JP2021110796A - Photosensitive resin composition, layered film, photosensitive layer, laminate, kit and semiconductor device - Google Patents

Abstract

To provide a new photosensitive resin composition which is used for formation of a photosensitive layer that enables positive type development using an organic solvent, a layered film which is composed of the photosensitive resin composition, a photosensitive layer which is formed from the photosensitive resin composition, a laminate including the photosensitive layer, a kit including the photosensitive resin composition, and a semiconductor device including a patterned organic layer using the photosensitive layer.SOLUTION: There are provided: a photosensitive resin composition which contains a resin having an acid group, a photoacid generator and a compound having a vinyl ether group and is used for formation of a photosensitive layer used for a positive type phenomenon using a developer containing an organic solvent; a layered film which is composed of the photosensitive resin composition; a photosensitive layer which is formed from the photosensitive resin composition; a laminate including the photosensitive layer; a kit including the photosensitive resin composition; and a semiconductor device including a patterned organic layer using the photosensitive layer.SELECTED DRAWING: Figure 1

Description

The present invention relates to photosensitive resin compositions, layered films, photosensitive layers, laminates, kits and semiconductor devices.

In recent years, electronic devices using organic semiconductors (organic semiconductor devices) have been widely used. Organic semiconductor devices have an advantage that they can be manufactured by a simple process as compared with conventional electronic devices using inorganic semiconductors such as silicon. Further, the material properties of an organic semiconductor can be easily changed by changing its molecular structure. In addition, there are a wide variety of materials, and it is thought that it will be possible to realize functions and elements that could not be achieved with inorganic semiconductors. Organic semiconductors can be applied to electronic devices such as organic solar cells, organic electroluminescence displays, organic optical detectors, organic field effect transistors, organic electroluminescent devices, gas sensors, organic rectifying devices, organic inverters, and information recording devices. There is sex.
It is known that such patterning of an organic layer such as an organic semiconductor is performed using a laminate including an organic layer and a layer such as a photosensitive layer (for example, a resist layer).

For example, Patent Document 1 has an organic semiconductor film, a protective film on the organic semiconductor film, and a resist film on the protective film, and the resist film is an organic acid having a pKa of a generated acid of -1 or less. Laminated with a photosensitive resin composition containing a photoacid generator (A) that generates The body is listed.

JP-A-2015-87609

The present invention comprises a novel photosensitive resin composition used for forming a photosensitive layer capable of positive development using an organic solvent, a layered film composed of the photosensitive resin composition, and the photosensitive resin composition. It is an object of the present invention to provide a semiconductor device including a formed photosensitive layer, a laminate containing the photosensitive layer, a kit containing the photosensitive resin composition, and an organic layer patterned using the photosensitive layer. ..

Typical embodiments of the present invention are shown below.
<1> Resin having an acid group,
Photoacid generator and
Contains compounds, which have a vinyl ether group,
A photosensitive resin composition used for forming a photosensitive layer to be used for positive development using a developing solution containing an organic solvent.
<2> The photosensitive resin composition according to <1>, wherein the compound having a vinyl ether group is a monofunctional vinyl ether compound.
<3> The photosensitive resin composition according to <1> or <2>, wherein the SP value of the compound having a vinyl ether group is 17 to 21 MPa ^1/2.
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the compound having a vinyl ether group is an alkyl vinyl ether compound.
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the compound having a vinyl ether group has a boiling point of 80 ° C. or higher.
<6> Any one of <1> to <5>, wherein the photoacid generator is a compound that generates one kind of acid selected from sulfonic acid, trialkylsulfonylmethidoic acid, and diallylsulfonylimide acid. The photosensitive resin composition according to.
<7> As the photoacid generator, a compound having at least one group selected from the group consisting of an oxime sulfonate group and an imide sulfonate group, and at least one cation selected from the group consisting of a sulfonium cation and an iodonium cation. The photosensitive resin composition according to any one of <1> to <6>, which comprises at least one compound selected from the group consisting of a compound having, a diazosulfone compound, and a disulfone compound.
<8> Any one of <1> to <7>, wherein the content of the acid group with respect to the total mass of the resin is 0.1 × 10 ^{-3 to} 6.0 × ^{10-3 mol / g.} The photosensitive resin composition according to 1.
<9> The photosensitive resin composition according to any one of <1> to <8>, wherein the acid group in the resin is a carboxy group or a phenolic hydroxy group.
<10> A layered film made of the photosensitive resin composition according to any one of <1> to <9>.
<11> A photosensitive layer formed from the photosensitive resin composition according to any one of <1> to <9>.
<12> A laminate containing the protective layer and the photosensitive layer according to <11>.
<13> The laminate according to <12>, further comprising an organic layer on the side opposite to the photosensitive layer of the protective layer.
<14> The photosensitive resin composition according to any one of <1> to <9> and a protective layer forming composition for forming a protective layer are included.
A kit used to form a laminate containing a photosensitive layer and a protective layer.
<15> A semiconductor device including an organic layer patterned using a photosensitive layer formed from the photosensitive resin composition according to any one of <1> to <9>.

According to the present invention, a novel photosensitive resin composition used for forming a photosensitive layer capable of positive development using an organic solvent, a layered film composed of the photosensitive resin composition, and the photosensitive resin composition. Provided are a semiconductor device including a photosensitive layer formed from an object, a laminate containing the photosensitive layer, a kit containing the photosensitive resin composition, and an organic layer patterned using the photosensitive layer.

It is sectional drawing which shows typically an example of the processing process of the laminated body using the photosensitive resin composition of this invention.

Hereinafter, typical embodiments of the present invention will be described. Each component will be described based on this representative embodiment for convenience, but the present invention is not limited to such embodiments.

In the present specification, the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
In the present specification, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
Regarding the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution means to include those having a substituent as well as those having no substituent. For example, when simply described as "alkyl group", this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). Means. Further, when simply described as "alkyl group", this means that it may be chain-like or cyclic, and in the case of chain-like, it may be linear or branched. These are also synonymous with other groups such as "alkenyl group", "alkylene group" and "alkenylene group".
In the present specification, "exposure" means not only drawing using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Examples of energy rays used for drawing include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, active rays such as extreme ultraviolet rays (EUV light) and X-rays, and particle beams such as electron beams and ion beams. Be done.
In the present specification, "light" includes not only light having wavelengths in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, and infrared regions, electromagnetic waves, but also radiation, unless otherwise specified. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet rays (EUV), and X-rays. Further, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. As these lights, monochrome light (single wavelength light) that has passed through an optical filter may be used, or light containing a plurality of wavelengths (composite light) may be used.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or , And "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.
In the present specification, the solid content in the composition means other components other than the solvent, and the content (concentration) of the solid content in the composition is, unless otherwise specified, based on the total mass of the composition. It is represented by the mass percentage of other components excluding the solvent.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101325 Pa (1 atm), and the relative humidity is 50% RH.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are shown as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. For the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, and TSKgel are used as columns. It can be obtained by using Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, the measurement is carried out using THF (tetrahydrofuran) as the eluent. Unless otherwise specified, a UV ray (ultraviolet) wavelength 254 nm detector is used for detection in GPC measurement.
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention contains a resin having an acid group, a photoacid generator, and a compound having a vinyl ether group, and is used for positive development using a developing solution containing an organic solvent. Used for the formation of.
Since the photosensitive layer formed by the photosensitive resin composition of the present invention contains a photoacid generator, it is considered that acid is generated in the exposed portion by exposure.
Here, it is considered that the generated acid causes the acid group and the compound having a vinyl ether group contained in the resin to form a crosslinked structure (for example, an acetal structure), and the solubility of the resin in a solvent is improved.
As a result, it is considered that the photosensitive layer can be subjected to positive development using a developing solution containing a solvent because the solubility of the resin in the solvent is improved in the exposed portion.
As described above, the present invention relates to a novel photosensitive resin composition used for forming a photosensitive layer capable of positive development using an organic solvent, a layered film composed of the photosensitive resin composition, and the photosensitive layer. Inventions relating to a photosensitive layer formed from a photosensitive resin composition, a laminate containing the photosensitive layer, a kit containing the photosensitive resin composition, and a semiconductor device including an organic layer patterned using the photosensitive layer. Is.

Conventionally, a resist pattern has been formed in a laminate having an organic layer and a photosensitive layer, and etching has been performed to form a pattern of the organic layer.
For example, the photosensitive layer contained in the laminate described in Patent Document 1 contains a resin whose dissolution rate in a developing solution containing an organic solvent is reduced in response to an acid generated from a photoacid generator in an exposed portion.
As described above, the photosensitive layer contained in the laminate described in Patent Document 1 contains a resin whose dissolution rate in a developing solution is reduced in the exposed portion of the photosensitive layer. That is, the photosensitive layer described in Patent Document 1 is used for negative type development using a developing solution containing an organic solvent, and development containing an organic solvent using the photosensitive resin composition of the present invention. It is completely different from the photosensitive layer used for positive development using a liquid.

Here, when a photosensitive layer used for negative type development using a developing solution containing an organic solvent as described above is used, the pattern collapses due to attenuation of exposure light or the like, resulting in a reverse taper pattern. There was room for improvement in the point that
For example, when the exposure is performed from the side opposite to the organic layer, the width of the pattern on the organic layer side (the side far from the exposure light source) of the pattern formed by the photosensitive layer due to the attenuation of the exposure light or the like is the above pattern. Since the width is smaller than the width on the opposite side of the organic layer, it is considered that pattern collapse may occur.
By using a photosensitive resin composition capable of positive development using a solvent, such as the photosensitive resin composition of the present invention, it is formed by the photosensitive layer even when the exposure light is attenuated. Since the width of the pattern on the organic layer side of the pattern (the side far from the exposure light source) is larger than the width on the side opposite to the organic layer of the above pattern (becomes a forward taper), it is considered that the pattern collapse is easily suppressed. Be done.

Further, in such a laminated body including a positive photosensitive layer and an organic layer, it is also a preferable embodiment that the laminated body is provided with a protective layer between the photosensitive layer and the organic layer.
By forming the protective layer in this way, even when the photosensitive layer is developed with a developing solution containing an organic solvent, the organic layer is damaged by the developing solution in the development of the photosensitive layer with the developing solution containing an organic solvent. Is thought to be suppressed.
In a laminate provided with such a protective layer, for example, after forming a pattern of the photosensitive layer, the protective layer and the organic layer are etched using the above pattern as a mask, and then the photosensitive layer is subjected to a stripping solution such as water. It is used in the organic layer patterning method of removing the pattern and the protective layer.
In the present invention, since the pattern shape tends to be forward-tapered, it is considered that the pattern collapse is suppressed even when a laminated body including such a protective layer is used.
Hereinafter, each component contained in the curable resin composition of the present invention will be described.

<Resin>
The resin contained in the photosensitive resin composition of the present invention has an acid group.
Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol in which the α-position is substituted with an electron-attracting group (for example, Hexafluoroisopropanol group), phenolic hydroxy and the like can be mentioned, and known acid groups can be used without particular limitation, but among these, a carboxy group or a phenolic hydroxy group is preferable, and a carboxy group is more preferable.

The content of the acid group with respect to the total mass of the resin is preferably 0.1 × 10 ^{-3 to} 6.0 × 10 ^-3 mol / g, and 0.2 × 10 ^{-3 to} 5.5 × 10. more preferably from ^-3 mol / g, further preferably ^{0.5 × 10 -3 ~5.0 × 10 -3} mol / g.

The resin is not particularly limited as long as it has an acid group, but an acrylic polymer or a styrene polymer is preferable, and an acrylic polymer is more preferable.
The "acrylic polymer" is an addition polymerization type resin, a polymer containing a repeating unit derived from (meth) acrylic acid or an ester thereof, and other than the repeating unit derived from (meth) acrylic acid or an ester thereof. The repeating unit of the above, for example, a repeating unit derived from styrenes, a repeating unit derived from a vinyl compound, and the like may be included. The acrylic polymer preferably contains a repeating unit derived from (meth) acrylic acid or an ester thereof in an amount of 50 mol% or more, more preferably 80 mol% or more, based on all the repeating units in the polymer. It is particularly preferable that the polymer consists only of repeating units derived from (meth) acrylic acid or an ester thereof. The upper limit of the content is not particularly limited and may be 100 mol%.
The "styrene-based polymer" is an addition polymerization type resin, a polymer containing a repeating unit derived from styrenes such as styrene, α-methylstyrene, hydroxystyrene, and carboxystyrene, and a repeating unit derived from styrenes. It may contain a repeating unit other than the above, for example, a repeating unit derived from (meth) acrylic acid or an ester thereof, a repeating unit derived from a vinyl compound, and the like. The styrene-based polymer preferably contains 50 mol% or more of repeating units derived from styrenes, and more preferably 80 mol% or more, based on all the repeating units in the polymer. The upper limit of the content is not particularly limited and may be 100 mol%.

式（Ａ１）〜式（Ａ５）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は水素原子又は１価の有機基を表し、Ａ^１、Ａ^２及びＡ^３は酸基を含む構造を表し、ｎ１及びｎ２は１〜５の整数を表し、ｎ３は１〜８の整数を表す。 The resin having an acid group preferably contains at least one selected from the group consisting of repeating units represented by any of the following formulas (A1) to (A5), and preferably contains the formula (A1) or the formula (A2). It is more preferable to include a repeating unit represented by.

Wherein (A1) ~ formula ^{(A5), R 1, R} 2, R 3, R 4, R 5 and ^{R 6} represents a hydrogen atom or a monovalent organic ^group, A 1, ^{A 2} and ^{A 3} are acid Represents a structure containing groups, n1 and n2 represent integers 1 to 5, and n3 represents integers 1-8.

In the formula (A1), R ¹ is preferably a hydrogen atom, an alkyl group, CF ₃ or CH ₂ OH, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a methyl group.

式（Ａ２−１）〜式（Ａ２−４）中、Ｌ^２１はｎ２１＋１価の連結基を表し、Ｒ^２２は１価の有機基を表し、Ｌ^２２は単結合又はｎ２２＋１価の連結基を表し、Ｌ^２３はｎ２３＋１価の連結基を表し、Ｌ^２４はｎ２４＋１価の連結基を表し、ｎ２１は１以上の整数を表し、ｎ２２は１以上の整数を表し、ｎ２３は１以上の整数を表し、ｎ２４は１以上の整数を表し、＊は他の構造との結合部位を表す。 In the formula (A2), R ² is preferably a hydrogen atom, an alkyl group, CF ₃ or CH ₂ OH, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a methyl group.
In the formula (A2), A ¹ represents a structure containing an acid group, and is preferably a group represented by any of the following formulas (A2-1) to (A2-4), preferably the following formula (A2-). It is more preferable that the group is represented by 1).
The number of acid groups contained in A ¹ is not limited, and may be 1 or more, but preferably 1 to 4, more preferably 1 or 2, and 1 or more. Is even more preferable.

In formulas (A2-1) to (A2-4), L ²¹ represents an n21 + 1-valent linking group, R ²² represents a monovalent organic group, and L ²² represents a single bond or an n22 + 1-valent linking group. , L ²³ represents a linking group of n23 + 1 valence, L ²⁴ represents a linking group of n24 + 1 valence, n21 represents an integer of 1 or more, n22 represents an integer of 1 or more, and n23 represents an integer of 1 or more. n24 represents an integer of 1 or more, and * represents a bonding site with another structure.

In formula (A2-1), L ²¹ consists of a hydrocarbon group or a group consisting of a hydrocarbon group, −O−, −S−, −C (= O) −, and −S (= O) _2−. It represents a group represented by at least two selected bonds, more preferably a hydrocarbon group.
As the hydrocarbon group, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a bond thereof is preferable, and the hydrocarbon group has 2 to 30 carbon atoms. Saturated aliphatic hydrocarbon groups are more preferred.
The aliphatic hydrocarbon group may be linear, branched or cyclic, or may be a group represented by a bond thereof.

In the formula (A2-1), n21 represents an integer of 1 or more, and is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.

In formula (A2-2), R ²² consists of a hydrocarbon group or a group consisting of a hydrocarbon group, −O−, −S−, −C (= O) −, and −S (= O) _2−. Represents a group represented by at least two selected bonds and is represented by a hydrocarbon group or at least two bonds selected from the group consisting of hydrocarbon groups -O- and -C (= O)-. It is preferable to represent the group to be used.
As the hydrocarbon group, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a bond thereof is preferable, and the hydrocarbon group has 2 to 30 carbon atoms. Saturated aliphatic hydrocarbon groups are more preferred.
The aliphatic hydrocarbon group may be linear, branched or cyclic, or may be a group represented by a bond thereof.
In the formula (A2-2), L ^{22 preferably represents a single bond or a group similar to L 21} of the formula (A2-1), and a single bond is more preferable.
In the formula (A2-2), n22 represents an integer of 1 or more, and is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.

In the formula (A2-3), L ^{23 is synonymous with L 21 in the} formula (A2-1), and the preferred embodiment is also the same.
In the formula (A2-3), n23 represents an integer of 1 or more, and is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.

In the formula (A2-4), L ^{24 is synonymous with L 21 in the} formula (A2-1), and the preferred embodiment is also the same.
In the formula (A2-4), n24 represents an integer of 1 or more, and is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.

In the formula (A3), R ³ is preferably a hydrogen atom, an alkyl group, CF ₃ or CH ₂ OH, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, further preferably a hydrogen atom or a methyl group, and a hydrogen atom. Is particularly preferable.
In the formula (A3), n1 is preferably 1 or 2, and more preferably 1.

In the formula (A4), R ⁴ is preferably a hydrogen atom, an alkyl group, CF ₃ or CH ₂ OH, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, further preferably a hydrogen atom or a methyl group, and a hydrogen atom. Is particularly preferable.
In the formula (A4), A ^{2 has the same meaning as A 1} in the formula (A2), and the preferred embodiment is also the same.
In the formula (A4), n2 is preferably 1 or 2, and more preferably 1.

In the formula (A5), R ⁵ and R ⁶ are independently hydrogen atom, alkyl group, CF ₃ or CH ₂ OH, more preferably hydrogen atom or alkyl group having 1 to 4 carbon atoms, and hydrogen atom or methyl. A group is more preferable, and a hydrogen atom is particularly preferable.
In the formula (A5), A ^{3 has the same meaning as A 1} in the formula (A2), and the preferred embodiment is also the same.
In the formula (A5), n3 is preferably 1 or 2, and more preferably 1.

Preferred examples of the repeating unit having an acid group include, but are not limited to, the following repeating unit. In the specific examples below, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

The content of the repeating unit having an acid group in the resin is preferably 0.1 to 60% by mass, more preferably 1 to 50% by mass, and further preferably 10 to 50% by mass with respect to the total mass of the resin.

式中、Ｒ_Ｘは、水素原子、メチル基、ヒドロキシメチル基、又は、トリフルオロメチル基を表す。
Ａｂは、単結合、又は２価の連結基を表す。
Ａｂにより表される２価の連結基としては、例えば、アルキレン基、シクロアルキレン基、エステル結合、アミド結合、エーテル結合、ウレタン結合、ウレア結合、又はその組み合わせ等が挙げられる。アルキレン基としては、炭素数１〜１０のアルキレン基が好ましく、炭素数１〜５のアルキレン基がより好ましく、例えば、メチレン基、エチレン基、プロピレン基等が挙げられる。
本発明の一形態において、Ａｂは、単結合、又は、アルキレン基であることが好ましい。
Ｒｐは、水素原子、ヒドロキシ基、又は、ヒドロキシアルキル基を表す。複数のＲｐは、同一でも異なっていても良いが、複数のＲｐの内の少なくとも１つは、ヒドロキシ基又はヒドロキシアルキル基を表す。 [Repeating unit having at least one of a hydroxy group and a cyano group]
The resin may have a repeating unit having at least one of a hydroxy group and a cyano group. This improves substrate adhesion and developer affinity. The repeating unit having at least one of a hydroxy group and a cyano group is preferably a repeating unit having a hydrocarbon structure substituted with at least one of a hydroxy group and a cyano group. The hydrocarbon structure is preferably an aliphatic hydrocarbon group having a linear, branched or cyclic structure, and more preferably a repeating unit having an alicyclic hydrocarbon structure. Further, it is preferable that the repeating unit having at least one of a hydroxy group and a cyano group does not have an acid-degradable group.
Further, the repeating unit having an alicyclic hydrocarbon structure substituted with at least one of a hydroxy group and a cyano group is preferably different from the repeating unit having an acid-degradable group (that is, a repeating unit stable to an acid). Is preferable).
The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with at least one of the hydroxy group and the cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group.
More preferably, a repeating unit represented by any of the following general formulas (AIIA) to (AIIc) can be mentioned.

In the formula, _RX represents a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group.
Ab represents a single bond or a divalent linking group.
Examples of the divalent linking group represented by Ab include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination thereof. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 5 carbon atoms is more preferable, and examples thereof include a methylene group, an ethylene group, and a propylene group.
In one embodiment of the invention, Ab is preferably a single bond or an alkylene group.
Rp represents a hydrogen atom, a hydroxy group, or a hydroxyalkyl group. The plurality of Rp may be the same or different, but at least one of the plurality of Rp represents a hydroxy group or a hydroxyalkyl group.

The resin may or may not contain a repeating unit having at least one of a hydroxy group and a cyano group, but if the resin contains a repeating unit having at least one of a hydroxy group and a cyano group. The content of the repeating unit having at least one of a hydroxy group and a cyano group is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, still more preferably 2 to 25% by mass, based on the total mass of the resin. %.
Specific examples of repeating units having a hydroxy group or a cyano group are given below, but the present invention is not limited thereto.

In addition, the resin may further contain repeating units corresponding to the monomers described in paragraph 0011 and after of paragraph 0011 of International Publication No. 2011/122336.

[Repeating unit having a hydrocarbon structure without polar groups and showing no acid degradability]
The resin in the present invention has a hydrocarbon structure having no polar group (for example, the above-mentioned acid group, hydroxy group, cyano group) and can have a repeating unit that does not exhibit acid decomposition. As a result, the solubility of the resin can be appropriately adjusted during development using a developing solution containing an organic solvent. Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In the general formula (IV), R ⁵ represents a hydrocarbon group having no polar group.
Ra represents a hydrogen atom, an alkyl group or a group represented by _{-CH 2-} O-Ra ^2. Ra ² represents a hydrogen atom, an alkyl group or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Hydrocarbon group having no polar group for R ⁵ is an alkyl group is preferable, more preferably, a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, n- propyl Examples thereof include a group, an i-propyl group, an n-butyl group, an i-butyl group, an n-amyl group, an i-amyl group, an n-hexyl group, an n-octyl group and a 2-ethylhexyl group. These groups may further have substituents. Examples of the substituent include a halogen atom such as a nitro group and a fluorine atom, an alkoxy group (preferably 1 to 15 carbon atoms), a cycloalkyl group (preferably 3 to 15 carbon atoms), and an aryl group (preferably 6 to 15 carbon atoms). 14), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms) and the like, but are limited thereto. It is not something that is done.
The alkyl group may have a substituent such as an aromatic hydrocarbon group.
The hydrocarbon group having no polar group of ^{R 5 may have a cyclic structure.} Cyclic structures include monocyclic hydrocarbon groups and polycyclic hydrocarbon groups. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group, and a cycloalkenyl group having 3 to 12 carbon atoms such as a cyclohexenyl group. The group is mentioned. A preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferably a cyclopentyl group or a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring-assembled hydrocarbon group and a cross-linked ring-type hydrocarbon group, and examples of the ring-assembled hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. Bicyclic hydrocarbon rings such as pinan, bornan, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [ 4.4.0.1 ^2,5 . ^{17 and 10} ] Dodecane, 4-cyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene rings and the like can be mentioned. In addition, the crosslinked cyclic hydrocarbon ring includes a fused cyclic hydrocarbon ring, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroinden, perhydro. A fused ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenanthrene ring are condensed is also included.

As preferred crosslinked-ring hydrocarbon rings, a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6] decanyl group, and the like. More preferable crosslinked cyclic hydrocarbon rings include a norbornyl group and an adamantyl group.

These alicyclic hydrocarbon groups may have a substituent, and preferred substituents include a halogen atom, an alkyl group, a hydroxy group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. Be done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and tert-butyl groups. The above alkyl group may further have a substituent, and the substituent which may further have is a halogen atom, an alkyl group, a hydroxy group substituted with a hydrogen atom, and an amino substituted with a hydrogen atom. The group can be mentioned.

Examples of the substituent of the hydrogen atom include an alkyl group (including a cycloalkyl group), an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, tert-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. , 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferably aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, and pivaloyl groups, alkoxycarbonyl. Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

The resin has a hydrocarbon structure having no polar group and may or may not contain a repeating unit that does not exhibit acid decomposition, but the resin has a hydrocarbon structure having no polar group and acid decomposition. When a repeating unit showing no property is included, the content of the repeating unit is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and 1 to 20% by mass with respect to the total mass of the resin. More preferred.
Specific examples of repeating units having a hydrocarbon structure having no polar group and not exhibiting acid decomposition are given below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

In the resin used in the photosensitive resin composition used in the present invention, the content ratio of each repeating unit is the dry etching resistance of the photosensitive resin composition, suitability for a standard developer, substrate adhesion, resist profile, and general resist. It is appropriately set to adjust the required performance such as resolution, heat resistance, and sensitivity.
The form of the resin in the present invention may be any of a random type, a block type, a comb type, and a star type. The resin can be synthesized, for example, by radical, cationic, or anionic polymerization of unsaturated monomers corresponding to each structure. It is also possible to obtain the desired resin by carrying out a polymer reaction after polymerization using an unsaturated monomer corresponding to a precursor of each structure.

The resin in the present invention can be synthesized according to a conventional method (for example, radical polymerization).
The weight average molecular weight of the resin used in the composition of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and even more preferably 2,000 to 200,000 in terms of polystyrene by the GPC method. It is 3,000 to 70,000, particularly preferably 5,000 to 50,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and the developability deteriorates or the viscosity increases and the film forming property deteriorates. Can be prevented.

The degree of dispersion (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.2 to 2.4, and particularly preferably 1.4 to 2.2. Those in the range of are used. When the molecular weight distribution satisfies the above range, the resolution and the resist shape are excellent, the side wall of the resist pattern is smooth, and the roughness is suppressed.
In the photosensitive resin composition of the present invention, the content of the resin is preferably 30 to 99% by mass, more preferably 60 to 95% by mass, based on the total solid content of the photosensitive resin composition.
Further, the photosensitive resin composition of the present invention may contain one kind of resin alone or two or more kinds of resin. When the photosensitive resin composition of the present invention contains two or more kinds of resins, the total amount thereof is preferably within the above range.

<Compound with vinyl ether group>
The compound having a vinyl ether group contained in the photosensitive resin composition of the present invention (hereinafter, also referred to as “vinyl ether compound”) is not particularly limited, and may be a monofunctional vinyl ether compound or a polyfunctional vinyl ether compound. The photosensitive resin composition of the present invention preferably contains at least one selected from the group consisting of a monofunctional vinyl ether compound and a bifunctional vinyl ether compound, and more preferably a monofunctional vinyl ether compound.
In the present invention, a compound having only one vinyl ether group in the structure is called a monofunctional vinyl ether compound, a compound having two or more vinyl ether groups in the structure is called a polyfunctional vinyl ether compound, and two vinyl ether groups in the structure. A compound having only a bifunctional vinyl ether compound is called a bifunctional vinyl ether compound.
Further, the vinyl ether group in the compound having a vinyl ether group may have a substituent on the vinyl group. Examples of the above-mentioned substituent include known substituents such as an alkyl group and an aryl group. Further, in the present invention, an embodiment in which the vinyl group does not have a substituent is also one of the preferred embodiments.

The compound having a vinyl ether group may have a vinyl ether group, but a compound in which a vinyl group and a hydrocarbon group are bonded by an ether bond, or a hydrocarbon group containing a vinyl group and an ether bond inside is used. It is preferably a compound bonded by an ether bond, and more preferably a compound in which a vinyl group and a hydrocarbon group are bonded by an ether bond.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aliphatic hydrocarbon group is preferable.
The aliphatic hydrocarbon group may be an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferable, an alkyl group or an alkylene group is more preferable, and an alkyl group is further preferable.
The carbon number of the aliphatic hydrocarbon group is preferably 1 to 20, and more preferably 2 to 10.
The aliphatic hydrocarbon group may be linear, branched or cyclic, or may have a structure represented by a combination thereof.
As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, and a group obtained by removing one or more hydrogen atoms from the benzene ring structure is more preferable.
As the hydrocarbon group containing the ether bond inside, a polyalkyleneoxy group is preferable, a polyethyleneoxy group, a polypropyleneoxy group, or a polybutyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable.
The number of repetitions of the alkyleneoxy group in the polyalkyleneoxy group is not particularly limited, but is preferably 2 to 10 and more preferably 2 to 4.

Among these, the alkyl vinyl ether compound is preferable as the compound having a vinyl ether group.
In the present invention, the alkyl vinyl ether compound refers to a compound in which an alkyl group and a vinyl group are bonded by an ether bond.
The alkyl group preferably has 1 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.
The alkyl group may be linear, branched or cyclic, or may have a structure represented by a combination thereof.
Preferred specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclohexyl group, a 2-ethylhexyl group and the like.

From the viewpoint of the developing property exposure unit, SP values of the compounds having a vinyl ether group is preferably 17～21MPa ^1/2, and more preferably 18~20MPa ^1/2.
In the present invention, the "SP value" means the "value of the solubility parameter". The SP value referred to in the present invention is the Hansen solubility parameter according to the formula explained in Hansen Solubility Parameter: A User's Handbook, Second Edition, CMHansen (2007), Taylor and Francis Group, LLC (HSPiP Manual). Using the solubility parameter HSPiP 3rd edition (software version 4.0.05), the SP value calculated by the following formula is used.
(SP value) ² = (δHd) ² + (δHp) ² + (δHh) ²
Hd: Dispersion contribution Hp: Polarity contribution Hh: Hydrogen bond contribution

The boiling point of the compound having a vinyl ether group is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and even more preferably 100 ° C. or higher.
The upper limit of the boiling point is not particularly limited, but can be, for example, 250 ° C. or lower.

The molecular weight of the compound having a vinyl ether group is preferably 72 to 2,000, more preferably 72 to 1,000, and even more preferably 72 to 500.

Specific examples of the compound having a vinyl ether group include, but are not limited to, alkyl ether compounds such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, and 2-ethylhexyl vinyl ether, diethylene glycol divinyl ether, and the like. Examples thereof include polyalkylene glycol divinyl ether compounds such as triethylene glycol divinyl ether, polyalkylene glycol monovinyl ether compounds such as diethylene glycol monovinyl ether and triethylene glycol monovinyl ether.

The content of the compound having a vinyl ether group in the photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive resin composition. More preferably, it is by mass%.
The content of the compound having a vinyl ether group in the photosensitive resin composition of the present invention is 2 to 100% by mass with respect to the total mass of the resin having an acid group contained in the photosensitive resin composition. It is preferably 5 to 50% by mass, more preferably 5 to 50% by mass.
The photosensitive resin composition of the present invention may contain a compound having a vinyl ether group alone or in combination of two or more. When two or more kinds are used in combination, the total content is preferably within the above range.

<Photoacid generator>
The photosensitive resin composition of the present invention contains a photoacid generator.
The photoacid generator is not particularly limited as long as it is a compound that generates an acid upon exposure, but a photoacid generator that generates an acid having a pKa of the generated acid of 0 or less is preferable. More preferably, it is a photoacid generator that generates an acid having a pKa of -1 or less. The lower limit of the pKa is not particularly limited, and may be, for example, -10 or more, and may be -5 or more.
In the present invention, pKa represents the logarithm of the reciprocal of the first dissociation constant of acid, and the Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; You can refer to the values described in Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMCet al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using ACD / pKa (manufactured by ACD / Labs) software is used as pKa.

The photoacid generator is preferably a compound that generates one kind of acid selected from sulfonic acid, trialkylsulfonylmethidoic acid and diallylsulfonylimide acid.
In the case of a compound that generates these acids, the bond between the acid group contained in the above-mentioned resin and the above-mentioned compound having a vinyl ether group can easily proceed efficiently.

The photosensitive resin composition of the present invention is a compound having at least one group selected from the group consisting of an oxime sulfonate group and an imide sulfonate group, and at least one cation selected from the group consisting of a sulfonium cation and an iodonium cation. It is preferable to contain at least one compound selected from the group consisting of a compound having, a diazosulfone compound, and a disulfone compound.
It is considered that by using these compounds, the efficiency of acid generation by exposure is improved, and the above-mentioned bonding between the acid group and the compound having a vinyl ether group is likely to proceed efficiently.

[Compound having at least one group selected from the group consisting of an oxime sulfonate group and an imide sulfonate group]
The compound having an oxime sulfonate group (hereinafter, also referred to as “oxime sulfonate compound”) is not particularly limited as long as it has an oxime sulfonate group, but the following formula (2), the formula (OS-103) described later, and the formula. (OS-104) or an oxime sulfonate compound represented by the formula (OS-105) is preferable.

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

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

^{R 4} in the formula (2) represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. It is preferably a halogenated alkoxy group of 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, or an alkoxy halide having 1 to 5 carbon atoms. Represents a group.
Specific examples of the alkyl group having 1 to 10 carbon atoms in R ⁴ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and tert. Examples thereof include -butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group.
Specific examples of the alkoxy group having 1 to 10 carbon atoms in R ⁴ include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an n-amyloxy group, and an n-octyloxy group. Examples thereof include an n-decyloxy group.
Specific examples of the alkyl halide group having 1 to 5 carbon atoms in R ⁴ include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, and a perfluoro-n. − Examples include amyl groups.
Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms in R ⁴ include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, and a perfluoro-n. − Examples include amyloxy groups.

Specific examples of the phenyl group optionally substituted with W in R ⁴ above include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group and p-ethyl. Phenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s-butyl) Phenyl group, p- (tert-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (tert-amyl) phenyl group, o-methoxyphenyl group, m -Methenylphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p − (N-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (tert-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p -(I-amyloxy) phenyl group, p- (tert-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group , 2,4-Difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, penta Fluorophenyl group, p-biphenylyl group and the like can be mentioned.

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

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

In formula (2), m is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴ is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-. Compounds that are 2-oxonorbornylmethyl groups or p-toluyl groups are particularly preferred.
Specific examples of the oxime sulfonate compound represented by the formula (2) include, but are not limited to, the compounds described in paragraphs 0054 to 0057 of International Publication No. 2015/064602.

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

(In formulas (OS-103) to (OS-105), R ¹¹ represents an alkyl group, an aryl group or a heteroaryl group, and a plurality of R ^12s are independently hydrogen atoms, alkyl groups, aryl groups or halogens. Representing an atom, each of the plurality of R ^16s independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, and n represents 1 or 2 represents, and m represents an integer of 0 to 6.)

In the above formulas (OS-103) to (OS-105), the alkyl group, aryl group or heteroaryl group represented by ^{R 11 may have a substituent.}
In the above formulas (OS-103) to (OS-105), the ^{alkyl group represented by R 11} is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.
Examples of the substituent that the alkyl group represented by R ¹¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group. Can be mentioned.

In the above formulas (OS-103) to (OS-105), the ^{alkyl group represented by R 11} includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and an s-butyl group. Group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, etc. Can be mentioned.

Further, in the above formulas (OS-103) to (OS-105), ^{as the aryl group represented by R 11} , an aryl group having a total carbon number of 6 to 30 which may have a substituent is preferable.
Examples of the substituent that the aryl group represented by R ¹¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group and an aryloxycarbonyl group. Examples thereof include an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group and an alkoxysulfonyl group.

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

Further, in the above formulas (OS-103) to (OS-105), ^{as the heteroaryl group represented by R 11} , a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent is preferable.
Examples of the substituent that the heteroaryl group represented by R ¹¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group and an aryloxycarbonyl group. , Aminocarbonyl group, sulfonic acid group, aminosulfonyl group, alkoxysulfonyl group.

In the above formulas (OS-103) to (OS-105), the ^{heteroaryl group represented by R 11} may have at least one complex aromatic ring, for example, the complex aromatic ring and the benzene ring. It may be fused.
The ^{heteroaryl group represented by R 11} may have a substituent, a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring. Examples thereof include a group obtained by removing one hydrogen atom from a ring selected from the group consisting of.

In the above formulas (OS-103) to (OS-105), R ¹² is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
In the above formulas (OS-103) to (OS-105), among R ¹² existing in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. , Aryl groups or halogen atoms are more preferred, one is an alkyl group and the rest are hydrogen atoms.
In the above formulas (OS-103) to (OS-105), the alkyl group or aryl group represented by ^{R 12 may have a substituent.}
Examples of the substituent that the alkyl group or aryl group represented by R ¹² may have include the same group as the substituent that the alkyl group or aryl group in ^{R 1 may have.}

In the above formulas (OS-103) to (OS-105), the ^{alkyl group represented by R 12} is preferably an alkyl group having a total carbon number of 1 to 12 which may have a substituent, and is substituted. More preferably, it is an alkyl group having a total carbon number of 1 to 6 which may have a group.
Examples of the alkyl group represented by R ¹² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group and allyl group. Chloromethyl group, bromomethyl group, methoxymethyl group and benzyl group are preferable, and methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and n-hexyl are preferable. Groups are more preferred, methyl groups, ethyl groups, n-propyl groups, n-butyl groups, n-hexyl groups are even more preferred, and methyl groups are particularly preferred.

In the above formulas (OS-103) to (OS-105), the ^{aryl group represented by R 12} is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.
As the ^{aryl group represented by R 12} , a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group and a p-phenoxyphenyl group are preferable.
Examples of the halogen atom represented by R ¹² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, chlorine atom and bromine atom are preferable.

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

In the above formulas (OS-103) to (OS-105), the alkyl group and the alkyloxy group represented by ^{R 16 may have a substituent.}
In the above formulas (OS-103) to (OS-105), the ^{alkyl group represented by R 16} is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.
Examples of the substituent that the alkyl group represented by R ¹⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group. Can be mentioned.

In the above formulas (OS-103) to (OS-105), the ^{alkyl group represented by R 16} includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and an s-butyl group. Group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group preferable.

In the above formulas (OS-103) to (OS-105), the ^{alkyloxy group represented by R 16} is preferably an alkyloxy group having a total carbon number of 1 to 30 which may have a substituent. ..
Examples of the substituent that the alkyloxy group represented by R ¹⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl. The group is mentioned.

In the above formulas (OS-103) to (OS-105), the ^{alkyloxy group represented by R 16} includes a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, and a trichloromethyloxy group. , Or an ethoxyethyloxy group is preferred.
Examples of the aminosulfonyl group in R ¹⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group.
Examples of the alkoxysulfonyl group represented by R ¹⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

Further, in the above formulas (OS-103) to (OS-105), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. It is particularly preferable to have.

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

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

(In formulas (OS-106) to (OS-111), R ¹¹ represents an alkyl group, an aryl group or a heteroaryl group, R ¹⁷ represents a hydrogen atom or a bromine atom, and R ¹⁸ represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups, R ¹⁹ represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups, and R ²⁰ represents a hydrogen atom or a methyl group.)

R ¹¹ in the formula (OS-106) ~ (OS -111) has the same meaning as R ¹¹ in the formula (OS-103) ~ (OS -105), preferable embodiments thereof are also the same.
^{R 17} in the above formula (OS-106) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
^{R 18} in the above formulas (OS-106) to (OS-111) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or It represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is more preferable, and it is particularly preferable that it is a methyl group.
^{R 19} in the above formulas (OS-108) and (OS-109) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
^{R 20} in the above formulas (OS-108) to (OS-111) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.

Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include, but are limited to, the compounds described in paragraphs 0077 to 0084 of International Publication No. 2015/064602. It is not something that is done.

Another preferred embodiment of the oxime sulfonate compound having at least one oxime sulfonate group includes a compound represented by the following formula (OS-101).

In the above formula (OS-101), R ¹¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group. Represents. R ¹² represents an alkyl group or an aryl group.
X is -O -, - S -, - NH -, - NR 15 -, - CH 2 -, - CR 16 H- or -CR ¹⁶ R ¹⁷ - represent, respectively the R ¹⁵ to R ¹⁷ independently represent an alkyl Represents a group or aryl group.
R ^{21 to} R ²⁴ are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group or aryl. Represents a group. Two of R ^{21 to} R ²⁴ may be combined with each other to form a ring.
As R ^{21 to} R ²⁴ , a hydrogen atom, a halogen atom or an alkyl group is preferable, ^{and an embodiment in which at least two of R 21 to} R ²⁴ are bonded to each other to form an aryl group is also preferable. Above ^{all, the embodiment in which R 21 to} R ²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the above-mentioned substituents may further have a substituent.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the following formula (OS-102).

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

Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.

Specific examples of the compound represented by the formula (OS-101) that can be suitably used in the present invention include, but are limited to, the compounds described in paragraphs 0092 to 0097 of International Publication No. 2015/064602. It is not something that is done.
Commercially available products include WPAG-336 (manufactured by Wako Pure Chemical Industries, Ltd.), WPAG-443 (structure below, manufactured by Wako Pure Chemical Industries, Ltd.), MBZ-101 (structure below, manufactured by Midori Kagaku Co., Ltd.). Etc. can be given.

Examples of the compound having an imide sulfonate group (hereinafter, also referred to as “imide sulfonate compound”) include a compound represented by the general formula (ZV).

In the general formula (ZV), R ²⁰⁸ represents an alkyl or aryl group. A represents an alkylene group, an alkaneylene group or an arylene group. When the alkyl group is a cyclic alkyl group, a ring may be formed via a carbonyl group.
The alkyl group of R ²⁰⁸ is preferably a linear alkyl group or a cyclic alkyl group. R ²⁰⁸ is preferably a linear or branched alkyl group or an aryl group. These groups may or may not be substituted. When the alkyl group is a cyclic alkyl group, a ring may be formed via a carbonyl group, and the cyclic alkyl group may be of a polycyclic type. Preferably, a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group) Or a norbonyl group). The alkyl group of R ²⁰⁸ may be further substituted with, for example, a halogen atom, an alkoxy group (eg, 1 to 5 carbon atoms), a hydroxy group, a cyano group and / or a nitro group.

The aryl group of R ²⁰⁸ is preferably a phenyl group or a naphthyl group.
^The aryl group of R 208 may be further substituted with, for example, a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxy group, a cyano group and / or a nitro group, but preferably 1 to 5 carbon atoms. 10 linear or branched alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group or pentyl group) and cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group or norbonyl group) Can be mentioned.

The alkylene group of A has an alkylene group having 1 to 12 carbon atoms (for example, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, etc.), and the alkenylene group of A has 2 carbon atoms. An alkenylene group of ~ 12 (for example, an ethenylene group, a propenylene group, a butenylene group, etc.) is used, and an arylene group having 6 to 10 carbon atoms (for example, a phenylene group, a trilene group, a naphthylene group, etc.) is used as the arylene group of A. Each can be listed. Among them, the naphthalene group is a preferable example when the i-line is used as the exposure wavelength.
Specific examples of the imide sulfonate compound include, but are not limited to, the compounds described in paragraphs 0092 to 097 of International Publication No. 2015/064602.

[Compound having at least one cation selected from the group consisting of a sulfonium cation and an iodonium cation]
A compound having at least one cation selected from the group consisting of a sulfonium cation and an iodonium cation is a compound having an anion that is non-nucleophilic and photoly decomposed to generate an organic acid having a pKa of -1 or less. Is preferable, and those having a sulfonic acid anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion are more preferable.
More preferably, a compound represented by the following general formula (ZI) or (ZII) can be mentioned.

In the above general formula (ZI)
R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represent an organic group.
The carbon number of the organic group as R ²⁰¹ , R ²⁰² and R ²⁰³ is generally 1 to 30, preferably 1 to 20.
Further, two of R ^{201 to} R ²⁰³ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbonyl group. Examples of the group formed by bonding two of R ^{201 to} R ²⁰³ include an alkylene group (for example, a butylene group and a pentylene group).
Z ⁻ is a sulfonic acid anion (aliphatic sulfonic acid anion, aromatic sulfonic acid anion, camphor sulfonic acid anion, etc.), carboxylic acid anion (aliphatic carboxylic acid anion, aromatic carboxylic acid anion, aralkyl carboxylic acid anion, etc.), Examples thereof include a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methide anion.

The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number of carbon atoms. Included are 3 to 30 cycloalkyl groups.

The aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion preferably includes an aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a tolyl group, a naphthyl group and the like.

The alkyl and aryl groups listed above may have substituents. Specific examples of this include halogen atoms such as nitro groups and fluorine atoms, carboxy groups, hydroxy groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), and cycloalkyl groups (preferably having 3 to 15 carbon atoms). 15), aryl group (preferably 6 to 14 carbon atoms), alkoxycarbonyl group (preferably 2 to 7 carbon atoms), acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 carbon atoms) ~ 7), Alkoxythio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (preferably 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), aryloxysulfonyl group (preferably 1 to 15 carbon atoms). 6 to 20 carbon atoms), alkylaryloxysulfonyl group (preferably 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably 10 to 20 carbon atoms), alkyloxyalkyloxy group (preferably 5 to 5 carbon atoms) 20), cycloalkylalkyloxyalkyloxy groups (preferably 8 to 20 carbon atoms) and the like can be mentioned. Regarding the aryl group and the ring structure of each group, an alkyl group (preferably having 1 to 15 carbon atoms) can be further mentioned as a substituent.

The aralkyl group in the aralkyl carboxylic acid anion preferably includes an aralkyl group having 7 to 12 carbon atoms, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylbutyl group and the like.

Examples of the sulfonylimide anion include a saccharin anion.

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

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

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

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

The alkyl groups of R ¹ and R ² may have a substituent (preferably a fluorine atom), and those having 1 to 4 carbon atoms are preferable. More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of alkyl groups having R ¹ and R ² _{substituents include CF 3} , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ and C ₇ F _15. , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ are mentioned, and CF ₃ is preferable.
R ¹ and R ² are preferably a fluorine atom or CF ₃ .

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

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

Further, as the cyclic organic group, a lactone structure can also be mentioned, and specific examples thereof are represented by the general formulas (LC1-1) to (LC1-17) which the above-mentioned resin (A) may have. The lactone structure to be formed can be mentioned.

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

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

When ^{two of R 201 to} R ²⁰³ are combined to form a ring structure, the structure represented by the following general formula (A1) is preferable.

In the general formula (A1),
R ^{1a to} R ^13a each independently represent a hydrogen atom or a substituent.
Of R ^{1a to} R ^13a , it is preferable that 1 to 3 are not hydrogen atoms, and it is more preferable that any one of ^{R 9a to} R ^{13a is not a hydrogen atom.}
Za is a single bond or divalent linking group.
X ⁻ is synonymous with ^{Z −} in the general formula (ZI).

Specific examples of cases where R ^{1a to} R ^13a are not hydrogen atoms include a halogen atom, a linear group, a branched group, a cyclic alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group and a carboxy group. , Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, amino Carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and Arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinyl amino group, a phosphono group, a silyl group, a hydrazino group, a ureido group, a boronic acid group (-B _(OH) 2), phosphato group (-OPO _(OH) 2), a sulfato group (-OSO ₃ H), and other known The substituent of is given as an example.
When R ^{1a to} R ^13a are not hydrogen atoms, they are preferably linear, branched, or cyclic alkyl groups substituted with hydroxy groups.

The divalent linking group of Za includes an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether bond, a thioether bond, an amino group, a disulfide group, and-(CH _2). ) _N −CO−, − (CH ₂ ) _n− SO ₂₋ , −CH = CH−, aminocarbonylamino group, aminosulfonylamino group and the like (n is an integer of 1 to 3).

When ^{at least one of R 201} , R ²⁰² and R ²⁰³ is not an aryl group, preferred structures are paragraphs 0046 to 0048 of JP-A-2004-233661 and paragraphs 0040 to JP-A-2003-35948. 0046, compounds exemplified as formulas (I-1) to (I-70) in US Patent Application Publication No. 2003/0224288A1, formula (IA-1) in US Patent Application Publication No. 2003/0077540A1. )-(IA-54), cation structures such as compounds exemplified by the formulas (IB-1)-(IB-24).

In the general formula (ZII), R ^{204 to} R ²⁰⁵ represent an aryl group.
The aryl group of R ^{204 to} R ²⁰⁵ is the same as the aryl group described as the aryl group ^{of R 201 to} R ²⁰³ in the above-mentioned compound (ZI).
The aryl groups of R ^{204 to} R ²⁰⁵ may have a substituent. Examples of this substituent include those that may be contained in the aryl groups ^{of R 201 to} R ²⁰³ in the above-mentioned compound (ZI).

Specific examples of the compound having at least one cation selected from the group consisting of sulfonium cations and iodonium cations include, but are limited to, the compounds described in paragraphs 0128 to 0133 of WO 2015/064602. It is not something that is done.

[Diazo sulfone compounds and disulfone compounds]
Examples of the diazodisulfone compound include compounds represented by the following general formula (ZIII).

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

In the general formulas (ZIV) to (ZVI), Ar ³ and Ar ⁴ each independently represent an aryl group.
Specific examples of the aryl groups of Ar ³ and Ar ⁴ include the same specific examples of the aryl groups as R ²⁰¹ , R ²⁰² and R ²⁰³ in the above general formula (ZI).
Specific examples of the diazosulfone compound and the disulfone compound include, but are not limited to, the compounds described in paragraph 0137 of WO2015 / 064602.

[Chinone diazide compound]
Further, the photosensitive resin composition in the present invention may contain a quinonediazide compound as a photoacid generator.
The quinone diazide compound is not particularly limited as long as it is a compound that generates an acid by light. , Polyhydroxypolyamino compound to which sulfonic acid of quinonediazide is bound by at least one of an ester bond and a sulfonamide bond. In the present invention, for example, it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.

In the present invention, as the quinone diazide, either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.

The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method.
Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. Be done.

In the photosensitive resin composition of the present invention, the content of the photoacid generator is preferably 0.1 to 20% by mass, preferably 0.5 to 18% by mass, based on the total solid content of the photosensitive resin composition. More preferably, it is by mass%.
The photosensitive resin composition of the present invention may contain one type of photoacid generator alone or two or more types. When the photosensitive resin composition of the present invention contains two or more photoacid generators, the total content thereof is preferably within the above range.

<Crosslinking agent>
The photosensitive resin composition of the present invention may contain a cross-linking agent.

The amount of the cross-linking agent added to the photosensitive resin composition used in the present invention is preferably 0.01 to 50 parts by mass, preferably 0.5 to 50 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive resin composition. It is more preferably 30 parts by mass, and even more preferably 2 to 10 parts by mass. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. Only one type of cross-linking agent may be used, or two or more types of cross-linking agents may be used in combination. When two or more types of cross-linking agents are used in combination, all the cross-linking agents are added together to calculate the content.

In the present invention, the cross-linking agent is used in an amount of preferably 3 to 65% by mass, more preferably 5 to 50% by mass, based on the solid content of the photosensitive resin composition. By setting the addition amount of the cross-linking agent to 3 to 65% by mass, it is possible to prevent the residual film ratio and the resolving power from being lowered, and to maintain good stability of the photosensitive resin composition during storage.

<Sensitizer>
The photosensitive resin composition used in the present invention may contain a sensitizing dye for the purpose of accelerating the decomposition of the photoacid generator. In particular, it is preferably used when at least one of a compound having a sulfonium cation, a compound having an iodonium cation, a diazodisulfone compound and a disulfone compound is used as the photoacid generator.
The sensitizing dye absorbs active light rays or radiation and becomes an electron-excited state. The sensitizing dye in the electron-excited state comes into contact with the photoacid generator to cause actions such as electron transfer, energy transfer, and heat generation. As a result, the photoacid generator undergoes a chemical change and decomposes to produce an acid.
Examples of preferable sensitizing dyes include compounds that belong to the following compounds and have an absorption wavelength in the range of 350 nm to 450 nm.

Multinuclear aromatics (eg pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (For example, fluoressein, eosin, erythrosin, rhodamine B, rosebengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg, thiacarbocyanine, oxacarbocyanine) For example, merocyanines, carbocyanines), rodocyanines, oxonors, thiazines (eg, thionin, methylcoumarin, toluisin blue), acridins (eg, acrydin orange, chloroflavin, acryflabin), acridons (eg, acrydon, etc.) 10-Butyl-2-chloroacrydone), anthracenes (eg, anthracene), squaryliums (eg, squarylium), styryls, base styryls (eg, 2- [2- [4- (dimethylamino) phenyl]] Ethenyl] benzoxazole), coumarins (eg, 7-diethylamino4-methylcoumarin, 7-hydroxy4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H- [1] Benzopyrano [6,7,8-ij] quinolidine-11-one).

Among these sensitizing dyes, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Among the polynuclear aromatics, anthracene derivatives are the most preferable.
Only one type of sensitizing dye may be used, or two or more types may be used. When two or more types are used, the total amount falls within the above range. The blending amount of the sensitizing dye is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass of the photoacid generator.

<Solvent>
The photosensitive resin composition of the present invention preferably contains a solvent.
As the solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, and 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 ethers Examples thereof include acetates, esters, ketones, amides, lactones and the like.

Examples of the solvent used in the photosensitive resin composition of the present invention include (1) ethylene glycol monoalkyl ethers such as (1) 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 monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene Ethylene glycol monoalkyl ether acetates such as glycol monobutyl ether acetate; (4) Propropylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; (5) Propropylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether;

(6) Propropylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; (7) Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl Diethylene glycol dialkyl ethers such as methyl ether; (8) Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate; (9) Dipropylene glycol monomethyl ether , Dipropylene glycol monoalkyl ethers such as dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether; (10) Dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether Dipropylene glycol dialkyl ethers such as;

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

(15) Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; (16) N-methylformamide, N, N-dimethyl Amides such as formamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; (17) lactones such as γ-butyrolactone and the like can be mentioned.
In addition, if necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, capricic acid, 1-octanol, 1-nonanol are added to these solvents. , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added.
Among the above-mentioned solvents, propylene glycol monoalkyl ether acetates and / or diethylene glycol dialkyl ethers are preferable, and diethylene glycol ethylmethyl ether and / or propylene glycol monomethyl ether acetate is particularly preferable.
These solvents can be used alone or in admixture of two or more.

When the photosensitive resin composition of the present invention contains a solvent, the content of the solvent is preferably 1 to 3,000 parts by mass, preferably 5 to 2,000 parts by mass, per 100 parts by mass of the resin having an acid group. Is more preferable, and 10 to 1,500 parts by mass is further preferable.
The solvent is preferably an amount such that the total solid content of the photosensitive resin composition is 20 to 80% by mass with respect to the total mass of the photosensitive resin composition, and is an amount of 20 to 60% by mass. It is more preferable to do so.
Only one type of solvent may be used, or two or more types may be used. When two or more types are used, the total amount is within the above range.

<Basic compound>
As the basic compound, a known basic compound can be arbitrarily selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, and 4-the photosensitive resin composition of the present invention has (components). I) It is preferable to contain a basic compound.
(Component I) As the basic compound, any one can be selected and used from those used in the chemically amplified resist. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, and the like. 4-Dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinolin, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, cyclohexylmorpholinoethylthiourea, piperazine, morpholin, 4-methylmorpholin, 1,5-diazabicyclo [4.3.0] -5-nonen, 1,8-diazabicyclo [5.3] .0] -7-Undesen 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 the carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

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

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

It is more preferable that the photosensitive resin composition of the present invention contains a fluorine-based surfactant and / or a silicone-based surfactant as the surfactant.
Examples of these fluorine-based surfactants and silicone-based surfactants include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-62-170950. The surfactants described in Kaisho 63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, and JP-A-2001-330953 are listed. It is possible to use a commercially available surfactant.
As commercially available surfactants that can be used, for example, Ftop EF301, EF303 (above, manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (above, manufactured by Sumitomo 3M Co., Ltd.), Megafuck F171, F173, F176. , F189, R08 (above, manufactured by DIC Co., Ltd.), Surfron S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox series such as PF-6320 (OMNOVA). Fluorescent surfactants such as (manufactured by) or silicone surfactants can be mentioned. Further, the polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone-based surfactant.

In addition, the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography when the surfactant contains the structural unit A and the structural unit B represented by the following formula (1) and uses tetrahydrofuran (THF) as a solvent. A copolymer having (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.

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

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

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

The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.
These surfactants can be used alone or in admixture of two or more.
When the photosensitive resin composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 10 parts by mass or less, preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the specific resin. Is more preferable, and 0.01 to 1 part by mass is further preferable.

Further, if necessary, the photosensitive resin composition of the present invention contains an antioxidant, a plasticizer, a thermal radical generator, a thermoacid generator, an acid growth agent, an ultraviolet absorber, a thickener, and an organic substance. Alternatively, known additives such as an inorganic anti-precipitation agent can be added. For these details, the description in paragraphs 0143 to 0148 of JP2011-209692A can be referred to, and these contents are incorporated in the present specification.

<Use>
The photosensitive resin composition of the present invention can be used for forming a photosensitive layer in the laminate of the present invention described later. In addition, the photosensitive resin composition of the present invention can be used as a composition capable of forming a positive resist layer in the field where a known photosensitive layer (resist layer) is used.

Further, the photosensitive resin composition of the present invention is subjected to positive development using a developing solution containing an organic solvent.
As the organic solvent contained in the developing solution used in the present invention, polar solvents such as ketone solvents, ester solvents and amide solvents and hydrocarbon solvents can be used.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methylamyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and the like. Examples thereof include methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl acetate, ethyl formate, butyl acetate, propyl acetate, ethyl lactate, butyl lactate, propyl lactate, etc. Can be mentioned.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
The above solvent may be used alone or in combination of two or more. Further, it may be used by mixing with a solvent other than the above. However, in order to fully exert the effect of the present invention, it is preferable that the water content of the developer as a whole is less than 10% by mass, and it is more preferable that the developer substantially does not contain water. The term "substantial" as used herein means that, for example, the water content of the developer as a whole is 3% by mass or less, and more preferably the measurement limit or less.
That is, the content of the organic solvent with respect to the total mass of the developing solution is preferably 90% by mass or more and 100% by mass or less, and preferably 95% by mass or more and 100% by mass or less with respect to the total mass of the developing solution. preferable.
In particular, the developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent and an amide solvent.
In addition, the developing solution may contain an appropriate amount of a basic compound, if necessary. Examples of basic compounds include those described above in the section on basic compounds.

The vapor pressure of the developing solution is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By reducing the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is improved. The sex improves.
Specific examples of the developing solution having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, 2-heptanone (methylamylketone), 4-heptanone, 2-hexanone, and the like. Ketone solvents such as diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylisobutylketone, butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, Ester solvents such as diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl silicate, propyl silicate, ethyl lactate, butyl lactate, propyl lactate, etc. , N-Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide amide solvent, aromatic hydrocarbon solvent such as toluene and xylene, aliphatic hydrocarbon solvent such as octane and decane. Can be mentioned.
Specific examples of the developing solution having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, 4-heptanone, 2-hexanone, diisobutylketone, and cyclohexanone. , Methylcyclohexanone, phenylacetone and other ketone solvents, 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-Methyl-2-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate and other ester solvents, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N- Examples thereof include an amide-based solvent of dimethylformamide, an aromatic hydrocarbon-based solvent such as xylene, and an aliphatic hydrocarbon-based solvent such as octane and decane.

An appropriate amount of surfactant may be added to the developing solution, if necessary.
The surfactant is not particularly limited, but for example, the surfactant described in the section of the composition for forming a protective layer described later is preferably used.
When a surfactant is blended in the developer, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0, based on the total amount of the developer. It is 5.5% by mass.

Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), and a method of developing by raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle). Method), a method of spraying the developer on the surface of the substrate (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic discharge method). Etc. can be applied.

(Layered film, photosensitive layer)
The layered film of the present invention is a layered film made of the photosensitive resin composition of the present invention.
Specifically, the layered film is formed by applying a photosensitive resin composition to a base such as a protective layer described later, for example. As the above-mentioned application method, for example, the application method of the photosensitive resin composition shown in the description of the photosensitive layer in the laminate described later can be used. The layered film made of the photosensitive resin composition means the photosensitive resin composition of the present invention which is layered and has not been dried yet.
The photosensitive layer of the present invention is a photosensitive layer formed from a photosensitive resin composition.
Specifically, the photosensitive layer can be formed by drying the above-mentioned layered film of the present invention. As the drying method, for example, the method for drying the layered film shown in the description of the photosensitive layer in the laminated body described later can be used.
The film thickness of the photosensitive layer and the layered film is preferably 0.1 to 10.0 μm, more preferably 0.5 to 5.0 μm, for example.

The laminate of the present invention includes a protective layer and a photosensitive layer of the present invention.
Further, in the laminated body of the present invention, the protective layer and the photosensitive layer may be in direct contact with each other, or may have another layer in between, but they are preferably in direct contact with each other.

Further, the laminate of the present invention preferably further contains an organic layer on the side of the protective layer opposite to the photosensitive layer, and may further contain a base material on the side of the organic layer opposite to the protective layer. More preferred.
That is, the laminate of the present invention is preferably a laminate in which an organic layer, a protective layer, and a photosensitive layer are laminated in this order, and a laminate in which a base material, an organic layer, a protective layer, and a photosensitive layer are laminated in this order. Is more preferable.
When the laminate of the present invention contains an organic layer, for example, the laminate of the present invention can be used for patterning the organic layer contained in the laminate.

FIG. 1 is a schematic cross-sectional view schematically showing an example of a processing process of a laminated body. Regarding the laminated body, the organic layer 3 (for example, the organic semiconductor layer) is arranged on the base material 4 as in the example shown in FIG. 1 (a). Further, the protective layer 2 that protects the organic layer 3 is arranged on the surface of the protective layer 2 in contact with the protective layer 2. Another layer may be provided between the organic layer 3 and the protective layer 2, but from the viewpoint of appropriately protecting the organic layer, it is preferable that the organic layer 3 and the protective layer 2 are in direct contact with each other. .. Further, the photosensitive layer 1 of the present invention is arranged 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. 1B shows an example of a state in which 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 after the exposure, the photosensitive layer 1 in the removing portion 5 which is the exposed portion is developed by developing with a developing solution containing an organic solvent. It is removed and the photosensitive layer 1a after exposure development is formed.
Further, in the above development, the protective layer 2 remains because it is difficult to be removed by the developer, and the organic layer 3 is protected from damage by the developer by the remaining protective layer 2.
Further, after the development, the photosensitive layer 1a may be further heated or exposed.

FIG. 1C shows an example of a state in which a part of the protective layer 2 and the organic layer 3 is removed. For example, by removing the protective layer 2 and the organic layer 3 in the removing portion 5 without the photosensitive layer (resist) 1a after development by dry etching treatment or the like, the removing portion 5a is formed in the protective layer 2 and the organic layer 3. Will be done. In this way, the organic layer 3 can be removed in the removing portion 5a. That is, the organic layer 3 can be patterned.

FIG. 1D shows an example in which 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 laminated body in the state shown in FIG. 1C are washed with a stripping solution containing water to wash the photosensitive layer 1a and the protective layer on the organic layer 3a after processing. 2 is removed.

As described above, a desired pattern can be formed on the organic layer 3 and the photosensitive layer 1 and the protective layer 2 can be removed by using the laminate containing the base material, the organic layer, the protective layer and the photosensitive layer in this order. .. Details of these steps will be described later.

<Base material>
The base material that may be contained in the laminate is formed of, for example, various materials such as silicon, quartz, ceramic, glass, polyester film such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), and polyimide film. Any base material may be selected depending on the intended use. For example, when used for a flexible element, a base material formed of a flexible material can be used. Further, 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. Further, the shape of the base material is not particularly limited and may be selected according to the intended use, and examples thereof include a plate-shaped base material (board). The thickness of the substrate is also not particularly limited.

<Organic layer>
The organic layer is a layer containing an organic material. The specific organic material is appropriately selected according to the use and function of the organic layer. Assumed functions of the organic layer include, for example, semiconductor characteristics, light emission characteristics, photoelectric conversion characteristics, light absorption characteristics, electrical insulation, ferroelectricity, transparency, insulation and the like. In the laminate, the organic layer may be contained above the base material, the base material may be in contact with the organic layer, or another layer may be further contained between the organic layer and the base material. May be.

The thickness of the organic layer is not particularly limited and varies depending on the type of electronic device used and the like, but is preferably 1 nm to 50 μm, more preferably 1 nm to 5 μm, and further preferably 1 nm to 500 nm.
In particular, an example in which the organic layer is an organic semiconductor layer will be described in detail below. The organic semiconductor layer is a layer containing an organic material exhibiting the characteristics of a semiconductor.

The organic semiconductor layer is an organic layer containing an organic semiconductor, and the organic semiconductor is an organic compound exhibiting the characteristics of a semiconductor. Similar to the case of semiconductors made of inorganic compounds, organic semiconductors include p-type semiconductors that conduct holes as carriers and n-type semiconductors that conduct electrons as carriers. The ease of carrier flow in the organic semiconductor layer is represented by the carrier mobility μ. Although it depends on the application, in general, the carrier mobility ^{is preferably high, preferably 10-7} cm ² / Vs or more, more preferably ^10-6 cm ² / Vs or more, and ^10-5 cm ^{2 or more.} It is more preferably / Vs or more. The carrier mobility can be determined based on the characteristics when the field effect transistor (FET) element is manufactured and the measured value by the flight time measurement (TOF) method.

As the p-type organic semiconductor that can be used in the organic semiconductor layer, any material may be used as long as it has hole transportability. The p-type organic semiconductor is preferably any one of a p-type π-conjugated polymer, a condensed polycyclic compound, a triarylamine compound, a hetero 5-membered ring compound, a phthalocyanine compound, a porphyrin compound, carbon nanotubes, and graphene. Further, as the p-type organic semiconductor, a plurality of kinds of compounds among these compounds may be used in combination. The p-type organic semiconductor is more preferably at least one of a p-type π-conjugated polymer, a condensed polycyclic compound, a triarylamine compound, a hetero 5-membered ring compound, a phthalocyanine compound, and a porphyrin compound, and more preferably. It is at least one of a p-type π-conjugated polymer and a condensed polycyclic compound.

The p-type π-conjugated polymer is, for example, substituted or unsubstituted polythiophene (for example, poly (3-hexylthiophene) (P3HT, manufactured by Sigma Aldrich Japan LLC)), polyselenophene, polypyrrole, polyparaphenylene, poly. Paraphenylene vinylene, polythiophene vinylene, polyaniline, etc. Condensed polycyclic compounds include, for example, substituted or unsubstituted anthracene, tetracene, pentacene, anthradithiophene, hexabenzocoronene and the like.

Triarylamine compounds include, for example, m-MTDATA (4,4', 4''-Tris [(3-methylphenyl) biphenyllamine), 2-TNATA (4,4', 4''-Tris [2- naphthyl (phenyl) amine), NPD (N, N'-Di (1-naphthyl) -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine), TPD (N) , N'-Diphenyl-N, N'-di (m-tool) benzidine), mCP (1,3-bis (9-carbazolyl) benzene), CBP (4,4'-bis (9-carbazolyl) -2 , 2'-biphenyl) and the like.

The hetero 5-membered ring compound is, for example, a substituted or unsubstituted oligothiophene, TTF (Tetrathiafulvalene), or the like.

Phthalocyanine compounds include substituted or unsubstituted phthalocyanines having various central metals, naphthalocyanines, anthracyanines, tetrapyrazinoporphyrazine and the like. Porphyrin compounds are substituted or unsubstituted porphyrins having various central metals. Further, the carbon nanotube may be a carbon nanotube whose surface is modified with a semiconductor polymer.

As the n-type organic semiconductor that can be used for the organic semiconductor layer, any material may be used as long as it has an electron transporting property. The n-type organic semiconductor is preferably a fullerene compound, an electron-deficient phthalocyanine compound, a fused polycyclic compound (naphthalene tetracarbonyl compound, perylene tetracarbonyl compound, etc.), a TCNQ compound (tetracyanoquinodimethane compound), and a polythiophene compound. , Benzidine-based compound, carbazole-based compound, phenanthroline-based compound, pyridinephenyl ligand iridium-based compound, quinolinol ligand alumnium-based compound, n-type π-conjugated polymer, and graphene. Further, as the n-type organic semiconductor, a plurality of kinds of compounds among these compounds may be used in combination. The n-type organic semiconductor is more preferably at least one of a fullerene compound, an electron-deficient phthalocyanine compound, a fused polycyclic compound, and an n-type π-conjugated polymer, and particularly preferably a fullerene compound and a condensed polycyclic ring. It is at least one of a compound and an n-type π-conjugated polymer.

The fullerene compound means a substituted or unsubstituted fullerene, and the fullerenes are C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₀ , C ₈₂ , C ₈₄ , C ₈₆ , C ₈₈ , C ₉₀ , C _96. , C ₁₁₆ , C ₁₈₀ , C ₂₄₀ , C ₅₄₀ and the like. The fullerene compound is preferably substituted or unsubstituted C ₆₀ , C ₇₀ , C ₈₆ fullerene, and particularly preferably PCBM ([6,6] -phenyl-C61-butyric acid methyl ester, manufactured by Sigma Aldrich Japan GK. etc.) and its analogs (e.g., those with substitution of C ₆₀ part C _70, C _86, etc., those with substitution of the benzene ring substituent in other aromatic ring or a hetero ring, n- butyl ester methyl ester, It is replaced with i-butyl ester or the like).

The electron-deficient phthalocyanine compound is a substituted or unsubstituted phthalocyanine, naphthalocyanine, anthracianine, tetrapyrazinoporphyrazine and the like having four or more electron-attracting groups bonded and having various central metals. Electron-deficient phthalocyanine compounds include, for example, fluorinated phthalocyanine (F ₁₆ MPc) and chlorinated phthalocyanine (Cl ₁₆ MPc). Here, M represents a central metal and Pc represents a phthalocyanine.

Any naphthalene tetracarbonyl compound may be used, but naphthalene tetracarboxylic dianhydride (NTCDA), naphthalene bisimide compound (NTCDI), and perinone pigments (Pigment Orange 43, Pigment Red 194, etc.) are preferable.

Any perylenetetracarbonyl compound may be used, but perylenetetracarboxylic dianhydride (PTCDA), perylenebisimide compound (PTCDI), and benzimidazole fused ring compound (PV) are preferable.

The TCNQ compound is a substituted or unsubstituted TCNQ and a compound in which the benzene ring portion of TCNQ is replaced with another aromatic ring or heterocycle. The TCNQ compounds include, for example, TCNQ, TCNAQ (Tetracyanoquinodimethane), TCN3T (2,2'-((2E, 2''E) -3', 4'-Alkyl subscribed-5H, 5''H. -[2,2': 5', 2''-terthiophene] -5,5''-diylidene) dimalononirile derivatives) and the like.

The polythiophene-based compound is a compound having a polythiophene structure such as poly (3,4-ethylenedioxythiophene). The polythiophene-based compound is, for example, PEDOT: PSS (complex composed of poly (3,4-ethylenedioxythiophene) (PEDOT) and polystyrene sulfonic acid (PSS)).

The benzidine-based compound is a compound having a benzidine structure in the molecule. Benzidine compounds include, for example, N, N'-bis (3-methylphenyl) -N, N'-diphenylbenzidine (TPD), N, N'-di-[(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 the molecule. Carbazole compounds include, for example, 4,4'-bis (N-carbazolyl) -1,1'-biphenyl (CBP).

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

The pyridinephenyl ligand iridium-based compound is a compound having an iridium complex structure having a phenylpyridine structure as a ligand. Pyridinephenyl ligands The iridium-based compounds include, for example, bis (3,5-difluoro-2- (2-pyridylphenyl- (2-carboxypyridyl) iridium (III) (FIrpic)) and tris (2-phenylpyridinato). ) Iridium (III) (Ir (ppy) ₃ ) and the like.

The quinolinol ligand alumnium-based compound is a compound having an aluminum complex structure having a quinolinol structure as a ligand, and is, for example, tris (8-quinolinolato) aluminum.

A particularly preferable example of the n-type organic semiconductor material is shown below. The R in the formula may be any, but is hydrogen atom, substituted or unsubstituted, branched or linear alkyl group (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably. 1 to 8), substituted or unsubstituted aryl groups (preferably those having 6 to 30, more preferably 6 to 20, still more preferably 6 to 14 carbon atoms). In the structural formula, Me represents a methyl group and M represents a metal atom.

The organic semiconductor contained in the organic semiconductor layer may be one type or two or more types. Further, the organic semiconductor layer may be a laminated or mixed layer of a p-type layer and an n-type layer.

The method for forming the organic layer may be a vapor phase method or a liquid phase method. In the case of the vapor phase method, a physical vapor deposition (PVD) method such as a vapor deposition method (vacuum vapor deposition method, molecular beam epitaxy method, etc.), a sputtering method, an ion plating method, or a chemical vapor deposition method such as a plasma polymerization method is used. A growth (CVD) method can be used, with a vapor deposition method being particularly preferred.

On the other hand, in the case of the liquid phase method, for example, the organic material is blended in a solvent to form a composition for forming an organic layer (composition for forming an organic layer). Then, this composition is supplied onto the substrate and dried to form an organic layer. As a supply method, coating is preferable. Examples of supply methods include slit coating method, casting method, blade coating method, wire bar coating method, spray coating method, dipping coating method, bead coating method, air knife coating method, curtain coating method, inkjet method, etc. Examples thereof include a spin coat method, a Langmuir-Blodgett (LB) method, and an edge cast method (for details, see Patent No. 6179930). It is more preferable to use the casting method, the spin coating method, and the inkjet method. Such a process makes it possible to produce an organic layer having a smooth surface and a large area at low cost.

Further, as the solvent used in the composition for forming an organic layer, an organic solvent is preferable. Examples of the organic solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene and 1,2-dichlorobenzene; for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like. Ketone-based solvent; for example, halogenated hydrocarbon-based solvent such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, etc .; eg, ester of ethyl acetate, butyl acetate, amyl acetate, etc. Solvents; alcohol solvents such as, for example, methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol; and ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole; for example. , N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, dimethylsulfoxide and other polar solvents. Only one kind of these solvents may be used, or two or more kinds may be used. The proportion of the organic material in the composition for forming an organic layer is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, whereby a film having an arbitrary thickness can be formed.

Further, a resin binder may be added to the composition for forming an organic layer. In this case, the material forming the film and the binder resin can be dissolved or dispersed in the above-mentioned suitable solvent to prepare a coating liquid, and a thin film can be formed by various coating methods. Resin binders include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulphon, polymethylmethacrylate, polymethylacrylate, cellulose, polyethylene, polypropylene, and their co-weights. Examples thereof include photoconductive polymers such as coalescing, polyvinylcarbazole and polysilane, and conductive polymers such as polythiophene, polypyrrole, polyaniline and polyparaphenylene vinylene. The resin binder may be used alone or in combination of two or more. Considering the mechanical strength of the thin film, a resin binder having a high glass transition temperature is preferable, and considering charge mobility, a resin binder having a structure containing no polar group or a conductive polymer is preferable.

When the resin binder is blended, the blending amount thereof is preferably 0.1 to 30% by mass in the organic layer. The resin binder may be used alone or in combination of a plurality of types. In the case of a combination of a plurality of types, it is preferable that the total amount thereof is within the above range.

Depending on the application, the organic layer may be a blended film composed of a plurality of material types, using a single solution or a mixed solution to which various organic materials and additives are added. For example, when producing a photoelectric conversion layer, a mixed solution using a plurality of types of semiconductor materials can be used.

Further, the base material may be heated or cooled at the time of film formation, and it is possible to control the film quality and the packing of molecules in the film by changing the temperature of the base material. The temperature of the base material is not particularly limited, but is preferably −200 ° C. to 400 ° C., more preferably −100 ° C. to 300 ° C., and even more preferably 0 ° C. to 200 ° C.

The properties of the formed organic layer can be adjusted by post-treatment. For example, it is possible to improve the properties by changing the morphology of the membrane and the packing of molecules in the membrane by heat treatment or exposure to a vaporized solvent. Further, by exposing to an oxidizing or reducing gas, solvent, substance or the like, or by using these methods in combination, an oxidation or reduction reaction can occur, and the carrier density in the membrane can be adjusted.

<Protective layer>
The laminate of the present invention includes a protective layer.
The protective layer is preferably a layer having a dissolution rate in a developing solution of 10 nm / s or less at 23 ° C., and more preferably a layer having a dissolution rate of 1 nm / s or less. The lower limit of the amount of dissolution is not particularly limited, and may be more than 0 nm / s.

-Water-soluble resin-
The protective layer preferably contains a water-soluble resin.
The water-soluble resin refers to a resin that dissolves 1 g or more in 100 g of water at 23 ° C. The water-soluble resin is preferably a resin that dissolves 5 g or more with respect to 100 g of water at 23 ° C., more preferably a resin that dissolves 10 g or more, and further preferably a resin that dissolves 30 g or more. There is no particular upper limit on the amount of dissolution, but it is practically about 100 g.

The water-soluble resin is preferably a resin containing a hydrophilic group, and examples of the hydrophilic group include a hydroxy group, a carboxy 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), and water-soluble polysaccharides (water-soluble cellulose (methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxy). (Propylmethyl cellulose, propylmethyl cellulose, etc.), purulan or purulan derivatives, starch (hydroxypropyl starch, carboxymethyl starch, etc.), chitosan, cyclodextrin), polyethylene oxide, polyethyloxazoline, methylolmelamine, polyacrylamide, phenolic resin, styrene / malein. Acid semi-esters and the like can be mentioned. Further, two or more kinds may be selected and used from these, or may be used as a copolymer. In the present invention, the protective layer preferably contains at least one selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, water-soluble polysaccharides, pullulan and pullulan derivatives among these resins, and polyvinylpyrrolidone and polyvinyl alcohol. And at least one selected from the group consisting of water-soluble polysaccharides. The water-soluble polysaccharide is particularly preferably cellulose, more preferably hydroxyethyl cellulose.

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 of the formulas (P1-1) to (P4-1).

Wherein ^{(P1-1) ~ (P4-1),} R P1 is hydrogen or ^{methyl, R P2} represents a hydrogen atom or a methyl ^group, the R p31 ^{to R p33} are each independently a substituent or hydrogen Representing an atom, R ^{p41 to} R ^p49 independently represent a substituent or a hydrogen atom.

式（Ｐ１−２）中、Ｒ^Ｐ１１はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ^Ｐ１２は置換基を表し、ｎｐ１及びｎｐ２は質量基準での分子中の構成比率を表す。
式（Ｐ１−２）中、Ｒ^Ｐ１１は式（Ｐ１−１）におけるＲ^Ｐ１と同義であり、好ましい態様も同様である。
式（Ｐ１−２）中、Ｒ^Ｐ１２としては−Ｌ^Ｐ−Ｔ^Ｐで表される基が挙げられる。Ｌ^Ｐは単結合又は後述する連結基Ｌである。Ｔ^Ｐは置換基であり、後述する置換基Ｔの例が挙げられる。なかでも、Ｒ^Ｐ１２としては、アルキル基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３が更に好ましい）、アルケニル基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３が更に好ましい）、アルキニル基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３が更に好ましい）、アリール基（炭素数６〜２２が好ましく、６〜１８がより好ましく、６〜１０が更に好ましい）、又はアリールアルキル基（炭素数７〜２３が好ましく、７〜１９がより好ましく、７〜１１が更に好ましい）等の炭化水素基が好ましい。これらのアルキル基、アルケニル基、アルキニル基、アリール基、アリールアルキル基は本発明の効果を奏する範囲で更に置換基Ｔで規定される基を有していてもよい。
式（Ｐ１−２）中、ｎｐ１及びｎｐ２は質量基準での分子中の構成比率を表し、それぞれ独立に、１０質量％以上１００質量％未満である。ただしｎｐ１＋ｎｐ２が１００質量％を超えることはない。ｎｐ１＋ｎｐ２が１００質量％未満の場合、その他の繰返し単位を含むコポリマーであることを意味する。 << Resin containing a repeating unit represented by the formula (P1-1) >>
Wherein ^{(P1-1), R P1} is preferably a hydrogen atom.
The resin containing the repeating unit represented by the formula (P1-1) may further contain a repeating unit different from the repeating unit represented by the 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 10 mol% to 100 mol% with respect to all the repeating units of the resin. , 30 mol% to 70 mol% is more preferable.
Examples of the resin containing the repeating unit represented by the formula (P1-1) include a resin containing two repeating units represented by the following formula (P1-2).

Wherein ^{(P1-2), R P11} each independently represent a hydrogen atom or a methyl ^{group, R P12} represents a substituent, np1 and np2 represent composition ratio in the molecule in mass.
Wherein ^{(P1-2), R P11} has the same meaning as ^{R P1} in formula (P1-1), preferable embodiments thereof are also the same.
Wherein ^(P1-2), include groups represented by ^-L P -T ^P as ^{R P12.} L ^P is a linking group L to a single bond or later. T ^P is a substituent, and examples of the substituent T described later can be mentioned. Among them, ^{as RP12} , an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms are more preferable). Preferably, 2-3 are more preferred), an alkynyl group (preferably 2-12 carbon atoms, more preferably 2-6, more preferably 2-3), an aryl group (preferably 6-22 carbon atoms, 6-18 carbon atoms). Is more preferable, 6 to 10 is more preferable), or a hydrocarbon group such as an arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, and 7 to 11 is more preferable) is preferable. These alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and arylalkyl groups may further have a group defined by a substituent T as long as the effects of the present invention are exhibited.
In the formula (P1-2), np1 and np2 represent the composition ratio in the molecule on a mass basis, and are independently 10% by mass or more and less than 100% by mass. However, np1 + np2 does not exceed 100% by mass. When np1 + np2 is less than 100% by mass, it means that the copolymer contains other repeating units.

式（Ｐ２−２）中、Ｒ^Ｐ２１はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ^Ｐ２２は置換基を表し、ｍｐ１及びｍｐ２は質量基準での分子中の構成比率を表す。
式（Ｐ２−２）中、Ｒ^Ｐ２１は式（Ｐ２−１）におけるＲ^Ｐ２と同義であり、好ましい態様も同様である。
式（Ｐ２−２）中、Ｒ^Ｐ２２としては−Ｌ^Ｐ−Ｔ^Ｐで表される基が挙げられる。Ｌ^Ｐは単結合又は後述する連結基Ｌである。Ｔ^Ｐは置換基であり、後述する置換基Ｔの例が挙げられる。なかでも、Ｒ^Ｐ２２としては、アルキル基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３が更に好ましい）、アルケニル基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３が更に好ましい）、アルキニル基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３が更に好ましい）、アリール基（炭素数６〜２２が好ましく、６〜１８がより好ましく、６〜１０が更に好ましい）、又はアリールアルキル基（炭素数７〜２３が好ましく、７〜１９がより好ましく、７〜１１が更に好ましい）等の炭化水素基が好ましい。これらのアルキル基、アルケニル基、アルキニル基、アリール基、アリールアルキル基は本発明の効果を奏する範囲で更に置換基Ｔで規定される基を有していてもよい。
式（Ｐ２−２）中、ｍｐ１及びｍｐ２は質量基準での分子中の構成比率を表し、それぞれ独立に、１０質量％以上１００質量％未満である。ただしｍｐ１＋ｍｐ２が１００質量％を超えることはない。ｍｐ１＋ｍｐ２が１００質量％未満の場合、その他の繰返し単位を含むコポリマーであることを意味する。 << Resin containing a repeating unit represented by the formula (P2-1) >>
Wherein ^{(P2-1), R P2} is preferably a hydrogen atom.
The resin containing the repeating unit represented by the formula (P2-1) may further contain a repeating unit different from the repeating unit represented by the 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 10% by mass to 100% by mass based on the total mass of the resin. It is more preferable to contain 30% by mass to 70% by mass.
Examples of the resin containing the repeating unit represented by the formula (P2-1) include a resin containing two repeating units represented by the following formula (P2-2).

Wherein ^{(P2-2), R P21} each independently represent a hydrogen atom or a methyl ^{group, R P22} represents a substituent, mp1 and mp2 represent composition ratio in the molecule in mass.
Wherein ^{(P2-2), R P21} has the same meaning as ^{R P2} in formula (P2-1), preferable embodiments thereof are also the same.
Wherein ^(P2-2), include groups represented by ^-L P -T ^P as ^{R P22.} L ^P is a linking group L to a single bond or later. T ^P is a substituent, and examples of the substituent T described later can be mentioned. Among them, ^{as RP22} , an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms are more preferable). Preferably, 2-3 are more preferred), an alkynyl group (preferably 2-12 carbon atoms, more preferably 2-6, even more preferably 2-3), an aryl group (preferably 6-22 carbon atoms, 6-18 carbon atoms). Is more preferable, 6 to 10 is more preferable), or a hydrocarbon group such as an arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, and 7 to 11 is more preferable) is preferable. These alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and arylalkyl groups may further have a group defined by a substituent T as long as the effects of the present invention are exhibited.
In the formula (P2-2), mp1 and mp2 represent the composition ratio in the molecule on a mass basis, and are independently 10% by mass or more and less than 100% by mass. However, mp1 + mp2 does not exceed 100% by mass. When mp1 + mp2 is less than 100% by mass, it means that the copolymer contains other repeating units.

<< Resin containing a repeating unit represented by the formula (P3-1) >>
In the formula (P3-1), R ^{p31 to} R ^p33 are each independently a hydrocarbon group or an acyl group which may have a substituent,-(CH ₂ CH ₂ O) _ma H, -CH ₂ COONa or hydrogen. It preferably represents an atom, more preferably a hydrocarbon group, a hydrocarbon group having a hydroxy group as a substituent, an acyl group or a hydrogen atom, and even more preferably a hydrogen atom. ma is or 2.
The number of carbon atoms of the hydrocarbon group which may have the above-mentioned substituent is preferably 1 to 10, and more preferably 1 to 4.
As the hydrocarbon group having a hydroxy group as a substituent, a hydrocarbon group having one hydroxy group and having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having 1 hydroxy group and having 1 to 4 carbon atoms is more preferable. -CH ₂ (OH), -CH ₂ CH ₂ (OH) or -CH ₂ CH (OH) CH ₃ are more preferred.
As the acyl group, an alkylcarbonyl group having 1 to 4 carbon atoms of the alkyl group is preferable, and an acetyl group is more preferable.
The resin containing the repeating unit represented by the formula (P3-1) may further contain a repeating unit different from the repeating unit represented by the 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% by mass to 100% by mass based on the total mass of the resin. It is more preferable to contain 30% by mass to 70% by mass.
Further, the hydroxy group described in the formula (P3-1) may be appropriately substituted with a substituent T or a group combining the substituent L with the substituent L. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the ring in the formula with or without the linking group L to form a ring.

<< Resin containing a repeating unit represented by the formula (P4-1) >>
In the formula (P4-1), R ^{P41 to} R ^P49 are each independently a hydrocarbon group or an acyl group which may have a substituent,-(CH ₂ CH ₂ O) _ma H, -CH ₂ COONa or hydrogen. It preferably represents an atom, more preferably a hydrocarbon group, a hydrocarbon group having a hydroxy group as a substituent, an acyl group or a hydrogen atom, and even more preferably a hydrogen atom. ma is 1 or 2.
The number of carbon atoms of the hydrocarbon group which may have the above-mentioned substituent is preferably 1 to 10, and more preferably 1 to 4.
As the hydrocarbon group having a hydroxy group as a substituent, a hydrocarbon group having one hydroxy group and having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having 1 hydroxy group and having 1 to 4 carbon atoms is more preferable. , -CH ₂ (OH), -CH ₂ CH ₂ (OH) or -CH ₂ CH (OH) CH ₃ is more preferred.
The resin containing the repeating unit represented by the formula (P4-1) may further contain a repeating unit different from the repeating unit represented by the 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 10% by mass to 100% by mass based on the total mass of the resin. It is more preferable to contain 30% by mass to 70% by mass.
Further, the hydroxy group described in the formula (P4-1) may be appropriately substituted with a substituent T or a group combining the substituent L with the substituent L. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the ring in the formula with or without the linking group L to form a ring.

As the substituent T, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) and an arylalkyl group (preferably 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms). , 7-11 is more preferred), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 and even more preferably 2 to 6), an alkynyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2-3 are more preferable), hydroxy group, amino group (preferably 0 to 24 carbon atoms, more preferably 0 to 12 and even more preferably 0 to 6), thiol group, carboxy group, aryl group (carbon). Numbers 6 to 22 are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable), alkoxyl groups (1 to 12 carbon atoms are preferable, 1 to 6 are more preferable, and 1 to 3 are more preferable), aryloxy. Group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10), acyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3) , Acyloxy group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), allylloyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms). (Preferably), allyloyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11), carbamoyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms 1). ~ 3 is more preferable), sulfamoyl group (preferably 0 to 12 carbon atoms, more preferably 0 to 6 and even more preferably 0 to 3), sulfo group, alkylsulfonyl group (preferably 1 to 12 carbon atoms, 1 to 1). 6 is more preferable, 1 to 3 are more preferable), an arylsulfonyl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), and a heteroaryl group (1 to 12 carbon atoms is preferable). Preferably, 1 to 8 are more preferable, 2 to 5 are even more preferable, and a 5-membered ring or a 6-membered ring is preferably contained), a (meth) acryloyl group, a (meth) acryloyloxy group, a halogen atom (for example, a fluorine atom). , a chlorine atom, a bromine atom, an iodine atom), oxo (= O), imino (= ^NR N), an alkylidene group _{^{(= C (R N) 2}} ) , and the like. ^RN is a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and a hydrogen atom, a methyl group, an ethyl group, or a propyl group is preferable. The alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be chain or cyclic, and may be linear or branched. When the substituent T is a group capable of taking a substituent, it may further have a substituent T. For example, the alkyl group may be an alkyl halide group, 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 carboxy group or an amino group, the group may form a salt.

As the linking group L, an alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) and an alkenylene group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). 2-3 are more preferred), alkynylene groups (2-12 carbon atoms are preferred, 2-6 are more preferred, 2-3 are more preferred), (oligo) alkyleneoxy groups (alkylene groups in one repeating unit. The number of carbon atoms is preferably 1-12, more preferably 1-6, still more preferably 1-3; the number of repetitions is preferably 1-50, more preferably 1-40, even more preferably 1-30), arylene group ( 6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, and 6 to 10 are more preferable), oxygen atom, sulfur atom, sulfonyl group, carbonyl group, thiocarbonyl group, -NR ^N- , and combinations thereof. Linking groups can be mentioned. In the present specification, the "(oligo) alkyleneoxy group" means a divalent linking group having one or more "alkyleneoxy" which is a constituent unit. The number of carbon atoms of the alkylene chain in the structural unit may be the same or different for each structural unit. The alkylene group may have a substituent T. For example, the alkylene group may have a hydroxy group. The number of atoms contained in the linking group L is preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30, excluding hydrogen atoms. The number of linked atoms means the number of atoms located in the shortest path among the atomic groups involved in the linking. For example, in the case of -CH _2- (C = O) -O-, the number of atoms involved in the connection is 6, and even excluding the hydrogen atom, it is 4. On the other hand, the shortest atom involved in the connection is -C-C-O-, which is three. The number of connected atoms is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6. The alkylene group, alkenylene group, alkynylene group, and (oligo) alkyleneoxy group may be chain-like or cyclic, and may be linear or branched. When the linking group is a group ^{capable of forming a salt such as −NR N−} , the group may form a salt.

Other examples of the water-soluble resin include polyethylene oxide, hydroxyethyl cellulose, carboxymethyl cellulose, water-soluble methylol melamine, polyacrylamide, phenol resin, styrene / maleic acid semi-ester, poly-N-vinylacetamide and the like.
A commercially available product may be used as the water-soluble resin, and the commercially available products include the Pittscol series (K-30, K-50, K-90, etc.) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. and UVITEC manufactured by BASF. Series (VA64P, VA6535P, etc.), Japan Vam & Poval Co., Ltd. PXP-05, JL-05E, JP-03, JP-03, AMPS (2-acrylamide-2-methylpropanesulfonic acid copolymer), Examples thereof include Nanocry manufactured by Aldrich.
Among these, it is preferable to use Pittscol K-90 or PXP-05.

For water-soluble resins, the resins described in WO 2016/175220 are cited and incorporated herein by reference.

The weight average molecular weight of the water-soluble resin is appropriately selected according to the type of the water-soluble resin. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the water-soluble resin are the values converted to polyether oxide by GPC measurement. In particular, when the water-soluble resin is a resin containing a repeating unit represented by the formula (p1-1) (for example, polyvinyl alcohol (PVA)), the weight average molecular weight is 10,000 to 100,000. Is preferable. The upper limit of this numerical range is preferably 80,000 or less, and more preferably 60,000 or less. Further, the lower limit of this numerical range is preferably 13,000 or more, and more preferably 15,000 or more. When the water-soluble resin is a resin represented by the formula (p2-2) (for example, polyvinylpyrrolidone (PVP)), the weight average molecular weight is preferably 20,000 to 2,000,000. The upper limit of this numerical range is preferably 1,800,000 or less, and more preferably 1,500,000 or less. Further, the lower limit of this numerical range is preferably 30,000 or more, and more preferably 40,000 or more. When the water-soluble resin is a resin containing a repeating unit represented by the formula (P3-1) or the formula (p4-1) (for example, a water-soluble polysaccharide), the weight average molecular weight is 50,000 to 2 , 000,000 is preferable. The upper limit of this numerical range is preferably 1,500,000 or less, and more preferably 1,300,000 or less. Further, the lower limit of this numerical range is preferably 70,000 or more, and more preferably 90,000 or more.

The molecular weight dispersion of the water-soluble resin (weight average molecular weight / number average molecular weight, also simply referred to as “dispersity”) is preferably 1.0 to 5.0, more preferably 2.0 to 4.0.

Further, in the present invention, the protective layer is a water-soluble resin having a high molecular weight resin (for example, a water-soluble resin having a weight average molecular weight of 10,000 or more) and a weight average molecular weight smaller than the weight average molecular weight of the high molecular weight resin. It is also preferable that the weight average molecular weight of the low molecular weight resin is half or less of the weight average molecular weight of the high molecular weight resin. As a result, the low molecular weight resin is rapidly eluted in the removing liquid (particularly water), and the high molecular weight resin is easily removed starting from the portion where the low molecular weight resin is eluted. The effect of further reduction can be obtained. Further, when the protective layer is formed by using the protective layer, it is possible to suppress the occurrence of cracks in the protective layer.

In the present invention, whether or not the protective layer contains the high molecular weight resin and the low molecular weight resin has two peak tops (maximum values) when, for example, the molecular weight distribution of the protective layer or the entire water-soluble resin is measured. Judgment can be made based on whether or not the above can be confirmed.

The weight average molecular weight of the high molecular weight resin is preferably 20,000 or more, and preferably 45,000 or more. The weight average molecular weight of the high molecular weight resin is preferably 2,000,000 or less, and may be 1,500,000 or less. The molecular weight ratio of the low molecular weight resin to the high molecular weight resin (= weight average molecular weight of the low molecular weight resin / weight average molecular weight of the high molecular weight resin) is preferably 0.4 or less. The upper limit of the molecular weight ratio is more preferably 0.3 or less, and further preferably 0.2 or less. The lower limit of the molecular weight ratio is not particularly limited, but is preferably 0.001 or more, and may be 0.01 or more.

Further, in the molecular weight distribution of the entire water-soluble resin used in the present invention, there are two or more peak tops, and among the two or more peak tops, the molecular weight corresponding to one peak top is the other one. It is also preferable that the molecular weight is less than half of the molecular weight corresponding to the peak top. As a result, the same effect as when the weight average molecular weight of the low molecular weight resin is half or less of the weight average molecular weight of the high molecular weight resin can be obtained. The water-soluble resin having the above molecular weight distribution can be obtained, for example, by mixing the above high molecular weight resin and the above low molecular weight resin. When multiple peaks are confirmed in the molecular weight distribution, two sets of peak tops are selected from those peak tops, and for at least one set of peak tops, the molecular weight corresponding to one peak top is determined. It may be less than half the molecular weight corresponding to the other peak top.

The larger of the corresponding molecular weights (peak top molecular weights) of the peak tops is preferably 20,000 or more, and preferably 45,000 or more. Further, the one having the larger peak top molecular weight is preferably 2,000,000 or less, and may be 1,500,000 or less. The smaller molecular weight ratio (= smaller peak top molecular weight / larger peak top molecular weight) to the larger peak top molecular weight is preferably 0.4 or less. The upper limit of the molecular weight ratio is more preferably 0.3 or less, and further preferably 0.2 or less. The lower limit of the molecular weight ratio is not particularly limited, but is preferably 0.001 or more, and may be 0.01 or more.

The difference between the weight average molecular weight of the high molecular weight resin and the weight average molecular weight of the low molecular weight resin (the molecular weight distance between the peaks when the molecular weight distribution of the entire water-soluble resin is taken) is when PVA is included as the high molecular weight resin. It is preferably 10,000 to 80,000, more preferably 20,000 to 60,000. When PVP is contained as the high molecular weight resin, the above difference is preferably 50,000 to 1,500,000, more preferably 100,000 to 1,200,000. When the high molecular weight resin contains a water-soluble polysaccharide, the above difference is preferably 50,000 to 1,500,000, more preferably 100,000 to 1,200,000.

In particular, in the present invention, the water-soluble resin preferably contains PVA having a weight average molecular weight of 20,000 or more as the high molecular weight resin. In this case, the weight average molecular weight is more preferably 30,000 or more, and further preferably 40,000 or more. Further, in the present invention, the water-soluble resin preferably contains PVP having a weight average molecular weight of 300,000 or more as the high molecular weight resin. In this case, the weight average molecular weight is more preferably 400,000 or more, and further preferably 500,000 or more. Further, in the present invention, the water-soluble resin preferably contains a water-soluble polysaccharide having a weight average molecular weight of 300,000 or more as the high molecular weight resin. In this case, the weight average molecular weight is more preferably 400,000 or more, and further preferably 500,000 or more.

A preferable combination of the high molecular weight resin and the low molecular weight resin is as follows, for example. The water-soluble resin may satisfy only one requirement of the following combination, but may also satisfy the requirements of two or more combinations at the same time.
-A combination of PVA (high molecular weight resin) having a weight average molecular weight Mw of 30,000 to 100,000 and PVA (low molecular weight resin) having a weight average molecular weight Mw of 10,000 to 40,000.
-A combination of PVP (high molecular weight resin) having an Mw of 500,000 to 1,500,000 and PVP (low molecular weight resin) having an Mw of 30,000 to 600,000.
-A combination of a water-soluble polysaccharide (high molecular weight resin) having an Mw of 500,000 to 1,500,000 and a water-soluble polysaccharide (low molecular weight resin) having an Mw of 50,000 to 600,000.
-A combination of PVP (high molecular weight resin) having an Mw of 500,000 to 1,500,000 and PVA (low molecular weight resin) having an Mw of 10,000 to 100,000.
-A combination of a water-soluble polysaccharide (high molecular weight resin) having an Mw of 500,000 to 1,500,000 and a PVA (low molecular weight resin) having an Mw of 10,000 to 100,000.
-A combination of a PVP (high molecular weight resin) having an Mw of 500,000 to 1,500,000 and a water-soluble polysaccharide (low molecular weight resin) having an Mw of 50,000 to 600,000.
-A combination of a water-soluble polysaccharide (high molecular weight resin) having an Mw of 500,000 to 1,500,000 and a PVP (low molecular weight resin) having an Mw of 30,000 to 600,000.

The content of the high molecular weight resin is preferably 50% by mass or less with respect to the total water-soluble resin. The upper limit of this numerical range is more preferably 40% by mass or less, and further preferably 30% by mass or less. Further, the lower limit of this numerical value range is more preferably 5% by mass or more, and further preferably 10% by mass or more.

On the other hand, the water-soluble resin may be in an embodiment that does not substantially contain the low molecular weight resin. In the present invention, "substantially free of low molecular weight resin" means that the content of the low molecular weight resin is 3% by mass or less with respect to the total water-soluble resin. In this embodiment, the content of the low molecular weight resin is preferably 1% by mass or less based on the total water-soluble resin.

The content of the water-soluble resin in the protective layer may be appropriately adjusted as necessary, but is preferably 20% by mass or more, more preferably 50% by mass or more, based on the total mass of the protective layer. , 70% by mass or more is more preferable. The upper limit of the content is preferably 100% by mass or less, more preferably 99% by mass or less, and further preferably 98% by mass or less.
The protective layer may contain only one type of water-soluble resin, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.

[Surfactant containing acetylene group]
From the viewpoint of suppressing the generation of residues, the protective layer preferably contains a surfactant containing an acetylene group.
The number of acetylene groups in the molecule in the surfactant containing an acetylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 2, and even 1 to 2. Is more preferable.

The molecular weight of the surfactant containing an acetylene group is preferably relatively small, preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less. There is no particular lower limit, but it is preferably 200 or more.

式中、Ｒ^９１及びＲ^９２は、それぞれ独立に、炭素数３〜１５のアルキル基、炭素数６〜１５の芳香族炭化水素基、又は、炭素数４〜１５の芳香族複素環基である。芳香族複素環基の炭素数は、１〜１２が好ましく、２〜６がより好ましく、２〜４が更に好ましい。芳香族複素環は５員環又は６員環が好ましい。芳香族複素環が含むヘテロ原子は窒素原子、酸素原子、又は硫黄原子が好ましい。
Ｒ^９１及びＲ^９２は、それぞれ独立に、置換基を有していてもよく、置換基としては上述の置換基Ｔが挙げられる。 -Compound represented by formula (9)-
The surfactant containing an acetylene group is preferably a compound represented by the following formula (9).

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

-Compound represented by formula (91)-
The compound represented by the formula (9) is preferably a compound represented by the following formula (91).

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

Ｒ^９３、Ｒ^９４、Ｒ^９７〜Ｒ^１００は、それぞれ独立に、炭素数１〜２４の炭化水素基であり、ｌ１１及びｌ１２は、それぞれ独立に、０以上１２以下の数である。
Ｒ^９３、Ｒ^９４、Ｒ^９７〜Ｒ^１００はなかでもアルキル基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３が更に好ましい）、アルケニル基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３が更に好ましい）、アルキニル基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３が更に好ましい）、アリール基（炭素数６〜２２が好ましく、６〜１８がより好ましく、６〜１０が更に好ましい）、アリールアルキル基（炭素数７〜２３が好ましく、７〜１９がより好ましく、７〜１１が更に好ましい）であることが好ましい。アルキル基、アルケニル基、アルキニル基は鎖状でも環状でもよく、直鎖でも分岐でもよい。Ｒ^９３、Ｒ^９４、Ｒ^９７〜Ｒ^１００は本発明の効果を奏する範囲で置換基Ｔを有していてもよい。また、Ｒ^９３、Ｒ^９４、Ｒ^９７〜Ｒ^１００は互いに結合して、又は連結基Ｌを介して環を形成していてもよい。置換基Ｔは、複数あるときは互いに結合して、あるいは連結基Ｌを介して又は介さずに式中の炭化水素基と結合して環を形成していてもよい。
Ｒ^９３、Ｒ^９４、Ｒ^９７〜Ｒ^１００は、それぞれ独立に、アルキル基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３が更に好ましい）であることが好ましい。なかでもメチル基が好ましい。
ｌ１１＋ｌ１２は０〜１２の数であることが好ましく、０〜８の数であることがより好ましく、０〜６の数が更に好ましく、０を超え６未満の数が一層好ましく、０を超え５以下の数がより一層好ましく、０を超え４以下の数が更に一層好ましく、０を超え３以下の数であってもよく、０を超え１以下の数であってもよい。なお、ｌ１１、ｌ１２は、式（９２）の化合物がその数において異なる化合物の混合物となる場合があり、そのときはｌ１１及びｌ１２の数、あるいはｌ１１＋ｌ１２が、小数点以下が含まれた数であってもよい。 -Compound represented by formula (92)-
The compound represented by the formula (91) is preferably a compound represented by the following formula (92).

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

Surfactants containing an acetylene group include Surfynol 104 series (trade name, Nisshin Kagaku Kogyo Co., Ltd.), Acetyrenol E00, E40, E13T, and 60 (all trade names, rivers). (Manufactured by Ken Fineke Chemical Co., Ltd.), among which Surfinol 104 series, acetylenol E00, E40 and E13T are preferable, and acetylenol E40 and E13T are more preferable. The Surfinol 104 series and acetylenol E00 are surfactants having the same structure.

[Other surfactants]
The protective layer may contain other surfactants other than the above-mentioned surfactant containing an acetylene group for the purpose of improving the coatability of the protective layer forming composition described later.
As the other surfactant, any surfactant such as nonionic type, anion type, amphoteric fluorine type, etc. may be used as long as it lowers the surface tension.
Examples of other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene nonylphenyl ether. Polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan triole Nonionic surfactants such as sorbitan alkyl esters such as ate, monoglyceride alkyl esters such as glycerol monostearate and glycerol monooleate, oligomers containing fluorine or silicon; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate. , Alkylnaphthalene sulfonates such as sodium butylnaphthalene sulfonate, sodium pentylnaphthalene sulfonate, sodium hexylnaphthalene sulfonate, sodium octylnaphthalene sulfonate, alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonic acid such as sodium dodecyl sulfonate, etc. Anionic surfactants such as salts and sulfosuccinate salts such as sodium dilauryl sulfosuccinate; and amphoteric surfactants such as alkyl betaines such as lauryl betaine and stearyl betaine and amino acids can be used.

When the protective layer contains at least one of a surfactant containing an acetylene group and at least one of the other surfactants, the total amount of the surfactant containing the acetylene group and the other surfactant is the total amount of the surfactant added. It is preferably 0.05 to 20% by mass, more preferably 0.07 to 15% by mass, and further preferably 0.1 to 10% by mass with respect to the total mass of the protective layer. These surfactants may be used alone or in combination of two or more. When a plurality of items are used, the total amount is within the above range.
Further, in the present invention, the structure 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 of the content of the surfactant containing an acetylene group, preferably 3% by mass or less, and 1% by mass or less. Is more preferable.

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

[Preservatives, fungicides (preservatives, etc.)]
It is also a preferred embodiment that the protective layer contains an antiseptic or antifungal agent.
The preservative and antifungal agent (hereinafter, preservative and the like) preferably contain at least one additive having an antibacterial or antifungal action and selected from water-soluble or water-dispersible organic compounds. .. Examples of the additive having an antibacterial or antifungal action such as an antiseptic include an organic antibacterial agent or an antifungal agent, an inorganic antibacterial agent or an antifungal agent, a natural antibacterial agent or an antifungal agent and the like. For example, as the antibacterial or antifungal agent, those described in "Antibacterial / Antifungal Technology" published by Toray Research Center Co., Ltd. can be used.
In the present invention, by blending a preservative or the like in the protective layer, the effect of suppressing the increase of coating defects due to the growth of bacteria inside the solution after long-term storage at room temperature is more effectively exhibited.

Examples of preservatives include phenol ether compounds, imidazole compounds, sulfone compounds, N. haloalkylthio compounds, anilide compounds, pyrrol compounds, quaternary ammonium salts, alcine compounds, pyridine compounds, and triazine compounds. , Benzoisothiazolin-based compounds, isothiazoline-based compounds and the like. Specifically, for example, 2 (4 thiocyanomethyl) benzimidazolone, 1,2 benzothiazolone, 1,2-benzisothiazolin-3-one, N-fluorodichloromethylthio-phthalimide, 2,3,5,6-tetrachloro. Isophthalonitrile, N-trichloromethylthio-4-cyclohexene-1,2-dicarboxyimide, copper 8-quinophosphate, bis (tributyltin) oxide, 2- (4-thiazolyl) benzimidazole, 2-benzimidazole carbamate Methyl, 10,10'-oxybisphenoxyarcin, 2,3,5,6-tetrachloro-4- (methylsulphon) pyridine, bis (2-pyridylthio-1-oxide) zinc, N, N-dimethyl-N '-(Fluorodichloromethylthio) -N'-Phenylsulfamide, Poly- (Hexamethylenebiguanide) Hydrochloride, Dithio-2-2'-Bis, 2-Methyl-4,5-Trimethylene-4-isothiazolin-3 -On, 2-bromo-2-nitro-1,3-propanediol, hexahydro-1,3-tris- (2-hydroxyethyl) -S-triazine, p-chloro-m-xylenol, 1,2-benz Examples thereof include isothiazolin-3-one and methylphenol.

Examples of the natural antibacterial agent or antifungal agent include chitosan, which is a basic polysaccharide obtained by hydrolyzing chitin contained in the crustacean of crab or shrimp. Nikko's "trade name Holon Killer Bees Cera", which is composed of an amino metal in which a metal is compounded on both sides of an amino acid, is preferable.

The content of the preservative or the like in the protective layer is preferably 0.005 to 5% by mass, more preferably 0.01 to 3% by mass, and 0.05 to 0.05 to the total mass of the protective layer. It is more preferably 2% by mass, and even more preferably 0.1 to 1% by mass. As the preservative or the like, one kind or a plurality of preservatives may be used. When a plurality of items are used, the total amount is within the above range.
The antibacterial effect of preservatives and the like can be evaluated in accordance with JIS Z 2801 (antibacterial processed product-antibacterial test method / antibacterial effect). In addition, the antifungal effect can be evaluated in accordance with JIS Z 2911 (mold resistance test).

[Shading agent]
The protective layer may contain a light shielding agent. By blending a light-shielding agent, the influence of light damage to the organic layer and the like can be further suppressed.
As the light-shielding agent, for example, a known colorant or the like can be used, and examples thereof include organic or inorganic pigments or dyes, preferably inorganic pigments, and more preferably carbon black, titanium oxide, titanium nitride and the like. ..
The content of the light-shielding agent is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and further preferably 5 to 25% by mass with respect to the total mass of the protective layer. As the light-shielding agent, one type or a plurality of types may be used. When a plurality of items are used, the total amount is within the above range.

[Composition for forming a protective layer]
In the laminate of the present invention, the protective layer can be formed, for example, by applying a protective layer forming composition on the organic layer and drying it.
As a method of applying the composition for forming a protective layer, coating is preferable. Examples of application methods include slit coating method, casting method, blade coating method, wire bar coating method, spray coating method, dipping (immersion) coating method, bead coating method, air knife coating method, curtain coating method, inkjet method, etc. Examples include the spin coat method and the Langmuir-Blodgett (LB) method. It is more preferable to use the casting method, the spin coating method, and the inkjet method. Such a process makes it possible to produce a protective layer having a smooth surface and a large area at low cost.
When the layered film is dried, it is preferable to heat the base material. The heating temperature is appropriately selected from the range of, for example, 50 to 200 ° C.
Further, the protective layer forming composition can also be formed by a method of transferring a coating film previously formed on a temporary support by the above-mentioned applying method or the like onto an application target (for example, an organic layer).
Regarding the transfer method, the description of paragraphs 0023, 0036 to 0051 of JP-A-2006-023696, paragraphs 096 to 0108 of JP-A-2006-047592, and the like can be referred to.

The composition for forming a protective layer contains components contained in the above-mentioned protective layer (for example, a water-soluble resin, a surfactant containing an acetylene group, another surfactant, a preservative, a light-shielding agent, etc.), and a solvent. Is preferable.
Regarding the content of the components contained in the protective layer forming composition, the content of each component with respect to the total mass of the protective layer may be read as the content with respect to the solid content of the protective layer forming composition. preferable.

Examples of the solvent contained in the composition for forming a protective layer include the above-mentioned aqueous solvent, and water or a mixture of water and a water-soluble solvent is preferable, and water is more preferable.
When the aqueous solvent is a mixed solvent, it is preferably a mixed solvent of an organic solvent having a solubility in water at 23 ° C. of 1 g or more and water. The solubility of the organic solvent in water at 23 ° C. is more preferably 10 g or more, further preferably 30 g or more.

The solid content concentration of the protective layer forming composition is preferably 0.5 to 30% by mass from the viewpoint of being more uniform in thickness when the protective layer forming composition is applied and being easy to apply. It is more preferably 0 to 20% by mass, and even more preferably 2.0 to 14% by mass.

<Photosensitive layer>
The laminate of the present invention includes a photosensitive layer.
In the laminate of the present invention, the photosensitive layer is a layer formed by the photosensitive resin composition of the present invention, and is a layer to be subjected to positive development using a developing solution containing an organic solvent.
Specifically, the photosensitive layer can be formed by applying a photosensitive resin composition on the protective layer to form a layered film made of the photosensitive resin composition, and then drying the layered film. can. As the application method and the drying method, for example, the description of the application method and the drying method of the protective layer forming composition in the protective layer can be referred to.

The thickness of the photosensitive layer in the laminated body is preferably 0.1 μm or more, more preferably 0.5 μm or more, and further preferably 1.0 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 even more preferably 3.0 μm or less.

<Manufacturing method of laminated body and patterning method of organic layer>
The following steps (1) to (6) are a series of work steps related to patterning of the organic layer. The method for producing the laminate includes at least the following step (1). The method for patterning the organic layer includes at least the following step (5).
(1) A step of forming a protective layer on an organic layer on a substrate.
(2) A step of forming a photosensitive layer on the protective layer.
(3) A step of exposing the photosensitive layer.
(4) A step of developing a photosensitive layer with a developing solution containing an organic solvent to prepare a mask pattern.
(5) A step of removing the protective layer and the organic layer of the non-masked portion.
(6) A step of removing the protective layer using a stripping solution.

[(1) Step of forming a protective layer on the organic layer]
The method for patterning an organic layer of the present embodiment includes a step of forming a protective layer on the organic layer. Usually, this step is performed after forming an organic layer on the base material. 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 other layers may be provided in between as long as the gist of the present invention is not deviated. Examples of the other layer include a fluorine-based undercoat layer and the like. Further, only one protective layer may be provided, or two or more protective layers may be provided. As described above, the protective layer is preferably formed using a composition for forming a protective layer.
For details of the forming method, refer to the method of applying the protective layer forming composition in the above-mentioned laminate.

[(2) Step of forming a photosensitive layer on the protective layer]
After the step (1) above, a photosensitive layer is formed on the surface of the protective layer opposite to the organic layer side (preferably on the surface). As described above, the photosensitive layer is formed by using the photosensitive resin composition of the present invention. For details of the forming method, refer to the method of applying the photosensitive resin composition in the above-mentioned laminate.

[(3) Step of exposing the photosensitive layer]
After forming the photosensitive layer in the step (2), the photosensitive layer is exposed. Specifically, for example, at least a part of the photosensitive layer is irradiated (exposed) with active light rays.
It is preferable that the exposure is performed so as to have a predetermined pattern. Further, the exposure may be performed through a photomask, or a predetermined pattern may be drawn directly.
The wavelength of the active light beam at the time of exposure may be determined in consideration of the absorption wavelength of the photoacid generator contained in the photosensitive layer, etc., but is preferably a wavelength of 180 nm or more and 450 nm or less, more preferably 365 nm (i-line). Active light with a wavelength of 248 nm (KrF line) or 193 nm (ArF line) can be used.

As the light source of the active light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a laser generator, a light emitting diode (LED) light source, or the like can be used.
When a mercury lamp is used as a light source, active rays having wavelengths such as g-ray (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used, and i-ray is more preferable.

When a laser generator is used as a light source, an active light having a wavelength of 343 nm and 355 nm is preferably used for a solid-state (YAG) laser, and 193 nm (ArF line), 248 nm (KrF line), and 351 nm (KrF line) for an excimer laser. An active ray having a wavelength of (Xe line) is preferably used, and further, an active ray having a wavelength of 375 nm or 405 nm is preferably used in a semiconductor laser. Among these, active rays having a wavelength of 355 nm or 405 nm are more preferable from the viewpoint of stability, cost and the like. The laser can irradiate the photosensitive layer once or in a plurality of times.

The exposure amount is preferably 40 to 120 mJ, more preferably 60 to 100 mJ.
The energy density per pulse of the laser ^{is preferably 0.1 mJ / cm 2} or more and 10,000 mJ / cm ² or less. In order to sufficiently cure the coating film, 0.3 mJ / cm ² or more is more preferable, and 0.5 mJ / cm ² or more is further preferable. From the viewpoint of suppressing decomposition of the photosensitive layer due ablation phenomenon, the exposure amount is preferably set to 1,000 mJ / cm ² or less, 100 mJ / cm ² or less being more preferred.

The pulse width is preferably 0.1 nanosecond (hereinafter referred to as “ns”) or more and 30,000 ns or less. In order to prevent the color coating film from being decomposed by the ablation phenomenon, 0.5 ns or more is more preferable, and 1 ns or more is more preferable. In order to improve the matching accuracy during scan exposure, 1,000 ns or less is more preferable, and 50 ns or less is further preferable.

When a laser generator is used as the light source, the frequency of the laser is preferably 1 Hz or more and 50,000 Hz or less, and more preferably 10 Hz or more and 1,000 Hz or less.
Further, in order to shorten the exposure processing time, the laser frequency is more preferably 10 Hz or higher, further preferably 100 Hz or higher, and further preferably 10,000 Hz or lower in order to improve the matching accuracy during scan exposure. It is more preferably 000 Hz or less.
The laser is preferable in that it is easier to focus than the mercury lamp, and the use of a photomask can be omitted in pattern formation in the exposure process.

The exposure apparatus is not particularly limited, but commercially available ones include Callisto (manufactured by V Technology Co., Ltd.), AEGIS (manufactured by V Technology Co., Ltd.), and DF2200G (Dainippon Screen Mfg. Co., Ltd.). It is possible to use (manufactured by). In addition, devices other than the above are also preferably used.
Further, if necessary, the amount of irradiation light can be adjusted through a spectroscopic filter such as a long wavelength cut filter, a short wavelength cut filter, and a bandpass filter.
Further, after the above exposure, a post-exposure heating step (PEB) may be performed if necessary.

[(4) Step of developing the photosensitive layer with a developing solution containing an organic solvent to prepare a mask pattern]
In the step (3), after exposing the photosensitive layer through a photomask, the photosensitive layer is developed using a developing solution.
When the laminate of the present invention is used, the development is a positive development, and the exposed portion of the photosensitive layer is removed by the development. The details of the developer are as described in the above description of the photosensitive layer.
Examples of the developing method include a method of immersing the base material in a tank filled with a developing solution for a certain period of time (dip method), and a method of developing by raising the developing solution on the surface of the base material by surface tension and allowing it to stand still for a certain period of time. (Paddle method), a method of spraying the developer on the surface of the base material (spray method), a method of continuing to discharge the developer while scanning the developer discharge nozzle at a constant speed on the base material rotating at a constant speed (spray method) Dynamic dispense method) etc. can be applied.

When the above-mentioned 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 velocity per unit area of the discharged developer) is determined. It is preferably 2 mL / sec / mm ² or less, more preferably 1.5 mL / sec / mm ² or less, and further preferably 1 mL / sec / mm ² or less. There is no particular lower limit on the discharge pressure, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput. By setting the discharge pressure of the developer to be discharged within the above range, defects in the pattern derived from the resist residue after development can be significantly reduced.

The details of this mechanism are not clear, but probably, by setting the discharge pressure within the above range, the pressure applied to the photosensitive layer by the developer becomes small, and the resist pattern on the photosensitive layer is inadvertently scraped or broken. It is thought that this is because it is suppressed. The discharge pressure of the developer (mL / sec / mm ² ) is a value at the outlet of the developing nozzle in the developing apparatus.
Examples of the method of adjusting the discharge pressure of the developing solution include a method of adjusting the discharge pressure with a pump and the like, a method of adjusting the pressure by supplying from a pressure tank, and the like.

Further, after the step of developing with a developing solution containing an organic solvent, a step of stopping the development while substituting with another organic solvent may be carried out.

[(5) Step of removing the protective layer and the organic layer of the non-masked portion]
After developing the photosensitive layer to prepare a mask pattern, at least the protective layer and the organic layer in the non-masked portion are removed by an etching process. The non-masked portion refers to a region not masked by a mask pattern formed by developing the photosensitive layer (a region in which the photosensitive layer has been 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 a single etching treatment, or after at least a part of the protective layer is removed by the etching treatment, the organic layer (and, if necessary, the protective layer) The balance) may be removed by etching.

Further, the etching process may be a dry etching process or a wet etching process, and the etching may be divided into a plurality of times to perform the dry etching process and the wet etching process. For example, the removal of the protective layer may be by dry etching or wet etching.

Examples of the method for removing the protective layer and the organic layer include a method A in which the protective layer and the organic layer are removed by a single dry etching treatment, and at least a part of the protective layer is removed by a wet etching treatment. After that, a method such as method B for removing the organic layer (and, if necessary, the rest of the protective layer) by dry etching can be mentioned.

The dry etching process in the method A, the wet etching process and the dry etching process in the method B can be performed according to a known etching method.

Hereinafter, details of one aspect of the above method A will be described. As a specific example of the above method B, the description of JP-A-2014-098889 can be referred to.

In the above method A, specifically, the protective layer and the organic layer of the non-masked portion can be removed by performing dry etching using the resist pattern as an etching mask (mask pattern). Typical examples of dry etching are JP-A-59-126506, JP-A-59-046628, JP-A-58-009108, JP-A-58-002809, and JP-A57. There is a method described in Japanese Patent Application Laid-Open No. 148706 and Japanese Patent Application Laid-Open No. 61-041102.

The dry etching is preferably performed in the following form from the viewpoint of forming the cross section of the pattern of the organic layer to be formed closer to a rectangle and further reducing the damage to the organic layer.
Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), etching is performed to the region (depth) where the organic layer is not exposed, and after this first-stage etching, nitrogen gas (nitrogen gas (O 2) A _{second-stage etching that uses a mixed gas of N 2} ) and oxygen gas (O ₂ ), preferably etching to the vicinity of the region (depth) where the organic layer is exposed, and over-etching that is performed after the organic layer is exposed. A form including and is preferable. Hereinafter, a specific method of dry etching, as well as first-stage etching, second-stage etching, and over-etching will be described.

The etching conditions in dry etching are preferably performed while calculating the etching time by the following method.
(A) The etching rate (nm / min) in the first-stage etching and the etching rate (nm / min) in the second-stage etching are calculated respectively.
(B) The time for etching the desired thickness in the first-stage etching and the time for etching the desired thickness in the second-stage etching are calculated, respectively.
(C) The first-stage etching is performed according to the etching time calculated in (B) above.
(D) The second stage etching is performed according to the etching time calculated in (B) above. Alternatively, the etching time may be determined by endpoint detection, and the second-stage etching may be performed according to the determined etching time.
(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 first-stage etching preferably contains _{a fluorine-based gas and an oxygen gas (O 2} ) from the viewpoint of processing the organic material to be etched into a rectangular shape. Further, in the first-stage etching, the laminated 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 the damage is slight at this stage.

Further, in the second-stage etching and the over-etching, it is preferable to perform the etching treatment using a mixed gas of nitrogen gas and oxygen gas from the viewpoint of avoiding damage to the organic layer.

It is important that the ratio of the etching amount in the first-stage etching to the etching amount in the second-stage etching is determined so as to have excellent rectangularity in the cross section of the pattern of the organic layer in the first-stage etching.

The ratio of the etching amount in the second stage etching to the total etching amount (the sum of the etching amount in the first stage etching and the etching amount in the second stage etching) is greater than 0% and 50% or less. Is preferable, and 10 to 20% is more preferable. The etching amount refers to an amount calculated from the difference between the remaining film thickness of the film to be etched and the film thickness before etching.

Further, the etching preferably includes an over-etching treatment. The over-etching treatment is preferably performed by setting the over-etching ratio. The over-etching ratio can be set arbitrarily, but it is preferably 30% or less of the total etching treatment time in the etching process in terms of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched (organic layer), and 5 to 5 It is more preferably 25%, and particularly preferably 10 to 15%.

[(6) Step of removing the protective layer using a stripping solution]
After etching, the protective layer is removed using a stripping solution (eg, water). The details of the stripping solution are as described in the above description of the protective layer.

Examples of the method of removing the protective layer with a stripping solution include a method of spraying the stripping solution onto the resist pattern from a spray-type or shower-type injection nozzle to remove the protective layer. Pure water can be preferably used as the stripping solution. Further, examples of the injection nozzle include an injection nozzle in which the entire base material is included in the injection range, and a movable injection nozzle in which the movable range includes the entire base material. Another embodiment is a mode in which 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 injection nozzle is movable, the resist pattern is removed more effectively by moving from the center of the base material to the end of the base material twice or more to inject the release liquid during the process of removing the protective layer. be able to.
It is also preferable to perform a step such as drying after removing the protective layer. The drying temperature is preferably 80 to 120 ° C.

(kit)
The kit of the present invention contains the photosensitive resin composition of the present invention and a composition for forming a protective layer for forming a protective layer, and is used for forming a laminate containing the photosensitive layer and the protective layer. Is.
The kit of the present invention is preferably a kit used for forming the laminate of the present invention.
Examples of the protective layer forming composition included in the kit of the present invention include the protective layer forming composition shown in the above description of the laminate.
In addition, the laminate forming kit of the present invention may further contain the above-mentioned organic layer forming composition.

(Semiconductor device)
The semiconductor device of the present invention includes an organic layer patterned by utilizing a photosensitive layer formed from the photosensitive resin composition of the present invention.
As a method of using the photosensitive layer in the semiconductor device of the present invention, a method of using the photosensitive layer including the above-mentioned steps (3) to (6) is preferable. Moreover, the utilization method including the above-mentioned steps (1) to (6) may be used.
That is, in the semiconductor device of the present invention, the photosensitive layer may be removed and may not remain.
Here, the semiconductor device is a device containing a semiconductor and having two or more electrodes, and controlling the current flowing between the electrodes and the generated voltage by electricity, light, magnetism, chemical substances, or the like. It is a device that generates light, electric field, magnetic field, etc. by the applied voltage and current.
Examples include organic photoelectric conversion elements, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifying elements, organic inverters, information recording elements, and the like. The organic photoelectric conversion element can be used for both optical sensor applications and energy conversion applications (solar cells). Among these, an organic electroluminescent transistor, an organic electroluminescent element, and an organic electroluminescent element are preferable, an organic field effect transistor and an organic photoelectric conversion element are more preferable, and an organic electroluminescent transistor is particularly preferable.
Further, the laminate of the present invention is preferably used for manufacturing the above-mentioned semiconductor device.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the examples, unless otherwise specified, "parts" and "%" are based on mass, and unless otherwise specified, the environmental temperature (room temperature) of each step is 23 ° C.
The weight average molecular weight (Mw) of the resin in the photosensitive resin composition was calculated as a polystyrene-equivalent value measured by GPC. HLC-8220 (manufactured by Tosoh Corporation) was used, and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15.0 cm) was used as a column.

<Synthesis of resin B-1>
PGMEA (propylene glycol monomethyl ether acetate, 30.00 g) was placed in a three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. Here, BzMA (benzyl methacrylate, 20.00 g), MMA (methyl methacrylate, 19.60 g), MAA (methacrylic acid, 0.40 g), and V-601 (0.50 g, Fujifilm Wako Pure Chemical Industries, Ltd.) (Manufactured) was dissolved in PGMEA (30.00 g) and added dropwise over 2 hours to prepare a reaction solution. Then, the reaction solution was stirred for 2 hours to terminate the reaction. Resin B-1 was obtained by recovering the white powder produced by re-precipitating the reaction solution in heptane by filtration. The weight average molecular weight (Mw) was 47,000.

<Synthesis of resin B-2>
PGMEA (30.00 g) was placed in a three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. BzMA (12.25 g), MMA (12.75 g), MAA (15.00 g), and V-601 (0.50 g) dissolved in PGMEA (30.00 g) were added dropwise thereto over 2 hours. Then, it was used as a reaction solution. Then, the reaction solution was stirred for 2 hours to terminate the reaction. Resin B-2 was obtained by recovering the white powder produced by re-precipitating the reaction solution in heptane by filtration. The weight average molecular weight (Mw) was 45,000.

<Synthesis of resin B-3>
PGMEA (30.00 g) was placed in a three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. BzMA (7.25 g), MMA (12.75 g), MAA (20.00 g), and V-601 (0.50 g) dissolved in PGMEA (30.00 g) were added dropwise thereto over 2 hours. Then, it was used as a reaction solution. Then, the reaction solution was stirred for 2 hours to terminate the reaction. Resin B-3 was obtained by recovering the white powder produced by re-precipitating the reaction solution in heptane by filtration. The weight average molecular weight (Mw) was 42,000.

<Synthesis of resin B-4>
PGMEA (30.00 g) was placed in a three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. MMA (20.00 g), MAA (20.00 g), and V-601 (0.50 g) dissolved in PGMEA (30.00 g) were added dropwise thereto over 2 hours to prepare a reaction solution. Then, the reaction solution was stirred for 2 hours to terminate the reaction. Resin B-4 was obtained by recovering the white powder produced by re-precipitating the reaction solution in heptane by filtration. The weight average molecular weight (Mw) was 45,000.

<Synthesis of resin B-5>
PGMEA (32.62 g) was placed in a three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. Here, BzMA (benzyl methacrylate, 16.65 g), THFMA (tetrahydrofurfuryl methacrylate, 21.08 g), t-BuMA (t-butyl methacrylate, 5.76 g), and V-601 (0.4663 g, Fuji). A solution prepared by dissolving Film Wako Pure Chemical Industries, Ltd. in PGMEA (32.62 g) was added dropwise over 2 hours to prepare a reaction solution. Then, the reaction solution was stirred for 2 hours to terminate the reaction. Resin B-5 was obtained by recovering the white powder produced by re-precipitating the reaction solution in heptane by filtration. The weight average molecular weight (Mw) was 45,000.

<Synthesis of resin BR-1>
With reference to the description in paragraphs 0294 to 0295 of JP2015-87609A, a resin BR-1 having a structure represented by the following formula (BR-1) was synthesized. The subscripts in parentheses represent the content ratio (molar ratio) of each repeating unit.

<Preparation of photosensitive resin composition>
In each Example or Comparative Example, the components described in the following composition were mixed to prepare a photosensitive resin composition.

[Composition of photosensitive resin composition]
-Resin shown in Table 1: Content (parts by mass) shown in Table 1.
-Photoacid generators shown in Table 1: Content (parts by mass) shown in Table 1.
-Vinyl ether compounds shown in Table 1: Content (parts by mass) shown in Table 1.
-Basic compound (compound having the structure represented by the following formula (Y), manufactured by DSP Gokyo Food & Chemical Co., Ltd.): 0.08 parts by mass-Surfactant (manufactured by OMNOVA, PF-6320): 0.08 Parts by mass ・ Propylene glycol monomethyl ether acetate: 69.5 parts by mass

Details of the abbreviations in Table 1 are as follows.
〔resin〕
B-1 to B-5, BR-1: B-1 to B-5, BR-1 synthesized in the above synthesis example.
[Photoacid generator]
A-1 to A-10: Compounds represented by the following formulas (A-1) to (A-10) [vinyl ether compounds]
-C-1: Ethyl vinyl ether-C-2: Butyl vinyl ether-C-3: Cyclohexyl vinyl ether-C-4: 2-Ethylhexyl vinyl ether-C-5: Diethylene glycol divinyl ether-C-6: Triethylene glycol divinyl ether

<Evaluation>
[Pattern collapse evaluation]
-Formation of organic semiconductor film (organic layer)-
In each of the examples and comparative examples, an organic semiconductor coating liquid (composition for forming an organic semiconductor) having the following composition is spin-coated on a 5 cm square glass substrate and dried at 130 ° C. for 10 minutes to be organic. A semiconductor film was formed. The film thickness was 150 nm.
<< Composition of organic semiconductor coating liquid >>
・ P3HT (manufactured by Sigma-Aldrich Japan GK): 10% by mass
・ PCBM (manufactured by Sigma-Aldrich Japan GK): 10% by mass
-Chloroform (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 80% by mass

-Formation of water-soluble resin layer (protective layer)-
In each of the Examples and Comparative Examples, a water-soluble resin composition having the following composition was spin-coated on the surface of the organic semiconductor film and dried at 100 ° C. for 1 minute to obtain a water-soluble resin layer having a thickness of 2 μm. Protective layer) was formed.

<< Composition of water-soluble resin composition >>
-Water-soluble resin (PVA-205 (Mw = 24,000) manufactured by Kuraray Co., Ltd.): 15 parts by mass-Pure water 84.5 parts by mass-Surfactant: Acetyleneol E00 (manufactured by Kawaken Fine Chemicals Co., Ltd.) 0.5 parts by mass

-Formation of photosensitive resin layer (photosensitive layer)-
In each of the Examples and Comparative Examples, the above-mentioned photosensitive resin composition was spin-coated on the surface of the formed water-soluble resin layer, dried at 100 ° C. for 1 minute, and the photosensitive resin layer having a thickness of 2 μm (photosensitivity). Layer) was formed.

-Exposure-
In each of the Examples and Comparative Examples, the photosensitive layer in the produced laminate was subjected to an i-line exposure machine and a binary mask in which a 1: 1 line-and-space pattern having a line width of 2.0 μm was formed. , I-line exposure. The exposure amount was set so that the line width of the pattern was 2 μm.

-Development-
Then, butyl acetate (nBA) was used as a developing solution for 50 seconds, and spin drying was performed to obtain a resist pattern.
The resist pattern was observed using an optical microscope, the total area of the portion where the pattern collapse occurred was calculated, and the evaluation was performed according to the following evaluation criteria. The evaluation results are described in the "Pattern collapse" column in Table 1. It can be said that the smaller the area is, the more the pattern collapse is suppressed.
<< Evaluation Criteria >>
A: No pattern collapse was observed.
B: The total area was 50 μm ² or less.
C: The total area was ^{larger than 50 μm 2} and 100 μm ² or less.
D: The total area was ^{larger than 100 μm 2} and 250 μm ² or less.
E: The total area was ^{larger than 250 μm 2} and 500 μm ² or less.

From the results shown in Table 1, it can be seen that according to the photosensitive resin composition of the present invention, a photosensitive layer capable of positive development using an organic solvent is formed.
Further, from the results shown in Table 1, it can be seen that the photosensitive resin composition of the present invention suppresses pattern collapse of the pattern formed by the photosensitive layer.
In the photosensitive resin composition described in Comparative Example 1, the resin does not contain a carboxy group. It can be seen that when the photosensitive layer is formed using such a comparative composition, pattern collapse is more likely to occur as compared with the case where the photosensitive resin composition of the present invention is used.
The comparative composition described in Comparative Example 2 is a composition that does not contain an ether compound and is used for negative development. It can be seen that when the photosensitive layer is formed using such a comparative composition, pattern collapse is more likely to occur as compared with the case where the photosensitive resin composition of the present invention is used.

A base material on which a gate electrode, a gate insulating film, a source electrode, and a drain electrode were formed was prepared by the same method as in Example 1 of International Publication No. 2018/061821.
An organic semiconductor layer, a protective layer, and a photosensitive layer were formed on the above-mentioned substrate by the same method as that shown in the pattern collapse evaluation in Example 1 of the present invention. After that, the photosensitive layer is developed, the protective layer and the organic semiconductor layer are etched by the same method as the method in the above evaluation, the organic semiconductor layer is formed so as to be in contact with the source electrode and the drain electrode, and an organic field effect transistor is manufactured. did.
The organic field effect transistor operated normally.

1 Photosensitive layer 1a Photosensitive layer after exposure development 2 Protective layer 3 Organic layer 3a Organic layer after processing 4 Base material 5 Removal part of photosensitive layer after development 5a Removal part of laminate after etching

Claims (15)

Resin with acid group,
Photoacid generator and
Contains compounds, which have a vinyl ether group,
A photosensitive resin composition used for forming a photosensitive layer to be used for positive development using a developing solution containing an organic solvent. The photosensitive resin composition according to claim 1, wherein the compound having a vinyl ether group is a monofunctional vinyl ether compound. The photosensitive resin composition according to claim 1 or 2, wherein the SP value of the compound having a vinyl ether group is 17 to 21 MPa ^1/2. The photosensitive resin composition according to any one of claims 1 to 3, wherein the compound having a vinyl ether group is an alkyl vinyl ether compound. The photosensitive resin composition according to any one of claims 1 to 4, wherein the compound having a vinyl ether group has a boiling point of 80 ° C. or higher. The photosensitive agent according to any one of claims 1 to 5, wherein the photoacid generator is a compound that generates one kind of acid selected from sulfonic acid, trialkylsulfonylmethidoic acid and diallylsulfonylimide acid. Resin composition. As the photoacid generator, a compound having at least one group selected from the group consisting of an oxime sulfonate group and an imide sulfonate group, and a compound having at least one cation selected from the group consisting of a sulfonium cation and an iodonium cation. The photosensitive resin composition according to any one of claims 1 to 6, which comprises at least one compound selected from the group consisting of the diazosulfone compound and the disulfone compound. The photosensitivity according to any one of claims 1 to 7, wherein the content of the acid group with respect to the total mass of the resin is 0.1 × 10 ^{-3 to} 6.0 × 10 ^{-3 mol / g.} Sex resin composition. The photosensitive resin composition according to any one of claims 1 to 8, wherein the acid group in the resin is a carboxy group or a phenolic hydroxy group. A layered film comprising the photosensitive resin composition according to any one of claims 1 to 9. A photosensitive layer formed from the photosensitive resin composition according to any one of claims 1 to 9. A laminate including a protective layer and a photosensitive layer according to claim 11. The laminate according to claim 12, further comprising an organic layer on the side opposite to the photosensitive layer of the protective layer. The photosensitive resin composition according to any one of claims 1 to 9 and a composition for forming a protective layer for forming a protective layer are included.
A kit used to form a laminate containing a photosensitive layer and a protective layer. A semiconductor device including an organic layer patterned using a photosensitive layer formed from the photosensitive resin composition according to any one of claims 1 to 9.

Images