TWI867013B - Composition for forming protective layer, layered film, protective layer, laminate, kit, and method for manufacturing semiconductor device - Google Patents

Abstract

The present invention provides a composition for forming a protective layer, a layered film using the composition for forming a protective layer, a protective layer, a laminate and a method for manufacturing a semiconductor device, wherein the composition for forming a protective layer contains a water-soluble resin, a compound having a weight average molecular weight of 100 or more and less than 2000 and having a plurality of oxyalkylene structures, and water.

Description

Composition for forming protective layer, layered film, protective layer, laminate, set and method for manufacturing semiconductor device

The present invention relates to a composition for forming a protective layer, a layered film, a protective layer, a laminate, a kit, and a method for manufacturing a semiconductor device.

In recent years, electronic devices using organic semiconductors (organic semiconductor devices) have been widely used. Compared with existing electronic devices using inorganic semiconductors such as silicon, organic semiconductor devices have the advantage of being manufactured by simple processes. Furthermore, organic semiconductors can easily change material properties by changing their molecular structure. In addition, the material has rich variation and can realize functions or components that cannot be achieved by inorganic semiconductors. Organic semiconductors may be used in electronic devices such as organic solar cells, organic electroluminescent displays, organic photodetectors, organic field effect transistors, organic electric field luminescent elements, gas sensors, organic rectifier elements, organic inverters, and information recording elements.

The main patterning methods for organic layers such as organic semiconductor layers include printing and lithography. From the perspective of micro-processing, lithography is advantageous.

For example, Patent Document 1 describes a method for patterning an organic semiconductor layer, wherein a laminate including an organic semiconductor layer, a water-soluble resin layer, and a photosensitive layer is formed on a substrate, the photosensitive layer is patterned by photolithography, and then the water-soluble resin layer and the organic semiconductor layer are dry-etched using the patterned photosensitive layer as a mask, thereby removing the water-soluble resin layer. Here, the water-soluble resin layer functions as a protective layer, that is, protecting the organic semiconductor layer from the chemical solution used during patterning (for example, the developer used to develop the photosensitive layer), thereby reducing damage to the organic semiconductor layer.

[Prior art literature]

[Patent Literature]

[Patent document 1] Japanese Patent Publication No. 2014-044810

However, the existing water-soluble resin layer (protective layer) has the problem that cracks are easily generated in the protective layer after etching, and residues are easily generated on the organic layer after the protective layer is removed.

The present invention is made in view of the above-mentioned problem, and its purpose is to provide a composition for forming a protective layer, which can suppress cracks in the protective layer after etching the organic layer and residues on the organic layer after removing the protective layer in patterning of the organic layer using lithography.

In addition, the purpose of the present invention is to provide a method for manufacturing a layered film, a protective layer, a laminate, and a semiconductor device using the protective layer-forming composition.

The above problem can be solved by adding a compound having a plurality of oxyalkylene structures (-OR-: here R represents an alkylene group) at a predetermined molecular weight to a composition for forming a protective layer containing a water-soluble resin. Specifically, the above problem is solved by the following means <1>, preferably by means <2> and later.

<1>

A protective layer forming composition comprising: a water-soluble resin; a compound having a weight average molecular weight of 100 or more and less than 2000 and having a plurality of oxyalkylene structures; and water.

<2>

The protective layer forming composition as described in <1>, wherein the compound has one or more hydroxyl groups.

<3>

The protective layer forming composition as described in <2>, wherein the number of hydroxyl groups possessed by the compound is 2 to 8.

<4>

A protective layer forming composition as described in any one of <1> to <3>, wherein the weight average molecular weight of the compound is 1600 or less.

<5>

The protective layer forming composition according to any one of <1> to <4>, wherein the compound comprises a compound represented by the following formula (OA-1):

In formula (OA-1), ^Ra1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ^Ra2 in each structural unit containing n independently represents a hydrogen atom or a monovalent organic group represented by the following formula (OA-2), ^Ra3 in each structural unit containing n independently represents a hydrogen atom or a monovalent organic group represented by the following formula (OA-2), m represents an integer of 2 to 50, n in each structural unit containing m independently represents an integer of 1 to 20, and p represents 0 or 1;

In formula (OA-2), R ^b1 independently represents an alkylene group having 1 to 20 carbon atoms in each structural unit having q, q represents an integer of 1 to 25, and r represents 0 or 1.

<6>

The protective layer forming composition as described in <5>, wherein in the formula (OA-1), m is 10 or less.

<7>

The protective layer forming composition as described in <5>, wherein in the formula (OA-1), m is 15 to 40.

<8>

A protective layer forming composition as described in any one of <5> to <7>, wherein in formula (OA-1), n is 10 or less.

<9>

A protective layer forming composition as described in any one of <1> to <8>, wherein the plurality of oxyalkylene structures include at least one of an oxyethylene structure and an oxypropylene structure.

<10>

A protective layer forming composition as described in any one of <1> to <9>, wherein the content of the compound is 1 mass % to 30 mass % relative to the content of the water-soluble resin.

<11>

The protective layer forming composition according to any one of <1> to <10>, wherein the ratio of the total formula weight _Moa of the oxyalkylene chains to the molecular weight _Malli of the compound ( _Moa / _Mall) is 50% or more in %.

<12>

A protective layer forming composition as described in any one of <1> to <11>, wherein the boiling point of the compound is 200°C or higher.

<13>

A protective layer forming composition as described in any one of <1> to <12>, wherein the water-soluble resin comprises at least one selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone and water-soluble polysaccharides.

<14>

A protective layer forming composition as described in any one of <1> to <13>, wherein the water-soluble resin comprises a high molecular weight resin and a low molecular weight resin having a weight average molecular weight smaller than the weight average molecular weight of the high molecular weight resin, and the weight average molecular weight of the low molecular weight resin is less than half of the weight average molecular weight of the high molecular weight resin.

<15>

The protective layer forming composition as described in <14>, wherein the content of the high molecular weight resin is 30% by mass or less relative to the total water-soluble resin.

<16>

A layered film comprising a protective layer-forming composition as described in any one of <1> to <15>.

<17>

A protective layer formed by the protective layer-forming composition described in any one of <1> to <15>.

<18>

A laminate comprising, in sequence: a substrate, an organic layer, and a protective layer as described in <17>.

<19>

The laminate as described in <18> further includes a photosensitive layer on the protective layer.

<20>

A kit for forming a laminate, the laminate comprising an organic layer, a protective layer for protecting the organic layer, and a photosensitive layer on the protective layer in sequence, the kit comprising: a protective layer forming composition as described in any one of <1> to <15>; and a photosensitive layer forming composition for forming a photosensitive layer.

<21>

A method for manufacturing a semiconductor device, comprising: patterning an organic layer using a protective layer formed from a protective layer forming composition as described in any one of <1> to <15>.

The protective layer forming composition of the present invention can suppress cracks in the protective layer after etching the organic layer and residues on the organic layer after removing the protective layer during patterning of the organic layer by lithography. Furthermore, the protective layer forming composition of the present invention can provide a manufacturing method for a layered film, a protective layer, a laminate, and a semiconductor device using the same.

1: Photosensitive layer

1a: Photosensitive layer after exposure and development

2: Protective layer

3: Organic layer

3a: Organic layer after processing

4: Base material

5: Removal of the photosensitive layer after development

5a: The removed part of the laminate after etching

Figure 1 (a) to Figure 1 (d) are cross-sectional views schematically showing the processing of a laminate using a protective layer forming composition.

The following is a description of a representative embodiment of the present invention. For the sake of convenience, each component is described based on the representative embodiment, but the present invention is not limited to this embodiment.

The numerical range indicated by the symbol "~" in this manual refers to the range that includes the numerical values before and after "~" as the lower limit and upper limit respectively.

In this specification, the term "step" refers not only to independent steps, but also to steps that cannot be clearly distinguished from other steps as long as the desired effect of the step can be achieved.

Regarding the description of the base (atomic group) in this specification, the description without mentioning substitution and unsubstituted means that it includes not only the base (atomic group) without substitution but also the base (atomic group) with substitution. For example, when only "alkyl" is mentioned, it means both the alkyl group without substitution (unsubstituted alkyl) and the alkyl group with substitution (substituted alkyl). In addition, when only "alkyl" is mentioned, it means that it can be a chain or a ring, and in the case of a chain, it means that it can be a straight chain or a branch. The same meaning applies to other groups such as "alkenyl", "alkylene" and "alkenylene".

In this manual, "exposure" includes not only drawing with light, but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified. Energy rays used for drawing include the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), actinic rays such as X-rays, and particle beams such as electron beams and ion beams.

In this specification, unless otherwise specified, "light" includes not only light of wavelengths in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, infrared and other regions, or electromagnetic waves, but also radiation. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet (EUV), and X-rays. In addition, laser light such as 248nm excimer laser, 193nm excimer laser, and 172nm excimer laser can also be used. These lights can use monochromatic light (single wavelength light) that passes through an optical filter, or light containing multiple wavelengths (composite light).

In this specification, "(meth)acrylate" refers to both or either "acrylate" and "methacrylate", "(meth)acrylic acid" refers to both or either "acrylic acid" and "methacrylic acid", and "(meth)acryl" refers to both or either "acryl" and "methacryl".

In this specification, the solid components in a composition refer to the components other than the solvent. The content (concentration) of the solid components in a composition is expressed as the mass percentage of the components other than the solvent relative to the total mass of the composition unless otherwise specified.

In this manual, unless otherwise specified, the temperature is 23°C and the air pressure is 101325Pa (one atmosphere).

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are expressed as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement). The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (manufactured by Tosoh Co., Ltd.) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Co., Ltd.) as columns. In addition, unless otherwise specified, tetrahydrofuran (THF) is used as the eluent for measurement. In addition, unless otherwise specified, it is assumed that an ultraviolet light (UV light) detector with a wavelength of 254 nm is used in the GPC measurement.

In this specification, when the positional relationship of each layer constituting a laminate is described as "upper" or "lower", it is sufficient that other layers exist on the upper side or lower side of the layer serving as a reference among the multiple layers concerned. That is, there may be a third layer or element between the layer serving as a reference and the other layers, and the layer serving as a reference and the other layers do not need to be in contact. In addition, unless otherwise specified, the direction in which the layers are overlapped with respect to the substrate is referred to as "upper", or, in the case of a photosensitive layer, the direction from the substrate toward the photosensitive layer is referred to as "upper", and the opposite direction is referred to as "lower". Furthermore, this setting of up and down directions is for the convenience of explanation in this manual. In actual situations, the "up" direction in this manual may also be different from the vertical direction.

<Composition for forming protective layer>

The protective layer forming composition of the present invention contains a water-soluble resin, a compound having a weight average molecular weight of 100 or more and less than 2000 and having a plurality of oxyalkylene structures (hereinafter also referred to as a "specific hydrophilic compound"), and water. In addition, the protective layer forming composition may also contain other components as needed. The protective layer forming composition of the present invention is used to form a protective layer contained in the laminate described later.

In the present invention, since the protective layer forming composition contains a specific hydrophilic compound, cracks in the protective layer after etching the organic layer and residues on the organic layer after removing the protective layer can be suppressed during patterning of the organic layer using lithography.

The reason is not certain, but it is believed to be as follows. Among compounds having multiple alkylene oxide structures, compounds with a small molecular weight such as diethylene glycol are liquid at room temperature (around 23°C), and if they are mixed into a resin, it can be expected that the resin will soften. On the other hand, it is known that compounds with a relatively large molecular weight such as polyethylene glycol can generally be used as plasticizers for resins. Therefore, it is speculated that the protective layer formed by the protective layer forming composition containing a specific hydrophilic compound is softened. As a result, the protective layer easily follows the step difference of the substrate, and the stress in the protective layer is easily relaxed, thereby suppressing the generation of cracks in the protective layer. In addition, the weight average molecular weight of the specific hydrophilic compound is less than 2000, which is smaller than the weight average molecular weight of the water-soluble resin. Therefore, the specific hydrophilic compound can be said to be a material that easily moves in the protective layer forming composition compared to the water-soluble resin. Therefore, it is inferred that when the protective layer forming composition is applied to the organic layer, the specific hydrophilic compound is adsorbed to the hydrophilic part of the organic layer more quickly than the water-soluble resin. As a result, the adsorption points between the organic layer and the water-soluble resin are reduced, and the protective layer formed on the organic layer is easily removed, which is considered to suppress the residue on the organic layer.

The following is a detailed description of each component of the protective layer forming composition of the present invention.

<<Water-soluble resin>>

A water-soluble resin refers to a resin that dissolves 1 g or more in 100 g of water at 23°C. In addition, a water-soluble resin preferably dissolves 5 g or more in 100 g of water at 23°C, more preferably 10 g or more, and even more preferably 30 g or more. There is no particular upper limit to the amount of dissolution, but in practice it is about 100 g.

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

Specific examples of the water-soluble resin include polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), water-soluble polysaccharides (water-soluble cellulose (methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, propylmethylcellulose, etc.), pullulan or polytrisucrose derivatives, starch (hydroxypropyl starch, carboxymethyl starch, etc.), chitosan, cyclodextrin), polyethylene oxide, polyethyloxazoline, hydroxymethylmelamine, polyacrylamide, phenolic resin, styrene/maleic acid half ester, etc. In addition, two or more of these can be selected for use, and they can also be used as copolymers. In the present invention, the protective layer forming composition preferably includes at least one selected from the group consisting of polyvinyl pyrrolidone, polyvinyl alcohol, water-soluble polysaccharides, polytrisaccharide and polytrisaccharide derivatives among these resins, and preferably includes at least one selected from the group consisting of polyvinyl pyrrolidone, polyvinyl alcohol and water-soluble polysaccharides. The water-soluble polysaccharide is particularly preferably cellulose, and more preferably hydroxyethyl cellulose.

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

In formula (P1-1) to formula (P4-1), ^RP1 represents a hydrogen atom or a methyl group, ^RP2 represents a hydrogen atom or a methyl group, ^RP3 represents (CH ₂ CH ₂ O) _ma H, CH ₂ COONa or a hydrogen atom, and ma represents 1 or 2.

[Resin containing the repeating unit represented by formula (P1-1)]

In formula (P1-1), R ^P1 is preferably a hydrogen atom.

The resin containing the repeating unit represented by formula (P1-1) may also contain a repeating unit different from the repeating unit represented by formula (P1-1). In the resin containing the repeating unit represented by formula (P1-1), the repeating unit represented by formula (P1-1) is preferably contained in an amount of 65% to 90% by mass, and more preferably 70% to 88% by mass, relative to the total mass of the resin.

As a resin containing the repeating unit represented by formula (P1-1), a resin containing two repeating units represented by the following formula (P1-2) can be cited.

In formula (P1-2), R ^P11 each independently represents a hydrogen atom or a methyl group, R ^P12 represents a substituent, and np1 and np2 represent the constituent ratio of the repeating unit in the molecule on a mass basis.

In formula (P1-2), R ^P11 has the same meaning as R ^P1 in formula (P1-1), and the preferred embodiment is also the same.

In formula (P1-2), as R ^P12 , a group represented by ^-LP - ^TP can be listed. L ^P is a single bond or a linking group L described later. ^TP is a substituent, and examples of the substituent T described later can be listed. Among them, as R ^P12 , a alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms) or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms) is preferred. These alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and arylalkyl groups may further have a group specified by the substituent T within the range where the effects of the present invention are exhibited.

In formula (P1-2), np1 and np2 represent the composition ratio of the repeating unit in the molecule on a mass basis, and are independently 10% by mass or more and less than 100% by mass. However, np1+np2 will not exceed 100% by mass. When np1+np2 is less than 100% by mass, it means that the water-soluble resin is a copolymer containing other repeating units.

[Resin containing the repeating unit represented by formula (P2-1)]

In formula (P2-1), R ^P2 is preferably a hydrogen atom.

The resin containing the repeating unit represented by formula (P2-1) may further contain repeating units different from the repeating units represented by formula (P2-1). In the resin containing the repeating unit represented by formula (P2-1), the repeating unit represented by formula (P2-1) is preferably contained in an amount of 50% to 98% by mass, and more preferably 70% to 98% by mass, relative to the total mass of the resin.

As a resin containing the repeating unit represented by formula (P2-1), a resin containing two repeating units represented by the following formula (P2-2) can be cited.

[Chemistry 5]

In formula (P2-2), R ^P21 each independently represents a hydrogen atom or a methyl group, R ^P22 represents a substituent, and mp1 and mp2 represent the constituent ratio of the repeating unit in the molecule on a mass basis.

In formula (P2-2), R ^P21 has the same meaning as R ^P2 in formula (P2-1), and the preferred embodiment is also the same.

In formula (P2-2), as R ^P22 , a group represented by ^-LP - ^TP can be listed. L ^P is a single bond or a linking group L described later. ^TP is a substituent, and examples of the substituent T described later can be listed. Among them, as R ^P22 , a alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3 carbon atoms), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10 carbon atoms) or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and further preferably 7 to 11 carbon atoms) is preferred. These alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and arylalkyl groups may further have a group specified by the substituent T within the range where the effects of the present invention are exhibited.

In formula (P2-2), mp1 and mp2 represent the composition ratio of the repeating units in the molecule on a mass basis, and are independently 10% by mass or more and less than 100% by mass. However, mp1+mp2 will not exceed 100% by mass. When mp1+mp2 is less than 100% by mass, it means that the water-soluble resin is a copolymer containing other repeating units.

[Resin containing the repeating unit represented by formula (P3-1)]

In formula (P3-1), ^RP3 is preferably a hydrogen atom.

The resin containing the repeating unit represented by formula (P3-1) may further contain repeating units different from the repeating units represented by formula (P3-1). In the resin containing the repeating unit represented by formula (P3-1), the repeating unit represented by formula (P3-1) is preferably contained in an amount of 10% to 90% by mass, and more preferably 30% to 80% by mass, relative to the total mass of the resin.

In addition, the hydroxyl group described in formula (P3-1) may be appropriately substituted by a substituent T or a group formed by combining the substituent T with a linking group L. When there are multiple substituents T, they may bond to each other, or bond to the ring in the formula via the linking group L or without the linking group L to form a ring.

[Resin containing the repeating unit represented by formula (P4-1)]

The resin containing the repeating unit represented by formula (P4-1) may further contain repeating units different from the repeating units represented by formula (P4-1). In the resin containing the repeating unit represented by formula (P4-1), the repeating unit represented by formula (P4-1) is preferably contained in an amount of 8% to 95% by mass, and more preferably 20% to 88% by mass, relative to the total mass of the resin.

In addition, the hydroxyl group described in formula (P4-1) may be appropriately substituted by a substituent T or a group formed by combining the substituent T with a linking group L. When there are multiple substituents T, they may bond to each other, or bond to the ring in the formula via the linking group L or without the linking group L to form a ring.

As the substituent T, there can be mentioned: alkyl (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 1 to 6), arylalkyl (preferably having 7 to 21 carbon atoms, more preferably 7 to 15, and further preferably 7 to 11), alkenyl (preferably having 2 to 24 carbon atoms, more preferably 2 to 12, and further preferably 2 to 6), alkynyl (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3), hydroxyl, amino (preferably having 0 to 24 carbon atoms, more preferably 0 to 1 2, preferably 0 to 6), thiol, carboxyl, aryl (preferably carbon number 6 to 22, more preferably 6 to 18, more preferably 6 to 10), alkoxy (preferably carbon number 1 to 12, more preferably 1 to 6, more preferably 1 to 3), aryloxy (preferably carbon number 6 to 22, more preferably 6 to 18, more preferably 6 to 10), acyl (preferably carbon number 2 to 12, more preferably 2 to 6, more preferably 2 to 3), acyloxy (preferably carbon number 2 to 12, more preferably 2 to 6, more preferably 2 to 3), aryl (preferably 7 to 23 carbon atoms, more preferably 7 to 19, more preferably 7 to 11), aryloxy (preferably 7 to 23 carbon atoms, more preferably 7 to 19, more preferably 7 to 11), aminoformyl (preferably 1 to 12 carbon atoms, more preferably 1 to 6, more preferably 1 to 3), aminosulfonyl (preferably 0 to 12 carbon atoms, more preferably 0 to 6, more preferably 0 to 3), sulfo, alkylsulfonyl (preferably 0 to 12 carbon atoms, more preferably 0 to 6, more preferably 0 to 3), The present invention also includes an arylsulfonyl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), a heteroaryl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 2 to 5 carbon atoms, and preferably including a five-membered ring or a six-membered ring), 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), a pendoxy group (=O), an imino group (=NR ^N ), an alkylene group (=C( ^RN ) ₂ ), and the like. ^RN is a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), and is preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group. The alkyl part, alkenyl part and alkynyl part contained in each substituent may be chain-shaped or cyclic-shaped, and may be straight chain or branched. When the substituent T is a group that can replace the substituent, it may further have a substituent T. For example, the alkyl group may be a halogenated alkyl group, or may be a (meth)acryloxyalkyl group, an aminoalkyl group or a carboxyalkyl group. When the substituent is a group that can form a salt, such as a carboxyl group or an amino group, the group may also form a salt.

Examples of the linking group L include an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and further preferably 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3 carbon atoms), an alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and further preferably 2 to 3 carbon atoms), an (oligo)oxyalkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and further preferably 1 to 3 carbon atoms in the alkylene group in one repeating unit; preferably 1 to 50 carbon atoms, more preferably 1 to 40, and further preferably 1 to 30 carbon atoms), an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and further preferably 6 to 10 carbon atoms), an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a thiocarbonyl group, -NR ^N -, and the linking groups related to the combination thereof. The alkylene group may also have a substituent T. For example, the alkylene group may have a hydroxyl group. The number of atoms contained in the linking group L, excluding hydrogen atoms, is preferably 1 to 50, more preferably 1 to 40, and further preferably 1 to 30. The number of linking atoms refers to the number of atoms located on the shortest path in the atomic group involved in the link. For example, if it is -CH ₂ -(C=O)-O-, the number of atoms involved in the link is 6, and 4 excluding the hydrogen atom. On the other hand, the shortest atom involved in the link is -CCO-, which is 3. As the number of linking atoms, it is preferably 1 to 24, more preferably 1 to 12, and further preferably 1 to 6. Furthermore, the alkylene group, alkenylene group, alkynylene group, and (oligo)oxyalkylene group may be chain-shaped or cyclic, and may be straight chain or branched. When the linking group is a group capable of forming a salt such as -NR ^N -, the group can also form a salt.

In addition, as a water-soluble resin, a commercial product can also be used. As commercial products, the following can be listed: PITZCOL series (K-30, K-50, K-80, K-90, V-7154, etc.) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.; LUVITEC series (VA64P, VA6535P, etc.) manufactured by BASF; PXP-05, JL-05E, JP-03, JP-04, AMPS manufactured by JAPAN VAM & POVAL Co., Ltd.; Nanoclay manufactured by Aldrich Corporation, etc.

Among these, PITZCOL K-90, PXP-05 or PITZCOL V-7154 is preferred, and PITZCOL V-7154 is more preferred.

Regarding water-soluble resins, the resins described in International Publication No. 2016/175220 are cited, and such resins are also incorporated into this specification.

The weight average molecular weight of the water-soluble resin is appropriately selected according to the type of the water-soluble resin. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the water-soluble resin are set as polyether oxide conversion values obtained by GPC measurement. In particular, when the water-soluble resin is polyvinyl alcohol (PVA), the weight average molecular weight is preferably 10,000~100,000. The upper limit of the numerical range is preferably 80,000 or less, and more preferably 60,000 or less. In addition, the lower limit of the numerical range is preferably 13,000 or more, and more preferably 15,000 or more. When the water-soluble resin is polyvinyl pyrrolidone (PVP), the weight average molecular weight is preferably 20,000~2,000,000. The upper limit of the numerical range is preferably 1,800,000 or less, and more preferably 1,500,000 or less. In addition, the lower limit of the numerical range is preferably 30,000 or more, and more preferably 40,000 or more. When the water-soluble resin is a water-soluble polysaccharide, the weight average molecular weight is preferably 50,000 to 2,000,000. The upper limit of the numerical range is preferably 1,500,000 or less, and more preferably 1,300,000 or less. In addition, the lower limit of the numerical range is preferably 70,000 or more, and more preferably 90,000 or more.

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

Furthermore, in the present invention, the protective layer forming composition preferably includes a high molecular weight resin (for example, a water-soluble resin with a weight average molecular weight of 10,000 or more) and a low molecular weight resin having a weight average molecular weight smaller than the weight average molecular weight of the high molecular weight resin as a water-soluble resin, and the weight average molecular weight of the low molecular weight resin is less than half of the weight average molecular weight of the high molecular weight resin. Thereby, the low molecular weight resin is rapidly dissolved into the removal liquid (especially water), and the high molecular weight resin is also easily removed starting from the portion where the low molecular weight resin is dissolved, thereby obtaining an effect of further reducing the residue of the protective layer after removing the protective layer. In addition, when the protective layer is formed using the protective layer forming composition, cracks in the protective layer can be suppressed.

In the present invention, whether the protective layer forming composition contains the high molecular weight resin and the low molecular weight resin can be determined, for example, based on whether two or more peaks (maximum values) can be confirmed when measuring the molecular weight distribution of the protective layer forming composition or the water-soluble resin as a whole.

The weight average molecular weight of the high molecular weight resin is preferably 20,000 or more, and more preferably 45,000 or more. In addition, 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. In addition, the lower limit of the molecular weight ratio is not particularly limited, and is preferably 0.001 or more, and may be 0.01 or more.

In addition, in the molecular weight distribution of the water-soluble resin used in the present invention as a whole, it is also preferred that there are two or more peaks, and the molecular weight corresponding to one of the two or more peaks is less than half of the molecular weight corresponding to the other peak. In this way, the same effect as when the weight average molecular weight of the low molecular weight resin is less than half of the weight average molecular weight of the high molecular weight resin is obtained. The water-soluble resin having the above molecular weight distribution can be obtained, for example, by mixing the high molecular weight resin and the low molecular weight resin. When multiple peaks are confirmed in the molecular weight distribution, two peaks are selected from the peaks as a group, and for at least one group of peaks, the molecular weight corresponding to one of the peaks is less than half of the molecular weight corresponding to the other peak.

The larger one of the molecular weights corresponding to the peak top (peak top molecular weight) is preferably 20,000 or more, and more preferably 45,000 or more. In addition, the larger one of the peak top molecular weight is preferably 2,000,000 or less, and may be 1,500,000 or less. The molecular weight ratio of the smaller one of the peak top molecular weight to the larger one (= the smaller one of the peak top molecular weight/the larger one of the 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. In addition, the lower limit of the molecular weight ratio is not particularly limited, and is preferably 0.001 or more, and may be 0.01 or more.

Regarding 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 (in the case of the molecular weight distribution of the entire water-soluble resin, it is the molecular weight distance between peaks), when PVA is included as the high molecular weight resin, it is preferably 10,000~80,000, and more preferably 20,000~60,000. When PVP is included as the high molecular weight resin, the difference is preferably 50,000~1,500,000, and more preferably 100,000~1,200,000. When a water-soluble polysaccharide is included as the high molecular weight resin, the difference is preferably 50,000~1,500,000, more preferably 100,000~1,200,000.

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

The preferred combination of high molecular weight resin and low molecular weight resin is as follows. The water-soluble resin may satisfy only one of the following necessary conditions for the combination, or may satisfy two or more of the necessary conditions for the combination at the same time.

． Combination of PVA (high molecular weight resin) with a weight average molecular weight Mw of 30,000~100,000 and PVA (low molecular weight resin) with a Mw of 10,000~40,000.

． Combination of PVP (high molecular weight resin) with Mw of 500,000~1,500,000 and PVP (low molecular weight resin) with Mw of 30,000~600,000.

． A combination of water-soluble polysaccharides (high molecular weight resins) with a Mw of 500,000~1,500,000 and water-soluble polysaccharides (low molecular weight resins) with a Mw of 50,000~600,000.

． Combination of PVP (high molecular weight resin) with Mw of 500,000~1,500,000 and PVA (low molecular weight resin) with Mw of 10,000~100,000.

． Combination of water-soluble polysaccharides (high molecular weight resin) with Mw of 500,000~1,500,000 and PVA (low molecular weight resin) with Mw of 10,000~100,000.

． Combination of PVP (high molecular weight resin) with Mw of 500,000~1,500,000 and water-soluble polysaccharides (low molecular weight resin) with Mw of 50,000~600,000.

． A combination of water-soluble polysaccharides (high molecular weight resins) with a Mw of 500,000~1,500,000 and PVP (low molecular weight resins) with a Mw of 30,000~600,000.

The content of high molecular weight resin is preferably 50% by mass or less relative to all water-soluble resins. The upper limit of the numerical range is preferably 40% by mass or less, and further preferably 30% by mass or less. In addition, the lower limit of the numerical range is preferably 5% by mass or more, and further preferably 10% by mass or more.

On the other hand, the water-soluble resin may be substantially free of low molecular weight resins. In the present invention, "substantially free of low molecular weight resins" means that the content of low molecular weight resins is 3% by mass or less relative to all water-soluble resins. In this embodiment, the content of low molecular weight resins is preferably 1% by mass or less relative to all water-soluble resins.

The content of all water-soluble resins in the protective layer forming composition can be appropriately adjusted as needed, and is preferably 5% to 15% by mass relative to the total amount of the protective layer forming composition. The upper limit of the numerical range is preferably 12% by mass or less, and more preferably 10% by mass or less. In addition, the lower limit of the numerical range is preferably 6% by mass or more, and more preferably 7% by mass or more. In addition, the content of all water-soluble resins in the protective layer forming composition is preferably 30% by mass or less in the solid component, more preferably 25% by mass or less, and more preferably 20% by mass or less. As the lower limit, it is preferably 1% by mass or more, more preferably 2% by mass or more, and more preferably 4% by mass or more.

In the protective layer forming composition, the water-soluble resin may be used alone or in combination of multiple types. In the case of multiple combinations, it is preferred that the total amount of these is within the above range.

<<Compounds having multiple oxyalkylene structures (specific hydrophilic compounds)>>

As described above, the specific hydrophilic compound contained in the protective layer forming composition of the present invention is a compound having a weight average molecular weight of 100 or more and less than 2000 and having multiple oxyalkylene structures. The specific hydrophilic compound exhibits hydrophilicity by having multiple oxyalkylene structures, and due to the hydrophilicity, has the property of being easily adsorbed on the hydrophilic parts of other organic materials. In the present invention, "oxyalkylene structure" refers to a divalent group (-OR-: here R represents an alkylene group) containing one oxygen atom and one alkylene group. The alkylene group may have a substituent on the side chain, or it may be unsubstituted, preferably unsubstituted.

The upper limit of the molecular weight of the specific hydrophilic compound is preferably 1600 or less, more preferably 1200 or less, further preferably 800 or less, and particularly preferably 400 or less. When the molecular weight of the specific hydrophilic compound is below the upper limit, the specific hydrophilic compound becomes more easily mobile in the protective layer forming composition. In addition, the lower limit of the molecular weight of the specific hydrophilic compound is preferably 110 or more, more preferably 120 or more, further preferably 130 or more, and particularly preferably 140 or more. When the molecular weight of the specific hydrophilic compound is above the lower limit, the specific hydrophilic compound becomes less volatile.

The specific hydrophilic compound can be a liquid or a solid at room temperature (about 23°C), preferably a liquid. By making the specific hydrophilic compound a liquid, the protective layer becomes easier to soften.

The boiling point of the specific hydrophilic compound is preferably above 200°C. Thereby, the specific hydrophilic compound becomes less volatile, and even if a heat treatment is performed in the drying step of the protective layer, the manufacturing step of the organic semiconductor, etc., the effect of the present invention is not impaired. The lower limit of the boiling point of the specific hydrophilic compound is preferably above 210°C, more preferably above 220°C, and further preferably above 240°C. In addition, the upper limit of the boiling point of the specific hydrophilic compound is not particularly limited as long as the specific hydrophilic compound does not volatilize, but is actually below 400°C.

In the specific hydrophilic compound, the carbon number of the alkylene chain in the oxyalkylene structure is preferably 2 to 20. The upper limit of the range is more preferably 10 or less, and further preferably 5 or less. More specifically, the oxyalkylene structure is preferably at least one of an oxyethylene structure (-OC ₂ H ₄ -) and an oxypropylene structure (-OC ₃ H ₆ -), and is more preferably an oxyethylene structure. In addition, the oxyalkylene structure may or may not have the substituent T in the side chain other than the terminal. The oxyalkylene structure preferably has no substituent in the side chain other than the terminal. In the specific hydrophilic compound, a plurality of oxyalkylene structures may be continuous or separated.

The specific hydrophilic compound preferably has at least one hydroxyl group, preferably 1 to 20 hydroxyl groups. The specific hydrophilic compound has a hydroxyl group, and the hydrophilicity of the specific hydrophilic compound is further improved. Furthermore, the upper limit of the number of hydroxyl groups possessed by the specific hydrophilic compound is preferably 10 or less, more preferably 8 or less, and further preferably 6 or less. In addition, the lower limit may be two, 3, or 4.

In the specific hydrophilic compound, the ratio of the total formula weight _Moa of the oxyalkylene chain to its molecular _{weight Mall} is preferably 50% or _more , expressed as %. The lower limit of the range is preferably 60% or more, more preferably 65% or more, further preferably 70% or more, particularly preferably 75% or more, and most preferably 80% or more. The upper limit of the range is actually less than 100%. When the weight average molecular weight Mw and the average addition mole number _Mav of the collection of specific hydrophilic compounds are known, the ratio _Moa / _Mall can be replaced by [formula weight of repeating unit× _mav ]/Mw×100(%).

"Oxyalkylene chain" refers to the partial structure of the oxyalkylene structure that does not contain a substituent. Specifically, an oxyalkylene chain contains an oxygen atom, a carbon atom bonded to the oxygen atom and constituting the main chain of the alkylene group, and a hydrogen atom bonded to the carbon atom. The formula weight of an oxyalkylene chain can be calculated by the sum of the atomic weights of these atoms.

For example, in the compound example ex-1 below, the parts of OL-1 and OL-2 are oxyalkylene chains (oxyethylene chains). Therefore, the formula weight of one oxyalkylene chain is 44 (=16+12×2+1×4), the total formula weight of oxyalkylene chains is 88 (=44×2), and the ratio _Moa / _Ma1l is 83% (=88÷106×100) in %.

In the calculation of the total formula weight _Moa of the oxyalkylene chain, the atoms are not counted repeatedly, and in the case of an alkylene branch, the oxyalkylene chain is set so that the carbon number becomes the largest. In addition, in the case where a substituent is considered to be bonded to the oxyalkylene chain, the formula weight of the oxyalkylene chain does not include the formula weight of the substituent. In addition, it is separately examined whether the substituent includes the oxyalkylene chain. If the oxyalkylene chain is included, its formula weight is also added to the total formula weight of the oxyalkylene chain. The derivation of the formula weight is repeated until the substituent disappears or the oxyalkylene chain is not included in the substituent.

For example, in the compound example ex-2 below, the parts of OL-3 to OL-7 are oxyalkylene chains, especially OL-3 and OL-4 are oxypropylene chains, and OL-5 to OL-7 are oxyethylene chains. OL-3 and OL-4 are considered to have substituents (methyl and hydroxyl, respectively), so after removing the substituents, the formula weight of OL-3 is 58 (=16+12×3+1×6), and the formula weight of OL-4 is 57 (=16+12×3+1×5). The formula weights of OL-5 to OL-7 are 44, respectively. Therefore, the total formula weight of the oxyalkylene chains is 247 (=58+57+44×3), and the ratio _Moa / _Ma1 is 88% (=247÷280×100) in terms of %.

For example, in the compound example ex-3 below, the parts of OL-8 to OL-13 are oxyalkylene chains, especially OL-8, OL-9 and OL-13 are oxypropylene chains, and OL-10 to OL-12 are oxyethylene chains. OL-13 can be called an oxyalkylene chain contained in the substituent bonded to OL-9. The formula weights of OL-8 and OL-13 are 59 (=16+12×3+1×7). Since OL-9 is regarded as having a substituent, the formula weight of OL-9 is 57 (=16+12×3+1×5) after removing the substituent. The formula weights of OL-10 to OL-12 are 44, respectively. Therefore, the total formula weight of the oxyalkylene chain is 307 (=59×2+57+44×3), and the ratio _Moa / _Ma1l expressed in % is 95% (=307÷322×100).

For example, in the compound example ex-4 below (polyethylene glycol), the repeating unit with m is an oxyalkylene chain. When the specific structure is known, the ratio _Moa / _Ma1l can be calculated based on the total formula weight and molecular weight of the actual oxyalkylene chain, as in the case of ex-1 to ex-3. When the weight average molecular weight Mw and the average addition mole number _Mav are known, the ratio _Moa / _Ma1l can be replaced by [44× _mav ]/Mw×100.

Furthermore, the protective layer forming composition of the present invention preferably contains a compound represented by the following formula (OA-1) as a specific hydrophilic compound.

In the formula (OA-1), ^Ra1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ^Ra2 in each structural unit containing n independently represents a hydrogen atom or a monovalent organic group represented by the following formula (OA-2), ^Ra3 in each structural unit containing n independently represents a hydrogen atom or a monovalent organic group represented by the following formula (OA-2), m represents an integer of 2 to 50, n in each structural unit containing m independently represents an integer of 1 to 20, and p represents 0 or 1; [Chemical 8] Formula (OA-2):

In formula (OA-2), R ^b1 independently represents an alkylene group having 1 to 20 carbon atoms in each structural unit having q, q represents an integer of 1 to 25, and r represents 0 or 1.

In formula (OA-1), ^Ra1 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Here, the alkyl group is preferably any one of a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, more preferably a methyl group or an ethyl group, and further preferably an ethyl group. When ^Ra1 is an alkyl group, the alkyl group may have a substituent such as the substituent T, or may be unsubstituted.

In an embodiment in which the molecular weight of the specific hydrophilic compound is relatively small, the upper limit of m is preferably 10 or less, more preferably 8 or less, and further preferably 6 or less. The lower limit of m may be 3 or 4. In this case, n is preferably 10 or less, more preferably 8 or less, and further preferably 6 or less, independently in each structural unit having m. The lower limit of n may be 2 or 3. p is preferably 1. On the other hand, in an embodiment in which the molecular weight of the specific hydrophilic compound is relatively large, the upper limit of m is preferably 45 or less, more preferably 40 or less, and further preferably 35 or less. The lower limit of m is preferably 11 or more, and may be 15 or more or 20 or more. In this case, n is also preferably 10 or less, more preferably 8 or less, and further preferably 6 or less, independently in each structural unit having m. The lower limit of n can be 2 or 3. The best value of p is 1.

In formula (OA-2), ^Rb1 is preferably an alkylene group having 1 to 10 carbon atoms independently in each structural unit having q. Here, the alkylene group is preferably any one of a methylene group, an ethylene group, an n-propylene group, and an n-butylene group, more preferably a methylene group or an ethylene group, and further preferably an ethylene group. When ^Rb1 is an alkylene group, the alkylene group may have a substituent such as the substituent T, and may further include a group having an oxyalkylene structure as a substituent. In addition, when ^Rb1 is an alkylene group, the alkylene group may be unsubstituted.

In the embodiment where the molecular weight of the specific hydrophilic compound is relatively small, the upper limit of q is preferably 5 or less, more preferably 4 or less, and further preferably 3 or less. The lower limit of q may be 1 or 2. r is preferably 1. On the other hand, in the embodiment where the molecular weight of the specific hydrophilic compound is relatively large, the upper limit of q is preferably 23 or less, more preferably 20 or less, and further preferably 18 or less. The lower limit of q is preferably 6 or more, and may be 8 or more or 10 or more. r is preferably 1.

Therefore, the monovalent organic group represented by the formula (OA-2) is, for example, a group _{having an alkoxy group at the terminal, such as -OCH3, -(OCH2)OCH3 , - ( OCH2 ) 2OCH3 , -} ( _{OCH2 )} 3OCH3, _-OC2H5 , _- ( _OC2H4 ) _{OC2H5 ,} -( _{OC2H4 )} 2OC2H5 _, -( _{OC2H4 ) 3OC2H5 , -OC3H7 , -} ( _{OC3H6 ) OC3H7} , -( _{OC3H6 ) 2OC3H7 ,} and -( _{OC3H6 ) 3OC3H7} ; or _a group _having an alkoxy group at the terminal _, such as _{-OCH2OH ,} -( _OCH2 ) _{2OH ,} -( _OCH2 ) _A group _{having a hydroxyl} group at _{the terminal such} as -( _OCH2 )4OH, _-OC2H4OH , -( _OC2H4 )2OH, -( _OC2H4 )3OH _, -( _{OC2H4 ) 4OH} , _-OC3H6OH , -( _OC3H6 ) _2OH , -( _OC3H6 ) _{3OH and - ( OC3H6} ) _4OH .

The protective layer-forming composition of the present invention also preferably contains a compound represented by the following formula (OA-3) as a specific hydrophilic compound. In particular, the following formula (OA-3) is equivalent to the following formula (OA-1) in which both ^Ra2 and ^Ra3 are hydrogen atoms.

In formula (OA-3), ^Ra1 , m, n and p have the same meanings as ^Ra1 , m, n and p in formula (OA-1), respectively.

Furthermore, in the present invention, the specific hydrophilic compound is preferably a compound satisfying ^Ra1 = H, n = 2 and p = 1 in formula (OA-3), that is, oligoethylene glycol or polyethylene glycol. Furthermore, in this case, m is preferably 2 to 10, more preferably 2 to 6, and further preferably 2 to 4. In addition, the specific hydrophilic compound is also preferably a compound satisfying ^Ra1 = H, n = 3 and p = 1 in formula (OA-3), that is, oligopropylene glycol or polypropylene glycol. Furthermore, in this case, m is preferably 2 to 10, more preferably 2 to 6, and further preferably 2 to 4.

The preferred embodiment of the specific hydrophilic compound represented by formula (OA-1) or formula (OA-3) is as follows. In the following formula, the formula with m represents polyethylene glycol, and m represents the number of repetitions of the oxyethyl group structure (average addition molar number). The preferred range of m is 2 to 10.

[Chemistry 10]

In the protective layer forming composition of the present invention, the content of the specific hydrophilic compound is preferably 0.01 mass% to 5 mass% relative to the total amount of the protective layer forming composition. When the content of the specific hydrophilic compound is within the above range, the effect of the present invention of suppressing cracks and residues of the protective layer is further improved. The upper limit of the content of the specific hydrophilic compound is more preferably 4.0 mass% or less, further preferably 3.5 mass% or less, and particularly preferably 3.0 mass% or less. In addition, the lower limit of the content of the specific hydrophilic compound is more preferably 0.05 mass% or more, further preferably 0.1 mass% or more, and particularly preferably 0.3 mass% or more. In addition, the content of the specific hydrophilic compound is preferably 0.1 mass% to 50 mass% relative to the content of the water-soluble resin. By setting the content of the specific hydrophilic compound to be within the above range, the effect of the present invention of suppressing cracks and residues in the protective layer is further improved. The upper limit of the content of the specific hydrophilic compound is preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less. In addition, the lower limit of the content of the specific hydrophilic compound is preferably 1% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more.

In the protective layer forming composition of the present invention, the specific hydrophilic compound can be used alone or in combination of multiple types. In the case of multiple combinations, it is preferred that the total amount of these is within the above range.

<<Solvent>>

The solvent used in the protective layer forming composition contains at least water as described above. In addition, the solvent may contain a water-soluble solvent as a solvent other than water. In addition, the protective layer forming composition may also be a state that does not contain a water-soluble solvent (that is, the solvent in the protective layer forming composition is only water).

The water-soluble solvent added to the protective layer forming composition is preferably an organic solvent having a solubility of 1 g or more in water at 23°C. The solubility of the organic solvent in water at 23°C is more preferably 10 g or more, and further preferably 30 g or more. Examples of such water-soluble solvents include: alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, and glycerin; ketone solvents such as acetone; amide solvents such as formamide, etc.

The content of the solvent as a whole including water and other solvents relative to the total amount of the protective layer forming composition is preferably 80 mass% to 95 mass%. The upper limit of the numerical range is preferably 93 mass% or less, and more preferably 90 mass% or less. In addition, the lower limit of the numerical range is preferably 83 mass% or more, and more preferably 85 mass% or more. That is, the solid content concentration of the protective layer forming composition of the present invention is preferably 5 mass% to 20 mass%. The upper limit of the numerical range is preferably 17 mass% or less, and more preferably 15 mass% or less. In addition, the lower limit of the numerical range is preferably 7 mass% or more, and more preferably 10 mass% or more.

The content of water in the protective layer forming composition is preferably 80% to 95% by mass relative to the total amount of the protective layer forming composition. The upper limit of the numerical range is preferably 93% by mass or less, and more preferably 90% by mass or less. In addition, the lower limit of the numerical range is preferably 83% by mass or more, and more preferably 85% by mass or more. In addition, the content of water in the protective layer forming composition is preferably 80% to 100% by mass relative to the content of the entire solvent. The upper limit of the numerical range may be 98% by mass or less, and may be 95% by mass or less. In addition, the lower limit of the numerical range is preferably 85% by mass or more, and more preferably 90% by mass or more.

The content of the water-soluble solvent in the protective layer forming composition is preferably 0 mass% to 10 mass% relative to the content of the entire solvent. The upper limit of the numerical range is preferably 8 mass% or less, and further preferably 5 mass% or less. In addition, the lower limit of the numerical range may exceed 0 mass%.

<<Other ingredients>>

In the present invention, the protective layer forming composition may include a resin soluble in a water-soluble solvent (such as alcohol), an acetylene-containing surfactant, other surfactants, a preservative, an anti-mold agent, and a sunscreen as other ingredients.

[Resins that can be dissolved in water-soluble solvents]

A resin that can be dissolved in a water-soluble solvent refers to a resin that can dissolve 1g or more relative to 100g of the water-soluble solvent at 23°C. Furthermore, the water-soluble resin is preferably a resin that can dissolve 5g or more relative to 100g of the water-soluble solvent at 23°C, more preferably a resin that can dissolve 10g or more, and even more preferably a resin that can dissolve 20g or more. There is no particular upper limit to the amount of dissolution, but it is actually about 30g.

The resin soluble in a water-soluble solvent is preferably an alcohol-soluble resin soluble in alcohol as a water-soluble solvent, and more preferably polyvinyl acetal.

[Surfactant containing acetylene group]

The protective layer forming composition can further suppress the generation of residues by containing an acetylene-containing surfactant.

In the surfactant containing acetylene groups, the number of acetylene groups in the molecule is not particularly limited, preferably one to ten, more preferably one to five, further preferably one to three, further preferably one to two.

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

-Compound represented by formula (9)-

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

[Chemical 11] R ⁹¹ -C≡CR ⁹² (9)

In the formula, R ⁹¹ and R ⁹² are independently an alkyl group having 3 to 15 carbon atoms, an aromatic alkyl group having 6 to 15 carbon atoms, or an aromatic heteroaryl group having 4 to 15 carbon atoms. The number of carbon atoms in the aromatic heteroaryl group is preferably 1 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The aromatic heterocyclic ring is preferably a five-membered ring or a six-membered ring. The heteroatom contained in the aromatic heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom.

R ⁹¹ and R ⁹² may each independently have a substituent, and as the substituent, the substituent T described above can be cited.

-Compound represented by formula (91)-

As the compound represented by formula (9), the compound represented by the following formula (91) is preferred.

R ⁹³ to R ⁹⁶ are each independently a alkyl group having 1 to 24 carbon atoms, n9 is an integer of 1 to 6, m9 is an integer twice n9, n10 is an integer of 1 to 6, m10 is an integer twice n10, and l9 and l10 are each independently a number of 0 to 12.

R ⁹³ to R ⁹⁶ are alkyl groups, preferably alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), alkynyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), and arylalkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms). Alkyl groups, alkenyl groups, and alkynyl groups may be straight chain groups or cyclic groups, and may be straight chain groups or branched groups. R ⁹³ to R ⁹⁶ may also have a substituent T within the scope of exerting the effect of the present invention. In addition, R ⁹³ to R ⁹⁶ may be bonded to each other or to form a ring via the linking group L. When there are plural substituents T, they may be bonded to each other or to the alkyl group in the formula via the linking group L described below or without the linking group L described below to form a ring.

R ⁹³ and R ⁹⁴ are preferably alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), and methyl groups are particularly preferred.

R ⁹⁵ and R ⁹⁶ are preferably alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 3 to 6 carbon atoms). Among them, -(C _n11 R ⁹⁸ _m11 )-R ⁹⁷ is preferred. R ⁹⁵ and R ⁹⁶ are particularly preferably isobutyl groups.

n11 is an integer between 1 and 6, preferably between 1 and 3. m11 is twice the value of n11.

R ⁹⁷ and R ⁹⁸ are each independently preferably a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms).

n9 is an integer between 1 and 6, preferably between 1 and 3. m9 is an integer twice that of n9.

n10 is an integer between 1 and 6, preferably between 1 and 3. m10 is an integer twice of n10.

l9 and l10 are independently a number of 0 to 12. Among them, l9+l10 is preferably a number of 0 to 12, more preferably a number of 0 to 8, further preferably a number of 0 to 6, further preferably a number greater than 0 and less than 6, further preferably a number greater than 0 and less than 3. In addition, regarding l9 and l10, the compound of formula (91) may be a mixture of compounds different in their number, in which case the numbers of l9 and l10, or l9+l10 may be a number containing decimal points.

-Compound represented by formula (92)-

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

R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ are each independently a alkyl group having 1 to 24 carbon atoms, and l11 and l12 are each independently a number of 0 to 12.

Among R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ , preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms). The alkyl group, the alkenyl group, and the alkynyl group may be in the form of a chain or a ring, and may be a straight chain or a branched chain. R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ may have a substituent T within the range that the effect of the present invention is exerted. In addition, R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ may be bonded to each other or to form a ring via a linking group L. When there are multiple substituents T, they may be bonded to each other or to the alkyl group in the formula via a linking group L or without a linking group L to form a ring.

R ⁹³ , R ⁹⁴ , 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 even more preferably 1 to 3 carbon atoms), and preferably a methyl group.

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

Examples of surfactants containing acetylene groups include Surfynol 104 series (trade names, Nissin Chemical Industry Co., Ltd.), Acetyrenol E00, Acetyrenol E40, Acetyrenol E13T, Acetyrenol 60 (all trade names, Sichuan (produced by Kensei Chemical Co., Ltd.), among which Surfynol 104 series, Acetyrenol E00, Acetyrenol E40, Acetyrenol E13T are preferred, and Acetyrenol E40 and Acetyrenol E13T are more preferred. Furthermore, Surfynol 104 series and Acetyrenol E00 are surfactants with the same structure.

[Other surfactants]

In order to improve coating properties, the protective layer forming composition may also contain other surfactants besides the above-mentioned acetylene group-containing surfactant.

As other surfactants, any surfactants may be non-ionic, anionic, amphoteric fluorine, etc., as long as they can reduce the surface tension of the protective layer forming composition.

As other surfactants, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan alkyl esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, and sorbitan trioleate, glycerol monostearate, sorbitan alkyl esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, and sorbitan trioleate can be used. Non-ionic surfactants such as fatty acid esters, monoglyceride alkyl esters such as glycerol monooleate, oligomers containing fluorine or silicon, etc.; alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate, alkyl naphthalene sulfonates such as sodium butylnaphthalene sulfonate, sodium amylnaphthalene sulfonate, sodium hexylnaphthalene sulfonate, sodium octylnaphthalene sulfonate, alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium dodecyl sulfonate, sulfosuccinates such as sodium dilauryl sulfosuccinate, etc.; anionic surfactants such as alkyl betaines such as lauryl betaine and stearyl betaine, and amphoteric surfactants such as amino acids.

When the protective layer forming composition contains an acetylene-containing surfactant and other surfactants, the amount of the surfactant added is preferably 0.05% by mass to 20% by mass, more preferably 0.07% by mass to 15% by mass, and further preferably 0.1% by mass to 10% by mass, based on the total amount of the acetylene-containing surfactant and other surfactants relative to the total mass of the protective layer forming composition. These surfactants can be used alone or in combination. In the case of multiple combinations, it is preferred that the total amount of these is within the above range.

In addition, in the present invention, a structure that substantially does not contain other surfactants can also be set. Substantially free means that the content of other surfactants is less than 5% by mass of the content of the acetylene group-containing surfactant, preferably less than 3% by mass, and more preferably less than 1% by mass.

In the protective layer forming composition, the content of other surfactants relative to the total mass of the protective layer forming composition is preferably 0.05 mass% or more, more preferably 0.07 mass% or more, and further preferably 0.1 mass% or more. In addition, the upper limit is preferably 20 mass% or less, more preferably 15 mass% or less, and further preferably 10 mass% or less. Such other surfactants can be used alone or in combination. In the case of multiple combinations, it is preferred that the total amount of these is within the above range.

The surface tension of a 0.1 mass% aqueous solution of other surfactants at 23°C is preferably 45mN/m or less, more preferably 40mN/m or less, and further preferably 35mN/m or less. As a lower limit, it is preferably 5mN/m or more, more preferably 10mN/m or more, and further preferably 15mN/m or more. The surface tension of the surfactant can be appropriately selected according to the type of other surfactant selected.

[Preservatives and mold inhibitors]

Since the protective layer forming composition contains a preservative and a mildew preventer, the quality of the protective layer forming composition can be maintained for a longer period of time.

As preservatives and mildew preventives, it is preferred that the additives have antibacterial or mildew preventive effects and contain at least one selected from water-soluble or water-dispersible organic compounds. As such additives, organic preservatives and mildew preventives, inorganic preservatives and mildew preventives, natural preservatives and mildew preventives, etc. can be listed. For example, preservatives and mildew preventives can use those described in "Antibacterial and Mildew Preventive Technology" issued by Toray Research Center (Co., Ltd.).

In the present invention, by mixing preservatives and anti-mold agents in the protective layer, the quality degradation of the composition caused by the proliferation of microorganisms in the solution after long-term storage at room temperature can be further suppressed, and as a result, the increase of coating defects can be further suppressed.

As preservatives and mold inhibitors, there can be mentioned: phenol ether compounds, imidazole compounds, sulfonium compounds, N-halogenated alkyl sulfide compounds, aniline compounds, pyrrole compounds, quaternary ammonium salts, arsine compounds, pyridine compounds, triazine compounds, benzoisothiazoline compounds, isothiazolinium compounds, etc. Specifically, for example, methylisothiazolinone, 2-(4-thiocyanomethyl)benzimidazole, 1,2-benzothiazolone, 1,2-benzoisothiazoline-3-one, N-fluorodichloromethylthio-o-phthalimide, 2,3,5,6-tetrachloroisophthalonitrile, N-trichloromethylthio-4-cyclohexene-1,2-dicarboxylic acid imide, 8-quinolinic acid copper, bis(tributyltin)oxide, 2-(4-thiazolyl)benzimidazole, 2-benzimidazolecarbamate, 10,10'-oxybis(phenoxarsine), 2,3,5,6-tetrachloroisophthalonitrile, N-trichloromethylthio-4-cyclohexene-1,2-dicarboxylic acid imide, 8-quinolinic acid copper, bis(tributyltin)oxide, 2-(4-thiazolyl)benzimidazole, 2-benzimidazolecarbamate, 10,10'-oxybis(phenoxarsine), 2,3, 5,6-tetrachloro-4-(methylsulfonate)pyridine, bis(2-pyridylthio-1-oxide)zinc, N,N-dimethyl-N'-(fluorodichloromethylthio)-N'-phenylsulfonamide, poly-(hexamethylenebiguanidine) hydrochloride, dithio-2-2'-bis(2-methyl-4,5-trimethylene-4-isothiazoline-3-one, 2- (Dichloro-fluoromethyl)sulfonyl isoindole-1,3-dione, 2-bromo-2-nitropropane-1,3-diol, methylsulfonyl tetrachloropyridine, hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, p-chloro-m-xylenol, 1,2-benzoisothiazoline-3-one, cresol, sodium diacetate, diiodomethyl p-tolylsulfonate, etc.

In the present invention, from the viewpoint of inhibiting mold formation in the protective layer forming composition, the protective layer forming composition preferably contains a mold inhibitor. In particular, among the above-mentioned compounds, the mold inhibitor preferably includes at least one of isothiazolinone compounds, 2-bromo-2-nitropropane-1,3-diol, methanesulfonyl tetrachloropyridine, 2-(dichloro-fluoromethyl)sulfonyl isoindole-1,3-dione, sodium diacetate and diiodomethyl p-tolyl sulfone, more preferably includes an isothiazolinone compound, and further preferably includes methylisothiazolinone.

As a natural antibacterial agent or mold preventer, there is chitosan, a basic polysaccharide obtained by hydrolyzing chitin contained in the shells of crabs and shrimps. A preferred one is "Holon Killer Beads Celler (trade name)" by Nichimin, which contains amine-based metals complexed on both sides of amino acids.

Relative to the total mass of the protective layer forming composition, the content of the preservative and mildew preventive in the protective layer forming composition is preferably 0.005 mass% to 5 mass%, more preferably 0.01 mass% to 3 mass%, further preferably 0.05 mass% to 2 mass%, further preferably 0.1 mass% to 1 mass%. The preservative and mildew preventive may be used alone or in combination. In the case of multiple combinations, it is preferred that the total amount of these is within the above range.

[Sunscreen]

The protective layer forming composition preferably contains a sunscreen. By adding a sunscreen, the effects of light damage on organic layers, etc., can be further suppressed.

As a sunscreen, for example, known coloring agents can be used, such as organic or inorganic pigments or dyes, preferably inorganic pigments, and more preferably carbon black, titanium oxide, titanium nitride, etc.

The content of the sunscreen is preferably 1% to 50% by mass, more preferably 3% to 40% by mass, and even more preferably 5% to 25% by mass relative to the total mass of the protective layer forming composition. Sunscreens can be used alone or in combination. In the case of multiple combinations, it is preferred that the total amount of these is within the above range.

<Layered body>

As described above, the protective layer forming composition of the present invention is used to form a laminate including a substrate (hereinafter also referred to as "substrate"), an organic layer and a protective layer in sequence, or a laminate including a substrate, an organic layer, a protective layer and a photosensitive layer in sequence. Furthermore, the laminate can be used in patterning the organic layer contained in the laminate.

FIG. 1 (a) to FIG. 1 (d) are schematic cross-sectional views schematically showing the processing process of the laminate. Regarding the laminate, as shown in the example of FIG. 1 (a), an organic layer 3 (for example, an organic semiconductor layer) is provided on a substrate 4. Furthermore, a protective layer 2 for protecting the organic layer 3 is provided on the surface of the organic layer 3 in a contacting manner. Other layers 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 preferred that the organic layer 3 and the protective layer 2 are in direct contact. In addition, a photosensitive layer 1 that functions as a photoresist is provided on the protective layer. The photosensitive layer 1 and the protective layer 2 may be in direct contact, or other layers may be provided between the photosensitive layer 1 and the protective layer 2.

FIG1(b) shows an example of a state where a portion of the photosensitive layer 1 is exposed and developed. For example, the photosensitive layer 1 is partially exposed by using a predetermined mask or the like, and after exposure, the developer such as an organic solvent is used for development, thereby removing the photosensitive layer 1 in the removal portion 5 to form the photosensitive layer 1a after exposure and development. At this time, the protective layer 2 is not easily removed by the developer, so it remains, and the organic layer 3 is protected by the remaining protective layer 2 to avoid being damaged by the developer.

FIG1(c) shows an example of a state where a portion of the protective layer 2 and the organic layer 3 are removed. For example, by dry etching, the protective layer 2 and the organic layer 3 in the removal portion 5 where the photosensitive layer (anti-etching agent) 1a does not exist after development are removed, thereby forming a removal portion 5a in the protective layer 2 and the organic layer 3. In this way, the organic layer 3 can be removed in the removal portion 5a. That is, the organic layer 3 can be patterned.

FIG1(d) shows an example of a state where the photosensitive layer 1a and the protective layer 2 are removed after the patterning. For example, by using a stripping liquid containing water to clean the photosensitive layer 1a and the protective layer 2 in the laminate shown in FIG1(c), the photosensitive layer 1a and the protective layer 2 on the processed organic layer 3a are removed.

As described above, a laminate including a substrate, an organic layer, a protective layer, and a photosensitive layer in sequence can be used to form a desired pattern on the organic layer 3, and the photosensitive layer 1 and the protective layer 2 can be removed. The details of these steps will be described below.

<<Base material>>

As the substrate used in the laminate, for example, substrates formed of various materials such as silicon, quartz, ceramics, glass, polyester films such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET), and polyimide films can be listed. Any substrate can be selected according to the application. For example, in the case of a flexible element, a substrate formed of a flexible material can be used. In addition, the substrate can also be a composite substrate formed of multiple materials, or a laminated substrate in which multiple materials are layered. In addition, the shape of the substrate is not particularly limited, as long as it is selected according to the application. For example, a plate-shaped substrate can be listed. There is no particular limitation on the thickness of the substrate, etc.

<<Organic layer>>

An organic layer is a layer containing organic materials. The specific organic material can be appropriately selected according to the purpose and function of the organic layer. Assumptions of the functions of the organic layer include semiconductor properties, luminescence properties, photoelectric conversion properties, light absorption properties, electrical insulation, strong dielectric properties, transparency, insulation, etc. In a laminate, the organic layer only needs to be included on the substrate, the substrate and the organic layer may be in contact, and other layers may be included between the organic layer and the substrate.

The thickness of the organic layer is not particularly limited and varies depending on the type of electronic device used, but is preferably 1nm~50μm, more preferably 1nm~5μm, and even more preferably 1nm~500nm.

In the following, an example in which the organic layer is an organic semiconductor layer is described in detail. The organic semiconductor layer is a layer containing an organic material that exhibits semiconductor characteristics.

The organic semiconductor layer is an organic layer including an organic semiconductor, which is an organic compound showing semiconductor characteristics. As in the case of semiconductors including inorganic compounds, organic semiconductors include p-type semiconductors that conduct electricity using holes as carriers and n-type semiconductors that conduct electricity using electrons as carriers. The mobility of carriers in the organic semiconductor layer is represented by the carrier mobility μ. Although it depends on the application, in general, a higher carrier mobility is preferred, preferably 10 ^-7 cm ² /Vs or more, more preferably 10 ^-6 cm ² /Vs or more, and even more preferably 10 ^-5 cm ² /Vs or more. The carrier mobility can be obtained based on the characteristics when manufacturing a field effect transistor (FET) device or the measured value by the time of flight (TOF) method.

As a p-type organic semiconductor that can be used in the organic semiconductor layer, any material can be used as long as it has hole transport properties. The p-type organic semiconductor is preferably any one of p-type π-conjugated polymers, condensed polycyclic compounds, triarylamine compounds, hetero-five-membered ring compounds, phthalocyanine compounds, porphyrin compounds, carbon nanotubes, and graphene. In addition, as a p-type organic semiconductor, a plurality of these compounds can also be used in combination. The p-type organic semiconductor is more preferably at least one of p-type π-conjugated polymers, condensed polycyclic compounds, triarylamine compounds, hetero-five-membered ring compounds, phthalocyanine compounds, and porphyrin compounds, and more preferably at least one of p-type π-conjugated polymers and condensed polycyclic compounds.

Examples of p-type π-conjugated polymers include substituted or unsubstituted polythiophenes (e.g., poly(3-hexylthiophene) (P3HT, manufactured by Sigma-Aldrich Japan Co., Ltd.), polyselenophene, polypyrrole, poly(p-phenylene vinylene), polythiophene vinylene, polyaniline, etc. Examples of condensed polycyclic compounds include substituted or unsubstituted anthracene, condensed tetraphenylene, condensed pentacene, dithiophene anthracene, hexabenzocoronene, etc.

Examples of the triarylamine compound include m-MTDATA (4,4',4"-Tris[(3-methylphenyl)phenylamino]triphenylamine), 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine), NPD (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine), and NPD (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine). (1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine), TPD (N,N'-diphenyl-N,N'-di(m-tolyl)benzidine), mCP (1,3-bis(9-carbazolyl)benzene), CBP (4,4'-bis(9-carbazolyl)-2,2'-biphenyl), etc.

Hetero five-membered ring compounds include, for example, substituted or unsubstituted oligothiophenes, tetrathiafulvalene (TTF), etc.

Phthalocyanine compounds are substituted or unsubstituted phthalocyanine, naphthalocyanine, anthraphthalocyanine, tetrapyrazinoporphyrazine, etc. with various central metals. Porphyrin compounds are substituted or unsubstituted porphyrins with various central metals. In addition, carbon nanotubes can be carbon nanotubes with semiconductor polymers modified on the surface.

As an n-type organic semiconductor that can be used in the organic semiconductor layer, any material can be used as long as it has electron transport properties. The n-type organic semiconductor is preferably any one of fullerene compounds, electron-deficient phthalocyanine compounds, condensed polycyclic compounds (naphthalenetetracarbonyl compounds, perylenetetracarbonyl compounds, etc.), tetracyanoquinodimethane compounds (Tetracyanoquinodimethane compounds, TCNQ compounds), polythiophene compounds, benzidine compounds, carbazole compounds, phenanthroline compounds, pyridinephenyl ligand iridium compounds, quinolinol alcohol ligand aluminum compounds, n-type π-conjugated polymers, and graphene. In addition, as an n-type organic semiconductor, a plurality of these compounds can also be used in combination. The n-type organic semiconductor is preferably at least one of a fullerene compound, an electron-deficient phthalocyanine compound, a condensed polycyclic compound, and an n-type π-conjugated polymer, and is particularly preferably at least one of a fullerene compound, a condensed polycyclic compound, and an n-type π-conjugated polymer.

The fullerene compound refers to a substituted or unsubstituted fullerene, and the fullerene may be any of the fullerenes represented by 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 _C60 fullerene, _C70 fullerene, or _C86 fullerene, and particularly preferably PCBM ([6,6]-phenyl-C61-butyric acid methyl ester, manufactured by Sigma-Aldrich Co., Ltd., Japan, etc.) and its analogs (for example, those in which _C60 is partially replaced by _C70 , _C86 , etc., those in which the benzene ring of the substituent is replaced by other aromatic rings or heterocyclic rings, and those in which the methyl ester is replaced by n-butyl ester, isobutyl ester, etc.).

Electron-deficient phthalocyanine compounds refer to substituted or unsubstituted phthalocyanine, naphthalocyanine, anthraphthalocyanine, tetrapyrazine tetrazoporphyrin, etc., which have four or more electron-withdrawing groups bonded and various central metals. Examples of electron-deficient phthalocyanine compounds are fluorinated phthalocyanine (F ₁₆ MPc) and chlorinated phthalocyanine (Cl ₁₆ MPc). Here, M represents a central metal, and Pc represents phthalocyanine.

The naphthalene tetracarbonyl compound may be any one, but preferably is naphthalene tetracarboxylic acid dianhydride (NTCDA), naphthalene tetracarboxylic diimide (NTCDI), perinone pigment (Pigment Orange 43, Pigment Red 194, etc.).

The perylene tetracarbonyl compound may be any one, but preferably perylene tetracarboxylic acid dianhydride (PTCDA), perylene tetracarboxylic diimide (PTCDI), or benzimidazole cyclocondensate (PV).

TCNQ compounds refer to substituted or unsubstituted TCNQ, and compounds in which the benzene ring of TCNQ is replaced by other aromatic rings or heterocyclic rings. Examples of TCNQ compounds include TCNQ, TCNAQ (tetracyanoanthraquinone dimethane), TCN3T (2,2'-((2E,2"E)-3',4'-alkyl substituted-5H,5"H-[2,2'：5',2"-terthiophene]-5,5"-diylidene) dimalon onitrile derivatives), etc.

Polythiophene compounds refer to compounds with a polythiophene structure such as poly(3,4-ethylenedioxythiophene). Examples of polythiophene compounds include PEDOT:PSS (a compound containing poly(3,4-ethylenedioxythiophene) (PEDOT) and polystyrene sulfonic acid (PSS)).

Benzidine compounds refer to compounds having a benzidine structure in the molecule. Examples of benzidine compounds include N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD), N,N'-di-[(1-naphthyl)-N,N'-diphenyl]-(1,1'-biphenyl)-4,4'-diamine (NPD), etc.

Carbazole compounds refer to compounds with a carbazole ring structure in the molecule. Examples of carbazole compounds include 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP).

Phenanthroline compounds refer to compounds with a phenanthroline ring structure in the molecule, such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine, BCP), etc.

Pyridylphenyl ligand iridium compounds are compounds having an iridium complex structure with a phenylpyridine structure as a ligand. Examples of pyridylphenyl ligand iridium compounds are bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl))iridium(III) (FIrpic), tris(2-phenylpyridine)iridium(III) (Ir(ppy) ₃ ), and the like.

Quinolinol ligand aluminum compounds refer to compounds with an aluminum complex structure with a quinolinol structure as a ligand, such as tris(8-hydroxyquinolinol)aluminum.

The following is a particularly preferred example of an n-type organic semiconductor material. Furthermore, R in the formula can be any one, but preferably is any one of a hydrogen atom, a substituted or unsubstituted branched or linear alkyl group (preferably an alkyl group with 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 1 to 8 carbon atoms), and a substituted or unsubstituted aryl group (preferably an aryl group with 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 6 to 14 carbon atoms). Me in the structural formula represents a methyl group, and M represents a metal atom.

[Chemistry 14]

[Chemistry 15]

The organic semiconductor layer may contain one type of organic semiconductor or two or more types of organic semiconductor. In addition, the organic semiconductor layer may be a stacked or mixed layer of a p-type layer and an n-type layer.

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

On the other hand, in the case of the liquid phase method, the organic material is usually mixed in a solvent to form a composition for forming an organic layer (composition for forming an organic layer). Then, the composition is supplied to a substrate and dried to form an organic layer. As a supply method, coating is preferred. Examples of the supply method include slit coating, casting, scraping, wire rod coating, spray coating, dipping, bead coating, air knife coating, curtain coating, inkjet, spin coating, Langmuir-Blodgett (LB), edge casting (for details, Japanese Patent No. 6179930), etc. Preferably, casting, spin coating and inkjet are used. By this process, a large-area organic layer with a smooth surface can be produced at low cost.

In addition, the solvent used in the composition for forming the organic layer is preferably an organic solvent. Examples of the organic solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, and 1,2-dichlorobenzene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene; ethyl acetate, butyl acetate, and the like. , pentyl acetate and other ester solvents; alcohol solvents such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl thiourea, ethyl thiourea, ethylene glycol and other alcohol solvents; ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole and other ether solvents; polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, dimethyl sulfoxide and the like. Only one of these solvents can be used, or two or more can be used. The proportion of organic material in the composition for forming the organic layer is preferably 1% by mass to 95% by mass, and more preferably 5% by mass to 90% by mass, thereby forming a film of any thickness.

In addition, a resin binder may be formulated in the composition for forming the organic layer. In this case, the film-forming material and the binder resin may be dissolved or dispersed in the appropriate solvent to prepare a coating liquid, and a thin film may be formed by various coating methods. Examples of the resin binder include: insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, polypropylene, and copolymers thereof; photoconductive polymers such as polyvinyl carbazole and polysilane; conductive polymers such as polythiophene, polypyrrole, polyaniline, polyphenylene vinylene, and the like. Resin adhesives can be used alone or in combination. If the mechanical strength of the film is taken into consideration, a resin adhesive with a high glass transition temperature is preferred. If the charge mobility is taken into consideration, a resin adhesive containing a photoconductive polymer or a conductive polymer having a structure without a polar group is preferred.

When preparing a resin adhesive, the amount thereof in the organic layer is preferably 0.1% to 30% by mass. The resin adhesive can be used alone or in combination. In the case of a combination of multiple types, it is preferred that the total amount of these is within the above range.

Depending on the application, the organic layer can be a blended membrane containing multiple types of materials, using a single organic material or a mixed solution containing various organic materials and additives. For example, when making a photoelectric conversion layer, a mixed solution using multiple semiconductor materials can be used.

In addition, the substrate can be heated or cooled during film formation, and the film quality or the accumulation of molecules in the film can be controlled by changing the temperature of the substrate. The temperature of the substrate is not particularly limited, but is preferably -200℃~400℃, more preferably -100℃~300℃, and even more preferably 0℃~200℃.

The properties of the formed organic layer can be adjusted by post-treatment. For example, by heat treatment or exposure to a vaporized solvent, the properties can be improved by changing the morphology of the film or the stacking of molecules in the film. In addition, the carrier density in the film can be adjusted by exposure to oxidizing or reducing gases, solvents, substances, etc., or by using these methods in combination to cause oxidation reactions or reduction reactions.

<<Protective layer>>

The protective layer is a layer formed by a protective layer-forming composition. Specifically, the protective layer can be formed, for example, by applying the protective layer-forming composition to a substrate such as an organic layer to form a layered film containing the protective layer-forming composition, and then drying the layered film. The layered film containing the protective layer-forming composition refers to the protective layer-forming composition of the present invention before the layered film is dried.

As an application method for the composition for forming the protective layer, coating is preferred. Examples of application methods include: slit coating, casting, scraping, wire rod coating, spray coating, dipping, bead coating, air knife coating, curtain coating, inkjet, spin coating, Langmuir-Blodgett (LB) method, etc. Casting, spin coating and inkjet are preferred. By this process, a large-area protective layer with a smooth surface can be produced at low cost.

When drying the coating film of the protective layer forming composition, it is preferred to heat the substrate. The heating temperature is appropriately selected from the range of 50°C to 200°C, for example.

In addition, the protective layer forming composition can also be formed by the following method, that is, transferring the coating formed by applying the coating to the temporary support body by the above-mentioned applying method to the application object (such as an organic layer). For the transfer method, reference can be made to paragraphs 0023, 0036 to 0051 of Japanese Patent Publication No. 2006-023696, paragraphs 0096 to 0108 of Japanese Patent Publication No. 2006-047592, etc.

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

The protective layer is preferably a layer whose solubility in the developer is less than 10nm/s at 23°C, and more preferably a layer whose solubility is less than 1nm/s. The lower limit of the solubility is not particularly limited, as long as it is greater than 0nm/s.

The protective layer is removed using a stripping liquid. The method for removing the protective layer using a stripping liquid will be described below.

As the stripping liquid, water, a mixture of water and a water-soluble solvent, a water-soluble solvent, etc. can be cited, and water or a mixture of water and a water-soluble solvent is preferred. As the water-soluble solvent, it is the same as the water-soluble solvent added to the protective layer forming composition.

Relative to the total mass of the stripping liquid, the water content is preferably 90 mass% to 100 mass%, and more preferably 95 mass% to 100 mass%. In addition, the stripping liquid may also be a stripping liquid consisting only of water.

In addition, in order to improve the removability of the protective layer, the stripping liquid may also contain a surfactant. As the surfactant, known compounds can be used, but non-ionic surfactants are preferred.

<<Photosensitive layer>>

The photosensitive layer is a layer used in the development using a developer. The development is preferably negative development. As the photosensitive layer, a known photosensitive layer used in the technical field (for example, a photoresist layer) can be appropriately used. In the laminate, the photosensitive layer can be a negative photosensitive layer or a positive photosensitive layer.

The photosensitive layer is preferably such that the exposed portion thereof is poorly soluble in a developer containing an organic solvent. The so-called poorly soluble means that the exposed portion is poorly soluble in the developer. The dissolution rate of the photosensitive layer in the exposed portion in the developer is preferably lower than the dissolution rate of the photosensitive layer in the unexposed portion in the developer (poorly soluble). Specifically, it is preferred that the polarity be changed by exposing the material to light of at least one wavelength of 365 nm (i-ray), 248 nm (KrF ray) and 193 nm (ArF ray) at an irradiation dose of ⁵⁰ mJ/cm2 or more, and the material be insoluble in a solvent having an sp value (solubility parameter) of less than 19.0 (MPa) ^1/2 , more preferably insoluble in a solvent having an sp value (solubility parameter) of less than 18.5 (MPa) ^1/2 , and even more preferably insoluble in a solvent having an sp value (solubility parameter) of less than 18.0 (MPa) ^1/2 .

The solubility parameter (sp value) is a value obtained by the Okizu method [unit: (MPa) ^1/2 ]. The Okizu method is one of the conventionally known methods for calculating the sp value, and is described in detail in, for example, Journal of the Japanese Adhesion Society Vol. 29, No. 6 (1993), pp. 249-259.

Furthermore, it is more preferred that the polarity be changed as described above by exposing to light of at least one wavelength of 365 nm (i-ray), 248 ^nm (KrF ray) and 193 ^nm (ArF ray) at an irradiation dose of 50 mJ/cm 2 to 250 mJ/cm 2.

The photosensitive layer is preferably sensitive to irradiation with i-rays. The so-called photosensitivity refers to the change in the dissolution rate of an organic solvent (preferably butyl acetate) by irradiation with at least one of actinic rays and radiation (irradiation with i-rays in the case of being sensitive to irradiation with i-rays).

As the photosensitive layer, there can be cited a photosensitive layer including a resin whose dissolution rate in a developer changes due to the action of an acid (hereinafter also referred to as a "specific resin for a photosensitive layer").

The change in dissolution rate in a specific resin for the photosensitive layer is preferably a decrease in the dissolution rate.

The dissolution rate of the specific resin for the photosensitive layer in an organic solvent having an sp value of 18.0 (MPa) ^1/2 or less before the dissolution rate changes is more preferably 40 nm/s or more.

The specific resin for the photosensitive layer preferably has a dissolution rate of less than 1 nm/s in an organic solvent having an sp value of 18.0 (MPa) ^1/2 or less after the dissolution rate changes.

In addition, the specific resin for the photosensitive layer is preferably a resin that is soluble in an organic solvent having an sp value (solubility parameter) of 18.0 (MPa) ^1/2 or less before the dissolution rate changes, and is poorly soluble in an organic solvent having an sp value of 18.0 (MPa) ^1/2 or less after the dissolution rate changes.

Here, "soluble in an organic solvent having an sp value (solubility parameter) of 18.0 (MPa) ^1/2 or less" means that a coating film (thickness 1 μm) of the compound (resin) formed by coating a solution of the compound (resin) on a substrate and heating the substrate at 100°C for 1 minute has a dissolution rate of 20 nm/s or more when immersed in a developer at 23°C, and "poorly soluble in an organic solvent having an sp value of 18.0 (MPa) ^1/2 or less" means that a coating film (thickness 1 μm) of the compound (resin) formed by coating a solution of the compound (resin) on a substrate and heating the substrate at 100°C for 1 minute has a dissolution rate of less than 10 nm/s in a developer at 23°C.

Examples of the photosensitive layer include a photosensitive layer containing a specific resin for the photosensitive layer and a photoacid generator, a photosensitive layer containing a polymerizable compound and a photopolymerization initiator, etc.

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

The following describes an example of a photosensitive layer including a specific resin for the photosensitive layer and a photoacid generator.

[Special resin for photosensitive layer]

The specific resin for the photosensitive layer is preferably an acrylic polymer.

"Acrylic polymer" is an addition polymerization type resin, and is a polymer containing repeating units derived from (meth) acrylic acid or its esters, and may also contain repeating units other than repeating units derived from (meth) acrylic acid or its esters, for example, repeating units derived from styrenes or repeating units derived from vinyl compounds. In acrylic polymers, it is preferred to contain more than 50 mol%, more preferably more than 80 mol% of repeating units derived from (meth) acrylic acid or its esters relative to all repeating units in the polymer, and it is particularly preferred to contain only repeating units derived from (meth) acrylic acid or its esters.

As a specific resin for the photosensitive layer, a resin containing a repeating unit having a structure in which an acid group is protected by an acid-degradable group is preferably listed. As the structure in which the acid group is protected by an acid-degradable group, a structure in which a carboxyl group is protected by an acid-degradable group, a structure in which a phenolic hydroxyl group is protected by an acid-degradable group, etc. can be listed.

In addition, as repeating units having a structure in which an acid group is protected by an acid-degradable group, there can be listed repeating units having a structure in which a carboxyl group in a monomer unit derived from (meth)acrylic acid is protected by an acid-degradable group; repeating units having a structure in which a phenolic hydroxyl group in a monomer unit derived from a hydroxystyrene such as p-hydroxystyrene and α-methyl-p-hydroxystyrene is protected by an acid-degradable group, etc.

As repeating units having a structure in which an acid group is protected by an acid-degradable group, repeating units including an acetal structure can be cited, and preferably repeating units including a cyclic ether ester structure in the side chain. As a cyclic ether ester structure, it is preferred that the oxygen atom in the cyclic ether structure and the oxygen atom in the ester bond are bonded to the same carbon atom to form an acetal structure.

In addition, as a repeating unit having a structure in which an acid group is protected by an acid-degradable group, a repeating unit represented by the following formula (1) is preferred.

Hereinafter, "the repeating unit represented by formula (1)" etc. will also be referred to as "repeating unit (1)" etc.

[Chemistry 16]

In formula (1), ^R8 represents a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), ^L1 represents a carbonyl group or a phenylene group, and ^R1 to ^R7 each independently represent a hydrogen atom or an alkyl group.

In formula (1), ^R8 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

In formula (1), ^L1 represents a carbonyl group or a phenylene group, preferably a carbonyl group.

In formula (1), R ¹ to R ⁷ each independently represent a hydrogen atom or an alkyl group. The alkyl group in R ¹ to R ⁷ has the same meaning as R ⁸ , and the preferred embodiment is also the same. In addition, it is preferred that at least one of R ¹ to R ⁷ is a hydrogen atom, and it is more preferred that all of R ¹ to R ⁷ are hydrogen atoms.

As the repeating unit (1), it is preferably a repeating unit represented by the following formula (1-A) or a repeating unit represented by the following formula (1-B).

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

In addition, as a repeating unit having a structure in which an acid group is protected by an acid-degradable group, a repeating unit represented by the following formula (2) can also be preferably cited.

In formula (2), A represents a hydrogen atom or a group that is released by the action of an acid. As the group that is released by the action of an acid, preferably an alkyl group (preferably a carbon number of 1 to 12, more preferably 1 to 6, and further preferably 1 to 3), an alkoxyalkyl group (preferably a carbon number of 2 to 12, more preferably 2 to 6, and further preferably 2 to 3), an aryloxyalkyl group (preferably a total carbon number of 7 to 40, more preferably 7 to 30, and further preferably 7 to 20), an alkoxycarbonyl group (preferably a carbon number of 2 to 12, more preferably 2 to 6, and further preferably 2 to 3), and an aryloxycarbonyl group (preferably a carbon number of 7 to 23, more preferably 7 to 19, and further preferably 7 to 11). A may further have a substituent, and as a substituent, examples of the substituent T described above can be cited.

In the formula (2), ^R10 represents a substituent, and examples of the substituent T are listed. ^R9 represents a group having the same meaning as ^R8 in the formula (1).

In formula (2), nx represents an integer from 0 to 3.

As the group that is released by the action of an acid, the compounds described in paragraphs 0039 to 0049 of Japanese Patent Publication No. 2008-197480 are preferably repeating units containing a group that is released by an acid. In addition, the compounds described in paragraphs 0052 to 0056 of Japanese Patent Publication No. 2012-159830 (Japanese Patent No. 5191567) are also preferably, and these contents are incorporated into this specification.

A specific example of the repeating unit (2) is shown below, but the present invention is not limited thereto.

[Chemistry 19]

[Chemistry 20]

The content of the repeating unit (preferably repeating unit (1) or repeating unit (2)) having a structure in which the acid group is protected by an acid-degradable group contained in the specific resin for the photosensitive layer is preferably 5 mol% to 80 mol%, more preferably 10 mol% to 70 mol%, and further preferably 10 mol% to 60 mol%. The acrylic polymer may contain only one type of repeating unit (1) or repeating unit (2), or may contain two or more types. When two or more types are used, it is preferred that the total amount of these is within the above range.

The specific resin for the photosensitive layer may also contain a repeating unit including a crosslinking group. For details of the crosslinking group, please refer to paragraphs 0032 to 0046 of Japanese Patent Publication No. 2011-209692, which are incorporated into this specification.

The specific resin for the photosensitive layer is also preferably in a state of containing a repeating unit containing a crosslinking group (repeating unit (3)), but it is preferably set to a structure that substantially does not contain a repeating unit (3) containing a crosslinking group. By adopting such a structure, the photosensitive layer can be removed more effectively after patterning. Here, the so-called substantially does not contain, for example, refers to less than 3 mol% of all repeating units of the specific resin for the photosensitive layer, preferably less than 1 mol%.

The specific resin for the photosensitive layer may also contain other repeating units (repeating units (4)). Examples of free radical polymerizable monomers for forming the repeating units (4) include compounds described in paragraphs 0021 to 0024 of Japanese Patent Publication No. 2004-264623. Preferred examples of the repeating units (4) include repeating units derived from at least one selected from the group consisting of hydroxyl-containing unsaturated carboxylates, alicyclic-containing unsaturated carboxylates, styrene, and N-substituted maleimide. Among these, preferred are (meth)acrylates containing an aliphatic ring structure such as benzyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yloxyethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-methylcyclohexyl (meth)acrylate, or hydrophobic monomers such as styrene.

When the specific resin for the photosensitive layer contains a repeating unit (4), the content of the monomer units forming the repeating unit (4) in all the monomer units constituting the specific resin for the photosensitive layer is preferably 1 mol% to 60 mol%, more preferably 5 mol% to 50 mol%, and further preferably 5 mol% to 40 mol%. The specific resin for the photosensitive layer may contain a single repeating unit (4) in its monomer units or contain the repeating unit (4) in a combination of two or more. In the case of a combination of two or more, it is preferred that the total amount of these is within the above range.

Various methods are known for synthesizing a specific resin for a photosensitive layer. As an example, a radical polymerization initiator is used to polymerize a radical polymerizable monomer mixture containing at least radical polymerizable monomers for forming repeating units (1) and repeating units (2), etc., in an organic solvent to synthesize the resin.

As a specific resin for the photosensitive layer, a copolymer obtained by adding 2,3-dihydrofuran to the anhydride group of a precursor copolymer obtained by copolymerizing unsaturated polycarboxylic acid anhydrides at a temperature of about room temperature (25°C) to 100°C in the absence of an acid catalyst is also preferred.

The following resins can also be cited as preferred examples of specific resins for photosensitive layers.

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

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

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

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

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

In addition, as a specific resin for the photosensitive layer used in positive development, the one described in Japanese Patent Publication No. 2013-011678 is exemplified, and the contents are incorporated into this manual.

From the perspective of achieving good pattern formation during development, the content of the specific resin in the photosensitive layer is preferably 20% to 99% by mass, more preferably 40% to 99% by mass, and even more preferably 70% to 99% by mass, relative to the total mass of the photosensitive layer.

In addition, relative to the total mass of the resin components contained in the photosensitive layer, the content of the specific resin used in the photosensitive layer is preferably 10 mass % or more, more preferably 50 mass % or more, and even more preferably 90 mass % or more.

The specific resin for the photosensitive layer can be used alone or in combination of multiple types. In the case of multiple combinations, it is preferred that the total amount of these resins is within the above range.

The weight average molecular weight of the specific resin used for the photosensitive layer is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 35,000 or more. There is no particular upper limit, but it is preferably 100,000 or less, and can be set to 70,000 or less, or 50,000 or less.

In addition, the amount of components having a weight average molecular weight of 1,000 or less contained in the specific resin for the photosensitive layer is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the specific resin for the photosensitive layer.

The molecular weight dispersion (weight average molecular weight/number average molecular weight) of the specific resin used in the photosensitive layer is preferably 1.0~4.0, and more preferably 1.1~2.5.

[Photoacid generator]

The photosensitive layer preferably further comprises a photoacid generator. The photoacid generator is preferably a photoacid generator that decomposes by more than 80 mol% when the photosensitive layer is exposed to an exposure amount of more than 100 mJ/cm ² at a wavelength of 365 nm.

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

A photosensitive layer is formed on a silicon wafer substrate using a composition for forming a photosensitive layer, and the layer is heated at 100°C for 1 minute. After heating, the photosensitive layer is exposed to light of a wavelength of 365nm at an exposure amount of 100mJ/ ^cm2 . The thickness of the heated photosensitive layer is set to 700nm. Thereafter, while applying ultrasonic waves, the silicon wafer substrate on which the photosensitive layer is formed is immersed in a methanol/tetrahydrofuran (THF) = 50/50 (mass ratio) solution for 10 minutes. After the immersion, the extract extracted from the solution is analyzed by high-performance liquid chromatography (HPLC), and the decomposition rate of the photoacid generator is calculated by the following formula.

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

As the photoacid generator, it is preferred that when the photosensitive layer is exposed to light at a wavelength of 365 nm and an exposure amount of 100 mJ/cm ² , it decomposes by 85 mol % or more.

-Oxime sulfonate compounds-

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

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

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group, or a halogen atom. When there are multiple X ³ , they may be the same or different. The alkyl group and alkoxy group in the X ³ may have a substituent. The alkyl group in the X ^{3 is preferably a straight chain or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group in the X 3 is} preferably a straight chain or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in the X ³ is preferably a chlorine atom or a fluorine atom.

In formula (OS-1), m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3, multiple ^X3 may be the same or different.

In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthracenyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

In formula (OS-1), particularly preferred is a compound wherein m3 is 3, ^X3 is methyl, the substitution position of ^X3 is an ortho position, and ^R34 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorbornylmethyl, or p-tolyl.

As specific examples of the oxime sulfonate compound represented by formula (OS-1), the following compounds described in paragraphs 0064 to 0068 of Japanese Patent Publication No. 2011-209692 and paragraphs 0158 to 0167 of Japanese Patent Publication No. 2015-194674 are exemplified, and these contents are incorporated into this specification.

[Chemistry 22]

In formula (OS-103) to formula (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, when there are multiple R ^s2 groups, they independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom, when there are multiple R ^s6 groups, they independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer of 0 to 6.

In Formula (OS-103) to Formula (OS-105), the ^alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by R s1 may have a substituent T.

In formula (OS-103) to formula (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and more preferably a hydrogen atom or an alkyl group. When there are two or more R ^s2 in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and more preferably one is an alkyl group, an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the rest are hydrogen atoms. The alkyl group or aryl group represented by R ^s2 may have a substituent T.

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

In formula (OS-103) to formula (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1. When Xs is S, ns is preferably 2.

In Formula (OS-103) to Formula (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 may have a substituent.

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

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

[Chemistry 23]

In formula (OS-106) to formula (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ^t2 represents a hydrogen atom or a methyl group.

In formula (OS-106) to formula (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

In formula (OS-106) to formula (OS-111), R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, 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, further preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

In formula (OS-106) to formula (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom.

R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

In addition, in the oxime sulfonate compound, the stereostructure (E, Z) of the oxime may be any one or a mixture.

As specific examples of the oxime sulfonate compounds represented by the formula (OS-103) to the formula (OS-105), compounds described in paragraphs 0088 to 0095 of Japanese Patent Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Publication No. 2015-194674 are exemplified, and these contents are incorporated into this specification.

As another preferred embodiment of the oxime sulfonate compound containing at least one oxime sulfonate group, the compounds represented by the following formula (OS-101) and formula (OS-102) can be cited.

In formula (OS-101) or formula (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfonyl group, a sulfonyl group, a cyano group, an aryl group, or a heteroaryl group. More preferably, R ^u9 is a cyano group or an aryl group, and still more preferably, R ^u9 is a cyano group, a phenyl group, or a naphthyl group.

In Formula (OS-101) or Formula (OS-102), R ^u2a represents an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, ^-NRu5- , _-CH2- , -CRu6H- or ^CRu6Ru7- , and ^Ru5 to ^Ru7 each independently represent ^an alkyl group or an aryl ^group .

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfonyl group, a cyano group or an aryl group. Two of R ^u1 to R ^u4 can be bonded to each other to form a ring. In this case, the ring can be condensed to form a condensed ring together with the benzene ring. As R ^u1 to R ^u4 , it is preferably a hydrogen atom, a halogen atom or an alkyl group. In addition, it is also preferred that at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group. Among them, it is preferred that R ^u1 to R ^u4 are all hydrogen atoms. The substituents can all have further substituents.

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

In addition, in the oxime sulfonate compound, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring may be any one or a mixture.

As specific examples of the compound represented by formula (OS-101), compounds described in paragraphs 0102 to 0106 of Japanese Patent Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Publication No. 2015-194674 are exemplified, and these contents are incorporated into this specification.

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

Commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemicals Co., Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemicals Co., Ltd.), and MBZ-101 (manufactured by Green Chemicals Co., Ltd.).

As a photoacid generator that is sensitive to actinic radiation, it is preferred that it does not contain 1,2-quinonediazide compounds. The reason is that 1,2-quinonediazide compounds generate carboxyl groups through a sequential photochemical reaction, but their quantum yield is less than 1, and their sensitivity is lower than that of oxime sulfonate compounds.

In contrast, the acid generated by the oxime sulfonate compound in response to actinic radiation acts as a catalyst for the deprotection of the protected acid group. Therefore, the acid generated by the action of one photon contributes to most deprotection reactions, and the quantum yield exceeds 1, for example, a value as large as 10. It is speculated that high sensitivity can be obtained as a result of so-called chemical amplification.

In addition, oxime sulfonate compounds have an extended π-conjugated system, so they have absorption up to the long-wavelength side, and show very high sensitivity not only under far ultraviolet rays (deep ultraviolet rays (DUV)), ArF rays, KrF rays, and i rays, but also under g rays.

By using tetrahydrofuranyl as the acid-degradable group in the photosensitive layer, the same or higher acid-degradability can be obtained compared to acetal or ketone. As a result, the acid-degradable group can be consumed reliably by post-baking for a shorter time. Furthermore, by using an oxime sulfonate compound as a photoacid generator in combination, the sulfonic acid generation rate is increased, thereby promoting the generation of acid and promoting the decomposition of the acid-degradable group of the resin. In addition, the acid obtained by decomposing the oxime sulfonate compound is a sulfonic acid with a small molecule, so the diffusion property in the cured film is also high, which can further achieve high sensitivity.

Relative to the total mass of the photosensitive layer, the photoacid generator is preferably used in an amount of 0.1 mass% to 20 mass%, more preferably 0.5 mass% to 18 mass%, further preferably 0.5 mass% to 10 mass%, further preferably 0.5 mass% to 3 mass%, further preferably 0.5 mass% to 1.2 mass%.

The photoacid generator can be used alone or in combination. In the case of multiple combinations, it is preferred that the total amount of these is within the above range.

[Alkaline compounds]

From the perspective of the liquid storage stability of the composition for forming the photosensitive layer described later, the photosensitive layer preferably contains an alkaline compound.

As the alkaline compound, any compound used in the known chemically amplified anticorrosive agent can be selected and used. For example, aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxide, and quaternary ammonium salts of carboxylic acids can be listed.

Examples of aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, etc.

Examples of aromatic amines include aniline, benzylamine, N,N-dimethylaniline, diphenylamine, etc.

Examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenyl Imidazole, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, oxazine, purine, pyrrolidine, piperidine, cyclohexylmorpholine ethylthiourea, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.3.0]-7-undecene, etc.

As quaternary ammonium hydroxides, for example, there can be listed: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, etc.

Examples of quaternary ammonium salts of carboxylic acids include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate, etc.

When the photosensitive layer contains an alkaline compound, the content of the alkaline compound is preferably 0.001 to 1 parts by mass, and more preferably 0.002 to 0.5 parts by mass, relative to 100 parts by mass of the specific resin for the photosensitive layer.

The alkaline compound may be a single compound or a combination of multiple compounds. In addition, the alkaline compound is preferably a combination of multiple compounds, more preferably a combination of two compounds, and particularly preferably a combination of two different heterocyclic amines. When the alkaline compound is a combination of multiple compounds, it is preferred that the total amount of these compounds is within the above range.

[Surfactant]

From the perspective of improving the coating properties of the photosensitive layer-forming composition described later, the photosensitive layer preferably contains a surfactant.

As a surfactant, anionic, cationic, non-ionic, or amphoteric surfactants can be used, and the preferred surfactant is a non-ionic surfactant.

Examples of non-ionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based, and silicone-based surfactants.

As the surfactant, it is more preferable to include a fluorine-based surfactant or a silicone-based surfactant.

Examples of the fluorine-based surfactants and silicone-based surfactants include Japanese Patent Laid-Open No. 62-036663, Japanese Patent Laid-Open No. 61-226746, Japanese Patent Laid-Open No. 61-226745, Japanese Patent Laid-Open No. 62-170950, Japanese Patent Laid-Open No. 63-034540, Surfactants described in Japanese Patent Publication No. 07-230165, Japanese Patent Publication No. 08-062834, Japanese Patent Publication No. 09-054432, Japanese Patent Publication No. 09-005988, and Japanese Patent Publication No. 2001-330953 may also be used as commercially available surfactants.

Examples of commercially available surfactants that can be used include fluorine-based surfactants such as Eftop EF301 and EF303 (manufactured by Shin-Akita Chemical Co., Ltd.), Fluorad FC430 and 431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, and R08 (manufactured by DIC Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, and 106 (manufactured by AGC Seimi Chemical Co., Ltd.), and PolyFox series (manufactured by OMNOVA) such as PF-6320, or silicone-based surfactants. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone-based surfactant.

In addition, as a surfactant, the following copolymer can be cited as a preferred example, the copolymer comprises a repeating unit A and a repeating unit B represented by the following formula (41), and the weight average molecular weight (Mw) of the polystyrene conversion measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent is 1,000 or more and 10,000 or less.

In formula (41), ^R41 and ^R43 each independently represent a hydrogen atom or a methyl group, ^R42 represents a linear alkyl group having 1 to 4 carbon atoms, ^R44 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^L4 represents an alkyl group having 3 to 6 carbon atoms, p4 and q4 are mass percentages representing polymerization ratios, p4 represents a value of 10% to 80% by mass, q4 represents a value of 20% to 90% by mass, r4 represents an integer of 1 to 18, and n4 represents an integer of 1 to 10.

In formula (41), ^L4 is preferably a branched alkyl group represented by the following formula (42). ^R45 in formula (42) represents an alkyl group having 1 to 4 carbon atoms, and in terms of wettability to the coated surface, is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 2 or 3 carbon atoms.

-CH ₂ -CH(R ⁴⁵ )- (42)

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

When the photosensitive layer contains a surfactant, the amount of the surfactant added is preferably 10 parts by mass or less, more preferably 0.01 parts by mass to 10 parts by mass, and even more preferably 0.01 parts by mass to 1 part by mass, relative to 100 parts by mass of the specific resin for the photosensitive layer.

Surfactants can be used alone or in combination. In the case of multiple combinations, it is preferred that the total amount of these is within the above range.

[Other ingredients]

In the photosensitive layer, one or more antioxidants, plasticizers, thermal free radical generators, thermal acid generators, acid proliferation agents, ultraviolet absorbers, thickeners, and organic or inorganic precipitation inhibitors and other known additives can be further added as needed. For details, please refer to the description of paragraphs 0143 to 0148 of Japanese Patent Publication No. 2011-209692, and these contents are incorporated into this manual.

From the perspective of improving the resolution, the thickness of the photosensitive layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 0.75 μm or more, and particularly preferably 0.8 μm or more. As the upper limit of the thickness of the photosensitive layer, it is preferably 10 μm or less, more preferably 5.0 μm or less, and further preferably 2.0 μm or less.

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

〔Developer〕

The photosensitive layer is used for development using a developer.

As the developer, one containing an organic solvent is preferred.

Relative to the total mass of the developer, the content of the organic solvent is preferably 90 mass% to 100 mass%, and more preferably 95 mass% to 100 mass%. In addition, the developer may also be a developer containing only an organic solvent.

The following describes the method of developing the photosensitive layer using a developer.

-Organic solvents-

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

As organic solvents contained in the developer, polar solvents such as ketone solvents, ester solvents, amide solvents, and hydrocarbon solvents can be listed.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol, acetylmethanol, acetophenone, methylnaphthyl ketone, isophorone, propyl carbonate, etc.

As ester solvents, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc.

As amide solvents, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphatriamidone, 1,3-dimethyl-2-imidazolidinone, etc. can be used.

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

The organic solvent may be used alone or in combination. In addition, it may be mixed with other organic solvents. The water content relative to the total mass of the developer is preferably less than 10 mass%, and it is more preferable that the developer is substantially free of water. The term "substantially free of water" here means, for example, that the water content relative to the total mass of the developer is less than 3 mass%, and it is more preferable that the water content is below the measurement limit.

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

The organic developer preferably contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents and amide solvents.

In addition, the organic developer may contain an appropriate amount of an alkaline compound as required. As examples of alkaline compounds, the compounds described in the above-mentioned alkaline compounds can be cited.

The vapor pressure of the organic developer is preferably below 5 kPa at 23°C, more preferably below 3 kPa, and further preferably below 2 kPa. By setting the vapor pressure of the organic developer to below 5 kPa, the evaporation of the developer on the photosensitive layer or in the developer cup is suppressed, the temperature uniformity within the surface of the photosensitive layer is improved, and as a result, the dimensional uniformity of the photosensitive layer after development is improved.

Specific examples of the solvent having a vapor pressure of 5 kPa or less include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl isobutyl ketone; butyl acetate, pentyl acetate, isopentyl acetate, and amyl acetate; acetate), propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate and other ester solvents; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and other amide solvents; toluene, xylene and other aromatic hydrocarbon solvents; octane, decane and other aliphatic hydrocarbon solvents.

Specific examples of solvents having a particularly preferred vapor pressure of 2 kPa or less include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and phenylacetone; butyl acetate, amyl acetate, and the like; acetate), propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate and other ester solvents; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and other amide solvents; xylene and other aromatic hydrocarbon solvents; octane, decane and other aliphatic hydrocarbon solvents.

-Surfactant-

The developer may also contain a surfactant.

There is no particular limitation on the surfactant, and for example, the surfactant described in the protective layer may be preferably used.

When a surfactant is mixed in a developer, the amount thereof is generally 0.001% to 5% by mass, preferably 0.005% to 2% by mass, and more preferably 0.01% to 0.5% by mass, relative to the total amount of the developer.

[Photosensitive layer forming composition]

The photosensitive layer forming composition is a composition used to form the photosensitive layer contained in the laminate.

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

The composition for forming the photosensitive layer preferably includes the components contained in the photosensitive layer (e.g., a specific resin for the photosensitive layer, a photoacid generator, an alkaline compound, a surfactant, and other components, etc.) and a solvent. The components contained in the photosensitive layer are preferably dissolved or dispersed in the solvent, and more preferably dissolved.

The content of the components contained in the photosensitive layer forming composition is preferably obtained by replacing the content of each component relative to the total mass of the photosensitive layer with the content relative to the solid content of the photosensitive layer forming composition.

-Organic solvents-

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

Examples of organic solvents include: (1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; (2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether; (3) ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate; (4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; (5) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether and propylene glycol diethyl ether; (6) propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate. (7) diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and other diethylene glycol dialkyl ethers; (8) diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate and other dipropylene glycol monoalkyl ether acetates; (9) dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether and other dipropylene glycol monoalkyl ethers; (10) dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether and other dipropylene glycol dialkyl ethers; (11) dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate (12) lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-pentyl lactate, isopentyl lactate; (13) aliphatic carboxylic acid esters such as n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate; (14) ethyl hydroxylate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxylate, ethyl ethoxylate, methyl 3-methoxypropionate, Esters, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetylacetate, ethyl acetylacetate, methyl pyruvate, ethyl pyruvate and other esters; (15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, etc.; (16) amides such as N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.; (17) lactones such as γ-butyrolactone, etc.

In addition, in these organic solvents, organic solvents such as benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethyl carbonate, propyl carbonate, etc. can also be added as needed.

Among the organic solvents, propylene glycol monoalkyl ether acetate or diethylene glycol dialkyl ether is preferred, and diethylene glycol ethyl methyl ether or propylene glycol monomethyl ether acetate is particularly preferred.

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

Organic solvents can be used alone or in combination. In the case of multiple combinations, it is preferred that the total amount of these is within the above range.

<Laminar body formation kit>

The laminate forming kit includes, for example, the protective layer forming composition and the photosensitive layer forming composition. In addition, the laminate forming kit may further include the organic layer forming composition.

<Method for manufacturing a laminate and method for patterning an organic layer>

The following steps (1) to (6) are a series of operation steps related to the patterning of the organic layer. The method for manufacturing the laminate includes at least the following step (1). In addition, the method for patterning the organic layer includes at least the following step (5).

(1) A step of forming a protective layer on the organic layer on the substrate.

(2) The step of forming a photosensitive layer on the protective layer.

(3) The step of exposing the photosensitive layer.

(4) The step of developing the photosensitive layer using a developer containing an organic solvent to produce a mask pattern.

(5) The step of removing the protective layer and organic layer of the non-masked part.

(6) The step of using a stripping fluid to remove the protective layer.

<<(1) Step of forming a protective layer on an organic layer>>

The patterning method of the organic layer of the present embodiment includes the step of forming a protective layer on the organic layer. Usually, this step is performed after the organic layer is formed on the substrate. In this case, the protective layer is formed on the surface of the organic layer opposite to the surface on the substrate side. The protective layer is preferably formed in direct contact with the organic layer, but other layers may be provided between the protective layer and the organic layer within the scope of the present invention. As other layers, fluorine-based primer layers and the like can be listed. In addition, the protective layer may be provided in only one layer or in two or more layers. As described above, the protective layer is preferably formed using a protective layer forming composition.

For details of the formation method, please refer to the application method of the protective layer forming composition in the laminate.

<<(2) Step of forming a photosensitive layer on the protective layer>>

After step (1), a photosensitive layer is formed on the side of the protective layer opposite to the organic layer side (preferably on the surface). As mentioned above, the photosensitive layer is preferably formed using a photosensitive layer forming composition. The details of the formation method can refer to the application method of the photosensitive layer forming composition in the laminate.

<<(3) Step of exposing the photosensitive layer>>

After forming the photosensitive layer in step (2), the photosensitive layer is exposed. Specifically, for example, at least a portion of the photosensitive layer is irradiated (exposed) with actinic radiation.

The exposure is preferably performed in a manner that forms a prescribed pattern. In addition, the exposure can be performed through a photomask or by directly drawing the prescribed pattern.

As the wavelength of the actinic radiation during exposure, an actinic radiation having a wavelength preferably greater than 180 nm and less than 450 nm, more preferably 365 nm (i radiation), 248 nm (KrF radiation) or 193 nm (ArF radiation) can be used.

As a light source of actinic rays, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, laser generating devices, light-emitting diode (LED) light sources, etc. can be used.

When using a mercury lamp as a light source, it is preferable to use actinic radiation having a wavelength of g-ray (436nm), i-ray (365nm), h-ray (405nm), etc., and it is more preferable to use i-ray.

When a laser generating device is used as a light source, if it is a solid (yttrium aluminum garnet (YAG)) laser, it is preferred to use actinic rays with a wavelength of 343nm or 355nm, if it is an excimer laser, it is preferred to use actinic rays with a wavelength of 193nm (ArF ray), 248nm (KrF ray), 351nm (Xe ray), and if it is a semiconductor laser, it is preferred to use actinic rays with a wavelength of 375nm or 405nm. Among these, actinic rays with a wavelength of 355nm or 405nm are more preferred in terms of stability, cost, etc. The laser can be irradiated to the photosensitive layer once or multiple times.

The optimal exposure is 40mJ~120mJ, and more preferably 60mJ~100mJ.

The energy density of each pulse of the laser is preferably 0.1 mJ/cm ² or more and 10,000 mJ/cm ² or less. In order to fully cure the coating, it is more preferably 0.3 mJ/cm ² or more, and further preferably 0.5 mJ/cm ² or more. From the viewpoint of suppressing the decomposition of the photosensitive layer due to ablation, it is preferably set to 1,000 mJ/cm ² or less, and more preferably 100 mJ/cm ² or less.

In addition, the pulse width is preferably 0.1 nanoseconds (hereinafter referred to as "ns") or more and 30,000ns or less. In order to prevent the color coating from being decomposed due to the burning phenomenon, it is more preferably 0.5ns or more, and more preferably 1ns or more. In order to improve the alignment accuracy during scanning exposure, it is more preferably 1,000ns or less, and more preferably 50ns or less.

When a laser generating device is used as a light source, the frequency of the laser is preferably greater than 1 Hz and less than 50,000 Hz, and more preferably greater than 10 Hz and less than 1,000 Hz.

Furthermore, in order to shorten the exposure processing time, the laser frequency is preferably above 10 Hz, and more preferably above 100 Hz. In order to improve the alignment accuracy during scanning exposure, it is preferably below 10,000 Hz, and more preferably below 1,000 Hz.

Compared with mercury lamps, lasers are easier to focus. In addition, the use of masks can be omitted in the pattern formation in the exposure step, which is also better in this regard.

There is no particular limitation on the exposure device, and commercially available ones include Callisto (manufactured by V-Technology), AEGIS (manufactured by V-Technology), DF2200G (manufactured by Dainippon Screen Mfg.), etc. In addition, devices other than those mentioned above can also be preferably used.

In addition, the amount of irradiated light can be adjusted as needed through a spectroscopic filter such as a long-wavelength cutoff filter, a short-wavelength cutoff filter, or a bandpass filter.

In addition, after the exposure, a post-exposure heating step (Post Exposure Bake (PEB)) can be performed as needed.

<<(4) Using a developer containing an organic solvent to develop the photosensitive layer and prepare a mask pattern>>

In step (3), after the photosensitive layer is exposed through a photomask, the photosensitive layer is developed using a developer.

The development is preferably negative. The details of the developer are as described in the description of the photosensitive layer.

As developing methods, for example, the following can be applied: a method of immersing the substrate in a tank filled with developer for a fixed time (immersion method); a method of developing by accumulating developer on the substrate surface by surface tension and keeping it still for a fixed time (puddle method); a method of spraying developer onto the substrate surface (spraying method); a method of continuously spraying developer onto a substrate rotating at a fixed speed while scanning a developer spray nozzle at a fixed speed (dynamic distribution method), etc.

When the various developing methods include the step of spraying a developer from a developing nozzle of a developing device onto a photosensitive layer, the spray pressure of the sprayed developer (the flow rate per unit area of the sprayed developer) is preferably 2 mL/s/mm ² or less, more preferably 1.5 mL/s/mm ² or less, and further preferably 1 mL/s/mm ² or less. There is no particular lower limit for the spray pressure, but if the processing volume is taken into consideration, it is preferably 0.2 mL/s/mm ² or more. By setting the spray pressure of the sprayed developer to the range, defects in the pattern caused by anti-etching agent residues after development can be significantly reduced.

Although the details of this mechanism are not clear, it is believed that the reason is that by setting the ejection pressure within the above range, the pressure applied by the developer to the photosensitive layer is reduced, and the unintentional scraping or collapse of the resist pattern on the photosensitive layer is suppressed. The ejection pressure of the developer (mL/s/mm ² ) is the value at the developer nozzle outlet in the developer device.

As methods for adjusting the ejection pressure of the developer, for example, there are: a method of adjusting the ejection pressure using a pump, etc., or a method of changing the ejection pressure by adjusting the pressure using the supply from a pressurized tank, etc.

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

<<(5) Step of removing the protective layer and organic layer of the non-masked part>>

After developing the photosensitive layer to produce a mask pattern, the protective layer and the organic layer in the non-mask portion are removed by etching. The so-called non-mask portion refers to the area that is not masked by the mask pattern formed by developing the photosensitive layer (the area where the photosensitive layer is removed by developing).

The etching process can also be divided into multiple stages. For example, the protective layer and the organic layer can be removed by a single etching process, or the organic layer (and the remaining portion of the protective layer as needed) can be removed by etching after at least a portion of the protective layer is removed by etching.

In addition, the etching process may be dry etching, wet etching, or a method in which the etching is divided into multiple steps and dry etching and wet etching are performed. For example, the removal of the protective layer may be performed by dry etching or wet etching.

As methods for removing the protective layer and the organic layer, for example, there can be listed: method A for removing the protective layer and the organic layer by a single dry etching process; method B for removing at least a portion of the protective layer by a wet etching process, and then removing the organic layer (and the remaining portion of the protective layer as needed) by dry etching, etc.

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 known etching process methods.

The following is a detailed description of one aspect of the method A. For a specific example of the method B, please refer to the description of Japanese Patent Publication No. 2014-098889, etc.

Specifically, in the method A, the anti-etching agent pattern can be used as an etching mask (mask pattern) to remove the protective layer and the organic layer in the non-masked part by dry etching. Representative examples of dry etching include methods described in Japanese Patent Laid-Open No. 59-126506, Japanese Patent Laid-Open No. 59-046628, Japanese Patent Laid-Open No. 58-009108, Japanese Patent Laid-Open No. 58-002809, Japanese Patent Laid-Open No. 57-148706, and Japanese Patent Laid-Open No. 61-041102.

As dry etching, from the perspective of making the cross-section of the pattern of the formed organic layer closer to a rectangle or further reducing the damage to the organic layer, it is preferably performed in the following form.

The preferred embodiment includes: a first stage etching using a mixed gas of a fluorine-based gas and oxygen (O ₂ ) to etch until the region (depth) where the organic layer is not exposed; after the first stage etching, a second stage etching using a mixed gas of nitrogen (N ₂ ) and oxygen (O ₂ ) to etch preferably until the vicinity of the region (depth) where the organic layer is exposed; and over etching after the organic layer is exposed. The specific dry etching method, as well as the first stage etching, the second stage etching, and the over etching are described below.

The best etching conditions for dry etching are to calculate the etching time by the following method.

(A) Calculate the etching rate (nm/min) of the first stage and the etching rate (nm/min) of the second stage respectively.

(B) Calculate the time required to etch the desired thickness by etching in the first stage and the time required to etch the desired thickness by etching in the second stage.

(C) Perform the first stage of etching according to the etching time calculated in (B).

(D) The second stage of etching is performed according to the etching time calculated in (B). Alternatively, the etching time may be determined by end point detection, and the second stage of etching may be performed according to the determined etching time.

(E) Calculate the etching time relative to the total time of (C) and (D) and perform etching.

The mixed gas used in the etching of the first stage preferably contains a fluorine-based gas and oxygen (O ₂ ) from the viewpoint of processing the organic material as the etched film into a rectangular shape. In addition, in the etching of the first stage, the laminate is etched to the area where the organic layer is not exposed. Therefore, it is considered that the organic layer is not damaged or is slightly damaged at this stage.

In addition, in the etching and over-etching of the second stage, from the perspective of avoiding damage to the organic layer, it is preferred to use a mixed gas of nitrogen and oxygen for etching.

The ratio of the etching amount of the first stage etching to the etching amount of the second stage etching is determined in such a way that the rectangularity of the pattern cross section of the organic layer in the first stage etching is excellent.

The ratio of the etching amount of the second stage to the total etching amount (the sum of the etching amount of the first stage and the etching amount of the second stage) is preferably greater than 0% and less than 50%, and more preferably 10% to 20%. The so-called etching amount refers to the amount calculated based on the difference between the remaining film thickness of the etched film and the film thickness before etching.

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

<<(6) Steps to remove the protective layer using a stripping fluid>>

After etching, the protective layer is removed using a stripping liquid (e.g. water). Details of the stripping liquid are as described in the instructions for the protective layer.

As a method of removing the protective layer using a stripping liquid, for example, a method of removing the protective layer by spraying a stripping liquid from a spray nozzle of a spray type or a shower type onto the anti-etching agent pattern can be cited. As the stripping liquid, pure water can be preferably used. In addition, as a spray nozzle, a spray nozzle including the entire substrate in its spray range, or a movable spray nozzle and a spray nozzle whose movable range includes the entire substrate can be cited. In addition, as another aspect, an aspect of dissolving and removing the residue of the protective layer remaining on the organic layer after mechanically stripping the protective layer can be cited.

When the spray nozzle is movable, it moves from the center of the substrate to the end of the substrate more than twice and sprays the stripping liquid during the step of removing the protective layer, thereby removing the anti-etching agent pattern more effectively.

After removing the protective layer, it is also better to perform drying steps. The drying temperature is preferably set to 80℃~120℃.

<Purpose>

The laminated body to which the protective layer forming composition is applied can be used to manufacture semiconductor devices (electronic devices) using organic semiconductors. Here, the so-called electronic device refers to a device containing a semiconductor and having two or more electrodes, and controlling the current flowing between the electrodes or the voltage generated by electricity, light, magnetism, chemical substances, etc.; or a device that generates light or an electric field, a magnetic field, etc. by the applied voltage or current.

As examples, organic photoelectric conversion elements, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifier elements, organic inverters, information recording elements, etc. Organic photoelectric conversion elements can be used for any of photosensor applications and energy conversion applications (solar cells). Among these, organic field effect transistors, organic photoelectric conversion elements, and organic electroluminescent elements are preferred as applications, organic field effect transistors and organic photoelectric conversion elements are more preferred, and organic field effect transistors and organic photoelectric conversion elements are particularly preferred.

[Implementation example]

The following examples are given to further illustrate the present invention. The materials, usage amounts, proportions, processing contents, processing sequence, etc. shown in the examples may be appropriately changed without departing from the main purpose 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 mass standards, and the ambient temperature (room temperature) of each step is 23°C.

<Preparation of composition for forming protective layer>

The raw materials were mixed in a manner to obtain the blending ratio (mass parts) shown in Table 1 below. After mixing, the protective layer forming composition was stirred separately under the following stirring conditions using a stirrer (hot magnetic stirrer, C-MAG HS4, manufactured by IKA). After the stirring was completed, a polyvinylidene fluoride (PVDF) membrane filter (Durapore, manufactured by Merck) with a pore size of 5 μm was set on a stainless steel pressure filter holder (manufactured by Sartorius), and each composition was filtered while being pressurized at 2 MPa.

<<Stirring conditions>>

． Atmosphere: atmospheric

．Stirring time: 240 minutes

．Stirring temperature: 50℃

．Speed of stirring component: 500rpm

[Table 1]

The specific specifications of each raw material are as follows.

<Raw materials>

<<Water-soluble resin>>

． PVA: PVA-205 manufactured by Kuraray, Mw=24000.

． PVP: PITZCOL K-90 manufactured by Daiichi Pharmaceutical Co., Ltd., Mw=1200000.

． HEC: 2-Hydroxyethylcellulose manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Mw=720000.

<<Specific hydrophilic compounds>>

Use compounds B-1 to B-8 having the following structures. In the formula, m represents the average added molar number of the oxyethyl structure.

． B-1: Diethylene glycol (molecular weight = 106. Produced by Fuji Films Wako Pure Chemical Industries, Ltd.)

． B-2: Tetraethylene glycol (molecular weight = 194. Produced by Fuji Films Wako Pure Chemical Industries, Ltd.)

． B-3: Polyethylene glycol 1000 (Mw=1000, average addition molar number m is 20. Produced by Fujifilm Wako Pure Chemical Industries, Ltd.)

． B-4: Polyethylene glycol 1540 (Mw=1540, average addition molar number m is 32. Produced by Fujifilm Wako Pure Chemical Industries, Ltd.)

． B-5: Dipropylene glycol (molecular weight = 134. Produced by Fuji Films Wako Pure Chemical Industries, Ltd.)

． B-6: Tripropylene glycol (molecular weight = 192. Produced by Fuji Films Wako Pure Chemical Industries, Ltd.)

． B-7: Compound with the following structure (molecular weight = 312)

．B-8: Compound with the following structure (molecular weight = 244)

． B-9: Tetraethylene glycol monomethyl ether (molecular weight = 208. Produced by Fuji Films Wako Pure Chemical Industries, Ltd.)

[Chemistry 26]

<<Hydrophilic compounds in comparison examples>>

． C-1: Ethylene glycol (molecular weight = 62. Produced by Fuji Films Wako Pure Chemical Industries, Ltd.)

． C-2: 1,3,5-adamantantriol (molecular weight = 184. Produced by Fuji Films Wako Pure Chemical Industries, Ltd.)

[Chemistry 27]

<<Surfactant>>

． E-1: Acetyrenol E00 (manufactured by Kawaken Fine Chemicals Co., Ltd.)

． E-2: EMALEX 710 (manufactured by Nippon Latex Co., Ltd.)

<<Solvent>>

．S-1: Distilled water

． S-2: Methanol (manufactured by Fuji Films and Wako Pure Chemical Industries, Ltd.)

<Evaluation>

In order to evaluate the effect of the protective layer forming composition of the present invention, a laminate including an organic layer, a protective layer formed using each protective layer forming composition of the embodiment and the comparative example, and a photosensitive layer as required was formed, and the effect of suppressing cracks in the protective layer after etching the organic layer and the effect of suppressing residues on the organic layer after removing the protective layer were evaluated.

<Evaluation of crack suppression>>

The evaluation of crack suppression was performed by observing the surface of the protective layer exposed to dry etching.

First, a laminate is formed by the following method. An organic layer-forming composition containing an organic semiconductor material as an organic material is spin-coated on a 5 cm square glass substrate, and dried at 80°C for 10 minutes to form an organic semiconductor layer (organic layer) with a thickness of 150 nm. Then, each protective layer-forming composition of the embodiment and the comparative example is spin-coated on the organic semiconductor layer, and dried at 80°C for 1 minute to form a protective layer with a thickness of 2 μm. That is, the laminate formed here has a structure including a glass substrate, an organic semiconductor layer (thickness 150 nm) and a protective layer (thickness 2 μm) in sequence.

<<<Composition of the organic layer forming composition>>>

The glass substrate side of the laminate was attached to an 8-inch wafer (1 inch is 25.4 mm) using heat-resistant Kapton (registered trademark) adhesive tape, and dry etching was performed under the following conditions. Then, an optical microscope was used to observe the surface of the laminate after etching (the surface of the topmost protective layer) over the entire range on the substrate with a field of view of 2.6 mm × 3.8 mm (magnification 5 times), and the number of cracks generated on the surface was counted. "Cracks" refer to cracks with a length of more than 1 μm. Then, corresponding to the number of cracks, the crack suppression effect was evaluated according to the following evaluation criteria.

<<<Dry Etching Conditions>>>

．Device: U621 manufactured by Hitachi High-Tech Corporation

． Source power: 1000W

．Wafer bias: 0W

． Gas flow rate: oxygen 500scm, nitrogen 50scm

．Processing time: 20s

<<<Evaluation Criteria>>>

． A: The number of cracks is 0 (no cracks).

． B: The number of cracks is more than 1 and less than 4.

． C: The number of cracks is 5 or more.

<<Evaluation of Residue Suppression>>

The evaluation of the residue suppression is performed by forming the laminate of the present invention, and in the process of removing the protective layer from the laminate, comparing the surface state of the organic semiconductor layer before and after the formation and removal of the protective layer.

First, as in the case of crack suppression evaluation, an organic semiconductor layer with a thickness of 150 nm is formed on a glass substrate. Here, the signal intensity I 0 originating from the organic semiconductor material is measured on the surface of the organic semiconductor layer using a Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) device (TOF.SIMS5 manufactured by ION-TOF ₎ . The signal originating from the organic semiconductor material or the organic material can be appropriately determined based on the organic semiconductor material or the organic material. For example, when the organic semiconductor material is PCBM, a signal of m/z=910 can be used as a signal originating from the organic semiconductor material. In this evaluation, the signal intensity of m/z=910 is also measured.

Then, similarly to the case of crack suppression evaluation, a protective layer with a thickness of 2 μm is formed on the organic semiconductor layer. Furthermore, a photosensitive resin composition of the following composition is spin-coated on the protective layer and dried at 80°C for 1 minute to form a photosensitive layer with a thickness of 2 μm. That is, the laminate formed here has a structure including a glass substrate, an organic semiconductor layer (thickness 150 nm), a protective layer (thickness 2 μm), and a photosensitive layer (thickness 2 μm) in sequence.

The laminate was subjected to 30-second overlay development using nBA (n-butyl acetate) twice to remove the photosensitive layer. Thereafter, the laminate was subjected to 30-second overlay development using water twice, and then spray-washed with water to remove the protective layer. In this way, a laminate with an organic semiconductor layer remaining on a glass substrate was obtained. Here, the surface of the laminate (i.e., the surface of the organic semiconductor layer as the top layer) was subjected to TOF-SIMS measurement again to measure the signal I derived from the organic semiconductor material.

Then, the intensity ratio of the signal I to the signal _I0 is calculated by the following formula. The larger the signal intensity ratio is, the closer the surface state of the organic semiconductor layer after removing the protective layer is to the surface state of the organic semiconductor layer before forming the protective layer, so it can be considered that the generation of residue is suppressed.

Signal strength ratio (%) = [I/I ₀ ] × 100

Wherein, I represents the signal intensity originating from the organic material on the surface of the organic layer after the protective layer is removed, and _I0 represents the signal intensity originating from the organic material on the surface of the organic layer before the protective layer is formed.

<<<Composition of photosensitive resin composition>>>

．．PGMEA: Propylene glycol monomethyl ether acetate

． Synthesis method of photosensitive resin A-1

First, BzMA (benzyl methacrylate, 16.65 g), THFMA (tetrahydrofurfuryl methacrylate, 21.08 g), t-BuMA (tert-butyl methacrylate, 5.76 g) and V-601 (0.4663 g, manufactured by Fuji Film and Koshun Chemical Co., Ltd.) were dissolved in PGMEA (32.62 g) to prepare a PGMEA solution. Then, PGMEA (32.62 g) was added to a three-necked flask equipped with a nitrogen inlet tube and a cooling tube, the temperature was raised to 86°C, and the PGMEA solution was dripped therein over 2 hours. Then, the solution was stirred for 2 hours, and then the reaction was terminated. The solution after the reaction was injected into heptane to re-precipitate the polymer component, and the white powder produced thereby was recovered by filtration. As a result, a photosensitive resin A-1 having a weight average molecular weight Mw of 45,000 was obtained. The content of components having a Mw of 1,000 or less was 3% by mass.

． Synthesis method of photosensitive resin A-2

First, BzMA (16.65 g), THFAA (tetrahydrofurfuryl acrylate, 19.19 g), t-BuMA (5.76 g) and V-601 (0.4663 g) were dissolved in PGMEA (32.62 g) to prepare a PGMEA solution. Then, PGMEA (32.62 g) was added to a three-necked flask equipped with a nitrogen inlet tube and a cooling tube, the temperature was raised to 86°C, and the PGMEA solution was dripped therein over 2 hours. Then, the solution was stirred for 2 hours, and then the reaction was terminated. The solution after the reaction was injected into heptane, the polymer component was reprecipitated, and the white powder produced was recovered by filtration. As a result, a photosensitive resin A-2 with a weight average molecular weight Mw of 45,000 was obtained. The content of components with Mw of 1000 or less is 3% by mass.

． Photoacid generator X: A compound having the following structure (wherein R ¹¹ represents a tolyl group and R ¹⁸ represents a methyl group). Produced by Daito Chemix Co., Ltd.

．Alkaline compound Y: A thiourea derivative having the following structure. Produced by DSP Gokyo Food & Chemical Co., Ltd.

．Surfactant B: manufactured by OMNOVA, PF-6320.

<Evaluation results>

The results of the embodiments and comparative examples are shown in Table 1. From the results, it can be seen that the composition for forming a protective layer of the present invention can suppress cracks in the protective layer after etching the organic layer and residues on the organic layer after removing the protective layer in patterning of the organic layer using lithography.

Furthermore, organic semiconductor devices were fabricated using laminates including protective layers obtained from the protective layer-forming compositions of the various embodiments. The performance of any of the organic semiconductor devices was satisfactory.

1: Photosensitive layer

1a: Photosensitive layer after exposure and development

2: Protective layer

3: Organic layer

3a: Organic layer after processing

4: Base material

5: Removal of the photosensitive layer after development

5a: The removed part of the laminate after etching

Claims (20)

A protective layer-forming composition comprises: a water-soluble resin; a compound having a weight average molecular weight of 100 or more and less than 2000 and having a plurality of oxyalkylene structures; and water, wherein the compound comprises a compound represented by the following formula (OA-1):

In formula (OA-1), ^Ra1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ^Ra2 in each structural unit containing n independently represents a hydrogen atom or a monovalent organic group represented by the following formula (OA-2), ^Ra3 in each structural unit containing n independently represents a hydrogen atom or a monovalent organic group represented by the following formula (OA-2), m represents an integer of 2 to 50, n in each structural unit containing m independently represents an integer of 1 to 20, and p represents 0 or 1; Formula (OA-2):

In formula (OA-2), R ^b1 in each structural unit with q independently represents an alkylene group having 1 to 20 carbon atoms, q represents an integer of 1 to 25, r represents 0 or 1, and relative to the total amount of the protective layer forming composition, the content of the water-soluble resin is 5 mass % to 15 mass %; the content of the compound is 0.01 mass % to 5 mass %; and the content of water is 80 mass % to 93 mass %. A composition for forming a protective layer as described in claim 1, wherein the compound has one or more hydroxyl groups. The protective layer forming composition as described in claim 2, wherein the number of hydroxyl groups possessed by the compound is 2 to 8. A protective layer forming composition as described in any one of claim 1 to claim 3, wherein the weight average molecular weight of the compound is 1600 or less. A protective layer forming composition as described in any one of claims 1 to 3, wherein in formula (OA-1), m is 10 or less. A protective layer forming composition as described in any one of claims 1 to 3, wherein in formula (OA-1), m is 15 to 40. A protective layer forming composition as described in any one of claim 1 to claim 3, wherein in formula (OA-1), n is 10 or less. A protective layer forming composition as described in any one of claim 1 to claim 3, wherein the plurality of oxyalkylene structures include at least one of an oxyethylene structure and an oxypropylene structure. A protective layer forming composition as described in any one of claim 1 to claim 3, wherein the content of the compound is 1 mass % to 30 mass % relative to the content of the water-soluble resin. The protective layer forming composition according to any one of claims 1 to 3, wherein the ratio of the total formula weight _Moa of the oxyalkylene chains to the molecular weight _Malli of the compound ( _Moa / _Mall) is 50% or more. A composition for forming a protective layer as described in any one of claims 1 to 3, wherein the boiling point of the compound is above 200°C. A protective layer forming composition as described in any one of claim 1 to claim 3, wherein the water-soluble resin comprises at least one selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone and water-soluble polysaccharides. A protective layer forming composition as described in any one of claim 1 to claim 3, wherein the water-soluble resin comprises a high molecular weight resin and a low molecular weight resin, the low molecular weight resin has a weight average molecular weight smaller than the weight average molecular weight of the high molecular weight resin, and the weight average molecular weight of the low molecular weight resin is less than half of the weight average molecular weight of the high molecular weight resin. The protective layer forming composition as described in claim 13, wherein the content of the high molecular weight resin is 30% by mass or less relative to the total water-soluble resin. A layered film comprising a protective layer-forming composition as described in any one of claims 1 to 14. A protective layer formed by a protective layer-forming composition as described in any one of claims 1 to 14. A laminate comprising, in sequence: a substrate, an organic layer, and a protective layer as described in claim 16. The laminate as described in claim 17 further comprises a photosensitive layer on the protective layer. A kit for forming a laminate, the laminate comprising an organic layer, a protective layer for protecting the organic layer, and a photosensitive layer on the protective layer in sequence, the kit comprising: a protective layer forming composition as described in any one of claim 1 to claim 14; and a photosensitive layer forming composition for forming the photosensitive layer. A method for manufacturing a semiconductor device, comprising: patterning an organic layer using a protective layer formed from a protective layer forming composition as described in any one of claims 1 to 14.