阅读说明：本技术 层叠体、组合物及层叠体形成用套组 (Laminate, composition, and laminate-forming kit ) 是由 中村敦 高桑英希 于 2020-03-23 设计创作，主要内容包括：本发明提供一种层叠体、用于形成上述层叠体中所包含的保护层或感光层的组合物及用于形成上述层叠体的层叠体形成用套组,该层叠体依次包含基材、有机层、保护层及感光层,上述感光层包含树脂,所述树脂具有含有下述式(A1)所表示的酸分解性基团的重复单元,相对于上述树脂的总质量,上述树脂中所包含的具有极性基团的重复单元的含量小于10质量％,上述感光层供于使用显影液的显影,上述保护层供于使用剥离液的去除。(The present invention provides a laminate comprising a substrate, an organic layer, a protective layer and a photosensitive layer in this order, wherein the photosensitive layer comprises a resin having a repeating unit containing an acid-decomposable group represented by the following formula (A1), the content of the repeating unit having a polar group in the resin is less than 10% by mass relative to the total mass of the resin, the photosensitive layer is used for development with a developer, and the protective layer is used for removal with a stripping liquid.)

1. A laminate comprising a substrate, an organic layer, a protective layer and a photosensitive layer in this order,

the photosensitive layer contains a resin having a repeating unit containing an acid-decomposable group represented by the following formula (A1),

the content of the repeating unit having a polar group contained in the resin is less than 10% by mass relative to the total mass of the resin,

the photosensitive layer is subjected to development using a developing solution,

the protective layer is provided for removal using a stripping liquid,

in the formula (A1), R¹、R²And R³Each independently represents a hydrocarbon group, a cyclic aliphatic group or an aromatic ring group, R¹、R²And R³Each through a carbon atom C¹、C²And C³To the carbon atom C in formula (A1), said C¹、C²And C³In which the primary carbon atom is 0 or 1, R¹、R²And R³At least 2 of which are optionally bonded to form a ring structure, representing the bonding site with other structures.

2. The laminate according to claim 1, wherein,

the acid-decomposable group contains an aromatic ring structure.

3. The laminate according to claim 1 or 2,

The acid-decomposable group has a monocyclic or aromatic ring structure having 7 or more rings, and R is¹、R²And R³At least 1 of which is isopropyl.

4. The laminate according to any one of claims 1 to 3,

the protective layer includes a water-soluble resin.

5. The laminate according to claim 4, wherein,

the water-soluble resin is a resin containing a repeating unit represented by any one of the following formulae (P1-1) to (P4-1);

in the formulae (P1-1) to (P4-1), R^P1Represents a hydrogen atom or a methyl group, R^P2Represents a hydrogen atom or a methyl group, R^P3Is represented by (CH)₂CH₂O)_maH、CH₂COONa or a hydrogen atom, and ma represents an integer of 1 to 2.

6. The laminate according to any one of claims 1 to 5,

the photosensitive layer further contains an onium salt type photoacid generator having a group containing a ring structure or a nonionic photoacid generator having a group containing a ring structure.

7. The laminate according to any one of claims 1 to 6,

the development is negative development.

8. The laminate according to any one of claims 1 to 7,

the content of the organic solvent is 90 to 100 mass% with respect to the total mass of the developing solution.

9. A composition for forming the protective layer contained in the laminate of any one of claims 1 to 8.

10. A composition for forming the photosensitive layer contained in the laminate of any one of claims 1 to 8,

the composition comprises a resin having a repeating unit containing an acid-decomposable group represented by the formula (A1),

the content of the repeating unit having a polar group contained in the resin is less than 10% by mass with respect to the total mass of the resin.

11. A laminate forming kit comprising the following components A and B,

a: a composition for forming the protective layer contained in the laminate of any one of claims 1 to 8;

b: a composition for forming the photosensitive layer contained in the laminate of any one of claims 1 to 8, comprising a resin having a repeating unit containing an acid-decomposable group represented by the formula (a1), the content of the repeating unit having a polar group contained in the resin being less than 10% by mass relative to the total mass of the resin.

Technical Field

The present invention relates to a laminate, a composition, and a laminate forming kit.

Background

In recent years, devices using a patterned organic layer, such as semiconductor devices using an organic semiconductor, have been widely used.

For example, a device using an organic semiconductor has the following characteristics compared to a conventional device using an inorganic semiconductor such as silicon: the material can be easily changed in properties by simple production steps and by changing the molecular structure. Also, it is considered that the change of the material is abundant and the function or the element which cannot be realized by the inorganic semiconductor can be realized. Organic semiconductors are used in electronic devices such as organic solar cells, organic electroluminescent displays, organic photodetectors, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifier elements, organic inverters, and information recording elements.

It is known to pattern an organic layer such as an organic semiconductor using a laminate including layers such as an organic layer and a photosensitive layer (e.g., a resist layer).

For example, patent document 1 describes a laminate formed of a photosensitive resin composition containing: an organic semiconductor film; a protective film over the organic semiconductor film; a photoacid generator (A) that has a resist film on the protective film and generates an organic acid that generates an acid and has a pKa of-1 or less; and a resin (B) which reacts with an acid generated from the photoacid generator to decrease a dissolution rate with respect to a developer containing an organic solvent.

Patent document 2 describes a pattern forming method including: a step of forming a film using an actinic ray-sensitive or radiation-sensitive resin composition which comprises (A) a resin containing a repeating unit having a group which is decomposed by the action of an acid to form a polar group and containing an aromatic group and having a reduced solubility in an organic solvent by the action of an acid, (B) a nonionic compound which generates an acid by irradiation with actinic rays or radiation, and (C) a solvent; exposing the film; and forming a negative pattern by developing the exposed film using a developer containing an organic solvent.

Prior art documents

Patent document

[ patent document 1 ] Japanese patent laid-open No. 2015-087609

[ patent document 2 ] Japanese patent laid-open publication No. 2013-050511

Disclosure of Invention

Technical problem to be solved by the invention

In this way, in patterning an organic layer such as an organic semiconductor, for example, the following method is performed: a pattern of the photosensitive layer is formed by exposing the photosensitive layer, heating after Exposure (PEB), and developing, and the organic layer is patterned by etching or the like using the pattern of the photosensitive layer as a mask pattern.

In the photosensitive layer, for example, a resin in which an acid group is protected by an acetal acid-decomposable group is used. When such a resin having an acetal acid-decomposable group is used, PEB may be performed at a high temperature (e.g., 110 ℃) in order to promote the removal of the acid-decomposable group and to improve the pattern shape of the photosensitive layer after development.

Among them, in the case of using a thermolabile organic layer or the like, PEB needs to be performed at a low temperature.

However, for example, when a resin in which an acid group is protected by an acetal acid-decomposable group is used for a photosensitive layer and PEB is performed at a low temperature (for example, 70 ℃), the following problems may occur: pattern collapse, a decrease in etching resistance (hereinafter, also simply referred to as "etching resistance") of the pattern of the photosensitive layer during etching of the organic layer, poor pattern transferability, and the like occur.

The purpose of the present invention is to provide a laminate, a composition for forming a protective layer or a photosensitive layer included in the laminate, and a laminate forming kit for forming the laminate, wherein pattern collapse of a pattern of a photosensitive layer after development is suppressed even when heating is performed after exposure at a low temperature, and pattern transferability is excellent.

Means for solving the technical problem

Hereinafter, representative embodiments of the present invention will be described.

< 1 > a laminate comprising a substrate, an organic layer, a protective layer and a photosensitive layer in this order,

the photosensitive layer contains a resin having a repeating unit containing an acid-decomposable group represented by the following formula (A1),

the content of the repeating unit having a polar group contained in the resin is less than 10% by mass relative to the total mass of the resin,

the photosensitive layer is subjected to development using a developing solution,

the protective layer is removed by using a stripping solution.

[ chemical formula 1]

In the formula (A1), R¹、R²And R³Each independently represents a hydrocarbon group, a cyclic aliphatic group or an aromatic ring group, R¹、R²And R³Each through a carbon atom C¹、C²And C³To the carbon atom C in the formula (A1) ¹、C²And C³In which the primary carbon atom is 0 or 1, R¹、R²And R³At least 2 of the groups may be bonded to form a ring structure, representing a bonding site with other structures.

< 2 > the laminate according to < 1 >, wherein the acid-decomposable group has an aromatic ring structure.

< 3 > the laminate according to < 1 > or < 2 >, wherein the acid-decomposable group has a monocyclic or aromatic ring structure having 7 or more rings, and R is¹、R²And R³At least 1 of which is isopropyl.

< 4 > the laminate according to any one of < 1 > to < 3 >, wherein the protective layer contains a water-soluble resin.

< 5 > the laminate according to < 4 >, wherein the water-soluble resin is a resin containing a repeating unit represented by any one of the following formulae (P1-1) to (P4-1);

[ chemical formula 2]

In the formulae (P1-1) to (P4-1), R^P1Represents a hydrogen atom or a methyl group, R^P2Represents a hydrogen atom or a methyl group, R^P3Is represented by (CH)₂CH₂O)_maH、CH₂COONa or a hydrogen atom, and ma represents an integer of 1 to 2.

< 6 > the laminate according to any one of < 1 > to < 5 >, wherein the photosensitive layer further comprises an onium salt type photoacid generator having a group containing a ring structure or a nonionic photoacid generator having a group containing a ring structure.

< 7 > the laminate according to any one of < 1 > to < 6 >, wherein the development is a negative development.

< 8 > the laminate according to any one of < 1 > to < 7 >, wherein the content of the organic solvent is 90 to 100% by mass based on the total mass of the developer.

< 9 > a composition for forming the above-mentioned protective layer contained in the laminate of any of < 1 > to < 8 >.

< 10 > a composition for forming the above-mentioned photosensitive layer contained in the laminate of any of < 1 > to < 8 >,

the composition comprises a resin having a repeating unit containing an acid-decomposable group represented by the formula (A1),

the content of the repeating unit having a polar group contained in the resin is less than 10% by mass relative to the total mass of the resin,

< 11 > a laminate-forming kit comprising the following A and B,

a: a composition for forming the above-mentioned protective layer contained in the laminate of any of < 1 > to < 8 >;

b: a composition for forming the above photosensitive layer contained in the laminate of any one of < 1 > to < 8 >, the composition comprising a resin having a repeating unit containing an acid-decomposable group represented by the above formula (a1), the content of the repeating unit having a polar group contained in the above resin being less than 10% by mass relative to the total mass of the above resin.

Effects of the invention

The present invention provides a laminate, a composition for forming a protective layer or a photosensitive layer included in the laminate, and a laminate forming kit for forming the laminate, wherein pattern collapse of a pattern of a photosensitive layer after development is suppressed even when heating is performed after exposure at a low temperature, and pattern transferability is excellent.

Drawings

Fig. 1 is a cross-sectional view schematically showing a process of processing a laminate according to a preferred embodiment of the present invention.

Detailed Description

The present invention will be described in detail below.

In the present specification, "to" is used to include numerical values before and after the "to" as a lower limit value and an upper limit value.

In the labeling of a group (atomic group) in the present specification, a substituted or unsubstituted label includes a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, "alkyl" means that an alkyl group having a substituent (substituted alkyl) is included as well as an alkyl group having no substituent (unsubstituted alkyl).

In the present specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of the light used for exposure include actinic rays or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser light, extreme ultraviolet rays (EUV light), X-rays, and electron beams.

In the present specification, "(meth) acrylate" represents both or either of acrylate and methacrylate, "(meth) acrylic acid" represents both or either of acrylic acid and methacrylic acid, and "(meth) acryloyl group" represents both or either of acryloyl group and methacryloyl group.

In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In the present specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of a water-soluble resin such as polyvinyl alcohol are values converted to polyethylene oxide (PEO) measured by a GPC (gel permeation chromatography) method.

In the present specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of a water-insoluble resin such as a (meth) acrylic resin are polystyrene converted values measured by a GPC method.

In the present specification, the total solid content means the total mass of components excluding the solvent from all the components of the composition.

In the present specification, the term "step" is not limited to an independent step, and is also included in the term as long as the intended function of the step is achieved even when the step cannot be clearly distinguished from other steps.

In the present specification, the terms "upper" and "lower" may be used to refer to the upper side or the lower side of the structure. That is, other structures may be inserted without contact. Unless otherwise specified, the direction of the photosensitive layer side viewed from the organic layer is referred to as "up", and the direction of the substrate side viewed from the organic layer is referred to as "down".

In the present specification, unless otherwise stated, the composition may contain, as each component contained in the composition, 2 or more compounds that conform to the component. Also, unless otherwise noted, the content of each component in the composition refers to the total content of all compounds corresponding to the component.

In the present specification, unless otherwise stated, a wavy line portion or an asterisk (asterisk) in the structural formula indicates a bonding position with another structure.

Unless otherwise specified, the air pressure in the present invention was set to 101,325Pa (1 air pressure). Unless otherwise stated, the temperature in the present invention is set to 23 ℃.

In this specification, a combination of preferred embodiments is a more preferred embodiment.

(laminated body)

Laminate of the present invention

Comprises a substrate, an organic layer, a protective layer and a photosensitive layer in sequence,

the photosensitive layer contains a resin containing a repeating unit having an acid-decomposable group represented by the following formula (A1),

The content of the repeating unit having a polar group contained in the resin is less than 10% by mass relative to the total mass of the resin,

the photosensitive layer is used for development by using a developing solution,

the protective layer is removed by using a stripping solution.

[ chemical formula 3]

In the formula (A1), R¹、R²And R³Each independently represents a hydrocarbon group, a cyclic aliphatic group or an aromatic ring group, R¹、R²And R³Each formed from a carbon atom C¹、C²And C³Bonded to the carbon atom C in the formula (A1)¹、C²And C³With 0 or 1 primary carbon atom, R¹、R²And R³At least 2 of the groups may be bonded to form a ring structure, representing a bonding site with other structures.

According to the laminate of the present invention, even when heating is performed after exposure at a low temperature, the pattern shape of the pattern of the photosensitive layer after development is excellent. The reason why the above-described effects can be obtained is presumed as follows.

The laminate of the present invention contains a resin having an acid-decomposable group having a specific structure as a resin contained in the photosensitive layer. It is considered that since the acid-decomposable group having the above-mentioned specific structure is easily released even when heated after exposure at low temperature, the solubility contrast of the resin with respect to the developer is easily improved in the presence of an acid at the exposed portion or the like.

And the content of the repeating unit having a polar group contained in the resin is less than 10% by mass with respect to the total mass of the resin. Therefore, it is considered that the mobility of the resin in the film is likely to be increased, and the acid-decomposable group in the exposed portion is likely to be detached.

As described above, even when heating is performed after exposure at a low temperature, a difference in solubility with respect to a developer is likely to occur in an exposed portion and an unexposed portion, and dissolution of the exposed portion by development is suppressed, so that it is considered that pattern collapse of a pattern of a photosensitive layer after development is suppressed.

Further, it is considered that the etching resistance is excellent because a structure with a small Ohnishi parameter can be applied.

Thus, it is considered that the laminate of the present invention suppresses pattern collapse of the developed photosensitive layer pattern and has excellent pattern transferability.

Among them, patent document 1 does not describe or suggest the use of a resin having the above-mentioned specific acid-decomposable group and having a content of a repeating unit having a polar group of less than 10% by mass based on the total mass of the resin.

The laminate of the present invention can be used for patterning of an organic layer included in the laminate.

Fig. 1 is a schematic cross-sectional view schematically showing a process of processing a laminate according to a preferred embodiment of the present invention. In one embodiment of the present invention, as in the example shown in fig. 1(a), an organic layer 3 (e.g., an organic semiconductor layer) is disposed on a substrate 4. Further, a protective layer 2 for protecting the organic layer 3 is disposed on the surface thereof so as to be in contact therewith. Another layer may be provided between the organic layer 3 and the protective layer 2, but from the viewpoint of more easily obtaining the effect of the present invention, a preferable embodiment is one in which the organic layer 3 and the protective layer 2 are in direct contact with each other. A photosensitive layer 1 is disposed on the protective layer. The photosensitive layer 1 and the protective layer 2 may be in direct contact with each other, or another layer may be provided between the photosensitive layer 1 and the protective layer 2.

Fig. 1(b) shows an example of a state where a part of the photosensitive layer 1 is exposed and developed. For example, the photosensitive layer 1 is partially exposed by a method such as using a predetermined mask, and the photosensitive layer 1 in the removal portion 5 is removed by development using a developer such as an organic solvent after exposure, thereby forming an exposed and developed photosensitive layer 1 a. At this time, since the protective layer 2 is not easily removed by the developer, the organic layer 3 remains and is protected from damage by the developer by the remaining protective layer 2.

Fig. 1(c) shows an example of a state where the protective layer 2 and a part of the organic layer 3 are removed. For example, the protective layer 2 and the organic layer 3 in the removal portion 5 where the developed photosensitive layer (resist) 1a does not exist are removed by dry etching or the like, and the removal portion 5a is formed in the protective layer 2 and the organic layer 3. The organic layer 3 can be removed in the removal portion 5a in this manner. That is, patterning of the organic layer 3 can be performed.

Fig. 1(d) shows an example of a state where the photosensitive layer 1a and the protective layer 2 are removed after the patterning. For example, the photosensitive layer 1a and the protective layer 2 in the laminate in the state shown in fig. 1(c) are cleaned with a stripping liquid containing water, whereby the photosensitive layer 1a and the protective layer 2 on the organic layer 3a after processing are removed.

As described above, according to the preferred embodiment of the present invention, a desired pattern can be formed on the organic layer 3, and the photosensitive layer 1 serving as a resist and the protective layer 2 serving as a protective film can be removed. Details of these steps will be described later.

< substrate >

The laminate of the present invention comprises a substrate.

Examples of the substrate include substrates made of various materials such as silicon, quartz, ceramics, glass, polyester films such as polyethylene naphthalate (PEN) and polyethylene titanate (PET), and polyimide films, and any substrate can be selected depending on the application. For example, in the case of using the film for a flexible element, a base material formed of a flexible material can be used. The base material may be a composite base material formed of a plurality of materials or a laminated base material in which a plurality of materials are laminated.

The shape of the base material is not particularly limited as long as it is selected according to the application, and examples thereof include a plate-shaped base material (hereinafter, also referred to as "substrate".

< organic layer >

The laminate in the present invention comprises an organic layer.

Examples of the organic layer include an organic semiconductor layer and a resin layer.

In the laminate of the present invention, the organic layer may be contained above the substrate, and the substrate may be in contact with the organic layer, or another layer may be further contained between the organic layer and the substrate.

[ organic semiconductor layer ]

The organic semiconductor layer is an organic material (also referred to as an "organic semiconductor compound") including a property showing a semiconductor.

Organic semiconductor compound-

As in the case of a semiconductor made of an inorganic material, an organic semiconductor compound includes a p-type organic semiconductor compound that conducts holes as carriers and an n-type organic semiconductor compound that conducts electrons as carriers.

The ease of carrier flow in the organic semiconductor layer is represented by the carrier mobility μ. Generally, a high mobility is preferred, preferably 10, although it depends on the application ^-7cm²More preferably 10 or more,/Vs^-6cm²More preferably 10 or more/Vs^{- 5}cm²Over Vs. The mobility μ can be determined by a characteristic or a time of flight (TOF) method in manufacturing a Field Effect Transistor (FET) device.

As the P-type organic semiconductor compound that can be used in the organic semiconductor layer, any of organic semiconductor materials can be used as long as it shows a hole (hole) transport property, but P-type pi conjugated polymer compounds (for example, substituted and unsubstituted polythiophene (for example, poly (3-hexylthiophene) (P3HT, manufactured by Sigma-Aldrich co. llc)) polyselenophene, polypyrrole, polyparaphenylene vinylene, polythienylenevinylene, polyaniline and the like), condensed polycyclic compounds (for example, substituted and unsubstituted anthracene, tetracene, pentacene, anthracenedithiophene (anthradithiophene), hexabenzocoronene and the like), and tristriphenylamine compounds (for example, m-MTDATA (4,4 ', 4 ″ -tris [ (3-methylphenyl) anilino ] triphenylamine (4, 4', 4 "-Tris [ (3-methylphenyl) phenylamido ] triphenylamine), 2-TNATA (4,4 ', 4" -Tris [2-naphthyl (phenyl) amino ] triphenylamine (4, 4', 4 "-Tris [2-naphthyl (phenyl) amino ] triphenylamine)), NPD (N, N '-bis [ (1-naphthyl) -N, N' -Diphenyl ] -1,1 '-biphenyl) -4, 4' -diamine (N, N '-Di [ (1-naphthyl) -N, N' -Diphenyl ] -1,1 '-biphenyl) -4, 4' -diamine), TPD (N, N '-Diphenyl-N, N' -Di (m-tolylyl) benzidine (TM-tolylidine)), mCP (1,3-bis (9-carbazolyl) benzene (1,3-bis (9-carbazolyl)) benzene)), CBP (4,4 '-bis (9-carbazolyl) -2, 2' -biphenyl (4,4 '-bis (9-carbazolyl) -2, 2' -biphenol)), etc.), hetero 5-membered ring compounds (e.g., substituted and unsubstituted oligothiophene, TTF (Tetrathiafulvalene), etc.), phthalocyanine compounds (substituted and unsubstituted phthalocyanine of various central metals, naphthalocyanine, anthraphthalocyanine, tetrapyrazino-tetraazaporphyrin), porphyrin compounds (substituted and unsubstituted porphyrins of various central metals), carbon nanotubes in which a semiconductor polymer is modified, any of graphenes, more preferably p-type pi-conjugated polymer compounds, and the like, Any of the condensed polycyclic compound, triarylamine compound, hetero 5-membered ring compound, phthalocyanine compound, and porphyrin compound is preferably a p-type pi conjugated polymer compound.

The n-type semiconductor compound that can be used in the organic semiconductor layer is not particularly limited as long as it has an electron-transporting property, the organic semiconductor material may be any of organic semiconductor materials, and is preferably a fullerene compound, electron deficient phthalocyanine compound, naphthalene tetracarbonyl compound, perylene tetracarbonyl compound, TCNQ compound (tetracyanoterephthalquinodimethane compound), hexaazatriphenylene compound, polythiophene compound, benzidine compound, carbazole compound, phenanthroline compound, perylene compound, quinazolinol ligand aluminum compound, pyridylbenzene ligand iridium compound, n-type pi conjugated polymer compound, more preferably a fullerene compound, electron deficient phthalocyanine compound, naphthalene tetracarbonyl compound, perylene tetracarbonyl compound, n-type pi conjugated polymer compound, and particularly preferably a fullerene compound or n-type pi conjugated polymer compound. In the present invention, the fullerene compound refers to substituted and unsubstituted fullerenes, and the fullerene may be C₆₀、C₇₀、C₇₆、C₇₈、C₈₀、C₈₂、C₈₄、C₈₆、C₈₈、C₉₀、C₉₆、C₁₁₆、C₁₈₀、C₂₄₀、C₅₄₀Any of fullerene and the like, but preferably substituted and unsubstituted C₆₀、C₇₀、C₈₆Fullerene, particularly preferably PCBM([6,6]-phenyl-C₆₁Methyl butyrate, manufactured by Sigma-Aldrich co.llc, etc.) and analogs thereof (C ₆₀Partial substitution with C₇₀、C₈₆And the like, compounds obtained by substituting a benzene ring of a substituent with another aromatic ring or heterocyclic ring, and compounds obtained by substituting a methyl ester with n-butyl ester, isobutyl ester, and the like).

The electron-deficient phthalocyanine compound is phthalocyanine (F) in which 4 or more electron-withdrawing groups are bonded to each central metal₁₆MPc, FPc-S8, etc., wherein M represents a central metal, Pc represents phthalo cyan, S8 represents (n-octylsulfonyl)), naphthalocyanine, anthracyanine, substituted and unsubstituted tetrapyrazino-porphyrazine (tetrapyrazino porphyrazine), etc. The naphthalenetetracarbonyl compound may be any compound, but is preferably naphthalenetetracarboxylic dianhydride (NTCDA), a naphthalenediimide compound (NTCDI), a perinone Pigment (Pigment Orange)43, Pigment Red (Pigment Red)194, or the like).

The perylene tetracarbonyl compound may be any compound, but is preferably perylene tetracarboxylic anhydride (PTCDA), perylene bisimide compound (PTCDI), or benzimidazole condensed compound (PV).

The TCNQ compound refers to substituted or unsubstituted TCNQ and compounds obtained by substituting the benzene ring portion of TCNQ with another aromatic ring or heterocyclic ring, and examples thereof include TCNQ, TCNAQ (tetracyanoquinodimethane), TCN3T (2,2 ' - ((2E,2 ' E) -3 ', 4 ' -Alkyl substituted-5H, 5 ' H- [2,2 ': 5 ', 2 ' -trithiophene ] -5,5 ' -diimine) dipropylenedinitrile derivatives (2,2 ' - ((2E,2 ' E) -3 ', 4 ' -Alkyl sulfonated-5H, 5 ' H- [2,2 ': 5 ', 2 ' -terthiophene ] -5, 5-diylidine) diamononitrile derivatives). Graphene may also be mentioned.

The hexaazatriphenylene compound is a compound having a 1,4,5,8,9, 12-hexaazatriphenylene skeleton, and preferably includes 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN).

The polythiophene-based compound is a compound having a polythiophene structure such as poly (3, 4-ethylenedioxythiophene), and examples thereof include PEDOT: PSS (a complex of poly (3, 4-ethylenedioxythiophene) (PEDOT) and polystyrenesulfonic acid (PSS)), and the like.

The benzidine-based compound is a compound having a benzidine structure in the molecule, and examples thereof include N, N '-bis (3-methylphenyl) -N, N' -diphenylbenzidine (TPD), N '-bis- [ (1-naphthyl) -N, N' -diphenyl ] -1,1 '-biphenyl) -4, 4' -diamine (NPD), and the like.

The carbazole-based compound is a compound having a carbazole ring structure in a molecule, and examples thereof include 4,4 '-bis (N-carbazolyl) -1, 1' -biphenyl (CBP).

The phenanthroline-based compound is a compound having a phenanthroline (phenanthroline) ring structure in the molecule, and examples thereof include 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP).

The pyridylphenyl ligand iridium-based compound is a compound having an iridium complex structure in which a phenylpyridine structure is used as a ligand, and examples thereof include bis (3, 5-difluoro-2- (2-pyridylphenyl- (2-carboxypyridyl) iridium (III) (FIrpic), tris (2-phenylpyridyl) iridium (III) (Ir (ppy) ₃) And the like.

The "quinalditol ligand aluminum-based compound" refers to a compound having an aluminum complex structure in which a quinalditol structure is used as a ligand, and examples thereof include tris (8-hydroxyquinoline) aluminum.

Hereinafter, a particularly preferable example of the n-type organic semiconductor compound is shown by a structural formula.

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

[ chemical formula 4]

[ chemical formula 5]

The number of the organic semiconductor compounds contained in the organic semiconductor layer may be 1, or 2 or more.

The content of the organic semiconductor compound is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, based on the total mass of the organic semiconductor layer.

Binder resin-

The organic semiconductor layer may further contain a binder resin.

Examples of the binder resin include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethacrylate, cellulose, polyethylene, and polypropylene, copolymers thereof, photoconductive polymers such as polyvinylcarbazole and polysilane, and conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyparaphenylene vinylene.

The organic semiconductor layer may contain only 1 binder resin, or may contain 2 or more species. In view of the mechanical strength of the organic semiconductor layer, a binder resin having a high glass transition temperature is preferable, and in view of the charge mobility, a binder resin composed of a photoconductive polymer or a conductive polymer having a structure without a polar group is preferable.

When the organic semiconductor layer contains a binder resin, the content of the binder resin is preferably 0.1 to 30% by mass based on the total mass of the organic semiconductor layer.

Film thickness-

The thickness of the organic semiconductor layer is not particularly limited, and varies depending on the type of the device to be finally manufactured, but is preferably 5nm to 50 μm, more preferably 10nm to 5 μm, and still more preferably 20nm to 500 nm.

Composition for forming organic semiconductor layer

The organic semiconductor layer is formed using, for example, a composition for forming an organic semiconductor layer containing a solvent and an organic semiconductor compound.

As an example of the forming method, a method of applying a composition for forming an organic semiconductor layer in a layered form to a substrate and forming a film by drying is given. As an application method, for example, a description can be given of an application method of a composition for forming a protective layer in a protective layer described later.

Examples of the solvent contained in the composition for forming an organic semiconductor layer include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, and 1-methylnaphthalene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene and chlorotoluene; ester-based solvents such as ethyl acetate, butyl acetate, and amyl acetate; alcohol solvents such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellulose solvent, ethyl cellulose solvent, and ethylene glycol; ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, and anisole; polar solvents such as N, N-dimethylformamide, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, and dimethyl sulfoxide. These solvents may be used in only 1 kind, or 2 or more kinds.

The content of the organic semiconductor compound is preferably 0.1 to 80% by mass, more preferably 0.1 to 30% by mass, based on the total mass of the composition for forming an organic semiconductor layer. The content of the organic semiconductor may be appropriately set according to the thickness of the organic semiconductor layer to be formed, and the like.

The composition for forming an organic semiconductor layer may further contain the binder resin.

The binder resin may be dissolved or may be dispersed in a solvent contained in the composition for forming an organic semiconductor layer.

When the composition for forming an organic semiconductor layer contains a binder resin, the content of the binder resin is preferably 0.1 to 30% by mass based on the total solid content of the composition for forming an organic semiconductor layer.

The composition for forming an organic semiconductor layer may contain a semiconductor material other than the organic semiconductor compound, and may further contain other additives. By using the composition for forming an organic semiconductor layer containing the above-mentioned other semiconductor material or the above-mentioned other additive, a blend film containing the other semiconductor material or the other additive can be formed.

For example, in the case of producing a photoelectric conversion layer, a composition for forming an organic semiconductor layer, which further contains another semiconductor material, or the like can be used.

In addition, during film formation, the substrate may be heated or cooled, and the film quality of the organic semiconductor layer or the deposition of molecules in the film may be controlled by changing the temperature of the substrate. The temperature of the substrate is not particularly limited, but is preferably-200 to 400 ℃, more preferably-100 to 300 ℃, and still more preferably 0 to 200 ℃.

The characteristics of the formed organic semiconductor layer can be adjusted by post-treatment. For example, it is also conceivable that desired characteristics or the like are obtained by changing the film form or the deposition of molecules in the film by performing heat treatment, treatment of exposure to a vaporized solvent, or the like on the formed organic semiconductor layer. The carrier density in the film can be adjusted by exposing the formed organic semiconductor layer to a substance such as an oxidizing or reducing gas or solvent, or by mixing these substances to cause an oxidation or reduction reaction.

[ resin layer ]

The resin layer is an organic layer other than the above-described organic semiconductor layer and is a layer containing a resin.

The resin contained in the resin layer is not particularly limited, and examples thereof include (meth) acrylic resins, olefin thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenyl resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, polyurethane resins, polyurea resins, and the like.

Among these, (meth) acrylic resins are preferable from the viewpoint of easily obtaining the effects of the present invention.

The resin contained in the resin layer is preferably a water-insoluble resin, more preferably a resin having a dissolution amount of 0.1g or less with respect to 100g of water at 25 ℃, and still more preferably a resin having a dissolution amount of 0.01g or less.

The resin layer may contain known additives such as a colorant, a dispersant, and a refractive index adjuster in addition to the resin. The kind and content of these additives may be appropriately designed according to the intended use with reference to known techniques.

Examples of the applications of the resin layer include a coloring layer such as a color filter, a high refractive index layer such as a refractive index adjusting layer, a low refractive index layer, and an insulating layer for wiring.

Film thickness-

The thickness of the resin layer is not particularly limited, and varies depending on the type of the device to be finally produced, the type of the organic layer itself, and the like, but is preferably 5nm to 50 μm, more preferably 10nm to 5 μm, and still more preferably 20nm to 500 nm.

Composition for forming resin layer

The resin layer is formed using, for example, a resin layer-forming composition containing a resin and a solvent. As an example of the forming method, a method of applying a resin layer forming composition in a layer form to a substrate and drying the composition to form a film can be given. As an application method, for example, a description can be given of an application method of a composition for forming a protective layer in a protective layer described later.

The resin layer may be formed using a resin layer-forming composition containing a raw material of a resin. For example, there is a method of forming a film by applying a resin layer-forming composition containing a resin as a precursor of the resin as a raw material of the resin, or a resin layer-forming composition containing a polymerizable compound (compound having a polymerizable group) constituting a monomer unit in the resin, a polymerization initiator (as necessary), and the like, in a layer form, to a substrate, and drying and curing the composition. As an application method, for example, a description can be given of an application method of a composition for forming a protective layer in a protective layer described later. As the curing method, a known method such as heating or exposure may be used depending on the type of the precursor of the resin, the type of the polymerization initiator, and the like.

< protective layer >

The protective layer preferably has a dissolution amount in a developer of 10nm/s or less at 23 ℃, more preferably 1nm/s or less. The lower limit of the amount of the above-mentioned solvent is not particularly limited, and may be 0nm/s or more.

Also, it is preferable that the protective layer contains a water-soluble resin.

The water-soluble resin is a resin in which 1g or more, preferably 5g or more, more preferably 10g or more, and still more preferably 30g or more is dissolved in 100g of water at 23 ℃. Although there is no upper limit, it is actually 100 g.

In the present invention, an alcohol-soluble resin can also be used as the water-soluble resin. The alcohol-soluble resin may be polyvinyl acetal. As the alcohol that can be used as the solvent, an alcohol that is generally used may be selected, and for example, isopropyl alcohol may be mentioned. The alcohol-soluble resin is a resin having a solubility of 1g or more, preferably 10g or more, and more preferably 20g or more, to 100g of an alcohol (for example) at 23 ℃. Although there is no upper limit, it is actually 30g or less. In addition, in the present invention, the alcohol-soluble resin is defined as being contained in the water-soluble resin, unless otherwise specified.

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

Specific examples of the water-soluble resin include polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), water-soluble polysaccharides (water-soluble celluloses (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, and the like), pullulan or pullulan derivatives, starch, hydroxypropyl starch, carboxymethyl starch, chitosan, cyclodextrin), polyethylene oxide, and polyethylene oxazoline. Further, 2 or more species selected from them may be used, and may be used as a copolymer.

In the protective layer of the present invention, it is preferable that at least 1 kind selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, water-soluble polysaccharides, polytriglucose, and polytriglucose derivatives is contained in these resins.

Specifically, in the present invention, the water-soluble resin contained in the protective layer is preferably a resin containing a repeating unit represented by any one of the formulae (P1-1) to (P4-1).

[ chemical formula 6]

In the formulae (P1-1) to (P4-1), R^P1Represents a hydrogen atom or a methyl group, R^P2Represents a hydrogen atom or a methyl group, R^P3Is represented by (CH)₂CH₂O)_maH、CH₂COONa or a hydrogen atom, and ma represents an integer of 1 to 2.

[ resin comprising a repeating unit represented by the formula (P1-1) ]

In the formula (P1-1), R^P1Preferably a hydrogen atom.

The resin comprising the repeating unit represented by formula (P1-1) may further comprise a repeating unit different from the repeating unit represented by formula (P1-1).

The resin containing the repeating unit represented by the formula (P1-1) preferably contains the repeating unit represented by the formula (P1-1) in an amount of 65 to 90% by mass, more preferably 70 to 88% by mass, based on the total mass of the resin.

Examples of the resin containing a repeating unit represented by the formula (P1-1) include resins containing 2 repeating units represented by the following formula (P1-2).

[ chemical formula 7]

Formula (P1-2)) In, R^P11Each independently represents a hydrogen atom or a methyl group, R^P12Each represents a substituent, and np1 and np2 represent the proportion of the structure in the molecule on a mass basis.

In the formula (P1-2), R^P11And R in the formula (P1-1)^P1The same meaning, and the same preferred mode.

In the formula (P1-2), as R^P12May include-L^P-T^PThe group shown. L is^PIs a single bond or a linking group L described later. T is^PExamples of the substituent include a substituent T described later. Wherein, as R^P12The hydrocarbon group is preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms), or the like. These alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and aralkyl groups may have the groups specified for the substituent T within the range in which the effects of the present invention are exhibited.

In the formula (P1-2), np1 and np2 represent the constituent ratio in the molecule on a mass basis, and are each independently 10 mass% or more and less than 100 mass%. Wherein np1+ np2 is not more than 100% by mass. When np1+ np2 is less than 100% by mass, it means a copolymer containing other repeating units.

[ resin comprising a repeating unit represented by the formula (P2-1) ]

In the formula (P2-1), R^P2Preferably a hydrogen atom.

The resin comprising the repeating unit represented by formula (P2-1) may further comprise a repeating unit different from the repeating unit represented by formula (P2-1).

The resin containing the repeating unit represented by the formula (P2-1) preferably contains the repeating unit represented by the formula (P2-1) in an amount of 50 to 98% by mass, more preferably 70 to 98% by mass, based on the total mass of the resin.

Examples of the resin containing a repeating unit represented by the formula (P2-1) include resins containing 2 repeating units represented by the following formula (P2-2).

[ chemical formula 8]

In the formula (P2-2), R^P21Each independently represents a hydrogen atom or a methyl group, R^P22And mp1 and mp2 represent the ratio of components in the molecule on a mass basis.

In the formula (P2-2), R^P21And R in the formula (P2-1)^P2The same meaning, and the same preferred mode.

In the formula (P2-2), as R^P22May include-L^P-T^PThe group shown. L is^PIs a single bond or a linking group L described later. T is^PExamples of the substituent include a substituent T described later. Wherein, as R^P22The hydrocarbon group is preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms) or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms). These alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and aralkyl groups may have the groups specified for the substituent T within the range in which the effects of the present invention are exhibited.

In the formula (P2-2), mp1 and mp2 represent the constituent ratios in the molecule on a mass basis, and are each independently 10 mass% or more and less than 100 mass%. Wherein mp1+ mp2 is not more than 100% by mass. In the case where mp1+ mp2 is less than 100% by mass, it means a copolymer containing other repeating units.

[ resin comprising a repeating unit represented by the formula (P3-1) ]

In the formula (P3-1)，R^P3Preferably a hydrogen atom.

The resin comprising the repeating unit represented by formula (P3-1) may further comprise a repeating unit different from the repeating unit represented by formula (P3-1).

The resin containing the repeating unit represented by the formula (P3-1) preferably contains the repeating unit represented by the formula (P3-1) in an amount of 10 to 90% by mass, more preferably 30 to 80% by mass, based on the total mass of the resin.

The hydroxyl group represented by the formula (P3-1) may be appropriately substituted with a substituent T or a combination of the substituent T and a linking group L. When a plurality of substituents T are present, they may be bonded to each other or to the ring in formula (iv) via a linking group L or not via the linking group L to form a ring.

[ resin comprising a repeating unit represented by the formula (P4-1) ]

The resin comprising the repeating unit represented by formula (P4-1) may further comprise a repeating unit different from the repeating unit represented by formula (P4-1).

The resin containing the repeating unit represented by the formula (P4-1) preferably contains the repeating unit represented by the formula (P4-1) in an amount of 8 to 95% by mass, more preferably 20 to 88% by mass, based on the total mass of the resin.

The hydroxyl group represented by the formula (P4-1) may be appropriately substituted with a substituent T or a combination of the substituent T and a linking group L. When a plurality of substituents T are present, they may be bonded to each other or to the ring in formula (iv) via a linking group L or not via the linking group L to form a ring.

Examples of the substituent T include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms), an aralkyl group (preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms, further preferably 7 to 11 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, further preferably 2 to 6 carbon atoms), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), a hydroxyl group, an amino group (preferably having 0 to 24 carbon atoms, more preferably 0 to 12 carbon atoms, further preferably 0 to 6 carbon atoms), a thiol group, a carboxyl group, and an aryl group (preferably having 6 carbon atoms)22, more preferably 6 to 18, further preferably 6 to 10), an alkoxy group (preferably having 1 to 12, more preferably 1 to 6, further preferably 1 to 3 carbon atoms), an aryloxy group (preferably having 6 to 22, more preferably 6 to 18, further preferably 6 to 10 carbon atoms), an acyl group (preferably having 2 to 12, more preferably 2 to 6, further preferably 2 to 3 carbon atoms), an acyloxy group (preferably having 2 to 12, more preferably 2 to 6, further preferably 2 to 3 carbon atoms), an aroyl group (preferably having 7 to 23, more preferably 7 to 19, further preferably 7 to 11 carbon atoms), an aroyloxy group (preferably having 7 to 23, more preferably 7 to 19, further preferably 7 to 11 carbon atoms), a carbamoyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, further preferably 1 to 3 carbon atoms), a pharmaceutically acceptable salt thereof, a pharmaceutically acceptable carrier, or a pharmaceutically acceptable carrier, An aminosulfonyl group (preferably having 0 to 12 carbon atoms, more preferably 0 to 6 carbon atoms, further preferably 0 to 3 carbon atoms), a sulfo group, an alkylsulfonyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), an arylsulfonyl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), a heterocyclic group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 2 to 5 carbon atoms, preferably a 5-or 6-membered ring), (meth) acryloyl group, (meth) acryloyloxy group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an oxo group (═ O), an imino group (═ NR { (O) ^N) Alkylene (═ C (R)^N)₂) And the like. R^NPreferably a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), a hydrogen atom, a methyl group, an ethyl group or a propyl group. The alkyl moiety, alkenyl moiety and alkynyl moiety included in each substituent may be linear, cyclic, linear or branched. When the substituent T is a group which may have a substituent, the substituent T may be further included. For example, the alkyl group may be a halogenated alkyl group, or may be a (meth) acryloyloxyalkyl group, an aminoalkyl group, or a carboxyalkyl group. When the substituent is a group capable of forming a salt, such as a carboxyl group or an amino group, the group may form a salt.

The linking group L is an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms), and further preferably a cyclic alkylene groupPreferably 1 to 6), an alkenylene group (preferably having 2 to 12, more preferably 2 to 6, further preferably 2 to 3 carbon atoms), an alkynylene group (preferably having 2 to 12, more preferably 2 to 6, further preferably 2 to 3 carbon atoms), and an (oligo) alkyleneoxy group (the alkylene group in 1 repeating unit preferably has 1 to 12, more preferably 1 to 6, further preferably 1 to 3 carbon atoms); the number of the repeating units is preferably 1 to 50, more preferably 1 to 40, further preferably 1 to 30), an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a thiocarbonyl group, or-NR ^N-and combinations of these. The alkylene group may have a substituent T. For example, the alkylene group may have a hydroxyl group. The number of atoms contained in the linking group L is preferably 1 to 50, more preferably 1 to 40, and still more preferably 1 to 30 in addition to a hydrogen atom. The number of connecting atoms is the number of atoms located on the shortest path among the groups related to the connection. For example, if it is-CH₂- (C ═ O) -O-, then the atoms involved in the linkage are 6, even if apart from hydrogen atoms, 4. On the other hand, the shortest atom associated with the linkage is-C-O-, and is 3. The number of the linking atoms is preferably 1 to 24, more preferably 1 to 12, and still more preferably 1 to 6. The alkylene group, alkenylene group, alkynylene group, and (oligo) alkyleneoxy group may be linear, cyclic, linear, or branched. In the linking group being-NR^N-and the like, which can form a salt, the group can form a salt.

Examples of the water-soluble resin include polyethylene oxide, hydroxyethyl cellulose, carboxymethyl cellulose, water-soluble methylolmelamine, polyacrylamide, phenol resin, and styrene/maleic acid half ester.

Further, as the water-soluble resin, commercially available products can be used, and examples thereof include Pitzkol series (K-30, K-50, K-90, V-7154, etc.) manufactured by DKS Co. Ltd., LUVITEC series (VA64P, VA6535P, etc.) manufactured by BASF Corporation, JAPAN VAM & POVAL CO., PXP-05, JL-05E, JP-03, JP-04, AMPS (2-acrylamide-2-methylpropanesulfonic acid copolymer), Nanoclay manufactured by Aldrich, and the like.

Among these, Pitzkol K-90, PXP-05 or Pitzkol V-7154 is preferably used, and Pitzkol V-7154 is more preferably used.

As the water-soluble resin, the resin described in international publication No. 2016/175220 is cited and incorporated in the present specification.

The weight average molecular weight of the water-soluble resin is preferably 50,000 to 400,000 in the case of polyvinylpyrrolidone, preferably 15,000 to 100,000 in the case of polyvinyl alcohol, and preferably in the range of 10,000 to 300,000 in the case of other resins.

The molecular weight dispersion (weight average molecular weight/number average molecular weight, also simply referred to as "dispersion") of the water-soluble resin used in the present invention is preferably 1.0 to 5.0, and more preferably 2.0 to 4.0.

The content of the water-soluble resin in the protective layer may be appropriately adjusted as needed, but is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less in the solid content. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 4% by mass or more.

The protective layer may contain only 1 kind of water-soluble resin, or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably within the above range.

[ surfactant containing ethynyl group ]

From the viewpoint of suppressing generation of residue, the protective layer preferably contains a surfactant containing an ethynyl group.

The number of ethynyl groups in the molecule of the ethynyl group-containing surfactant is not particularly limited, and is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and further preferably 1 to 2.

The molecular weight of the surfactant containing an ethynyl group is preferably relatively small, preferably 2,000 or less, more preferably 1,500 or less, and further preferably 1,000 or less. The lower limit is not particularly limited, and is preferably 200 or more.

A compound represented by the formula (9)

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

[ chemical formula 9]

R⁹¹-C≡C-R⁹² (9)

In the formula, R⁹¹And R⁹²Each independently an alkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, or an aromatic heterocyclic group having 4 to 15 carbon atoms. The number of carbon atoms of the aromatic heterocyclic group is preferably 1 to 12, more preferably 2 to 6, and further preferably 2 to 4. The aromatic heterocycle is preferably a 5-or 6-membered ring. The hetero atom contained in the aromatic heterocyclic ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom.

R⁹¹And R⁹²Each of the substituents may independently have a substituent, and examples of the substituent include the substituent T.

A compound represented by the formula (91)

The compound represented by formula (9) is preferably a compound represented by formula (91) below.

[ chemical formula 10]

R⁹³～R⁹⁶Each independently a hydrocarbon group having 1 to 24 carbon atoms, n9 is an integer of 1 to 6, m9 is an integer 2 times n9, n10 is an integer of 1 to 6, m10 is an integer 2 times n10, and l9 and l10 are each independently a number of 0 or more and 12 or less.

R⁹³～R⁹⁶The alkyl group is preferably an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an alkynyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms). Alkyl, alkenyl,The alkynyl group may be linear, cyclic, linear or branched. Within the range in which the effects of the present invention are exhibited, R ⁹³～R⁹⁶May have a substituent T. And, R⁹³～R⁹⁶The groups may be bonded to each other or may form a ring via the above-mentioned linking group L. When a plurality of substituents T are present, they may be bonded to each other or to the hydrocarbon group in the formula via the following linker L or without the linker L to form a ring.

R⁹³And R⁹⁴Preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms). Among them, methyl is preferable.

R⁹⁵And R⁹⁶Preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 3 to 6 carbon atoms). Among them, - (C) is preferred_n11R⁹⁸ _m11)-R⁹⁷。R⁹⁵、R⁹⁶Isobutyl is particularly preferred.

n11 is an integer of 1 to 6, preferably an integer of 1 to 3. m11 is a number 2 times that of n 11.

R⁹⁷And R⁹⁸Preferably, each independently represents a hydrogen atom or an alkyl group (preferably, a carbon number of 1 to 12, more preferably 1 to 6, further preferably 1 to 3).

n9 is an integer of 1 to 6, preferably an integer of 1 to 3. m9 is an integer 2 times n 9.

n10 is an integer of 1 to 6, preferably an integer of 1 to 3. m10 is an integer 2 times n 10.

l9 and l10 are each independently a number of 0 to 12. Of these, l9+ l10 is preferably a number of 0 to 12, more preferably a number of 0 to 8, further preferably a number of 0 to 6, further preferably a number exceeding 0 and less than 6, and further preferably a number exceeding 0 and 3 or less. In addition, in l9 and l10, the compound of formula (91) may be a mixture of compounds having different numbers, and in this case, the numbers of l9 and l10, or l9+ l10 may be numbers including decimal points or less.

A compound represented by the formula (92)

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

[ chemical formula 11]

R⁹³、R⁹⁴、R⁹⁷～R¹⁰⁰Each independently a hydrocarbon group having 1 to 24 carbon atoms, and l11 and l12 each independently a number of 0 to 12 inclusive.

R⁹³、R⁹⁴、R⁹⁷～R¹⁰⁰Of these, preferred are an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms). The alkyl group, alkenyl group and alkynyl group may be linear, cyclic, linear or branched. Within the range in which the effects of the present invention are exhibited, R⁹³、R⁹⁴、R⁹⁷～R¹⁰⁰May have a substituent T. And, R⁹³、R⁹⁴、R⁹⁷～R¹⁰⁰May be bonded to each other or form a ring via a linking group L. The substituent T may be bonded to each other when plural, or bonded to the hydrocarbon group in the formula via the linking group L or not via the linking group L to form a ring.

R⁹³、R⁹⁴、R⁹⁷～R¹⁰⁰The alkyl groups are preferably each independently an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms). Among them, methyl is preferable.

l11+ l12 is preferably a number of 0 to 12, more preferably a number of 0 to 8, further preferably a number of 0 to 6, further preferably a number exceeding 0 and less than 6, further preferably a number exceeding 0 and 5 or less, further preferably a number exceeding 0 and 4 or less, may be a number exceeding 0 and 3 or less, or may be a number exceeding 0 and 1 or less. In addition, in l11 and l12, the compound of formula (92) may be a mixture of compounds having different numbers, and in this case, the numbers of l11 and l12, or l11+ l12 may be numbers including decimal points or less.

Examples of the surfactant containing an ethynyl group include sanonol (Surfynol)104 series (product name, Nissin Chemical Industry co., Ltd.), acetorenol E00, acetorenol E40, acetorenol E13T, and acetorenol 60 (both product names, manufactured by Kawaken Fine Chemicals co., Ltd.), among which sanonol 104 series, acetorenol E00, acetorenol E40, and acetorenol E13T are preferable, and acetorenol E40 and acetorenol E13T are more preferable. In addition, the safranol 104 series and Acetylenol E00 are surfactants with the same structure.

[ other surfactants ]

The protective layer may contain a surfactant other than the above-mentioned surfactant containing an ethynyl group in order to improve the coatability and the like of the composition for forming a protective layer described later.

The other surfactant may be any of nonionic, anionic, amphoteric fluorine-based, and the like, as long as it lowers the surface tension.

Examples of the other surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether and polyoxyethylene stearyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan oleate, sorbitan trioleate, and monoglycerides such as glycerin monostearate and glycerin monooleate, and oligomers containing fluorine or silicon; anionic surfactants such as alkylbenzenesulfonate salts such as sodium dodecylbenzenesulfonate, alkylnaphthalenesulfonate salts such as sodium butylnaphthalenesulfonate, sodium pentylnaphthalenesulfonate, sodium hexylnaphthalenesulfonate and sodium octylnaphthalenesulfonate, alkylsulfonate salts such as sodium lauryl sulfate, alkylsulfonate salts such as sodium dodecylbenzenesulfonate, and sulfosuccinate salts such as sodium dilaurylsulfosuccinate; alkyl betaines such as lauryl betaine and stearyl betaine, and amphoteric surfactants such as amino acids.

When the protective layer contains the surfactant containing an ethynyl group and the other surfactant, the amount of the surfactant added is preferably 0.05 to 20% by mass, more preferably 0.07 to 15% by mass, and still more preferably 0.1 to 10% by mass, based on the total amount of the surfactant containing an ethynyl group and the other surfactant, relative to the total mass of the protective layer. These surfactants may be used in 1 kind or in plural kinds. In the case where a plurality of kinds are used, the total amount thereof is within the above range.

In the present invention, the surfactant may be substantially free of other surfactants. The term "substantially free" means that the content of the other surfactant is 5% by mass or less, preferably 3% by mass or less, and more preferably 1% by mass or less of the content of the surfactant containing an ethynyl group.

The protective layer may contain both a surfactant containing an ethynyl group and another surfactant, or may contain only either one as a surfactant.

The content of the surfactant in the protective layer is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and still more preferably 0.1% by mass or more, based on the total mass of the protective layer. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. The surfactant may be used in 1 kind or in plural kinds. When a plurality of such compounds are used, the total amount thereof is preferably within the above range.

The surface tension of the surfactant in a 0.1 mass% aqueous solution at 23 ℃ is preferably 45mN/m or less, more preferably 40mN/m or less, and still more preferably 35mN/m or less. The lower limit is preferably 5mN/m or more, more preferably 10mN/m or more, and still more preferably 15mN/m or more. The surface tension of the surfactant may be appropriately selected depending on the kind of the selected surfactant.

[ antiseptic, antifungal agent (antiseptic, etc.) ]

It is also preferred that the protective layer contains a preservative or antifungal agent.

As the preservative/antifungal agent (hereinafter, preservative and the like), an additive containing an antibacterial or antifungal action, and preferably containing at least 1 selected from water-soluble or water-dispersible organic compounds. Examples of the additive having an antibacterial or antifungal effect such as a preservative include an organic antibacterial agent or antifungal agent, an inorganic antibacterial agent or antifungal agent, and a natural antibacterial agent or antifungal agent. For example, as the antibacterial or antifungal agent, a product described in "antibacterial/antifungal technology" issued by Toray Research Center, inc.

In the present invention, by adding a preservative or the like to the protective layer, the effect of suppressing the increase in coating defects due to the growth of bacteria in the solution after long-term storage at room temperature can be more effectively exhibited.

Examples of the preservative include phenol ether compounds, imidazole compounds, sulfone compounds, N-haloalkylthio compounds, aniline compounds, pyrrole compounds, quaternary ammonium salts, arsine compounds, pyridine compounds, triazine compounds, benzisothiazoline compounds, isothiazoline compounds, and the like. Specific examples thereof include 2- (4-thiocyanomethyl) benzimidazole, 1, 2-benzothiazolone, 1, 2-benzisothiazolin-3-one, N-fluorodichloromethylthiophthalimide, 2,3,5, 6-tetrachloroisophthalonitrile, N-trichloromethylthio-4-cyclohexene-1, 2-dicarboximide, 8-quinolinedione, bis (tributyltin) oxide, 2- (4-thiazolyl) benzimidazole, methyl 2-benzimidazolecarboxylate, 10' -oxybisphenoxarsine, 2,3,5, 6-tetrachloro-4- (methylsulfonyl) pyridine, bis (2-pyridylthio-1-oxide) zinc, N-dimethyl-N ' - (fluorodichloromethylthio) -N ' -benzenesulfonamide Poly- (hexamethylene biguanide) hydrochloride, disulfide-2, 2' -bis-2-methyl-4, 5-trimethylene-4-isothiazolin-3-one, 2-bromo-2-nitro-1, 3-propanediol, hexahydro-1, 3-tris- (2-hydroxyethyl) -S-triazine, p-chloro-m-xylenol, 1, 2-benzisothiazolin-3-one, methylphenol, and the like.

As natural antibacterial or antifungal agents, chitosan, which is a basic polysaccharide obtained by hydrolyzing chitin contained in the shell of crabs and shrimps, is used. Preferably a product name of "Holon Killer Beads Celler" by Nikko, which is formed of an amino metal complexed with a metal on both sides of an amino acid.

The content of the preservative and the like in the protective layer is preferably 0.005 to 5% by mass, more preferably 0.01 to 3% by mass, even more preferably 0.05 to 2% by mass, and even more preferably 0.1 to 1% by mass, based on the total mass of the protective layer. The preservative may be used in 1 kind or in plural kinds. In the case where a plurality of kinds are used, the total amount thereof is within the above range.

The antibacterial effect of preservatives and the like can be evaluated in accordance with JIS Z2801 (antibacterial processed products — antibacterial test method and antibacterial effect). The antifungal effect can be evaluated in accordance with JIS Z2911 (mold resistance test).

[ opacifier ]

Preferably, the protective layer comprises a sunscreen agent. The incorporation of the light-shading agent further suppresses the influence of damage or the like to the organic layer or the like caused by light.

As the light-shading agent, for example, a known coloring agent or the like can be used, and organic or inorganic pigments or dyes can be mentioned, and inorganic pigments can be preferably mentioned, and among them, carbon black, titanium oxide, titanium nitride and the like can be more preferably mentioned.

The content of the light-shading agent is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and still more preferably 5 to 25% by mass, based on the total mass of the protective layer. The sunscreen agent may be used in 1 kind or in plural kinds. In the case where a plurality of kinds are used, the total amount thereof is within the above range.

[ thickness ]

The thickness of the protective layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1.0 μm or more, and still more preferably 2.0 μm or more. The upper limit of the thickness of the protective layer is preferably 10 μm or less, more preferably 5.0 μm or less, and still more preferably 3.0 μm or less.

[ stripping solution ]

The protective layer in the present invention provides for removal using a stripping solution.

The method for removing the protective layer using the stripping liquid will be described later.

Examples of the stripping liquid include water, a mixture of water and a water-soluble solvent, and water or a mixture of water and a water-soluble solvent is preferable.

The content of water is preferably 90 to 100% by mass, and more preferably 95 to 100% by mass, based on the total mass of the stripping liquid. The stripping liquid may be a stripping liquid composed of only water.

In the present specification, water, a mixture of water and a water-soluble solvent, and a water-soluble solvent may be collectively referred to as an aqueous solvent.

The water-soluble solvent is preferably an organic solvent having a solubility in water at 23 ℃ of 1g or more, more preferably 10g or more, and still more preferably 30g or more.

Examples of the water-soluble solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, and glycerol; ketone solvents such as acetone; amide solvents such as formamide.

Further, the stripping liquid may contain a surfactant in order to improve the removability of the protective layer.

As the surfactant, a known compound can be used, and a nonionic surfactant can be preferably used.

[ composition for Forming protective layer ]

The protective layer-forming composition of the present invention is a composition for forming a protective layer included in the laminate of the present invention.

In the laminate of the present invention, the protective layer can be formed, for example, by applying the protective layer forming composition to the organic layer and drying the composition.

The method of applying the composition for forming a protective layer is preferably coating. Examples of the application method include a slit coating method, a casting method, a blade coating method, a bar coating method, a spray coating method, a Dipping (Dipping) coating method, a liquid bead coating method, an air knife coating method, a curtain coating method, an ink jet method, a spin coating method, and a Langmuir-Blodgett (LB) method. More preferably, the casting method, the spin coating method and the ink jet method are used. By such a process, a protective layer having a smooth surface and a large area can be produced at low cost.

The protective layer-forming composition can also be formed by a method of transferring a coating film formed by applying a coating film to a dummy support in advance by the above-described application method or the like onto an application object (for example, an organic layer).

As for the transfer method, reference can be made to the descriptions of paragraphs 0023, 0036 to 0051 of Japanese patent application laid-open No. 2006 and 023696, paragraphs 0096 to 0108 of Japanese patent application laid-open No. 2006 and 047592, and the like.

The protective layer forming composition preferably contains the components contained in the protective layer (for example, a water-soluble resin, a surfactant containing an ethynyl group, another surfactant, a preservative, a light-screening agent, and the like) and a solvent.

The content of the component contained in the composition for forming a protective layer is preferably such that the content of each component with respect to the total mass of the protective layer is replaced with the content with respect to the amount of the solid component of the composition for forming a protective layer.

Examples of the solvent contained in the composition for forming a protective layer include the above-mentioned aqueous solvents, preferably water or a mixture of water and a water-soluble solvent, and more preferably water.

When the aqueous solvent is a mixed solvent, a mixed solvent of an organic solvent having a solubility in water at 23 ℃ of 1g or more and water is preferable. The solubility of the organic solvent in water at 23 ℃ is more preferably 10g or more, and still more preferably 30g or more.

The solid content concentration of the composition for forming a protective layer is preferably 0.5 to 30% by mass, more preferably 1.0 to 20% by mass, and still more preferably 2.0 to 14% by mass, from the viewpoint of facilitating application of the composition for forming a protective layer with a more nearly uniform thickness.

< photosensitive layer >

The laminate of the present invention contains a photosensitive layer.

The photosensitive layer in the present invention contains a resin (also referred to as a "specific resin") containing a repeating unit having an acid-decomposable group represented by the formula (a1), and the content of the repeating unit having a polar group contained in the resin is less than 10% by mass based on the total mass of the resin.

In the present invention, the photosensitive layer is a layer for development using a developer.

The development is preferably negative development.

In the laminate of the present invention, the photosensitive layer may be a negative photosensitive layer or a positive photosensitive layer.

The photosensitive layer is preferably a layer whose exposed portion is hardly soluble in a developer containing an organic solvent. Insoluble means that the exposed portion is not easily dissolved in the developer.

The dissolution rate of the photosensitive layer in the exposed portion to the developer is preferably lower (less soluble) than the dissolution rate of the photosensitive layer in the unexposed portion to the developer.

Specifically, the concentration of the active carbon is controlled at 50mJ/cm²The above irradiation dose exposes light with at least 1 wavelength of 365nm (i-ray), 248nm (KrF-ray) and 193nm (ArF-ray) to change polarity, and preferably has an sp value (solubility parameter) of less than 19.0(MPa)^1/2Becomes insoluble, and is more preferably 18.5(MPa)^1/2The following solvents are hardly soluble, and more preferably 18.0(MPa)^1/2The following solvents become insoluble.

In the present invention, the solubility parameter (sp value) is a value [ unit: (MPa)^1/2And (c) a temperature sensor. The Okitsu method is one of previously known methods for calculating an sp value, and is described in detail in, for example, Japan society for subsequent Engineers Vol.29, No.6 (1993) pages 249-259.

More preferably, the radiation having at least 1 wavelength selected from 365nm (i-ray), 248nm (KrF-ray) and 193nm (ArF-ray) is irradiated at 50-250 mJ/cm²The polarity is changed as described above by performing exposure with the irradiation amount of (2).

The photosensitive layer preferably has photosensitivity to irradiation of i-rays.

The photosensitivity means that the dissolution rate of the organic solvent (preferably butyl acetate) is changed by irradiation with at least one of actinic rays and radiation (i-ray irradiation when the i-ray irradiation has photosensitivity).

The specific resin contained in the photosensitive layer is preferably a resin whose dissolution rate of the developer is changed by the action of an acid.

With respect to the change in the dissolution rate in the specific resin, it is preferable that the dissolution rate is decreased.

The sp value of the specific resin before changing the dissolution rate was 18.0(MPa)^1/2The dissolution rate of the organic solvent is more preferably 40 nm/sec or more.

The sp value of the specific resin after changing the dissolution rate was 18.0(MPa)^1/2The dissolution rate of the organic solvent is more preferably less than 1 nm/sec.

And the specific resin has a sp value (solubility parameter) of 18.0(MPa) before the dissolution rate is changed^1/2The following organic solvents are soluble, and after the dissolution rate is changed, it is preferable that the sp value is 18.0(MPa)^1/2The following organic solvents are hardly soluble resins.

Here, the "sp-soluble value (solubility parameter) was 18.0(MPa)^1/2The organic solvent "means that a coating film (thickness: 1 μm) of a compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating the coating film at 100 ℃ for 1 minute has a dissolution rate of 20 nm/sec or more when immersed in a developer at 23 ℃ and has a" hard-to-dissolve sp value of 18.0(MPa)^1/2The organic solvent "means that the dissolution rate of a coating film (thickness of 1 μm) of a compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating at 100 ℃ for 1 minute to a developer at 23 ℃ is less than 10 nm/sec.

Examples of the photosensitive layer include a photosensitive layer containing a specific resin and a photoacid generator.

In addition, from the viewpoint of achieving both high storage stability and fine pattern formability, the photosensitive layer is preferably a chemically amplified photosensitive layer.

The details of each component contained in the photosensitive layer will be described below.

[ specific resin ]

The photosensitive layer in the present invention contains a specific resin.

The specific resin is preferably an acrylic polymer or a styrene polymer.

The "acrylic polymer" is an addition polymerization type resin, is a polymer containing a repeating unit derived from (meth) acrylic acid or an ester thereof, and may contain a repeating unit other than a repeating unit derived from (meth) acrylic acid or an ester thereof, for example, a repeating unit derived from a styrene or a repeating unit derived from a vinyl compound. In the acrylic polymer, the repeating unit derived from (meth) acrylic acid or an ester thereof is preferably contained in an amount of 50 mol% or more, more preferably 80 mol% or more, and particularly preferably a polymer composed only of repeating units derived from (meth) acrylic acid or an ester thereof, based on all repeating units in the polymer.

The "styrenic polymer" is an addition polymerization type resin, is a polymer containing a repeating unit derived from styrene or a styrene derivative, and may contain a repeating unit other than a repeating unit derived from styrene or a styrene derivative, for example, a repeating unit derived from (meth) acrylic acid or an ester thereof, a repeating unit derived from a vinyl compound, or the like. The styrenic polymer preferably contains 40 mol% or less, more preferably 30 mol% or less, of repeating units derived from styrene or a styrene derivative, relative to all repeating units in the polymer. The content is preferably 10 mol% or more.

Examples of the styrene derivative include substituted styrene derivatives such as α -methylstyrene, hydroxystyrene, and carboxystyrene, and styrene derivatives having an acid group such as hydroxystyrene and carboxystyrene, the acid group may be protected by an acid-decomposable group represented by formula (a 1).

A repeating unit having an acid-decomposable group represented by the formula (A1) -

The specific resin contains a repeating unit having an acid-decomposable group represented by the following formula (A1).

[ chemical formula 12]

In the formula (A1), R¹、R²And R³Each independently represents a hydrocarbon group, a cyclic aliphatic group or an aromatic ring group, R¹、R²And R³Each formed from a carbon atom C¹、C²And C³Bonded to the carbon atom C in the formula (A1)¹、C²And C³With 0 or 1 primary carbon atom, R¹、R²And R³At least 2 of the groups may be bonded to form a ring structure, representing a bonding site with other structures.

Specifically, R is as defined above¹To comprise the above-mentioned C¹The group of (A), the above R²To comprise the above-mentioned C²The group of (A), the above R³To comprise the above-mentioned C³The group of (A), C¹And the above-mentioned C²And the above-mentioned C³Are bonded to the carbon atom C in the formula (A1), respectively.

A primary carbon atom is a carbon atom having only 1 covalent bond with other carbon atoms. For example, carbon atom C ¹When it is a primary carbon atom, it represents a carbon atom C¹Having no covalent bond to carbon other than the covalent bond to carbon atom C in formula (A1), carbon atom C¹In the case where it is not a primary carbon atom, it represents a carbon atom C¹And a carbon other than carbon atom C in formula (A1).

In the formula (A1), R¹、R²And R³Each of the groups is preferably a saturated hydrocarbon group or an aromatic ring group, preferably an alkyl group or an aryl group, and more preferably an alkyl group having 3 to 10 carbon atoms or a phenyl group.

Examples of the alkyl group include an isopropyl group, an adamantyl group, a tert-butyl group, a tert-amyl group, a cyclohexyl group, a norbornyl group and the like.

In the present specification, when simply described as an alkyl group, the alkyl group includes a straight-chain alkyl group, a branched-chain alkyl group, a cyclic alkyl group, and a group in which 2 or more of these groups are bonded, unless otherwise specified.

In the formula (A1), R¹、R²And R³Each formed from a carbon atom C¹、C²And C³Bonded to the carbon atom C in the formula (A1)¹、C²And C³The number of the primary carbon atoms is 0 or 1, and is preferably 0 from the viewpoint of reducing activation energy for desorption, and is preferably 1 from the viewpoint of long-term stability at room temperature.

In the formula (A1), R¹、R²And R³At least 2 groups in the above groups may be bonded to form a ring structure, and examples of the ring structure to be formed include an aliphatic saturated hydrocarbon ring structure or an aromatic ring structure, preferably an aliphatic saturated hydrocarbon structure having 7 to 12 carbon atoms or a benzene ring structure, and more preferably an aliphatic saturated hydrocarbon ring structure having 7 to 12 carbon atoms.

In the formula (A1), R¹、R²And R³2 of which form a ring structure, and preferably 1 group is alkyl, R¹、R²And R³2 groups in (a) form a saturated hydrocarbon ring structure, and more preferably 1 group is a branched alkyl group, R¹、R²And R³Wherein 2 groups form a saturated hydrocarbon ring structure having 7 to 12 carbon atoms, and more preferably 1 group is a branched alkyl group having 3 to 10 carbon atoms, R¹、R²And R³2 groups in the (A) form a saturated hydrocarbon ring structure with 7-12 carbon atoms, and 1 group is particularly preferably isopropyl.

The acid-decomposable group preferably contains an aromatic ring structure from the viewpoint of ease of synthesis. The aromatic ring structure is preferably an aromatic ring structure having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and still more preferably a phenyl group. The aromatic ring structure is preferably an aromatic hydrocarbon ring structure.

The acid-decomposable group may have an aromatic ring structure¹、R²And R³Any one of them being an aromatic ring group and R¹、R²And R³2 groups of the above groups are bonded to form an aromatic ring structure.

The acid-decomposable group includes a monocyclic or aromatic ring structure having 7 or more rings, and R is preferably the same as R in view of lowering the activation energy for elimination ¹、R²And R³At least 1 of which is an isopropyl group, a monocyclic structure containing 7-to 12-membered rings, and more preferably the above R¹、R²And R³At least 1 of which is isopropyl. The monocyclic structure having 7 or more membered rings is a monocyclic structure having 7 or more ring members, and the monocyclic structure may form a condensed ring with another ring. The monocyclic structure having 7 or more membered rings is preferably a hydrocarbon ring structure, and more preferably a saturated hydrocarbon ring structure.

The acid-decomposable group may have a monocyclic or aromatic ring structure having 7 or more rings, and R may be¹、R²And R³Any one of them is a monocyclic structure or an aromatic ring structure of 7-or more-membered ring, and R¹、R²And R³Wherein 2 groups are bonded to form a 7-membered or higher monocyclic or aromatic ring structure.

The repeating unit is preferably a repeating unit in which an acid group is protected by an acid-decomposable group represented by the formula (a 1).

Examples of the acid group include a carboxyl group and a phenolic hydroxyl group, and a carboxyl group is preferable from the viewpoint of developability.

When the repeating unit is a repeating unit having a carboxyl group protected by an acid-decomposable group represented by formula (a1), the repeating unit preferably has a partial structure represented by formula (a2) below as a partial structure containing the acid-decomposable group represented by formula (a 1).

[ chemical formula 13]

In the formula (A2), R¹～R³Are respectively reacted with R in the formula (A1)¹～R³The same meaning of (a) indicates a bonding site with other structures.

The repeating unit having an acid group protected by an acid-decomposable group represented by formula (a1) is preferably a repeating unit represented by formula (R1).

[ chemical formula 14]

In the formula (R1), L¹Represents a single bond or a 2-valent linking group, R^R1Represents a hydrogen atom or a methyl group, R¹～R³Are respectively reacted with R in the formula (A1)¹～R³Have the same meaning.

In the formula (R1), L¹The linking group represents a single bond or a 2-valent linking group, and is preferably a single bond, an alkylene group, an arylene group, an ester bond (-C (═ O) O-), an ether bond (-O-), or a group in which 2 or more of these groups are bonded, and more preferably a single bond.

Specific examples of the repeating unit having an acid-decomposable group represented by formula (a1) include the following repeating units, but are not limited thereto. In the following repeating units, a represents a bonding site with another repeating unit.

[ chemical formula 15]

[ chemical formula 16]

[ chemical formula 17]

The content of the repeating unit having an acid-decomposable group represented by the formula (a1) is preferably 40 to 50% by mass, more preferably 50 to 60% by mass, based on the total mass of the specific resin.

-repeating units having polar groups-

In the specific resin, the content of the repeating unit having a polar group is less than 10% by mass.

The polar group in the repeating unit having a polar group is a group having a structure in which the difference in electronegativity between adjacent 2 atoms is large, and specific examples thereof include a hydroxyl group, a carboxyl group, an amino group, a nitro group, and a cyano group.

In the specific resin, the content of the repeating unit having a polar group is preferably less than 9% by mass.

Also, the content of the repeating unit having a polar group in the specific resin is preferably less than 8% by mass, more preferably less than 6% by mass.

A repeating unit having a structure in which an acid group is protected by an acid-decomposable group-

The specific resin may further contain a repeating unit having a structure in which an acid group is protected by an acid-decomposable group (also referred to as "other repeating unit having an acid-decomposable group") in addition to the repeating unit having an acid-decomposable group represented by the above formula (a 1). As the repeating unit having another acid-decomposable group, for example, reference is made to the description of an acid-dissociable group described in paragraphs 0048 to 0145 of Japanese patent application laid-open No. 2018-077533, the contents of which are incorporated herein by reference.

Although a mode in which the specific resin contains a repeating unit having another acid-decomposable group is also preferable, a configuration in which the specific resin does not substantially contain a repeating unit having another acid-decomposable group is preferable. With this configuration, a pattern of the developed photosensitive layer having an excellent pattern shape can be obtained. The term "substantially not containing a repeating unit having another acid-decomposable group" means that, for example, the content of the repeating unit having another acid-decomposable group is 3 mol% or less, preferably 1 mol% or less, of all the repeating units of the specific resin.

Repeating units containing crosslinkable groups

The specific resin may further contain a repeating unit containing a crosslinkable group. For details of the crosslinkable group, reference can be made to the descriptions of paragraphs 0032 to 0046 of Japanese patent application laid-open No. 2011-209692, and these contents are incorporated in the present specification.

Although an embodiment in which the specific resin contains a repeating unit containing a crosslinkable group is also preferable, a configuration in which the repeating unit containing a crosslinkable group is substantially not contained is preferable. By adopting such a configuration, the photosensitive layer can be more easily removed after patterning. The term "substantially free of a crosslinkable group-containing repeating unit" means that, for example, the crosslinkable group-containing repeating unit is contained in an amount of 3 mol% or less, preferably 1 mol% or less, based on all repeating units of the specific resin.

Other repeating units-

The particular resin may contain other repeating units. Examples of the radical polymerizable monomer for forming another repeating unit include compounds described in paragraphs 0021 to 0024 of Japanese patent application laid-open No. 2004-264623. Preferable examples of the other repeating units include at least 1 repeating unit derived from a group consisting of a hydroxyl group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene and an N-substituted maleimide. Among them, preferred are benzyl (meth) acrylate and tricyclo [5.2.1.0 ] meth (acrylate) ^2,6]Decan-8-yl, tricyclo (meth) acrylates [5.2.1.0^2,6]Decane-8-yloxyethyl ester, (isobornyl (meth) acrylate, (cyclohexyl (meth) acrylate), alicyclic structure-containing (meth) acrylate of 2-methylcyclohexyl (meth) acrylate, or a hydrophobic monomer such as styrene.

The other repeating units may be used in 1 kind, or 2 or more kinds may be used in combination. The content of the monomer unit forming another repeating unit in the case where the other repeating unit is contained in all the monomer units constituting the specific resin is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, and still more preferably 5 to 40 mol%. In the case of using 2 or more species, the total amount is preferably within the above range.

Examples of methods for synthesizing specific resins-

Various methods are known for synthesizing the specific resin, but in one example, the specific resin can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer for forming at least a repeating unit having an acid-decomposable group represented by the above formula (a1) in an organic solvent using a radical polymerization initiator.

The specific resin is also preferably a copolymer obtained by adding 2, 3-dihydrofuran to an acid anhydride group in a precursor copolymer obtained by copolymerizing unsaturated polycarboxylic acid anhydrides at a temperature of about room temperature (25 ℃) to 100 ℃ in the absence of an acid catalyst.

Specific examples of the specific resin include, but are not limited to, resins represented by the following formulae (A-1) to (A-6). In the following specific examples, a/b/c is 30/60/10 or the like indicating the content ratio (molar ratio) of each constituent unit.

[ chemical formula 18]

[ chemical formula 19]

The content of the specific resin is preferably 20 to 99% by mass, more preferably 40 to 99% by mass, and even more preferably 70 to 99% by mass, based on the total mass of the photosensitive layer, from the viewpoint of improving the pattern formability during development. The photosensitive layer may contain 1 specific resin or 2 or more specific resins. In the case of using 2 or more species, the total amount is preferably within the above range.

The content of the specific resin is preferably 10 mass% or more, more preferably 50 mass% or more, and still more preferably 90 mass% or more, based on the total mass of the resin components contained in the photosensitive layer.

The weight average molecular weight of the specific resin is preferably 10,000 or more, more preferably 20,000 or more, and further preferably 35,000 or more. The upper limit value is not particularly limited, but is preferably 100,000 or less, may be 70,000 or less, and may be 50,000 or less.

The amount of the component having a weight average molecular weight of 1,000 or less contained in the specific resin is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the specific resin.

The molecular weight dispersion (weight average molecular weight/number average molecular weight) of the specific resin is preferably 1.0 to 4.0, more preferably 1.1 to 2.5.

[ photoacid generators ]

The photosensitive layer may further comprise a photoacid generator.

As the photoacid generator, it is preferable if the photosensitive layer is 100mJ/cm in the wavelength of 365nm²And (3) a photoacid generator which decomposes at 80 mol% or more when exposed to light.

The decomposition degree of the photoacid generator can be determined by the following method. The details of the photosensitive layer-forming composition described below will be described later.

Using the composition for forming photosensitive layer, forming a photosensitive layer on a silicon wafer substrate, heating at 100 deg.C for 1 min, and heating with light having a wavelength of 365nm at a concentration of 100mJ/cm²The photosensitive layer is exposed with the exposure amount of (2). The thickness of the photosensitive layer after heating was set to 700 nm. Then, the silicon wafer substrate on which the photosensitive layer was formed was immersed in a solution of methanol/Tetrahydrofuran (THF) ═ 50/50 (mass ratio) for 10 minutes while applying ultrasonic waves. The extract extracted from the solution after the impregnation was analyzed by HPLC (high performance liquid chromatography), and the decomposition rate of the photoacid generator was calculated from the following formula.

Decomposition rate (%) — amount of decomposition product (mole)/amount of photoacid generator (mole) × 100 contained in photosensitive layer before exposure

As a photoacid generator, at a wavelength of 365nm, at 100mJ/cm²When the photosensitive layer is exposed to the light exposure of (3), the light exposure is preferably conducted at 85 mol% or more of the light yield of decompositionAn acid agent.

Oxime sulfonate compounds

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

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

[ chemical formula 20]

In the formula (OS-1), X³Represents an alkyl group, an alkoxy group or a halogen atom. In the presence of a plurality of X³In this case, they may be the same or different. X is above³The alkyl group and the alkoxy group in (1) may have a substituent. As the above X³The alkyl group in (1) is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. As the above X³The alkoxy group in (3) is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. As the above X³The halogen atom in (2) is preferably a chlorine atom or a fluorine atom.

In the formula (OS-1), m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3, plural X' s³May be the same or different.

In the formula (OS-1), R³⁴Represents an alkyl group or an aryl group, and is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W, or a benzoylimidoyl group which may be substituted by W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

In the formula (OS-1), m3 is 3, X³Is a methyl group, and the compound is,X³the substitution position of (A) is ortho, with R being particularly preferred³⁴A linear alkyl group having 1 to 10 carbon atoms, a 7, 7-dimethyl-2-oxonorbornanyl group or a p-toluyl group.

Specific examples of the oxime sulfonate compound represented by the formula (OS-1) include the following compounds described in the paragraphs 0064 to 0068 of Japanese patent laid-open publication No. 2011-209692 and 0158 to 0167 of Japanese patent laid-open publication No. 2015-194674, and these contents are incorporated in the present specification.

[ chemical formula 21]

In the formulae (OS-103) to (OS-105), R ^s1Represents an alkyl group, an aryl group or a heteroaryl group, and a plurality of R may be present^s2Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and there may be a plurality of R^s6Each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer of 0 to 6.

In the formulae (OS-103) to (OS-105), R is represented by^s1The alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) may have a substituent T.

In the formulae (OS-103) to (OS-105), R^s2Preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), more preferably a hydrogen atom or an alkyl group. Sometimes there are more than 2R in the compound^s2Of (3) is preferably 1 or 2 alkyl, preferably aryl or halogen atoms, more preferably 1 alkyl, aryl or halogen atom, especially preferably 1 alkyl and the remainder hydrogen atoms. From R^s2The alkyl group or aryl group represented may have a substituent T.

In the formula (OS-103), the formula (OS-104) or the formula (OS-105), Xs represents O or S, preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-or 6-membered ring.

In the formulae (OS-103) to (OS-105), ns represents 1 or 2, ns is preferably 1 in the case where Xs is O, and ns is preferably 2 in the case where Xs is S.

In the formulae (OS-103) to (OS-105), R is represented by^s6The alkyl group (preferably having 1 to 30 carbon atoms) and the alkoxy group (preferably having 1 to 30 carbon atoms) may have a substituent.

In the formulae (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

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

[ chemical formula 22]

In the formulae (OS-106) to (OS-111), R^t1Represents alkyl, aryl or heteroaryl, R^t7Represents a hydrogen atom or a bromine atom, R^t8Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, chloromethyl group, bromomethyl group, bromoethyl group, methoxymethyl group, phenyl group or chlorophenyl group, R^t9Represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R ^t2Represents a hydrogen atom or a methyl group.

In the formulae (OS-106) to (OS-111), R^t7Represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

In the formulae (OS-106) to (OS-111), R^t8Preferably represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, chloromethyl group, bromomethyl group, bromoethyl group, methoxymethyl group, phenyl group or chlorophenyl group, an alkyl group having 1 to 8 carbon atoms, a halogen atom or phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably a alkyl group having 1 to 6 carbon atomsThe alkyl group of (1) is particularly preferably a methyl group.

In the formulae (OS-106) to (OS-111), R^t9Represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

R^t2Represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

In the oxime sulfonate compound, the oxime may have either one or a mixture of the three-dimensional structures (E, Z).

Specific examples of the oxime sulfonate compounds represented by the above-mentioned formulas (OS-103) to (OS-105) include the compounds described in paragraphs No. 0088 to 0095 of Japanese patent laid-open No. 2011-209692 and paragraphs No. 0168 to 0194 of Japanese patent laid-open No. 2015-194674, and these contents are incorporated in the present specification.

As a preferred other embodiment of the oxime sulfonate compound having at least 1 oxime sulfonate group, compounds represented by the following formulae (OS-101) and (OS-102) can be mentioned.

[ chemical formula 23]

In the formula (OS-101) or the formula (OS-102), R^u9Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group. More preferably R^u9In the form of cyano or aryl, R is more preferably^u9In cyano, phenyl or naphthyl form.

In the formula (OS-101) or the formula (OS-102), R^u2aRepresents an alkyl group or an aryl group.

In the formula (OS-101) or the formula (OS-102), Xu represents-O-, -S-, -NH-, -NR-^u5-、-CH₂-、-CR^u6H-or-CR^u6R^u7-，R^u5～R^u7Each independently represents an alkyl group or an aryl group.

In the formula (OS-101) or the formula (OS-102), R^u1～R^u4Each independently represents a hydrogen atom, a halogen atom, an alkaneA group, alkenyl, alkoxy, amino, alkoxycarbonyl, alkylcarbonyl, arylcarbonyl, amido, sulfo, cyano or aryl. R^u1～R^u42 of them may be bonded to each other to form a ring. In this case, the ring may be condensed to form a condensed ring together with the benzene ring. As R^u1～R^u4Is preferably a hydrogen atom, a halogen atom or an alkyl group, and is also preferably R^u1～R^u4At least 2 of them are bonded to each other to form an aryl group. Among them, R is preferred^u1～R^u4All by way of hydrogen atoms. The above-mentioned substituents may each have a substituent.

More preferably, the compound represented by the above formula (OS-101) is a compound represented by the formula (OS-102).

In the oxime sulfonate compound, the three-dimensional structures (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture thereof.

Specific examples of the compound represented by the formula (OS-101) include the compounds described in the paragraphs No. 0102 to No. 0106 of Japanese patent application laid-open No. 2011-209692 and the paragraphs No. 0195 to 0207 of Japanese patent application laid-open No. 2015-194674, and these contents are incorporated in the present specification.

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

Examples of commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Corporation), MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

As the photoacid generator which senses actinic rays, a photoacid generator which does not contain 1, 2-quinonediazide is preferable. The reason for this is that 1, 2-quinonediazide generates a carboxyl group by a stepwise photochemical reaction, but has a quantum yield of 1 or less and is less sensitive than an oxime sulfonate compound.

On the other hand, since the oxime sulfonate compound acts as a catalyst for deprotection of an acid-protected acid group generated by the induction of actinic rays, an acid generated by the action of 1 photon contributes to a plurality of deprotection reactions, and the quantum yield exceeds 1, for example, a value as large as a number square of 10, and it is presumed that high sensitivity can be obtained as a result of so-called chemical amplification.

Further, since the oxime sulfonate compound contains a pi-conjugated system having a wide range, it has absorption up to a long wavelength side, and shows very high sensitivity not only to Deep Ultraviolet (DUV), ArF radiation, KrF radiation, i-radiation, but also to g-radiation.

By using a tetrahydrofuranyl group as the acid-decomposable group in the photosensitive layer, an acid decomposability equivalent to or higher than that of an acetal or ketal can be obtained. This enables the acid-decomposable groups to be reliably consumed by a shorter time of post-baking. Further, by using an oxime sulfonate compound as a photoacid generator in combination, the generation rate of sulfonic acid is increased, so that the generation of acid is promoted, and the decomposition of the acid-decomposable group of the resin is promoted. Further, 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 further high sensitivity can be achieved.

Onium salt type photoacid generators

Further, it is also preferable that the photosensitive layer contains an onium salt type photoacid generator as the photoacid generator.

The onium salt type photoacid generator is a salt having a cation portion and an anion portion of an onium structure, and the cation portion and the anion portion may be bonded to each other through a covalent bond or may not be bonded to each other through a covalent bond.

Examples of the onium salt type photoacid generator include an ammonium salt compound, a sulfonium salt compound, and an iodonium salt compound, and examples thereof include a quaternary ammonium salt compound, a triarylsulfonium salt compound, and a diaryliodonium salt compound.

Examples of the quaternary ammonium salts include tetramethylammoniumbutyltris (2, 6-difluorophenyl) borate, tetramethylammoniumhexyltris (p-chlorophenyl) borate, tetramethylammoniumthyltris (3-trifluoromethylphenyl) borate, benzyldimethylphenylammonium butyltris (2, 6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, and benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate.

Examples of the triarylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyl diphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyl diphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfinyltrifluoromethanesulfonate, and 4-phenylthiophenyldiphenylsulfinyltrifluoroacetate.

Examples of diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethane sulfonate, 4-methoxyphenyliodonium trifluoroacetate, phenyl-4- (2 '-hydroxy-1' -tetradecyloxy) phenyliodonium trifluoromethane sulfonate, 4- (2 '-hydroxy-1' -tetradecyloxy) phenyliodonium hexafluoroantimonate, and phenyl-4- (2 '-hydroxy-1' -tetradecyloxy) phenyliodonium iodonium hexafluoroantimonate, and phenyl-4- (2 '-hydroxy-1' -tetradecyloxy) phenyliodonium-p-toluenesulfonate.

In addition, from the viewpoint of compatibility with a specific resin, the photosensitive layer preferably contains an onium salt type photoacid generator having a group containing a ring structure or a nonionic photoacid generator having a group containing a ring structure.

The cyclic structure in the onium salt type photoacid generator having a group containing the cyclic structure or the nonionic photoacid generator having a group containing the cyclic structure is preferably a saturated aliphatic hydrocarbon ring, a saturated aliphatic heterocyclic ring, an aromatic hydrocarbon ring, or an aromatic heterocyclic ring, and more preferably a saturated aliphatic hydrocarbon ring, a saturated aliphatic heterocyclic ring, or an aromatic hydrocarbon ring.

Examples of the hetero atom in the saturated aliphatic heterocyclic ring or the aromatic heterocyclic ring include a nitrogen atom, an oxygen atom, a sulfur atom, and the like.

The number of ring members in the ring structure is preferably 4 to 20, more preferably 4 to 10.

These ring structures may further have a condensed ring.

These photoacid generators may have only 1 ring structure, or may have 2 or more. When the photoacid generator has 2 or more ring structures, the 2 or more ring structures may be the same or different.

As the onium salt type photoacid generator having a group containing a ring structure, a compound having a ring structure in the above onium salt type photoacid generator can be preferably exemplified.

The oxime sulfonate compound is preferably used as a nonionic photoacid generator having a group containing a ring structure.

Preferable examples of the onium salt type photoacid generator having a group having a ring structure or the nonionic photoacid generator having a ring structure include a camphor ring structure, a naphthalene ring structure, an adamantyl ring structure, and a ring structure in which these rings are substituted with a substituent or a heteroatom.

The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, even more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass, based on the total mass of the photosensitive layer.

The photoacid generator may be used alone in 1 kind, or may be used in combination in 2 or more kinds. In the case of using 2 or more species, the total amount is preferably within the above range.

[ basic Compound ]

From the viewpoint of the liquid storage stability of the composition for forming a photosensitive layer, the photosensitive layer preferably contains a basic compound.

The basic compound can be arbitrarily selected from compounds used in known chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.

Examples of the aromatic amine include aniline, benzylamine, N-dimethylaniline, and diphenylamine.

As the heterocyclic amine, for example, examples thereof include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4, 5-triphenylimidazole, nicotinic acid amide, quinoline, 8-oxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, cyclohexyl-vinylethylthiourea, piperazine, oridine, 4-methyloridine, 1, 5-diazabicyclo [4.3.0] -5-nonene, 1, 8-diazabicyclo [5.3.0] -7-undecene and the like.

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

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

When the photosensitive layer contains a basic compound, the content of the basic compound is preferably 0.001 to 1 part by mass, more preferably 0.002 to 0.5 part by mass, per 100 parts by mass of the specific resin.

The basic compound may be used singly or in combination of 1 or more, but preferably 2 or more, more preferably 2 or more, and still more preferably 2 heterocyclic amines. In the case of using 2 or more species, the total amount is preferably within the above range.

[ surfactant ]

The photosensitive layer preferably contains a surfactant from the viewpoint of improving the coatability of the composition for forming a photosensitive layer described later.

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

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based surfactants, and silicon-based surfactants.

The surfactant more preferably contains a fluorine-based surfactant or a silicon-based surfactant.

Examples of the fluorine-based surfactant and the silicon-based surfactant include those described in Japanese patent application laid-open Nos. 62-036663, 61-226746, 61-226745, 62-170950, 63-034540, 07-230165, 08-062834, 09-054432, 09-005988, 2001-330953, and commercially available surfactants can also be used.

Examples of commercially available surfactants that can be used include fluorine-based surfactants and silicon-based surfactants such as Eftop EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Fluorad FC430 and 431 (manufactured by Sumitomo 3M Limited), Megaface F171, F173, F176, F189, and R08 (manufactured by DIC CORPORATION), Surflon S-382, SC101, 102, 103, 104, 105, and 106 (manufactured by Sumitomo S. AGC SEIMI CHEMICAL CO., LTD.), and PolyFox series (manufactured by OMNOVA SOLUTION INC., PF-6320). Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicone surfactant.

Further, as a preferable example, there can be mentioned a copolymer containing the repeating unit a and the repeating unit B represented by the following formula (41) and having a weight average molecular weight (Mw) as measured by gel permeation chromatography in terms of polystyrene when Tetrahydrofuran (THF) is used as a solvent, of 1,000 or more and 10,000 or less.

[ chemical formula 24]

In the formula (41), R⁴¹And R⁴³Each independently represents a hydrogen atom or a methyl group, R⁴²Represents a linear alkylene group having 1 to 4 carbon atoms, R⁴⁴Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L⁴Represents an alkylene group having 3 to 6 carbon atoms, and p4 and q4 represent a polymerization ratioP4 represents a numerical value of 10 to 80 mass%, q4 represents a numerical value of 20 to 90 mass%, r4 represents an integer of 1 to 18, and n4 represents an integer of 1 to 10.

In the formula (41), L⁴A branched alkylene group represented by the following formula (42) is preferable. R in the formula (42)⁴⁵The alkyl group having 1 to 4 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 2 or 3 carbon atoms, from the viewpoint of wettability to the surface to be coated.

-CH₂-CH(R⁴⁵)-(42)

The weight average molecular weight of the copolymer is more preferably 1,500 or more and 5,000 or less.

When the photosensitive layer contains a surfactant, the amount of the 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 part by mass, per 100 parts by mass of the specific resin.

The surfactant can be used alone in 1 kind, or can be mixed with 2 or more kinds. In the case of using 2 or more species, the total amount is preferably within the above range.

[ other Components ]

The photosensitive layer may further contain 1 or 2 or more kinds of known additives such as an antioxidant, a plasticizer, a thermal radical generator, a thermal acid generator, an acid amplifier, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor, as required. The details of these can be referred to the descriptions of paragraphs 0143 to 0148 of Japanese patent application laid-open No. 2011-209692, and these contents are incorporated in the present specification.

[ thickness ]

From the viewpoint of improving the analytical ability, the thickness (film thickness) of the photosensitive layer in the present invention is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 0.75 μm or more, and particularly preferably 0.8 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 still more preferably 2.0 μm or less.

The total thickness of the photosensitive layer and the protective layer is preferably 0.2 μm or more, more preferably 1.0 μm or more, and still more preferably 2.0 μm or more. The upper limit is preferably 20.0 μm or less, more preferably 10.0 μm or less, and still more preferably 5.0 μm or less.

[ developer ]

The photosensitive layer in the present invention is for development using a developer.

As the developer, a developer containing an organic solvent is preferable.

The content of the organic solvent is preferably 90 to 100% by mass, and more preferably 95 to 100% by mass, based on the total mass of the developer. The developer may be a developer composed only of an organic solvent.

The method of developing the photosensitive layer using the developer will be described later.

Organic solvents-

The sp value of the organic solvent contained in the developer is preferably less than 19MPa^1/2More preferably 18MPa^1/2The following.

Examples of the organic solvent contained in the developer include polar solvents such as ketone solvents, ester solvents, and amide solvents, and hydrocarbon solvents.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone (ionone), diacetone alcohol, acetyl alcohol, acetophenone, methylnaphthyl ketone, isophorone, and propylene carbonate.

Examples of the ester-based solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate (amyl acetate), isoamyl 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 the amide solvent include N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, hexamethylphosphoric triamide, and 1, 3-dimethyl-2-imidazolidinone.

Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene; and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

The organic solvent may be used in only 1 kind, or may be used in 2 or more kinds. Further, it may be used in combination with an organic solvent other than the above. The content of water is preferably less than 10% by mass based on the total mass of the developer, and more preferably, water is substantially not contained. Here, the term "substantially free of water" means, for example, that the content of water is 3% by mass or less with respect to the total mass of the developer, and more preferably, it means that the content is not more than the measurement limit.

That is, the amount of the organic solvent used relative to the organic developer is preferably 90 mass% or more and 100 mass% or less, and more preferably 95 mass% or more and 100 mass% or less, relative to the total amount of the developer.

In particular, it is preferable that the organic developer contains at least 1 organic solvent selected from the group consisting of ketone solvents, ester solvents, and amide solvents.

The organic developer may contain an appropriate amount of an alkali compound as needed. Examples of the basic compound include the compounds described in the above section of the basic compound.

The vapor pressure of the organic developer is preferably 5kPa or less, more preferably 3kPa or less, and further preferably 2kPa or less under the condition of 23 ℃. By setting the vapor pressure of the organic developer to 5kPa or less, evaporation on the photosensitive layer of the developer or in the developing cup can be suppressed, and the temperature uniformity in the surface of the photosensitive layer is improved, and as a result, the dimensional uniformity of the developed photosensitive layer is improved.

Specific examples of the solvent having a vapor pressure of 5kPa or less include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl isobutyl ketone; ester solvents such as butyl acetate, amyl acetate, isoamyl 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, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate; amide solvents such as N-methyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene; and aliphatic hydrocarbon solvents such as octane and decane.

Specific examples of the solvent having a vapor pressure of 2kPa or less in a particularly preferable range include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and phenyl acetone; ester-based solvents such as 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, and propyl lactate; amide solvents such as N-methyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide; aromatic hydrocarbon solvents such as xylene; and aliphatic hydrocarbon solvents such as octane and decane.

Surfactants-

The developer may contain a surfactant.

The surfactant is not particularly limited, and for example, the surfactant described in the above item of the protective layer can be preferably used.

When a surfactant is added to the developer, the amount of the surfactant added 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.

[ composition for Forming photosensitive layer ]

The composition for forming a photosensitive layer of the present invention contains a specific resin, and is a composition for forming a photosensitive layer contained in the laminate of the present invention.

In the laminate of the present invention, the photosensitive layer can be formed, for example, by applying the photosensitive layer forming composition to the protective layer and drying the composition. As an application method, for example, a description can be given of an application method of a composition for forming a protective layer in a protective layer described later.

The composition for forming a photosensitive layer preferably contains the components contained in the photosensitive layer (for example, a specific resin, a photoacid generator, a basic compound, a surfactant, and other components) and a solvent. The components contained in these photosensitive layers are preferably dissolved or dispersed in a solvent, and more preferably dissolved in a solvent.

The content of the components contained in the composition for forming a photosensitive layer is preferably set such that the content of each component with respect to the total mass of the photosensitive layer is replaced with the content with respect to the amount of the solid component of the composition for forming a photosensitive layer.

Organic solvents-

As the organic solvent used in the composition for forming a photosensitive layer, known organic solvents can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like.

Examples of the organic solvent include,

(1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

(2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether;

(3) ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate;

(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 ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate;

(7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;

(8) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monobutyl ether acetate;

(9) Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether;

(10) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether;

(11) dipropylene glycol monoalkylether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate;

(12) lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-pentyl lactate, and isoamyl lactate;

(13) aliphatic carboxylic acid esters such as n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, and isobutyl butyrate;

(14) other esters such as ethyl glycolate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxymethylpropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, and ethyl pyruvate;

(15) Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl n-butanone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone;

(16) amides such as N-methylformamide, N-dimethylformamide, N-methylacetamide, N-dimethylacetamide, and N-methylpyrrolidone;

(17) lactones such as γ -butyrolactone.

Further, if necessary, an organic solvent such as benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate, or the like may be added to these organic solvents.

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

When the composition for forming a photosensitive layer contains an organic solvent, the content of the organic solvent is preferably 1 to 3,000 parts by mass, more preferably 5 to 2,000 parts by mass, and still more preferably 10 to 1,500 parts by mass per 100 parts by mass of the specific resin.

These organic solvents can be used alone in 1 kind, or can be mixed with 2 or more kinds.

In the case of using 2 or more species, the total amount is preferably within the above range.

(set for forming laminate)

The kit for forming a laminate of the present invention comprises the following components A and B.

A: a composition for forming the above protective layer contained in the laminate of the present invention;

b: the composition for forming the photosensitive layer contained in the laminate of the present invention contains a resin containing a repeating unit having an acid-decomposable group represented by the formula (a1), and the content of the repeating unit having a polar group contained in the resin is less than 10% by mass relative to the total mass of the resin.

The laminate-forming kit of the present invention may further contain the above-mentioned composition for forming an organic semiconductor layer or composition for forming a resin layer.

(method of patterning organic layer)

The following embodiments can be mentioned as a pattern forming method that can be preferably employed in the present invention.

The method for patterning an organic layer according to the present embodiment includes:

(1) a step of forming a protective layer on the organic layer;

(2) a step of forming a photosensitive layer on the side of the protective layer opposite to the organic layer;

(3) Exposing the photosensitive layer;

(4) developing the photosensitive layer using a developing solution containing an organic solvent to produce a mask pattern;

(5) removing the protective layer and the organic layer in the non-mask portion;

(6) and removing the protective layer by using a stripping liquid.

[ 1 ] Process for producing protective layer on organic layer

The method for patterning an organic layer according to the present embodiment includes a step of forming a protective layer on the organic layer. Generally, this step is performed after an organic layer is formed on a substrate. In this case, the protective layer is formed on the surface of the organic layer opposite to the surface on the substrate side. The protective layer is preferably formed so as to be in direct contact with the organic layer, but another layer may be provided therein without departing from the scope of the present invention. Examples of the other layer include a fluorine-based primer layer. The protective layer may be provided with only 1 layer, or may be provided with 2 or more layers. As described above, the protective layer is preferably formed using the protective layer forming composition.

The details of the formation method can be referred to the application method of the protective layer-forming composition in the laminate of the present invention described above.

< 2) Process for producing photosensitive layer on side of protective layer opposite to organic layer

After the step (1), a photosensitive layer is formed on the side (preferably, on the surface) of the protective layer opposite to the organic layer side.

As described above, the photosensitive layer is preferably formed using a composition for forming a photosensitive layer.

The details of the forming method can be referred to the application method of the composition for forming a photosensitive layer in the laminate of the present invention.

< 3 > Process for exposing photosensitive layer

After the photosensitive layer is formed in the step (2), the photosensitive layer is exposed. Specifically, for example, at least a part of the photosensitive layer is irradiated with (exposed to) actinic rays.

The exposure is preferably performed so as to form a predetermined pattern. Further, exposure may be performed through a photomask, or a predetermined pattern may be directly drawn.

As the wavelength of the actinic ray at the time of exposure, an actinic ray having a wavelength of preferably 180nm or more and 450nm or less, more preferably a wavelength of 365nm (i-ray), 248nm (KrF-ray) or 193nm (ArF-ray) can be used.

As the light source of actinic rays, 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, and the like can be used.

When a mercury lamp is used as the light source, actinic rays having a wavelength of g-ray (436nm), i-ray (365nm), h-ray (405nm), or the like can be preferably used. In the present invention, it is preferable to use i-rays because the effects thereof can be preferably exerted.

When a laser generator is used as the light source, actinic rays having a wavelength of 343nm or 355nm are preferably used for a solid-state (YAG) laser, actinic rays having a wavelength of 193nm (ArF ray), 248nm (KrF ray) or 351nm (Xe ray) are preferably used for an excimer laser, and actinic rays having a wavelength of 375nm or 405nm are preferably used for a semiconductor laser. Among them, actinic rays having a wavelength of 355nm or 405nm are more preferable from the viewpoint of stability, cost, and the like. The photosensitive layer can be irradiated with the laser light 1 time or a plurality of times.

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

The energy density per 1 pulse of the laser is preferably 0.1mJ/cm²Above and 10,000mJ/cm²The following. More preferably 0.3mJ/cm for sufficient curing of the coating film²Above, more preferably 0.5mJ/cm²The above. From the viewpoint of suppressing decomposition of the photosensitive layer or the like due to ablation (ablation), it is preferable to set the exposure dose to 1,000mJ/cm ²Hereinafter, more preferably 100mJ/cm²The following.

The pulse width is preferably 0.1 nanosecond (hereinafter, referred to as "ns") or more and 30,000ns or less. In order to avoid the decomposition of the color coating film due to the ablation phenomenon, it is more preferably 0.5ns or more, and still more preferably 1ns or more. In order to improve the alignment accuracy in the scanning exposure, it is more preferably 1,000ns or less, and still more preferably 50ns or less.

When a laser generator is used as the light source, the frequency of the laser is preferably 1Hz to 50,000Hz, and more preferably 10Hz to 1,000 Hz.

Further, the frequency of the laser beam is more preferably 10Hz or more, and still more preferably 100Hz or more in order to shorten the exposure processing time, and is more preferably 10,000Hz or less, and still more preferably 1,000Hz or less in order to improve the alignment accuracy at the time of scanning exposure.

The laser beam is more easily focused than a mercury lamp, and is also preferable in that a photomask can be omitted in pattern formation in the exposure step.

The exposure apparatus is not particularly limited, but commercially available products such as Callisto (V-Technology co., ltd.), AEGIS (V-Technology co., ltd.), DF2200G (Dainippon Screen mfg.co., ltd.) and the like can be used. Also, devices other than those described above may also be preferably used.

Further, the irradiation light amount can be adjusted by a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter, as necessary.

After the exposure, a post-exposure heating step (PEB) may be performed as necessary.

The heating mechanism in the PEB is not particularly limited, and examples thereof include a hot plate.

The heating time in the PEB is, for example, preferably 30 to 300 seconds, and more preferably 60 to 120 seconds.

In the case of PEB, it is also preferable to heat the substrate immediately after exposure, and for example, the waiting time may be within 1 hour, which can be determined depending on the apparatus used, the production environment of the laminate, and the like.

The heating temperature in the post-exposure heating step is preferably 30 to 100 ℃, more preferably 50 to 70 ℃ from the viewpoint of easily obtaining the effects of the present invention.

< (4) Process for producing mask Pattern by developing photosensitive layer with developer containing organic solvent

In the step (3), the photosensitive layer is exposed through a photomask and then developed with a developer.

The development is preferably negative.

The details of the developing solution are as described in the above description of the photosensitive layer.

As the developing method, for example, the following methods can be applied: a method of immersing a base material in a tank filled with a developer for a certain period of time (immersion method), a method of developing by stacking a developer on a surface of a base material by surface tension and standing still for a certain period of time (liquid coating method), a method of spraying a developer on a surface of a base material (spray method), a method of continuously discharging a developer while scanning a developer discharge nozzle at a constant speed on a base material rotating at a constant speed (dynamic dispensing method), and the like.

In the case where the above-described various developing methods include a step of discharging the developer from the developing nozzle of the developing device toward the photosensitive layer, the discharge pressure of the discharged developer (flow rate per unit area of the discharged developer) is preferably 2 mL/sec/mm²Hereinafter, more preferably 1.5 mL/sec/mm²Hereinafter, more preferably 1 mL/sec/mm²The following. The discharge pressure is not particularly limited, but is preferably 0.2 mL/sec/mm in consideration of the throughput²The above. By setting the discharge pressure of the discharged developer within the above range, pattern defects caused by resist residue after development can be significantly reduced.

Although the details of this mechanism are not clear, it is presumably because the discharge pressure is set within the above range, and the pressure applied to the photosensitive layer by the developer is reduced, thereby suppressing the resist pattern on the photosensitive layer from being unintentionally erased or destroyed.

Further, the discharge pressure of the developer (mL/sec/mm)²) Is the value in the outlet of the developing nozzle in the developing device.

Examples of the method of adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure by a pump or the like, and a method of adjusting the pressure by supply from a pressure tank to change the pressure.

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

< 5 > Process for removing protective layer and organic layer of non-mask portion

After the photosensitive layer is developed to produce a mask pattern, at least the protective layer and the organic layer in the non-mask portion are removed by etching. The non-mask portion refers to a region not masked by a mask pattern formed by developing the photosensitive layer (a region where the photosensitive layer is removed by development).

The etching process may be performed in a plurality of stages. For example, the protective layer and the organic layer may be removed by etching at one time, or after at least a part of the protective layer is removed by etching, the organic layer (and the remaining part of the protective layer as needed) may be removed by etching.

The etching process may be a dry etching process or a wet etching process, and may be a method of dividing etching into a plurality of times and performing the dry etching process and the wet etching process. For example, the protective layer may be removed by dry etching or wet etching.

Examples of the method for removing the protective layer and the organic layer include a method a of removing the protective layer and the organic layer by 1 dry etching treatment, a method B of removing at least a part of the protective layer by wet etching treatment, and then removing the organic layer (and the remaining part of the protective layer if necessary) by dry etching, and the like.

The dry etching treatment in the above-described method a, the wet etching treatment and the dry etching treatment in the above-described method B, and the like can be performed according to a known etching treatment method.

Hereinafter, a detailed description will be given of an embodiment of the method a. As a specific example of the method B, reference can be made to the description of japanese patent application laid-open No. 2014-098889 and the like.

In the method a, specifically, the protective layer and the organic layer in the unmasked portion can be removed by dry etching using the resist pattern as an etching mask (mask pattern). Typical examples of dry etching include the methods described in Japanese patent application laid-open Nos. 59-126506, 59-046628, 58-009108, 58-002809, 57-148706 and 61-041102.

The dry etching is preferably performed in the following manner from the viewpoint of forming the cross section of the pattern of the organic layer to be formed to be more rectangular or from the viewpoint of further reducing damage to the organic layer.

The etching method preferably includes the following steps: the etching in stage 1 is carried out using a fluorine-based gas and oxygen (O)₂) Etching is performed until the organic layer is not exposed to the area (depth); etching in stage 2, and nitrogen (N) gas is used after the etching in stage 1₂) And oxygen (O)₂) Etching is performed until the vicinity of a region (depth) where the organic layer is preferably exposed; and over-etching, after the organic layer is exposed. Hereinafter, a specific method of dry etching, as well as etching at stage 1, etching at stage 2, and overetching will be described.

The etching conditions for the dry etching are preferably performed by calculating the etching time by the following method.

(A) The etching rate (nm/min) in the etching of the 1 st stage and the etching rate (nm/min) in the etching of the 2 nd stage were calculated, respectively.

(B) The time to etch the desired thickness by the 1 st stage etching and the time to etch the desired thickness by the 2 nd stage etching are calculated, respectively.

(C) The etching in stage 1 was performed according to the etching time calculated in (B) above.

(D) The etching in the 2 nd stage was performed according to the etching time calculated in the above (B). Or the etching time may be determined by end point detection and the etching of the 2 nd stage may be performed according to the determined etching time.

(E) The overetching time is calculated with respect to the total time of the above (C) and (D), and the overetching is performed.

The mixed gas used in the etching in the 1 st stage preferably contains a fluorine-based gas and oxygen (O) gas from the viewpoint of processing the organic material as the film to be etched into a rectangular shape₂). In the etching at stage 1, the stacked body is etched to a region where the organic layer is not exposed. Therefore, it is considered that the organic layer is not damaged or damaged slightly at this stage.

In the etching of the 2 nd step and the overetching, it is preferable to perform the etching process using a mixed gas of nitrogen and oxygen in order to avoid damage of the organic layer.

It is important that the ratio of the etching amount in the etching of the 1 st stage to the etching amount in the etching of the 2 nd stage is determined so that the rectangularity in the cross section of the pattern of the organic layer in the etching of the 1 st stage is excellent.

The ratio of the etching amount in the etching of the 2 nd stage to the total etching amount (the sum of the etching amount in the etching of the 1 st stage and the etching amount in the etching of the 2 nd stage) is preferably greater than 0% and 50% or less, and more preferably 10 to 20%. The etching amount is an amount calculated from the difference between the remaining film thickness of the film to be etched and the film thickness before etching.

Also, the etching preferably includes an over-etching treatment. The overetching treatment is preferably performed by setting an overetching ratio.

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 (organic layer), it is preferably 30% or less, more preferably 5 to 25%, and particularly preferably 10 to 15% of the total etching treatment time in the etching step.

< 6 > Process for removing protective layer Using stripping liquid

After etching, the protective layer is removed using a stripping liquid (e.g., water). By the removal of the protective layer, the pattern formed in the photosensitive layer is also removed.

The details of the stripping liquid are as described in the description of the protective layer above.

As a method for removing the protective layer using the stripping liquid, for example, a method for removing the protective layer by spraying the stripping liquid from a spray type or shower type spray nozzle to the resist pattern can be cited. As the stripping liquid, pure water can be preferably used. Examples of the spray nozzle include a spray nozzle that includes the entire substrate within its spray range, and a spray nozzle that is a movable spray nozzle and includes the entire substrate within its movable range. In another embodiment, the protective layer is mechanically peeled off, and then the residue of the protective layer remaining on the organic layer is dissolved and removed.

When the spray nozzle is movable, the resist pattern can be more effectively removed by moving the spray nozzle 2 or more times from the center of the substrate to the edge of the substrate in the step of removing the protective layer and spraying the stripping liquid.

After the protective layer is removed, a step such as drying is also preferably performed. The drying temperature is preferably 80 to 120 ℃.

(use)

The laminate of the present invention can be used for manufacturing an electronic device using an organic semiconductor. Here, the electronic device includes a semiconductor, has 2 or more electrodes, and controls a current flowing between the electrodes or a voltage generated by the current, light, magnetism, a chemical substance, or the like, or generates light, an electric field, a magnetic field, or the like by an applied voltage or a current.

Examples thereof include an organic photoelectric conversion element, an organic field effect transistor, an organic electroluminescent element, a gas sensor, an organic rectifier element, an organic inverter, and an information recording element.

The organic photoelectric conversion element can be used for any one of light sensing applications and energy conversion applications (solar cells).

Among them, the organic field effect transistor, the organic photoelectric conversion element, and the organic electroluminescent element are preferable, the organic field effect transistor and the organic photoelectric conversion element are more preferable, and the organic field effect transistor is particularly preferable.

Examples

The present invention will be described in more detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the treatment, the treatment steps, and the like shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Unless otherwise specified, "%" and "part(s)" are based on mass.

The weight average molecular weight (Mw) of the water-soluble resin such as polyvinyl alcohol is calculated as a polyether oxide conversion value measured based on GPC. HLC-8220 (manufactured by TOSOH CORPORATION) was used as the device, and SuperMultipore PW-N (manufactured by TOSOH CORPORATION) was used as the column.

The weight average molecular weight (Mw) of a water-insoluble resin such as a (meth) acrylic resin is calculated as a polystyrene equivalent value measured by GPC. HLC-8220 (manufactured by TOSOH CORPORATION) was used as the device, and TSKgel Super AWM-H (manufactured by TOSOH CORPORATION, 6.0 mmID. times.15.0 cm) was used as the column.

(Synthesis of specific resin)

The specific resin was synthesized by the following synthesis method. The compounds A-1 to A-6 used in the following examples are the same compounds as the compounds A-1 to A-6 described above as specific examples of the specific resin.

< Synthesis example 1: synthesis of A-1

PGMEA (propylene glycol monomethyl ether acetate, 32.62g) was placed in a three-necked flask equipped with a nitrogen inlet tube and a cooling tube, and the temperature was raised to 86 ℃. To this solution, BzMA (benzyl methacrylate, 16.65g), 1-isopropyl-1-cyclooctane methacrylate, 56.35g), t-BuMA (t-butyl methacrylate, 4.48g), and V-601(0.4663g, manufactured by FUJIFILM Wako Pure Chemical Corporation) were dissolved in PGMEA (32.62g) and added dropwise over 2 hours. Then, the reaction solution was stirred for 2 hours to complete the reaction. The reaction solution was reprecipitated in heptane to yield white powder, which was recovered by filtration, thereby obtaining specific resin a-1. The weight average molecular weight (Mw) was 20,000.

< Synthesis of A-2 to A-6 and CA-1 to CA-3 >

The specific resins A-2 to A-6 and the resins used in the comparative examples, namely, the resins CA-1 to CA-3, were synthesized in the same manner as the specific resin A-1, except that the raw material compounds were appropriately changed.

The resins used in the comparative examples, namely, the resins CA-1 to CA-3, had the following structures. The term "a/b/c" refers to 34/53/13 and the like, which indicate the content ratio (molar ratio) of each constituent unit.

[ chemical formula 25]

(other Components)

The details of the components other than those described above in the components of the protective layer-forming composition or the photosensitive layer-forming composition described in tables 1 to 2 are as follows.

< composition for forming protective layer >

PVA: polyvinyl alcohol PXP-05(JAPAN VAM & POVAL CO., LTD. manufactured)

Sorbitol: sorbitol D sorbitol FP (B Food Science Co., Ltd.; manufactured by Ltd.)

CyTop: CyTop (manufactured by AGC Inc.)

Surfactant E00: a compound represented by the following formula (E00), manufactured by Acetyrenol E00, Kawaken Fine Chemicals Co., Ltd

Solvent water: pure water

[ chemical formula 26]

< composition for forming photosensitive layer >

Photoacid generator B-1: in the following formula (OS-107), R is used¹¹Tolyl radical, R¹⁸A compound of the group methyl.

Quencher (basic compound) Y: a thiourea derivative represented by the following formula (Y1).

Surfactant PF-6320: manufactured by OMNOVA Solutions Inc. of PF-6320

Solvent PGMEA: propylene glycol monomethyl ether acetate

[ chemical formula 27]

(examples and comparative examples)

In each of the examples and comparative examples, a laminate was produced by preparing a composition for forming a protective layer, preparing a composition for forming a photosensitive layer, forming an organic semiconductor layer, forming a protective layer, and forming a photosensitive layer.

< preparation of composition for Forming protective layer >

The components shown in the column of "composition for formation" of "protective layer" in tables 1 to 2 were mixed at the ratio (mass%) shown in tables 1 to 2 to obtain a uniform solution, which was then filtered using a DFA 1J 006 SW44 filter (equivalent to 0.6 μm) manufactured by Pall corporation to prepare a water-soluble resin composition.

In table 1 or table 2, the expression "-" indicates that the corresponding component is not contained.

< preparation of composition for Forming photosensitive layer >

The components shown in the column of "composition for forming" of "photosensitive layer" in tables 1 to 2 were mixed at the ratio (mass%) shown in tables 1 to 2 to obtain a uniform solution, and then filtered using a DFA1 FTE SW44 filter (equivalent to 0.1 μm) manufactured by Pall corporation to prepare a composition for forming a photosensitive layer.

< production of base Material >

A substrate was prepared by depositing ITO (indium tin oxide) on one surface of a 5cm square glass substrate.

Specifically, a CM616 vapor deposition machine manufactured by Canon Tokki Corporation was used to heat and evaporate the powdered organic material in vacuum with a heater, and was attached to the surface of the substrate at a rate of 0.05 nm/min to form a thin film.

< preparation of organic layer >

In tables 1 to 2, in the case where "HAT-CN" is described in the column of "kind" of "organic layer", HAT-CN (2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene) is deposited on the surface of the substrate on which ITO is deposited, and an organic layer (organic semiconductor layer) is formed. The thickness of the organic layer is shown in the column "thickness (nm)" of the "organic layer" in tables 1 to 2.

Specifically, a CM616 vapor deposition machine manufactured by Canon Tokki Corporation was used to heat and evaporate the powdered organic material in vacuum with a heater, and was attached to the surface of the substrate at a rate of 0.05 nm/min to form a thin film.

In the examples described as "circulator P" in the column of "type of" organic layer "in tables 1 to 2, the resin layer-forming composition having the following composition was spin-coated and dried at the temperature described in the column of" forming method "of" organic layer "in tables 1 to 2 for 10 minutes to form an organic layer. The film thickness is shown in tables 1 to 2.

[ composition of composition for resin layer formation ]

CYCLOMER P (ACA) Z200M (manufactured by DAICEL-ALLNEX ltd.): 50% by mass

Propylene glycol monomethyl ether: 50% by mass

< formation of protective layer >

In the examples described as "PVA" or "cytotop" in the column of "kind of" resin "in tables 1 to 2, the protective layer forming composition was applied to the surface of the organic layer, and dried at the temperature described in the column of" baking temperature (c.) "of" protective layer "in table 1 or 2 for 1 minute to form the protective layer having the thickness (film thickness (μm)) shown in table 1 or 2.

In the examples described as "sorbitol" in the column of "type of resin" in tables 1 to 2, an organic layer (organic semiconductor layer) was formed by depositing sorbitol on the surface of the organic layer. The thickness of the organic layer is shown in the column "thickness (nm)" of the "organic layer" in tables 1 to 2.

Specifically, a CM616 vapor deposition machine manufactured by Canon Tokki Corporation was used to heat and evaporate the powdered organic material in vacuum with a heater, and was attached to the surface of the substrate at a rate of 0.03 nm/min to form a thin film.

< formation of intermediate layer >

In the examples described as "parylene" in the column of "type" of the intermediate layer in tables 1 to 2, parylene (parylene) was deposited by CVD (chemical vapor deposition) at the thickness described in tables 1 to 2 after forming the protective layer. In the examples described as "none" in the column of "kind" of intermediate layer in tables 1 to 2, the intermediate layer was not formed.

< formation of photosensitive layer >

The surface of the protective layer thus formed (in the example where the intermediate layer was formed, the surface of the intermediate layer) was spin-coated with the photosensitive layer forming composition, and dried at the temperature described in the column of "baking temperature (c.)" of the "photosensitive layer" in tables 1 to 2 for 1 minute, to form a photosensitive layer having the thickness (film thickness (μm)) shown in tables 1 to 2 as a laminate.

< evaluation of Pattern collapse >

In each of examples and comparative examples, an i-ray projection exposure apparatus NSR2005i9C (manufactured by Nikon Corporation) was used, and the exposure was performed in a NA: 0.50, sigma: the photosensitive layer in each of the laminates prepared was subjected to i-ray exposure under optical conditions of 0.60. The exposure was performed through a binary mask of 1:1 line and gap pattern with a line width of 2 μm. The exposure amount is appropriately set so that the line width of the lines and spaces in the line and space pattern becomes about 1: 1.

After heating at the temperature described in "PEB temperature (c)" in tables 1 to 2 for 60 seconds, a resist pattern of 1:1 lines and spaces with a line width of 2 μm was obtained by spin drying after developing for 50 seconds using butyl acetate (nBA) or a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) as a developing solution. In each of examples and comparative examples, table 1 to table 2 show which of nBA and TMAH aqueous solutions was used as a developer. The cross section of the resist pattern was observed using a scanning electron microscope, and the collapse of the resist pattern was determined in a range of 20 μm 20 μm square for the 2 μm line and space pattern according to the following evaluation criteria. The evaluation results are shown in the column of "pattern collapse" in tables 1 and 2. It can be said that the less the pattern collapse, the more the pattern collapse is suppressed.

[ evaluation criteria ]

A: no collapse was observed.

B: pattern collapse was observed in an area less than 5%.

C: pattern collapse was observed in an area of 5% or more.

< evaluation of the shape of the scum and resist Pattern >

In each of the examples and comparative examples, a resist pattern as a 2 μm line-and-space pattern was formed on the protective layer by the same method as the evaluation of the pattern collapse described above. The exposure amount was set to an exposure amount at which the line width of the 2 μm line and the gap became 1: 1.

After the formation of the resist pattern, whether or not there was a residue or an undercut (Footing) of the photosensitive layer in the removed portion of the photosensitive layer by development was observed by a scanning electron microscope, and evaluated. The evaluation criteria are as follows. The evaluation results are shown in the column "residue" in table 1 or table 2.

[ evaluation criteria ]

A: no residue of the photosensitive layer was confirmed in the removed portion of the photosensitive layer, and no underprint was confirmed at the boundary between the resist pattern and the protective layer.

B: the residue was confirmed, but the bottom impression was not confirmed.

C: the residue was not confirmed, but the underprint was confirmed.

D: both the residue and the underprint were confirmed.

The details of the developing solutions described in tables 1 to 2 are as follows.

nBA: acetic acid n-butyl ester

TMAHaq: 2.38% by mass aqueous solution of tetramethylammonium hydroxide

< evaluation of post-etching shape >

In each of the examples and comparative examples, a resist pattern as a 2 μm line-and-space pattern was formed on the protective layer by the same method as the evaluation of the pattern collapse described above.

Then, etching was performed under the following etching conditions. The line width of the protective layer remaining after etching was observed using a top-down scanning electron microscope, and the results were determined according to the following criteria, and are shown in the column of "shape after etching" in tables 1 and 2.

Conditions are as follows: source power 200W, gas: oxygen flow rate of 500ml/min, nitrogen flow rate of 25ml/min, and time of 3 min

[ evaluation criteria ]

A: no surface roughness was observed in the transferred pattern, and the cross-sectional shape was rectangular.

B: no surface roughness was observed in the transferred pattern, but the cross-sectional shape was not rectangular.

C: surface roughness was observed in the transferred pattern.

< manufacturing and luminescence of light emitting element >

In each of examples and comparative examples, a protective layer, an intermediate layer, and a protective layer, an intermediate layer (if necessary), and a photosensitive layer were produced in the same manner as in the formation of the photosensitive layer, and the resultant was used as a laminate for forming a light-emitting element, except that a layer in which the HIL, the HTL, the EML, the ETL, and the EIL described in table 3 below were laminated in this order from the ITO side on the substrate was used as an organic layer. The lamination is performed by sequentially forming films using a deposition machine.

The obtained laminate for forming a light-emitting element was subjected to formation of a resist pattern by the same method as the evaluation of pattern collapse described above except that a 100 μm square binary mask was used as a photomask instead of the binary mask having a 1:1 line and gap pattern with a line width of 2 μm.

The resist pattern obtained was used as a mask pattern, and dry etching of the substrate was performed under the following conditions to remove the protective film layer of the non-mask pattern portion and the organic layer of the non-mask pattern portion.

Conditions are as follows: source power 200W, gas: oxygen flow rate of 500ml/min, nitrogen flow rate of 25ml/min, and time of 3 min

In the example described as "rotation" in the column of "peeling method" in table 1 or table 2, water was supplied as a peeling liquid using a transfer pipe. During this time, the substrate was rotated at 1,000rpm (revolutions per minute). The water supply using the transfer pipe was performed 5 times in total. Spin drying was performed after 15 seconds from the last water supply. In the example described as "heptafluorotributylamine" in the column of "peeling method" in table 1 or table 2, peeling was performed by the same method as the method using water described above, except that perfluorotributylamine was used as the peeling liquid instead of water. In comparative example 4, the separation using the above-described separation liquid was not performed.

After the protective layer was peeled off, an aluminum layer (100nm) was formed on the surface of the Alq3 layer by vapor deposition, and a light-emitting element device was produced as a cathode electrode. When light is emitted, a voltage of 12V is applied between the ITO layer (anode electrode) on the substrate and the cathode electrode from the outside to emit light. The illuminance of the light-emitting element at this time was 1,000 nit.

The abbreviations in table 3 are detailed as follows.

EIL: electron injection layer

ETL: electron transport layer

EML: luminescent layer

HTL: hole transport layer

HIL: hole injection layer

Alq 3: tris (8-quinolinato) aluminium

BAlq: bis (2-methyl-8-quinolinate) -4- (phenylphenol) aluminum

CBP: 4, 4' -bis (9-carbazolyl) biphenyl

Ir (ppy) 3: tris (2-phenylpyridyl) iridium (III)

NPD: diphenylnaphthalene diamine

HAT-CN: 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene

[ evaluation of light-emitting region after patterning ]

The light-emitting element was allowed to emit light in the air for 3 days, and then the area ratio of non-light-emitting regions (black dot regions) in a light-emitting region of 10 μmx10 μm in the center of the light-emitting element was calculated. The area ratio was calculated by taking a photograph using an optical microscope. The obtained area ratio was used and evaluated according to the following evaluation criteria. The evaluation results are shown in the column of "black dots" in table 1 or table 2. It can be said that the smaller the area ratio of the black dot region, the more excellent the light emission.

A: the area ratio of the black dot region is less than 10 area% of the whole.

B: the area ratio of the black dot region is 10 area% or more and less than 30 area% of the entire region.

C: the area ratio of the black dot region is 30 area% or more of the entire region.

[ Table 1]

[ Table 2]

[ Table 3]

As is clear from the results shown in tables 1 to 2, when the laminate of the present invention of each example was used, pattern collapse of the pattern of the photosensitive layer after development was suppressed and pattern transferability was excellent, as compared with the case of using the laminate of the comparative example.

In the laminate of comparative example 1, the content of the repeating unit having a polar group contained in the resin contained in the photosensitive layer is 10 mass% or more with respect to the total mass of the resins. Therefore, it is understood that in comparative example 1, the shape of the resist after etching is poor, and the pattern transferability is poor.

In the laminate of comparative example 2 or comparative example 3, the resin contained in the photosensitive layer does not contain a repeating unit having an acid-decomposable group represented by formula (a 1). Therefore, it is found that in comparative example 2 or comparative example 3, the shape of the resist after etching is poor, and the pattern transferability is poor.

In comparative example 4, the protective layer was not subjected to removal using a stripping liquid. It is found that, in this method, the protective layer remains without being removed in the obtained device, and therefore, the device cannot be used for forming an organic electroluminescent element used for the evaluation of light emission.

Description of the symbols

1-a photosensitive layer, 1 a-a photosensitive layer after exposure development, 2-a protective layer, 3-an organic layer, 3 a-an organic layer after processing, 4-a substrate, 5-a removed portion, 5 a-a removed portion after etching.