass filter.

<<(4) Process of developing and manufacturing a mask pattern using a developer containing an organic solvent>>

In 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). The development is preferably negative. Sp value of the solvent contained in the developing solution, it is less than 19MPa ^1/2 is preferred, and more preferably not more than 18MPa ^1/2.

As the organic solvent contained in the developer, polar solvents such as ketone-based solvents, ester-based solvents, and amide-based solvents, and hydrocarbon-based solvents can be used.

As a ketone solvent, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methylamylketone), 4-heptanone, 1-hexanone, 2- Hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetoneylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone , Methyl naphthyl ketone, isophorone, propylene carbonate, and the like.

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, and the like.

Examples of amide solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl- 2-imidazolidinone and the like can be used.

Examples of the hydrocarbon-based solvent include aromatic hydrocarbon-based solvents such as toluene and xylene, and aliphatic hydrocarbon-based 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 use it, mixing with an organic solvent other than the above. However, it is preferable that the water content of the developer as a whole is less than 10% by mass, and it is more preferable that it does not contain substantially moisture. Substantial here means, for example, that the water content of the developer as a whole is 3% by mass or less, more preferably less than the measurement limit.

That is, the amount of the organic solvent to be used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the developer.

In particular, it is preferable that the organic developer contains at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, and an amide solvent.

Further, the organic developer may contain an appropriate amount of a basic compound as necessary. Examples of the basic compound include those described in the section of the basic compound.

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and still more preferably 2 kPa or less at 20°C. When the vapor pressure of the organic developer is 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, the temperature uniformity in the wafer surface is improved, and as a result, the dimensional uniformity in the wafer surface is improved.

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 (methylamylketone), 4-heptanone, and 2-hexanone , Diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone and other ketone solvents, 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, Ester solvents such as 3-methyl-3-methoxybutylacetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, And amide-based solvents such as N,N-dimethylformamide, aromatic hydrocarbon-based solvents such as toluene and xylene, and aliphatic hydrocarbon-based solvents such as octane and decane.

Specific examples of the solvent having a vapor pressure of 2 kPa or less, which is a particularly preferred range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutylketone, Ketone solvents such as cyclohexanone, 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, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, lactic acid Ester solvents such as propyl, amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, aromatic hydrocarbon solvents such as xylene, Aliphatic hydrocarbon solvents, such as octane and decane, are mentioned.

An appropriate amount of one or two or more surfactants may be added to the developer as needed.

Although it does not specifically limit as surfactant, For example, the surfactant described in the section of the above water-soluble resin composition is preferably used.

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, and more preferably 0.01 to 0.5% by mass, based on the total amount of the developer.

As a developing method, for example, a method in which a substrate is immersed in a bath filled with a developer for a certain period of time (dip method), a method in which a developing solution is raised on the surface of the substrate by surface tension and stopped for a certain period of time (Puddle method), and a substrate A method of spraying a developer onto the surface (spray method), a method of continuously discharging the developer while scanning a developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method), etc. can be applied.

When the various developing methods include a step of discharging a developer from a developing nozzle of a developing device toward the photosensitive layer, the discharge pressure of the discharged developer (flow rate per unit area of the discharged developer) is preferably 2 mL/sec/ It is mm ² or less, more preferably 1.5 mL/sec/mm ² or less, and still more preferably 1 mL/sec/mm ² or less. There is no particular lower limit of the flow rate, but 0.2 mL/sec/mm ² or more is preferable in consideration of throughput. By setting the discharge pressure of the developer to be discharged within the above range, defects in the pattern resulting from the resist residue after development can be remarkably reduced.

Although the details of this mechanism are not certain, it is probably because the pressure applied by the developer to the photosensitive layer is reduced by setting the discharge pressure in the above range, and it is believed that the resist pattern on the photosensitive layer is prevented from being inadvertently sharpened or collapsed.

In addition, the discharge pressure (mL/sec/mm ² ) of the developer is a value at the outlet of the developing nozzle in the developing device.

As a method of adjusting the discharge pressure of the developer, for example, a method of adjusting the discharge pressure with a pump or the like, a method of changing by adjusting the pressure by supply from a pressurized tank, and the like can be mentioned.

Further, after the step of developing using a developer containing an organic solvent, a step of stopping the development may be performed while replacing with another organic solvent.

<<(5) Process of removing at least the water-soluble resin layer and organic semiconductor layer of the non-mask part by dry etching treatment>>

After developing the photosensitive layer to form a mask pattern, at least the water-soluble resin layer and the organic semiconductor layer in the non-mask portion are removed by etching treatment. The non-mask portion indicates a location where the photosensitive layer has been removed in the developing step.

Specifically, in 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. As representative examples of dry etching, JP-A-59-126506, JP-A 59-046628, JP 58-009108, JP 58-002809, JP 57- There is a method described in Japanese Patent Laid-Open No. 148706 and 61-041102.

As dry etching, it is preferable to perform it in the following form from a viewpoint of forming a pattern cross-section to be closer to a rectangle, or from a viewpoint of further reducing damage to an organic semiconductor layer.

Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), etching is performed in a first step of etching to a region (depth) where the organic semiconductor layer is not exposed, and after the first step of etching, nitrogen gas (N ₂₎ ) And oxygen gas (O ₂ ), preferably the second step of etching to the vicinity of the area (depth) where the organic semiconductor layer is exposed, and over-etching after the organic semiconductor layer is exposed. The form to include is preferable. Hereinafter, a specific method of dry etching, as well as first step etching, second step 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 step etching and the etching rate (nm/min) in the second step etching are calculated, respectively. (2) Time for etching the desired thickness by the first step of etching and time for etching the desired thickness by the second step of etching are respectively calculated. (3) The first step is etched according to the etching time calculated in (2) above. (4) The second step of etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by detection of an end point, and the second step may be etched according to the determined etching time. (5) The over-etching time is calculated with respect to the total time of the above (3) and (4), and over-etching is performed.

The mixed gas used in the first step etching process preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material as a film to be etched into a rectangle. In addition, in the first step of etching, damage to the organic semiconductor layer can be avoided by etching to a region where the organic semiconductor layer is not exposed. In addition, in the second-step etching process and the over-etching process, the organic semiconductor layer is damaged after 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-step etching process. From the viewpoint of avoidance, it is preferable to perform the etching treatment using a mixed gas of nitrogen gas and oxygen gas.

It is important to determine the ratio of the etching amount in the first step etching step and the etching amount in the second step etching step so as not to impair the rectangularity by the etching treatment in the first step etching step. In addition, the ratio of the latter in the total amount of etching (the total amount of the etching amount in the first-stage etching process and the amount of etching in the second-stage etching step) is preferably in the range of more than 0% and not more than 50%, and 10 to 20% is more preferable. The etching amount refers to an amount calculated from the difference between the remaining film thickness of the film to be etched and the film thickness before etching.

Moreover, it is preferable that etching includes an over-etching process. It is preferable to perform the over-etching process by setting an over-etching ratio. In addition, it is preferable to calculate the over-etching ratio from the first etching treatment time. The over-etching ratio can be arbitrarily set, but from the viewpoint of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched, it is preferably 30% or less of the etching treatment time in the etching process, more preferably 5 to 25%. And it is particularly preferably 10 to 15%.

<<(6) Process of removing the water-soluble resin layer>>

After etching, it is preferable to remove the water-soluble resin layer using a solvent (usually water).

As a method of removing the water-soluble resin layer with water, for example, a method of removing the water-soluble resin layer by spraying washing water onto the resist pattern from a spray-type or shower-type spray nozzle is mentioned. As the washing water, pure water can be preferably used. Further, examples of the spray nozzle include a spray nozzle in which the entire substrate is included in the spray range, or a movable spray nozzle in which the movable range includes the entire substrate.

When the spray nozzle is a movable type, the resist pattern can be removed more effectively by moving the water-soluble resin layer from the center of the substrate to the end of the substrate twice or more and spraying the washing water during the process of removing the water-soluble resin layer.

After removing water, it is also preferable to perform a process such as drying. As a drying temperature, it is preferable to set it as 80-120 degreeC.

<use>

The photosensitive layer of the present invention can be used for manufacturing an electronic device using an organic semiconductor. Here, an electronic device is a device that contains a semiconductor and has two or more electrodes, and controls the electric current or generated voltage between the electrodes by electricity, light, magnetism, chemical substances, etc., or the applied voltage or It is a device that generates light, an electric field, a magnetic field, and the like by electric current. Examples include organic photoelectric conversion elements, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifying elements, organic inverters, and information recording elements. The organic photoelectric conversion element can be used for either an optical sensor application or an energy conversion application (solar cell). Among these, organic field effect transistors, organic photoelectric conversion elements, and organic electroluminescent elements are preferable for use, more preferably organic field effect transistors and organic photoelectric conversion elements, and particularly preferably organic field effect transistors.

Example

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited to the following examples unless it exceeds the gist. In addition, unless otherwise specified, "%" and "parts" are based on mass.

<Measurement method of weight average molecular weight (Mw)>

The Mw of the resin was measured according to the following method.

<Measurement method of weight average molecular weight (Mw)>

The molecular weight of the water-soluble resin was measured according to the method described in paragraphs 0067 to 0071 of WO2015/098978A.

For other resins, molecular weight was measured by gel permeation chromatography (GPC measurement) under the following measurement conditions.

Polystyrene conversion value

Equipment: HLC-8220 (manufactured by Tosoh Corporation)

Column: Guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation)

Eluent: THF (tetrahydrofuran)

Detector: UV (ultraviolet) wavelength 254 nm

Examples 1 to 11 and Comparative Examples 1 to 3

<Preparation of water-soluble resin composition>

In the following formulation, each component was mixed to obtain a uniform solution, and then filtered using a nylon filter having a pore diameter of 0.8 μm to prepare a water-soluble resin composition.

<<PVA-1>>

PVA 15.0 parts by mass

Surfactant D-1 (below) 0.008 parts by mass

water 84.9 parts by mass

PVA (PVA-203, manufactured by Kurare Corporation, 88.0% degree of saponification, degree of polymerization 300)

<<PVP-1>>

PVP 7.9 parts by mass

Surfactant D-1 (below) 0.008 parts by mass

water 92.1 parts by mass

PVP (Mw=360,000 Polyvinylpyrrolidone K90 manufactured by Tokyo Kasei)

<Preparation of the water-insoluble resin composition of a comparative example>

<<FR-1>>

In the following formulation, each component was mixed to obtain a uniform solution, and then filtered using a polypropylene filter having a pore diameter of 0.6 μm to prepare a water-insoluble resin composition.

CYTOP (registered trademark) CTL-809AP2: manufactured by Asahi Glass Corporation 4.0 parts by mass

Sumitomo 3M Fluorine Nut FC77 96.0 parts by mass

<Preparation of photosensitive resin composition>

Each acid-reactive resin was synthesized as follows.

<<Synthesis of acid-reactive resin A-1>>

<Synthesis of acid-reactive resin A-1 (Mw=25,000)>

PGMEA (propylene glycol monomethyl ether acetate) (32.62 g) was put in a 200 mL 3-neck flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86°C. Here, what dissolved BzMA (16.65 g), THFMA (21.08 g), t-BuMA (5.76 g), and V-601 (1.0686 g) in PGMEA (32.62 g) was added dropwise for 2 hours. Then, the reaction solution was stirred for 2 hours, and the reaction was terminated. The white powder generated by reprecipitation of the reaction solution in heptane was collected by filtration to obtain an acid-reactive resin A-1. The obtained resin had a total protection ratio of 65 mol% of THFMA and t-BuMA monomers, a weight average molecular weight of 25,000, and a dissolution rate of 100 nm/s. The amount of the component having Mw of 1,000 or less was 3% by mass.

<<Synthesis of acid-reactive resin A-2>>

<Synthesis of acid-reactive resin A-2 (Mw=57,000)>

PGMEA (32.62 g) was put into 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, what dissolved BzMA (16.65 g), THFMA (21.08 g), t-BuMA (5.76 g), and V-601 (0.2157 g) in PGMEA (32.62 g) was added dropwise over 2 hours. Then, the reaction solution was stirred for 2 hours, and the reaction was terminated. The white powder generated by reprecipitation of the reaction solution in heptane was recovered by filtration to obtain an acid-reactive resin A-2. The obtained resin had a total protection ratio of 65 mol% of THFMA and t-BuMA monomers, a weight average molecular weight of 57,000, and a dissolution rate of 19 nm/s. The amount of the component having Mw of 1,000 or less was 4% by mass.

<<Synthesis of acid-reactive resin A-3>>

<Synthesis of acid-reactive resin A-3 (Mw=9,000)>

PGMEA (32.62 g) was put into 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, what dissolved BzMA (16.65 g), THFMA (21.08 g), t-BuMA (5.76 g), and V-601 (2.2622 g) in PGMEA (32.62 g) was added dropwise over 2 hours. Then, the reaction solution was stirred for 2 hours, and the reaction was terminated. The white powder generated by reprecipitation of the reaction solution in heptane was collected by filtration to obtain an acid-reactive resin A-3. The obtained resin had a total protection ratio of 65 mol% of THFMA and t-BuMA monomers, a weight average molecular weight of 9,000, and a dissolution rate of 432 nm/s. The amount of the component having Mw of 1,000 or less was 3% by mass.

<<Synthesis of acid-reactive resin A-4>>

PGMEA (32.62 g) was put into 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, what dissolved BzMA (16.65 g), THFMA (21.08 g), t-BuMA (5.76 g), and V-601 (1.9329 g) in PGMEA (32.62 g) was added dropwise over 2 hours. Then, the reaction solution was stirred for 2 hours, and the reaction was terminated. The white powder generated by reprecipitation of the reaction solution in heptane was collected by filtration to obtain an acid-reactive resin A-4. The obtained resin had a cyclic ether ester protection rate of 50 mol%, a weight average molecular weight of 15,000, and a dissolution rate of 200 nm/s. The amount of the component having Mw of 1,000 or less was 3% by mass.

<<Synthesis of acid-reactive resin A-5>>

PGMEA (32.62 g) was put into 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, what dissolved BzMA (16.65 g), THFMA (21.08 g), t-BuMA (5.76 g), and V-601 (0.3060 g) in PGMEA (32.62 g) was added dropwise over 2 hours. Then, the reaction solution was stirred for 2 hours, and the reaction was terminated. The white powder generated by reprecipitation of the reaction solution in heptane was collected by filtration to obtain an acid-reactive resin A-5. The obtained resin had a total protection ratio of 65 mol% of THFMA and t-BuMA monomers, a weight average molecular weight of 50,000, and a dissolution rate of 32 nm/s. The amount of the component having Mw of 1,000 or less was 3% by mass.

<<Synthesis of acid-reactive resin A-6>>

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

<<Synthesis of acid-reactive resin A-7>>

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

By the formulation shown in Table 1 or Table 2, each component was mixed to obtain a uniform solution, and then filtered using a nylon filter having a pore diameter of 0.45 μm to prepare a photosensitive resin composition. In addition, the details of each component are shown in Table 1 or Table 2.

<Production of organic semiconductor substrate>

An organic semiconductor layer was formed by spin-coating an organic semiconductor coating liquid (composition for organic semiconductor formation) composed of the following composition on a circular glass substrate and drying at 130°C for 10 minutes. The film thickness was 150 nm.

<<Composition of organic semiconductor coating liquid>>

P3HT (manufactured by Sigma Aldrich Japan joint company) 10% by mass

PCBM (manufactured by Sigma Aldrich Japan joint company) 10% by mass

Chloroform (made by Wako Junyaku Co., Ltd.) 80% by mass

<Formation of water-soluble resin layer>

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

<Evaluation of dissolution rate>

A photosensitive resin composition was applied onto a crystal vibrator microbalance (electrode of QCM) as a substrate, and heated at 100° C. for 1 minute to form a 2 μm-thick film (photosensitive layer). About the dissolution rate in butyl acetate at 23 degreeC, the QCM method was used and it computed from the time when the coating film of 2 micrometers film thickness melt|dissolves (relative index).

A: 50 nm or more per second and 150 nm or less per second

B: 20 nm or more and less than 50 nm per second, or more than 150 nm and 200 nm or less per second

C: less than 20 nm per second, or more than 200 nm per second

<Measurement of the amount of metal ions>

In the measurement of the total content of sodium ions, potassium ions, and calcium ions in the photosensitive resin composition, the metal content in the composition was measured on the order of 1 ppt to 1000 ppb by ICP-MS (Inductively Coupled Plasma Mass Spectrometry).

<Measurement of moisture content>

After the liquid preparation, the moisture content in the composition was measured using a Karl Fischer moisture meter in the composition.

<Measurement of stop contact angle>

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

<Lithographic property of line pattern>

A photosensitive resin composition (resist) was applied on the water-soluble resin layer prepared above, and dried (prebaked) at 100°C for 1 minute to form a photosensitive layer. The film thickness was 2 μm. Next, using a parallel exposure machine, through a binary mask made of quartz glass having a mask size of 2 μm and a half pitch of 2 μm, exposure was performed with a light source shown in Table 1 or 2 so that the exposure amount shown in Table 1 or Table 2 might be used. Then, it post-baked (PEB) under the conditions shown in Table 1 or Table 2, and developed with butyl acetate at the developing treatment time shown in Table 1 or Table 2. After development, the number of lines lost due to over development among four line and space patterns (L/S) having a width of 2 μm was counted.

The results are shown in Table 1 or Table 2. Here, no pattern means that the 2 μm pattern is not resolved because the dissolution rate is low. No peeling means no pattern loss.

<Over phenomenon coefficient>

The over-development coefficient in the lithographic property of the line pattern was measured.

The over development coefficient was calculated according to the following formula.

Over development coefficient = [Development treatment time (s)/[(film thickness of photosensitive layer (nm)/dissolution rate (nm/sec))]

<Evaluation of adhesion of the island pattern>

A photosensitive resin composition (resist) was applied on the water-soluble resin layer prepared above, and dried (prebaked) at 100°C for 1 minute to form a photosensitive layer. The film thickness was 2 μm. Next, exposure was performed with a light source shown in Table 1 or 2 at an exposure amount such that 25 patterns of 1 μm in all directions were formed using a parallel exposure machine. Then, it post-baked (PEB) under the conditions shown in Table 1 or Table 2, and developed with butyl acetate at the developing treatment time shown in Table 1 or Table 2. Of the obtained 25 patterns, the number in which peeling occurred was confirmed.

[Table 1]

[Table 2]

The details in the table are as follows.

PEB: Post-baking treatment conditions

Exposure: The exposure light source at the time of development is described.

Hiring: means hiring the applicable one

<Acid Generator>

B-1

[Formula 13]

<Basic compound>

C-1

[Formula 14]

C-2

2,6-diisopropylaniline (primary amine, manufactured by Tokyo Kasei Kogyo Co., Ltd.)

<Surfactant>

D-1: OMNOVA, PF6320

[Formula 15]

D-2

MegaPak F-430, manufactured by DIC Corporation

<solvent>

E-1: Propylene glycol monomethyl ether acetate (PGMEA)

E-2: ethyl 3-ethoxypropionate

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

A photosensitive resin composition using C-2 (2,6-diisopropylaniline, manufactured by Tokyo Kasei Kogyo Co., Ltd.) in place of the basic compound C-1 of Example 1, and D-2 (mega Pak F-430, photosensitive resin composition using DIC (manufactured by DIC Co., Ltd.), using a mixed solvent of E-1:E-2 (ethyl 3-ethoxypropionate) = 70:30 (mass ratio) instead of the solvent E-1 The photosensitive resin composition, the photosensitive resin composition in which the mass ratio of the resin and the acid generator was 25.18:0.16 (mass ratio), and the photosensitive resin composition in which the mass ratio of the resin and the acid generator was 24.98:0.36 (mass ratio) were prepared, respectively. A sample of the laminate was prepared using each photosensitive resin composition. As a result of evaluating the over-development coefficient, lithography property, and adhesion for each sample, good results were obtained for any substrate.

1 photosensitive layer
2 water-soluble resin layer
3 organic semiconductor layer
4 substrate
5 Remover

Claims (14)

A photosensitive layer included in a laminate having a water-soluble resin layer and a photosensitive layer,
The photosensitive layer is formed of a photosensitive resin composition comprising a compound that generates an acid by irradiation with actinic rays or radiation and a resin in which a change in dissolution rate for butyl acetate occurs due to the action of the acid. As a result, the resin in which the dissolution rate for butyl acetate is changed has a weight average molecular weight of 10,000 to 50,000, and a group soluble in an aqueous alkali solution of 50 to 100 mol% of the total structural units is protected by a hydrophobic protecting group. It is a hydrophobic resin soluble in butyl acetate at 23°C,
The dissolution rate when the unirradiated photosensitive layer is immersed in butyl acetate at 23° C. is 20 nm/s or more and 200 nm/s or less,
The photosensitive layer on the aqueous solution resin layer, wherein the stop contact angle of the photosensitive resin composition is 60° or less. The method according to claim 1,
The photosensitive layer, wherein the photosensitive layer has a photosensitive ability against i-ray irradiation. The method according to claim 1 or 2,
The photosensitive layer, wherein the content of water in the photosensitive resin composition is 0.01% by mass or more and 1% by mass or less. The method according to any one of claims 1 to 3,
The photosensitive layer in which the change in the dissolution rate is a decrease in the dissolution rate. The method according to any one of claims 1 to 4,
A photosensitive layer in which the resin contained in the photosensitive layer has a structural unit represented by the following formula (1);
[Formula 1]

In the formula, R ⁸ represents a hydrogen atom or an alkyl group, L ¹ represents a carbonyl group or a phenylene group, and R ¹ to R ⁷ each independently represent a hydrogen atom or an alkyl group. The method according to any one of claims 1 to 5,
The photosensitive layer, wherein the total content of sodium ions, potassium ions, and calcium ions in the photosensitive resin composition is 1 mass ppt to 1000 mass ppb. The method according to any one of claims 1 to 6,
Photosensitive layer for processing organic semiconductor layers. A laminate comprising the photosensitive layer and the water-soluble resin layer according to any one of claims 1 to 7. The method of claim 8,
A layered product further comprising an organic semiconductor layer, wherein the organic semiconductor layer, the water-soluble resin layer, and the photosensitive layer are stacked in this order. The method according to claim 8 or 9,
The layered product, wherein the resin in which the dissolution rate of butyl acetate changes due to the action of the acid is a mixture of a resin having a high dissolution rate in butyl acetate and a resin having a low dissolution rate in butyl acetate. As a photosensitive resin composition for forming a photosensitive layer,
The photosensitive layer is a layer that forms a laminate in combination with a water-soluble resin layer, and the dissolution rate when the unexposed photosensitive layer is immersed in butyl acetate is 20 nm/s or more and 200 nm/second or less,
The photosensitive resin composition contains a compound that generates an acid by irradiation with actinic rays or radiation and a resin in which a change in dissolution rate for butyl acetate occurs by the action of the acid,
The resin having a change in the dissolution rate for butyl acetate by the action of the acid has a weight average molecular weight of 10,000 to 50,000, and a group soluble in an aqueous alkali solution in which 50 to 100 mol% of the total constituent units is a hydrophobic protecting group. A photosensitive resin composition, which is a hydrophobic resin that is protected by butyl acetate and is soluble in a hydrophobic resin and has a static contact angle of 60° or less on the water-soluble resin layer. The method of claim 11,
A photosensitive resin composition for processing an organic semiconductor layer. As a kit for forming a water-soluble resin layer and a photosensitive layer in this order, a kit comprising the photosensitive resin composition and water-soluble resin composition according to claim 11 or 12. The method of claim 13,
Kit for organic semiconductor layer processing.

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