JP7149418B2 - Method for producing composition for forming protective layer, method for storing composition for forming protective layer, and application of this method for storing - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a composition for forming a protective layer, a method for storing a composition for forming a protective layer, and applications of this method for storing.

In recent years, electronic devices using organic semiconductors (organic semiconductor devices) have been widely used. An advantage of organic semiconductor devices is that they can be manufactured by a simpler process than conventional electronic devices using inorganic semiconductors such as silicon. Furthermore, organic semiconductors can easily change their material properties by changing their molecular structure. In addition, there are many variations of materials, and it is thought that it will be possible to realize functions and elements that could not be achieved with inorganic semiconductors. Organic semiconductors can be applied to electronic devices such as organic solar cells, organic electroluminescence displays, organic light detectors, organic field effect transistors, organic electroluminescence devices, gas sensors, organic rectifying devices, organic inverters, and information recording devices. have a nature.

The main patterning methods for organic semiconductors include, for example, the printing method and the lithography method, and the lithography method is advantageous from the viewpoint of microfabrication.

For example, in Patent Document 1, an organic semiconductor layer, a protective layer containing a water-soluble resin, and a photosensitive layer are sequentially formed on a substrate, the photosensitive layer is patterned by photolithography, and then the protective layer and the organic semiconductor layer are formed. A method for patterning an organic semiconductor layer by dry etching is described. Here, the protective layer serves to reduce damage to the organic semiconductor layer by protecting the organic semiconductor layer from chemicals used in patterning (for example, developer for developing the photosensitive layer). there is

WO2016/175220

As described above, a protective layer-forming composition containing a water-soluble resin and water is used to form a protective layer that protects an organic layer such as an organic semiconductor layer from a chemical solution. When the composition is stored for a long period of time, microorganisms such as mold may develop and the quality of the composition may deteriorate.

The present invention has been made in view of the above problems, and an object thereof is to provide a method for producing a composition for forming a protective layer whose quality is less likely to deteriorate even when stored for a long period of time, and a method for storing the composition for forming a protective layer. and

The above problem has been solved by quickly storing the stirred composition in a specific temperature range after stirring the raw materials of the composition for forming a protective layer. Specifically, the above problem has been solved by means <1> below, preferably by means <2> and later.
<1>
A method for producing a protective layer-forming composition laminated on an organic layer and used for forming a water-soluble protective layer for protecting the organic layer from a chemical solution,
After stirring the composition containing the water-soluble resin and the solvent, the container containing the stirred composition is continuously exposed to an environment in the temperature range of 0 to 18 ° C. for 24 hours or more,
A method for producing a composition for forming a protective layer, wherein the period of exposure to the environment is started within 72 hours after the end of stirring.
<2>
The start of the period of exposure to the environment is within 24 hours after the end of stirring.
The production method according to <1>.
<3>
The period of continuous exposure to the above environment is 1 month or more,
The manufacturing method according to <1> or <2>.
<4>
The temperature range when exposing the container to the environment is 0 to 10 ° C.
The manufacturing method according to any one of <1> to <3>.
<5>
filtering the composition after agitation and prior to exposure to the environment;
The production method according to any one of <1> to <4>.
<6>
wherein the composition during agitation comprises an antifungal agent;
The production method according to any one of <1> to <5>.
<7>
The composition for forming a protective layer contains, as an antifungal agent, an isothiazolinone compound, 2-bromo-2-nitropropane-1,3-diol, methylsulfonyltetrachloropyridine, 2-(dichloro-fluoromethyl)sulfanylisoindole- 1,3-dione, sodium diacetate and at least one of diiodomethylparatolylsulfone,
The production method according to <6>.
<8>
The water-soluble resin contains at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and water-soluble polysaccharides,
The production method according to any one of <1> to <7>.
<9>
The water-soluble resin contains a high molecular weight body and a low molecular weight body having a weight average molecular weight smaller than the weight average molecular weight of the high molecular weight body,
The weight average molecular weight of the low molecular weight is less than half the weight average molecular weight of the high molecular weight,
The production method according to any one of <1> to <8>.
<10>
The content of the high molecular weight substance is 30% by mass or less with respect to the total water-soluble resin,
The production method according to <9>.
<11>
As a high molecular weight body, polyvinyl alcohol having a weight average molecular weight of 20,000 or more,
The manufacturing method according to <9> or <10>.
<12>
including polyvinylpyrrolidone having a weight average molecular weight of 300,000 or more as the high molecular weight body,
The production method according to any one of <9> to <11>.
<13>
A water-soluble polysaccharide having a weight average molecular weight of 300,000 or more as a high molecular weight body,
The production method according to any one of <9> to <12>.
<14>
the water-soluble polysaccharide is cellulose,
The production method according to <13>.
<15>
Two or more peak tops exist in the molecular weight distribution of the water-soluble resin,
Of the two or more peak tops, the molecular weight corresponding to one peak top is less than half the molecular weight corresponding to the other one peak top,
The production method according to any one of <1> to <14>.
<16>
A method for storing a composition for forming a protective layer laminated on an organic layer and used for forming a water-soluble protective layer for protecting the organic layer from a chemical solution,
After stirring the composition containing the water-soluble resin and the solvent, storing the container containing the composition after stirring while continuously exposing it to an environment in the temperature range of 0 to 18 ° C. for 24 hours or more,
A method for storing a composition for forming a protective layer, wherein the period of exposure to the above environment starts within 72 hours after the end of stirring.
<17>
A method for producing a laminate, comprising applying a protective layer-forming composition stored by the storage method according to <16> onto an organic layer.
<18>
A method for manufacturing a semiconductor device, comprising the method for manufacturing a laminate according to <17> as a step.
<19>
A protective layer obtained from a protective layer-forming composition stored by the storage method according to <16>.
<20>
A laminate comprising the protective layer according to <19> and an organic layer.

According to the method for producing a composition for forming a protective layer of the present invention, a composition for forming a protective layer whose quality is less likely to deteriorate even when stored for a long period of time can be obtained.

FIG. 4 is a cross-sectional view schematically showing the process of processing a laminate to which the composition for forming a protective layer is applied.

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

In this specification, a numerical range represented by the symbol "to" means a range including the numerical values before and after "to" as lower and upper limits, respectively.

As used herein, the term "process" is meant to include not only independent processes, but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.

Regarding the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or unsubstituted means that not only those not having substituents but also those having substituents are included. For example, when simply describing an "alkyl group", this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). Meaning. Further, when simply described as an "alkyl group", it may be chain or cyclic, and in the case of chain, it may be linear or branched. The same applies to other groups such as "alkenyl group", "alkylene group" and "alkenylene group".

In this specification, the term “exposure” includes not only drawing using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Energy rays used for drawing include emission line spectra of mercury lamps, active rays such as far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light) and X-rays, and particle beams such as electron beams and ion beams. be done.

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

As used herein, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic" means both "acrylic" and "methacrylic", or , and “(meth)acryloyl” means either or both of “acryloyl” and “methacryloyl”.

As used herein, the solid content in the composition means other components excluding the solvent, and the solid content (concentration) in the composition is, unless otherwise stated, relative to the total mass of the composition, It is represented by the mass percentage of other components excluding the solvent.

In this specification, the temperature is 23° C. and the pressure is 101325 Pa (1 atm) unless otherwise specified.

In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are shown as polystyrene equivalent values according to gel permeation chromatography (GPC measurement), unless otherwise specified. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) are measured by using, for example, HLC-8220 (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel. It can be obtained by using Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). In addition, unless otherwise stated, measurements are taken using THF (tetrahydrofuran) as an eluent. Unless otherwise specified, a UV ray (ultraviolet) wavelength detector of 254 nm is used for detection in GPC measurement.

In this specification, when the positional relationship of each layer constituting the laminate is described as "above" or "below", it means that another layer is above or below the reference layer among the layers of interest. It would be nice if there was That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. In addition, unless otherwise specified, the direction in which the layers are stacked with respect to the base material is referred to as "upper", or when there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as "upper". The opposite direction is called "down". It should be noted that such setting of the vertical direction is for the sake of convenience in this specification, and in an actual aspect, the "upward" direction in this specification may differ from the vertical upward direction.

<Method for Producing and Preserving Protective Layer-Forming Composition>
The method for producing a composition for forming a protective layer of the present invention is a method for producing a composition for forming a protective layer which is laminated on an organic layer and used for forming a water-soluble protective layer for protecting the organic layer from chemical solutions. After stirring the composition containing the water-soluble resin and the solvent, the container containing the composition after stirring is placed in an environment with a temperature range of 0 to 18 ° C. (hereinafter also referred to as "low temperature environment"). It includes continuous exposure for 24 hours or more, and the start time of the period of exposure to the environment is within 72 hours after the end of the stirring.

Further, the method for storing a composition for forming a protective layer of the present invention includes storing a composition for forming a protective layer which is laminated on an organic layer and used for forming a water-soluble protective layer for protecting the organic layer from chemical solutions. In the method, after stirring a composition containing a water-soluble resin and a solvent, the container containing the composition after stirring is stored while being continuously exposed to an environment in the temperature range of 0 to 18 ° C. for 24 hours or more. and the start time of the period of exposure to the environment is within 72 hours after the end of the stirring.

In the above two methods of the present invention, there is no difference in the act of exposing the container to the low temperature environment, but in the above production method, the composition for forming a protective layer is stored while being exposed to the low temperature environment by the storage method, and then protected. It is different in that it can include a step of removing the layer-forming composition from the low-temperature environment and a step of packing for transportation and shipment.

In the present invention, after each raw material of the composition for forming a protective layer is mixed and stirred, the composition is exposed to a low-temperature environment rapidly for a predetermined period or more as described above (hereinafter, also referred to as “low-temperature storage”. ) makes it possible to obtain a composition for forming a protective layer that does not deteriorate in quality even when stored for a long period of time. The reason for this is not clear, but by quickly storing the raw materials at low temperature after stirring, oxygen mixed in the composition for forming a protective layer during production (for example, the step of mixing and stirring each raw material) can be dissolved. This is thought to be due to the fact that the amount is reduced and the growth of microorganisms is suppressed.

In general, antiseptic agents and antifungal agents, which will be described later, are used from the viewpoint of suppressing quality deterioration of compositions containing water-soluble resins. However, it has been found that even if a preservative or an antifungal agent is used, the quality of the protective layer-forming composition may not be sufficiently maintained for a long period of time, for example, on the order of years.

According to the present invention, the quality of the composition for forming a protective layer can be sufficiently maintained for a long period of time regardless of the presence or absence of the antiseptic or antifungal agent. Furthermore, in the present invention, if a preservative or an antifungal agent is used in combination, it is possible to further extend the period during which the quality of the composition for forming a protective layer can be maintained.

The protective layer-forming composition obtained by the production method of the present invention contains at least a water-soluble resin and a solvent, and as described above, forms a water-soluble protective layer that is laminated on the organic layer and protects the organic layer from chemicals. Used for shaping. Such a protective layer is used to form a laminate comprising a substrate, an organic layer, a protective layer and a photosensitive layer in that order. Details regarding the use of raw materials for the protective layer-forming composition and the laminate will be described later.

<<(a) Stirring and Other Processing of Compositions Containing Raw Materials>>
In the production method of the present invention, the method for stirring the composition containing the raw materials of the protective layer-forming composition is not particularly limited, and may be performed manually or using a stirring device. From the viewpoint of uniform stirring in a short period of time, it is preferable to stir the composition with a stirring device. For example, as such a stirring device, in addition to a general magnetic stirrer, a motor-type stirrer equipped with various stirring rods (for example, a PTFE jet-type stirring rod manufactured by Fron Chemical Co., etc.) can be used.

The stirring process may be performed in one stage or in two or more stages. In other words, all raw materials of the composition for forming a protective layer may be mixed at once, and the stirring may be completed in one time. of stirring may be carried out. Furthermore, for all or some of the raw materials, the raw materials may be added to a solvent in advance and stirred to prepare a diluted solution, and then the diluted solution may be mixed with other raw materials or other diluted solutions and stirred. good. From the viewpoint of stirring efficiency, the number of stages of stirring is preferably 1 to 4 stages, more preferably 1 to 3 stages, and even more preferably 1 stage or 2 stages.

Conditions for stirring are not particularly limited.

For example, the atmosphere during stirring may be an air atmosphere or an atmosphere substituted with an inert gas such as nitrogen. The temperature of the composition during stirring (stirring temperature) is not particularly limited as long as it does not interfere with the stirring of the raw materials, and is, for example, 1 to 99°C. From the viewpoint of stirring efficiency, the upper limit of this numerical range is preferably 80° C. or lower, more preferably 70° C. or lower. Also, the lower limit of this numerical range is preferably 25° C. or higher, more preferably 30° C. or higher. The difference between the stirring temperature and the temperature of the low-temperature environment described later is not particularly limited, but is adjusted appropriately as necessary, for example, within the range of 7 to 80°C. From the viewpoint of stirring uniformity and cooling efficiency, the upper limit of this numerical range is preferably 60° C. or lower, more preferably 40° C. or lower. Also, the lower limit of this numerical range is preferably 15° C. or higher, more preferably 25° C. or higher.

The stirring method may be mechanical stirring in which the raw material is directly stirred with a stirring member such as a stirring rod or stirring blade, or may be ultrasonic or electromagnetic stirring in which the raw material is stirred without contact. From the viewpoint of productivity and the like, mechanical stirring is preferable as the stirring method. The rotational speed of the stirring member is, for example, in the range of 10 to 1000 rpm, and is appropriately adjusted according to the raw material viscosity. From the viewpoint of stirring uniformity and stirring efficiency, the upper limit of this numerical range is preferably 900 rpm or less, more preferably 800 rpm or less. Also, the lower limit of this numerical range is preferably 30 rpm or more, more preferably 50 rpm or more. The stirring time is, for example, in the range of 30 minutes to 72 hours, and is appropriately adjusted according to the raw material viscosity and the desired degree of homogeneity. From the viewpoint of stirring uniformity and stirring efficiency, the upper limit of this numerical range is preferably 48 hours or less, more preferably 24 hours or less. Moreover, the lower limit of this numerical range is preferably 60 minutes or more, more preferably 120 minutes or more.

Moreover, when stirring is carried out a plurality of times, other processing of the raw material may be carried out in addition to the addition of the raw material in the period between each stirring. Such other treatments include, for example, degassing of raw materials. Furthermore, in the production method of the present invention, after stirring is completed, additional treatment such as deaeration of the protective layer-forming composition may be performed before exposing the protective layer-forming composition to a low-temperature environment. In the present specification, "end" of stirring is performed based on the stoppage of external force application for stirring. For example, in the case of mechanical stirring, stopping the application of external force means stopping the operation of a stirring rod or stirring blade, and in the case of non-contact stirring, stopping the application of ultrasonic waves or electromagnetic force. Moreover, when stirring is performed multiple times, the "end" of the stirring means the end of the last stirring.

Filtration of the composition for forming a protective layer is preferably filtration using a filter.

Filtration with a single-stage filter is effective, but filtration with a two-stage or more filter is more preferable. Filtration by two or more stages of filters refers to filtering by arranging two or more filters in series. In the present invention, filtration through a 1- to 4-stage filter is preferred, and filtration through a 2- to 4-stage filter is more preferred.

The component (material component) that constitutes the material of the filter preferably contains a resin. The resin is not particularly limited, and those known as filter materials can be used. A preferred embodiment of the component (material component) constituting the material of the filter is a polymer grafted with at least one type of neutral group (grafted polymer). The neutral group is preferably at least one selected from a hydroxyl group and a carboxy group, more preferably a hydroxyl group. Preferably, the grafted polymer is a grafted polyolefin, more preferably a grafted polyethylene. The description of the grafted polymer can be referred to the description of WO 2016/081729, the contents of which are incorporated herein.

The pore size of the filter used in the present invention is preferably 5 μm or less, more preferably 3 μm or less, even more preferably 1 μm or less, still more preferably 0.5 μm or less, and may be 0.2 μm or less. Impurities can be more effectively reduced by setting the pore size of the filter within the above range. Although the lower limit of the pore size of the filter is not particularly defined, it is preferably 1 nm or more, for example. By setting the pore size of the filter to 1 nm or more, an unnecessarily large pressure is not applied during filtration, thereby improving productivity and effectively suppressing breakage of the filter. When filtration is performed in stages, the first stage of filtration uses a filter with a pore size of 0.2 to 5 μm (preferably a filter with a pore size of 0.2 to 1 μm), and the second stage of filtration uses a filter with a pore size of 7 nm. Filters with a pore size of less than 1 nm (preferably filters with pore sizes of less than 7 nm and greater than or equal to 1 nm) can be used. Moreover, the difference in pore size between the first stage and the second stage, the second stage and the third stage, etc., from the previous stage is preferably 0.1 to 2 μm.

Degassing of the raw material and protective layer-forming composition is not particularly limited, and a known method can be employed as appropriate. For example, there is degassing treatment using at least one of ultrasonic waves, vacuum (reduced pressure), heating, stirring, centrifugal force and hollow fiber membranes.

<<(b) Filling the container with the composition for forming a protective layer>>
The container is not particularly limited as long as the quality of the composition for forming a protective layer can be maintained. density polyethylene), etc.) can be used. From the viewpoint of maintaining the quality more stably, the container is preferably a glass container. A container is usually composed of a container body and a lid for sealing the container body. The materials of the container body and lid may be the same or different.

From the viewpoint of cooling efficiency, the container is preferably made of a material having a thermal conductivity of 0.1 W/(m·K) or higher. The thermal conductivity of the container material is more preferably 0.3 W/(mK) or more, further preferably 0.8 W/(mK) or more, and 1.0 W/(mK). ) or more is particularly preferred. The upper limit of the thermal conductivity of the container material is not particularly limited, but is practically 250 W/(mK) or less, may be 100 W/(mK) or less, or may be 50 W/(mK) or less. .

The container preferably has a light-shielding function so that deterioration of the protective layer-forming composition due to light is more effectively suppressed. In particular, the container is preferably capable of blocking ultraviolet light (eg, light with a wavelength of 290-380 nm), visible light (eg, light with a wavelength of 380-750 nm) and infrared light (eg, light with a wavelength of 750-1100 nm). Here, blocking means that the transmittance of light of each wavelength is 50% or less. In particular, for ultraviolet rays, the maximum transmittance is preferably 20% or less, more preferably 5% or less. Regarding ultraviolet rays, the minimum transmittance is not particularly limited, and is preferably 0%, and may be about 1%. Also, the maximum transmittance for visible light and infrared light is preferably 90% or less, more preferably 80% or less. For visible and infrared light, the minimum transmission may be 0% or greater. Although the container may be opaque, it is preferably transparent, more preferably colored transparent, and even more preferably transparent in brown, blue or green, in order to facilitate confirmation of the contents.

The volume of the container is not particularly limited, and is, for example, 10 mL to 50 L. The upper limit of this numerical range is preferably 10 L or less, more preferably 5 L or less, from the viewpoint of ease of handling. Moreover, the lower limit of this numerical range may be 25 mL or more, or 50 mL or more. Commonly there are containers such as 50 mL, 100 mL, 250 mL, 1 L and 3.8 L.

In particular, the container is made of a material having a thermal conductivity of 0.1 W/(m·K) or more, has a maximum ultraviolet transmittance of 5% or less, and is a transparent container made of glass or plastic. Among them, a colored transparent container made of glass is more preferable.

The filling rate (%) of the container (=amount of the protective layer forming composition filled in the container/volume of the container×100) is not particularly limited, but is preferably 50 to 98%. The upper limit of this numerical range is more preferably 95% or less, and even more preferably 93% or less. Also, the lower limit of this numerical range is more preferably 60% or more, and even more preferably 65% or more. By setting the filling rate to 98% or less, the space in the container that is not filled with the composition for forming a protective layer becomes a region for discharging oxygen in excess of the saturated dissolution amount in the composition for forming a protective layer. Reduction of the oxygen concentration in the layer-forming composition is facilitated. In addition, by setting the filling rate to 50% or more, it is possible to suppress contamination of the protective layer-forming composition with dust and microorganisms in the atmosphere, and further improve the production efficiency. As a result, the growth of microorganisms can be further suppressed, and the convenience in taking out the protective layer-forming composition from the container and the production efficiency of the protective layer-forming composition are further improved.

After filling the container with the composition for forming a protective layer, it is not essential to seal the container, but from the viewpoint of maintaining the quality of the composition for forming a protective layer, it is preferable to seal the container after filling. When the container is sealed, the type of gas in the portion of the internal space of the container that is not filled with the protective layer-forming composition is not particularly limited, and may be air derived from the atmosphere or an inert gas such as nitrogen. . By sealing the container in an atmosphere filled with an inert gas, the portion not filled with the composition for forming a protective layer can be filled with the inert gas.

From the viewpoint of preventing contamination of the protective layer-forming composition with microorganisms, the container is preferably sterilized in advance. Sterilization can be performed, for example, by UV ozone treatment or heat treatment of the container. In addition, from the viewpoint of preventing reattachment of microorganisms to the container, sterilization is preferably performed within 48 hours, more preferably within 24 hours, before filling the protective layer-forming composition into the container. preferable.

From the viewpoint of preventing contamination of the protective layer-forming composition with microorganisms, it is preferable to fill the container with the protective layer-forming composition within 72 hours after the end of stirring the protective layer-forming composition. , more preferably within 48 hours.

<<(c) Low temperature storage of composition for forming protective layer>>
In the manufacturing method of the present invention, for example, a refrigerator can be used to create a low-temperature environment. From the viewpoint of further suppressing the growth of microorganisms in the composition for forming a protective layer, the upper limit of the temperature range is preferably 15°C or lower, more preferably 10°C or lower, and 8°C or lower. is more preferred. The lower limit of the temperature range is preferably 1°C or higher, more preferably 2°C or higher, and even more preferably 3°C or higher. In addition, the temperature of the low-temperature environment may be appropriately changed stepwise or continuously within the range of 0 to 18°C during the storage period. As a mode of temperature change, for example, from the viewpoint of cooling efficiency, low temperature storage is started at a low temperature at the beginning of the storage period, and then the temperature is gradually increased. An atmosphere (an atmosphere whose temperature is adjusted from the air) or an atmosphere substituted with an inert gas such as nitrogen may be used, but from the viewpoint of convenience, an atmosphere derived from the air is preferable.

By setting the length of the period during which the container is exposed to the low-temperature environment (hereinafter also referred to as "storage period") to 24 hours or more, the interior of the protective layer-forming composition can be sufficiently cooled. From the viewpoint of further suppressing the growth of microorganisms in the composition for forming a protective layer, the lower limit of the storage period is preferably 1 week or longer, more preferably 1 month or longer, and 6 months or longer. One year or more is more preferable, and one year or more is particularly preferable. Although the upper limit of the storage period is not particularly limited, it is practically two years or less, and preferably one year and six months or less.

By starting the storage period within 72 hours after the end of the stirring, it is possible to suppress the growth of microorganisms that have entered the composition for forming a protective layer. From the viewpoint of further suppressing the growth of microorganisms, the start of the storage period is preferably within 60 hours, more preferably within 40 hours, and even more preferably within 30 hours after the end of the stirring. , particularly preferably within 24 hours. Moreover, it is practical to start the storage period at least 6 hours after the end of the stirring, and it may be at least 12 hours.

<Composition for Forming Protective Layer>
The protective layer-forming composition obtained by the production method of the present invention will be described. The protective layer-forming composition contains a water-soluble resin and a solvent, and may contain other components as necessary.

<<Water-soluble resin>>
A water-soluble resin is a resin that dissolves in 100 g of water at 23° C. in an amount of 1 g or more. The water-soluble resin is preferably a resin that dissolves 5 g or more in 100 g of water at 23° C., more preferably a resin that dissolves 10 g or more, and even more preferably a resin that dissolves 30 g or more. Although there is no particular upper limit for the amount of dissolution, it is practically about 100 g.

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

Specific examples of water-soluble resins include polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), water-soluble polysaccharides (water-soluble cellulose (methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxy propylmethylcellulose, propylmethylcellulose, etc.), pullulan or pullulan derivatives, starch (hydroxypropyl starch, carboxymethyl starch, etc.), chitosan, cyclodextrin), polyethylene oxide, polyethyloxazoline, methylolmelamine, polyacrylamide, phenolic resin, styrene/malein Acid half esters and the like can be mentioned. Two or more of these may be selected and used, or may be used as a copolymer. In the present invention, the composition for forming a protective layer preferably contains at least one selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, water-soluble polysaccharides, pullulan and pullulan derivatives among these resins. It preferably contains at least one selected from the group consisting of pyrrolidone, polyvinyl alcohol and water-soluble polysaccharides. The water-soluble polysaccharide is preferably cellulose, more preferably hydroxyethyl cellulose.

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

In formulas (P1-1) to (P4-1), R ^P1 represents a hydrogen atom or a methyl group, R ^P2 represents a hydrogen atom or a methyl group, R ^P3 represents (CH ₂ CH ₂ O) _ma H, CH ₂ COONa or a hydrogen atom, ma represents 1 or 2;

[Resin Containing Repeating Unit Represented by Formula (P1-1)]
In formula (P1-1), R ^{1 P1} is preferably a hydrogen atom.
The resin containing repeating units represented by formula (P1-1) may further contain repeating units different from the repeating units represented by formula (P1-1). The resin containing the repeating unit represented by formula (P1-1) preferably contains 65% to 90% by mass of the repeating unit represented by formula (P1-1) with respect to the total mass of the resin, It is more preferable to contain 70% by mass to 88% by mass.

Resins containing repeating units represented by formula (P1-1) include resins containing two repeating units represented by the following formula (P1-2).

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 composition ratio in the molecule on a mass basis.
In formula (P1-2), R 2 ^P11 has the same meaning as R 2 ^P1 in formula (P1-1), and preferred embodiments are also the same.

In formula (P1-2), R ^P12 includes a group represented by -L ^P -T ^P. LP 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 given. Among them, R ^P12 is an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 , more preferably 2 to 3), alkynyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), aryl groups (preferably 6 to 22 carbon atoms, preferably 6 to 18 more preferably 6 to 10), or a hydrocarbon group such as an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, even more preferably 7 to 11 carbon atoms). These alkyl groups, alkenyl groups, alkynyl groups, aryl groups and arylalkyl groups may further have a group defined by the substituent T as long as the effects of the present invention are exhibited.

In formula (P1-2), np1 and np2 represent the constituent ratios in the molecule on a mass basis, and are each independently 10% by mass or more and less than 100% by mass. However, np1+np2 does 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 Repeating Unit Represented by Formula (P2-1)]
In formula (P2-1), R 2 ^P2 is preferably a hydrogen atom.
The resin containing repeating units represented by formula (P2-1) may further contain repeating units different from the repeating units represented by formula (P2-1). The resin containing the repeating unit represented by formula (P2-1) preferably contains 50% by mass to 98% by mass of the repeating unit represented by formula (P2-1) with respect to the total mass of the resin, It is more preferable to contain 70% by mass to 98% by mass.

Resins containing repeating units represented by formula (P2-1) include resins containing two repeating units represented by the following formula (P2-2).

In the formula (P2-2), R 2 ^P21 each independently represents a hydrogen atom or a methyl group, R 2 ^P22 represents a substituent, and mp1 and mp2 represent the composition ratio in the molecule on a mass basis.
In formula (P2-2), R 2 ^P21 has the same definition as R 2 ^P2 in formula (P2-1), and preferred embodiments are also the same.

In formula (P2-2), R ^P22 includes a group represented by -L ^P -T ^P. LP 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 given. Among them, R ^P22 is an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). , more preferably 2 to 3), alkynyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), aryl groups (preferably 6 to 22 carbon atoms, preferably 6 to 18 more preferably 6 to 10), or a hydrocarbon group such as an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, even more preferably 7 to 11 carbon atoms). These alkyl groups, alkenyl groups, alkynyl groups, aryl groups and arylalkyl groups may further have a group defined by the substituent T as long as the effects of the present invention are exhibited.

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

[Resin Containing Repeating Unit Represented by Formula (P3-1)]
In formula (P3-1), R ^{3 P3} is preferably a hydrogen atom.
The resin containing repeating units represented by formula (P3-1) may further contain repeating units different from the repeating units represented by formula (P3-1). The resin containing the repeating unit represented by formula (P3-1) preferably contains 10% by mass to 90% by mass of the repeating unit represented by formula (P3-1) with respect to the total mass of the resin, It is more preferable to contain 30% by mass to 80% by mass.

Further, the hydroxyl group described in formula (P3-1) may be optionally substituted with a substituent T or a group obtained by combining it with a linking group L. When there are a plurality of substituents T, they may be bonded to each other or may be bonded to the ring in the formula with or without a linking group L to form a ring.

[Resin Containing Repeating Unit Represented by Formula (P4-1)]
The resin containing repeating units represented by formula (P4-1) may further contain repeating units different from the repeating units represented by formula (P4-1). The resin containing the repeating unit represented by formula (P4-1) preferably contains 8% by mass to 95% by mass of the repeating unit represented by formula (P4-1) with respect to the total mass of the resin, It is more preferable to contain 20% by mass to 88% by mass.

Further, the hydroxyl group described in formula (P4-1) may be optionally substituted with a substituent T or a group obtained by combining it with a linking group L. When there are a plurality of substituents T, they may be bonded to each other or may be bonded to the ring in the formula with or without a linking group L to form a ring.

The substituent T is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms), an arylalkyl group (preferably 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms). , more preferably 7 to 11), alkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), alkynyl groups (preferably 2 to 12 carbon atoms, 2 to 6 are more preferably 2 to 3), hydroxyl group, amino group (preferably 0 to 24 carbon atoms, more preferably 0 to 12 carbon atoms, more preferably 0 to 6 carbon atoms), thiol group, carboxy group, aryl group (carbon number 6 to 22 are preferred, 6 to 18 are more preferred, and 6 to 10 are more preferred), alkoxyl groups (having 1 to 12 carbon atoms are preferred, 1 to 6 are more preferred, and 1 to 3 are even more preferred), aryloxy groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, more preferably 6 to 10 carbon atoms), acyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), Acyloxy group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), arylyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, more preferably 7 to 11 ), an aryloyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, more preferably 7 to 11 carbon atoms), a carbamoyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, 1 to 3 is more preferred), sulfamoyl group (preferably 0 to 12 carbon atoms, more preferably 0 to 6, more preferably 0 to 3), sulfo group, alkylsulfonyl group (preferably 1 to 12 carbon atoms, 1 to 6 is more preferred, 1 to 3 are more preferred), arylsulfonyl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), heteroaryl groups (preferably 1 to 12 carbon atoms , more preferably 1 to 8, more preferably 2 to 5, preferably containing a 5- or 6-membered ring), (meth)acryloyl group, (meth)acryloyloxy group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), oxo group (=O), imino group (=NR ^N ), alkylidene group (=C(R ^N ) ₂ ) and the like. R 3 ^N is a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms), preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group. The alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be chain or cyclic, linear or branched. When the above substituent T is a group capable of taking a substituent, it may further have a substituent T. For example, the alkyl group may be a halogenated alkyl group, a (meth)acryloyloxyalkyl group, an aminoalkyl group or a carboxyalkyl group. When the substituent is a group capable of forming a salt such as a carboxy group or an amino group, the group may form a salt.

As the linking group L, an alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms), an alkenylene group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, 2 to 3 are more preferred), an alkynylene group (having preferably 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3), an (oligo) alkyleneoxy group (an alkylene group in one repeating unit The number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, more preferably 1 to 3; the repeating number is preferably 1 to 50, more preferably 1 to 40, more preferably 1 to 30), an arylene group ( preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a thiocarbonyl group, -NR ^N -, and combinations thereof A linking group can be mentioned. As used herein, the term “(oligo)alkyleneoxy group” means a divalent linking group having one or more structural units “alkyleneoxy”. The number of carbon atoms in the alkylene chains in the structural units may be the same or different for each structural unit. The alkylene group may have a substituent T. For example, the alkylene group may have a hydroxyl group. The number of atoms contained in the linking group L is preferably 1 to 50, more preferably 1 to 40, even more preferably 1 to 30, excluding hydrogen atoms. The number of connected atoms means the number of atoms located in the shortest path among the atomic groups involved in the connection. For example, -CH ₂ -(C=O)-O- has 6 atoms involved in the linking, and 4 atoms excluding hydrogen atoms. On the other hand, the shortest atoms involved in linkage are -C-C-O-, which is three. The number of connecting atoms is preferably 1 to 24, more preferably 1 to 12, even more preferably 1 to 6. The alkylene group, alkenylene group, alkynylene group, and (oligo)alkyleneoxy group may be chain or cyclic, and may be linear or branched. When the linking group is a group capable of forming a salt such as —NR ^N —, the group may form a salt.

In addition, as the water-soluble resin, a commercially available product may be used. 7154, etc.), BASF LUVITEC series (VA64P, VA6535P, etc.), PXP-05, JL-05E, JP-03, JP-04, JP-03, JP-04, AMPS, Aldrich Nanoclay, etc. be done.
Among these, it is preferable to use Pitzkol K-90, PXP-05 or Pitzkol V-7154, and it is more preferable to use Pitzkol V-7154.

As for the water-soluble resin, the resin described in WO2016/175220 is cited and incorporated herein.

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

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

Furthermore, in the present invention, the composition for forming a protective layer contains, as water-soluble resins, a high molecular weight (for example, a water-soluble resin having a weight average molecular weight of 10,000 or more) and a weight average molecular weight of this high molecular weight and a low molecular weight substance having a small weight average molecular weight, and the weight average molecular weight of the low molecular weight substance is preferably half or less of the weight average molecular weight of the high molecular weight substance. As a result, the low-molecular-weight substances are rapidly eluted into the removal solution (especially water), and the high-molecular-weight substances are also easily removed starting from the eluted portion of the low-molecular-weight substances, so that the residue of the protective layer after removal of the protective layer is A further reduction effect is obtained. Moreover, when forming a protective layer using the composition for forming a protective layer, it is possible to suppress the occurrence of cracks in the protective layer.

In the present invention, whether or not the composition for forming a protective layer contains the high molecular weight substance and the low molecular weight substance can be determined, for example, by measuring the molecular weight distribution of the composition for forming a protective layer or the water-soluble resin. It can be determined based on whether or not two or more (maximal values) can be confirmed.

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

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

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

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

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

Preferred combinations of high-molecular-weight and low-molecular-weight materials are, for example, as follows. The water-soluble resin may satisfy only one of the following combinations, or may simultaneously satisfy the requirements of two or more combinations.
A combination of PVA (high molecular weight material) having a weight average molecular weight Mw of 30,000 to 100,000 and PVA (low molecular weight material) having an Mw of 10,000 to 40,000.
A combination of PVP (high molecular weight) with Mw of 500,000 to 1,500,000 and PVP (low molecular weight) with Mw of 30,000 to 600,000.
A combination of a water-soluble polysaccharide (high molecular weight) with Mw of 500,000 to 1,500,000 and a water-soluble polysaccharide (low molecular weight) with Mw of 50,000 to 600,000.
• A combination of PVP (high molecular weight) with Mw of 500,000 to 1,500,000 and PVA (low molecular weight) with Mw of 10,000 to 100,000.
A combination of a water-soluble polysaccharide (high molecular weight substance) with Mw of 500,000 to 1,500,000 and PVA (low molecular weight substance) of Mw from 10,000 to 100,000.
• A combination of PVP (high molecular weight) with Mw of 500,000 to 1,500,000 and water-soluble polysaccharide (low molecular weight) with Mw of 50,000 to 600,000.
A combination of a water-soluble polysaccharide (high molecular weight substance) with Mw of 500,000 to 1,500,000 and PVP (low molecular weight substance) of Mw from 30,000 to 600,000.

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

On the other hand, the water-soluble resin may be in an aspect substantially free of low-molecular-weight substances. In the present invention, "substantially free of low-molecular-weight substances" means that the content of low-molecular-weight substances is 3% by mass or less relative to the total water-soluble resin. In this aspect, the content of the low-molecular weight substance is preferably 1% by mass or less with respect to the total water-soluble resin.

The content of all the water-soluble resins in the composition for forming a protective layer may be appropriately adjusted as necessary. It is preferably 20% by mass or less, and more preferably 20% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more.

The composition for forming a protective layer may contain only one type of water-soluble resin, or may contain two or more types. When two or more kinds of water-soluble resins are contained, it is preferable that the total amount thereof falls within the above range.

<<other ingredients>>
In the present invention, the composition for forming a protective layer contains, as other components, a resin soluble in a water-soluble solvent (such as alcohol), a surfactant containing an acetylene group, other surfactants, a preservative, and an antiseptic, which will be described later. Water-soluble solvents can be included as mildew agents, sunscreens, and other solvents.

[Resin that can be dissolved in a water-soluble solvent]
A resin that is soluble in a water-soluble solvent refers to a resin that dissolves in an amount of 1 g or more in 100 g of a water-soluble solvent at 23°C. The water-soluble resin is preferably a resin that dissolves 5 g or more in 100 g of the water-soluble solvent at 23° C., more preferably a resin that dissolves 10 g or more, and further preferably a resin that dissolves 20 g or more. preferable. Although there is no particular upper limit for the amount of dissolution, it is practically about 30 g.

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

[Surfactant containing acetylene group]
By including a surfactant containing an acetylene group in the protective layer-forming composition, it is possible to further suppress the generation of residues.

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

The surfactant containing an acetylene group preferably has a relatively small molecular weight, preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less. Although there is no particular lower limit, it is preferably 200 or more.

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

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

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

R ⁹³ to R ⁹⁶ are each independently a hydrocarbon group having 1 to 24 carbon atoms, n9 is an integer of 1 to 6, m9 is an integer twice n9, and n10 is an integer of 1 to 6. is an integer, m10 is an integer twice as large as n10, l9 and l10 are each independently a number of 0 or more and 12 or less.
R ⁹³ to R ⁹⁶ are hydrocarbon groups, and among them, alkyl groups (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), alkenyl groups (having 2 to 12 carbon atoms preferably 2 to 6, more preferably 2 to 3), alkynyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), aryl group (6 to 22 is preferred, 6 to 18 are more preferred, and 6 to 10 are more preferred), and an arylalkyl group (having preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11) is preferred. . Alkyl groups, alkenyl groups, and alkynyl groups may be linear or cyclic, and may be linear or branched. R ⁹³ to R ⁹⁶ may have a substituent T as long as the effects of the present invention are exhibited. In addition, R ⁹³ to R ⁹⁶ may be bonded to each other or may form a ring through the linking group L described above. When there are a plurality of substituents T, they may be bonded to each other or may be bonded to a hydrocarbon group in the formula with or without a linking group L below to form a ring.
R ⁹³ and R ⁹⁴ are preferably alkyl groups (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms). Among them, a methyl group is preferred.
R ⁹⁵ and R ⁹⁶ are preferably alkyl groups (having preferably 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 3 to 6 carbon atoms). Of these, -(C _n11 R ⁹⁸ _m11 )-R ⁹⁷ is preferred. R ⁹⁵ and R ⁹⁶ are particularly preferably isobutyl groups.

n11 is an integer of 1-6, preferably an integer of 1-3. m11 is twice the number of n11.
R ⁹⁷ and R ⁹⁸ are each independently preferably a hydrogen atom or an alkyl group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms).
n9 is an integer of 1-6, preferably an integer of 1-3. m9 is an integer twice as large as n9.
n10 is an integer of 1-6, preferably an integer of 1-3. m10 is an integer that is twice n10.
l9 and l10 are each independently a number from 0 to 12. However, l9+l10 is preferably a number from 0 to 12, more preferably a number from 0 to 8, more preferably a number from 0 to 6, more preferably a number greater than 0 and less than 6, more than 0 A number of 3 or less is even more preferred. Regarding l9 and l10, the compound of formula (91) may be a mixture of compounds with different numbers, in which case the number of l9 and l10 or l9+l10 is a number including decimal places. may

-Compound represented by formula (92)-
The compound represented by formula (91) is preferably a compound represented by formula (92) below.

R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ are each independently a hydrocarbon group having 1 to 24 carbon atoms, and l11 and l12 are each independently a number of 0 or more and 12 or less.
Among R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ are alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms) and alkenyl groups (preferably 2 to 12 carbon atoms). , more preferably 2 to 6, more preferably 2 to 3), alkynyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), aryl group (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, and 6 to 10 are even more preferred), and arylalkyl groups (having preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11 carbon atoms) are preferred. Alkyl groups, alkenyl groups, and alkynyl groups may be chain or cyclic, and may be linear or branched. R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ may have a substituent T as long as the effects of the present invention are exhibited. In addition, R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ may be bonded to each other or may form a ring through the linking group L. When there are a plurality of substituents T, they may be bonded to each other or bonded to the hydrocarbon group in the formula with or without a linking group L to form a ring.
R ⁹³ , R ⁹⁴ , and R ⁹⁷ to R ¹⁰⁰ are each independently preferably an alkyl group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms). Among them, a methyl group is preferred.
l11+l12 is preferably a number of 0 to 12, more preferably a number of 0 to 8, more preferably a number of 0 to 6, more preferably a number of more than 0 and less than 6, more than 0 and 5 or less More preferably, the number is more than 0 and 4 or less is even more preferable, it may be more than 0 and 3 or less, or it may be more than 0 and 1 or less. Note that l11 and l12 may be a mixture of compounds of formula (92) differing in number, in which case the number of l11 and l12 or l11+l12 is a number including decimal places good too.

Examples of surfactants containing an acetylene group include Surfynol 104 series (trade name, Nissin Chemical Industry Co., Ltd.), Acetyrenol E00, E40, E13T, and 60 (all trade names, Kawa Ken Fine Chemical Co., Ltd.), and among them, Surfynol 104 series, Acetynol E00, E40 and E13T are preferable, and Acetynol E40 and E13T are more preferable. Surfynol 104 series and acetylenol E00 are surfactants having the same structure.

[Other surfactants]
The composition for forming a protective layer may contain other surfactants other than the surfactant containing the acetylene group for the purpose of improving coating properties.

Other surfactants may be nonionic, anionic, amphoteric fluorine, etc., as long as they reduce the surface tension.

Other surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and the like. polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate sorbitan alkyl esters such as ate, monoglyceride alkyl esters such as glycerol monostearate and glycerol monooleate, nonionic surfactants such as oligomers containing fluorine or silicon; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate , sodium butylnaphthalenesulfonate, sodium pentylnaphthalenesulfonate, sodium hexylnaphthalenesulfonate, sodium octylnaphthalenesulfonate and other alkylnaphthalenesulfonates, sodium laurylsulfate and other alkylsulfates, and alkylsulfonic acids such as sodium dodecylsulfonate Anionic surfactants such as salts and sulfosuccinic acid ester salts such as sodium dilaurylsulfosuccinate; amphoteric surfactants such as alkylbetaines such as lauryl betaine and stearyl betaine; and amino acids.

When the protective layer-forming composition contains an acetylene group-containing surfactant and another surfactant, the total amount of the acetylene group-containing surfactant and the other surfactant is the surfactant is preferably 0.05 to 20% by mass, more preferably 0.07 to 15% by mass, and still more preferably 0.1 to 10% by mass, based on the total mass of the composition for forming a protective layer. . These surfactants may be used singly or in combination. When using more than one, the total amount thereof falls within the above range.

Moreover, in the present invention, it is also possible to adopt a configuration that does not substantially contain other surfactants. The term "substantially free" means that the content of other surfactants is 5% by mass or less of the content of surfactants containing acetylene groups, preferably 3% by mass or less, and 1% by mass or less. is more preferred.

In the protective layer-forming composition, the content of the other surfactant is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and still more preferably 0.05% by mass or more, based on the total mass of the protective layer. It is 1% by mass or more. Also, the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. Other surfactants may be used singly or in combination. When using a plurality of substances, it is preferable that the total amount of them falls within the above range.

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

[Preservatives and fungicides]
By containing a preservative and an antifungal agent in the protective layer-forming composition, the quality of the protective layer-forming composition can be maintained for a longer period of time.

The antiseptic and antifungal agents preferably contain at least one selected from water-soluble or water-dispersible organic compounds, which are additives having antibacterial or antifungal action. Examples of such additives include organic preservatives and fungicides, inorganic preservatives and fungicides, natural preservatives and fungicides, and the like. For example, antiseptics and antifungal agents described in "Antibacterial and antifungal technology" published by Toray Research Center Co., Ltd. can be used.

In the present invention, by blending a preservative and an antifungal agent in the protective layer, it is possible to further suppress deterioration of the composition due to the growth of microorganisms inside the solution after long-term storage at room temperature, and as a result, further suppress the increase in coating defects. be able to.

Preservatives and antifungal agents include phenol ether compounds, imidazole compounds, sulfone compounds, N-haloalkylthio compounds, anilide compounds, pyrrole compounds, quaternary ammonium salts, arsine compounds, pyridine compounds, triazine-based compounds, benzisothiazoline-based compounds, isothiazoline-based compounds, and the like. Specifically, for example, methylisothiazolinone, 2(4thiocyanomethyl)benzimidazole, 1,2 benzothiazolone, 1,2-benzisothiazolin-3-one, N-fluorodichloromethylthio-phthalimide, 2,3, 5,6-tetrachloroisophthalonitrile, N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide, copper 8-quinolinate, bis(tributyltin) oxide, 2-(4-thiazolyl)benzimidazole, 2-benzimidazole methyl carbamate, 10,10'-oxybisphenoxyarsine, 2,3,5,6-tetrachloro-4-(methylsulfone)pyridine, bis(2-pyridylthio-1-oxide)zinc, N ,N-dimethyl-N'-(fluorodichloromethylthio)-N'-phenylsulfamide, poly-(hexamethylenebiguanide) hydrochloride, dithio-2-2'-bis, 2-methyl-4,5-trimethylene -4-isothiazolin-3-one, 2-(dichloro-fluoromethyl)sulfanylisoindole-1,3-dione, 2-bromo-2-nitropropane-1,3-diol, methylsulfonyltetrachloropyridine, hexahydro- 1,3-tris-(2-hydroxyethyl)-S-triazine, p-chloro-m-xylenol, 1,2-benzisothiazolin-3-one, methylphenol, sodium diacetate, diiodomethylparatolylsulfone, etc. is mentioned.

In the present invention, from the viewpoint of suppressing the growth of mold in the composition for forming a protective layer, the composition for forming a protective layer preferably contains an antifungal agent. In particular, among the above compounds, the antifungal agent is an isothiazolinone compound, 2-bromo-2-nitropropane-1,3-diol, methylsulfonyltetrachloropyridine, 2-(dichloro-fluoromethyl)sulfanylisoindole It preferably contains at least one of -1,3-dione, sodium diacetate and diiodomethylparatolylsulfone, more preferably contains an isothiazoline compound, and further preferably contains methylisothiazolinone.

As a natural antibacterial agent or antifungal agent, there is chitosan, which is a basic polysaccharide obtained by hydrolyzing chitin contained in the crustaceans of crabs and shrimps. Nikko's "Holon Killer Bice Cera (trade name)", which is an amino metal in which metals are combined on both sides of an amino acid, is preferred.

The content of the antiseptic and antifungal agent in the protective layer-forming composition is preferably 0.005 to 5% by mass, preferably 0.01 to 3% by mass, based on the total mass of the protective layer-forming composition. is more preferably 0.05 to 2% by mass, and even more preferably 0.1 to 1% by mass. As the antiseptic agent and the antifungal agent, one kind or a plurality of kinds may be used. When using a plurality of substances, it is preferable that the total amount of them falls within the above range.

[Light shielding agent]
The protective layer-forming composition preferably contains a light-shielding agent. By blending the light-shielding agent, the effects of light damage on the organic layer and the like can be further suppressed.

As the light-shielding agent, for example, a known coloring agent or the like can be used, and organic or inorganic pigments or dyes can be used, inorganic pigments are preferable, and carbon black, titanium oxide, titanium nitride and the like are more preferable. .

The content of the light-shielding agent is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, still more preferably 5 to 25% by mass, based on the total mass of the composition for forming a protective layer. As the light shielding agent, one kind or a plurality of kinds may be used. When using a plurality of substances, it is preferable that the total amount of them falls within the above range.

〔solvent〕
The solvent used in the protective layer-forming composition preferably contains water. Moreover, the solvent can contain a water-soluble solvent as a solvent other than water. In addition, the composition for forming a protective layer may be in an aspect in which it does not contain a water-soluble solvent (that is, the solvent in the composition for forming a protective layer is water only).

The water-soluble solvent added to the composition for forming a protective layer is preferably an organic solvent having a solubility in water of 1 g or more at 23°C. The solubility of the organic solvent in water at 23° C. is more preferably 10 g or more, more 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.

<Laminate>
As described above, the composition for forming a protective layer obtained by the production method of the present invention is used to form a laminate comprising a substrate, an organic layer, a protective layer and a photosensitive layer in this order. Then, the laminate can be used for patterning the organic layers included in the laminate.

FIG. 1 is a schematic cross-sectional view schematically showing the process of processing a laminate. As for the laminate, an organic layer 3 (for example, an organic semiconductor layer) is disposed on a base material 4, as in the example shown in FIG. 1(a). Further, a protective layer 2 for protecting the organic layer 3 is provided on the surface in contact therewith. Another layer may be provided between the organic layer 3 and the protective layer 2, but from the viewpoint of appropriately protecting the organic layer, it is preferable that the organic layer 3 and the protective layer 2 are in direct contact. . Also, a photosensitive layer 1 is arranged on this protective layer. The photosensitive layer 1 and the protective layer 2 may be in direct contact with each other, or another layer may be provided between the photosensitive layer 1 and the protective layer 2 .

FIG. 1(b) shows an example of a state in which a part of the photosensitive layer 1 is exposed and developed. For example, the photosensitive layer 1 is partially exposed by a method such as using a predetermined mask or the like, and after the exposure, the photosensitive layer 1 is removed in the removal portion 5 by developing using a developer such as an organic solvent. A photosensitive layer 1a is formed after development. At this time, the protective layer 2 remains because it is difficult to be removed by the developer, and the organic layer 3 is protected from damage by the developer by the remaining protective layer 2 .

FIG. 1(c) shows an example of a state in which a part of the protective layer 2 and the organic layer 3 are removed. For example, a removed portion 5a is formed in the protective layer 2 and the organic layer 3 by removing the protective layer 2 and the organic layer 3 in the removed portion 5 without the photosensitive layer (resist) 1a after development by dry etching or the like. be done. In this manner, the organic layer 3 can be removed at the removal portion 5a. That is, patterning of the organic layer 3 can be performed.

FIG. 1(d) shows an example of a state in which the photosensitive layer 1a and the protective layer 2 are removed after the patterning. For example, by washing the photosensitive layer 1a and the protective layer 2 in the laminate in the state shown in FIG. 2 is removed.

As described above, using a laminate containing a base material, an organic layer, a protective layer and a photosensitive layer in this order, a desired pattern is formed on the organic layer 3, and the photosensitive layer 1 serving as a resist and the protection of the organic layer 3 The protective layer 2, which becomes a film, can be removed. Details of these steps will be described later.

<<Base material>>
Examples of substrates used in the laminate include substrates formed of various materials such as silicon, quartz, ceramics, glass, polyester films such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), and polyimide films. Any base material may be selected depending on the application. For example, when used for a flexible element, a substrate made of a flexible material can be used. Moreover, the base material may be a composite base material formed of a plurality of materials, or a laminated base material in which a plurality of materials are laminated. Further, the shape of the substrate is not particularly limited, and may be selected depending on the intended use. The thickness of the substrate and the like are also not particularly limited.

<<Organic layer>>
An organic layer is a layer that includes an organic material. A specific organic material is appropriately selected according to the application and function of the organic layer. Possible functions of the organic layer include, for example, semiconducting properties, light emitting properties, photoelectric conversion properties, light absorption properties, electrical insulating properties, ferroelectric properties, transparency, insulating properties, and the like. In the laminate, the organic layer may be included above the substrate, the substrate and the organic layer may be in contact, or another layer may be further included between the organic layer and the substrate. may be

The thickness of the organic layer is not particularly limited and varies depending on the type of electronic device used, etc., but is preferably 1 nm to 50 μm, more preferably 1 nm to 5 μm, still more preferably 1 nm to 500 nm.
In the following, an example in which the organic layer is an organic semiconductor layer will be described in detail. An organic semiconductor layer is a layer containing an organic material that exhibits semiconductor properties.

An organic semiconductor layer is an organic layer that includes an organic semiconductor, and an organic semiconductor is an organic compound that exhibits semiconductor properties. As with semiconductors made of inorganic compounds, organic semiconductors include p-type semiconductors that conduct holes as carriers and n-type semiconductors that conduct electrons as carriers. The ease with which carriers flow in the organic semiconductor layer is represented by the carrier mobility μ. Although it depends on the application, the carrier mobility is generally better, preferably 10 ⁻⁷ cm ² /Vs or more, more preferably 10 ⁻⁶ cm ² /Vs or more, and 10 ⁻⁵ cm ² . /Vs or more is more preferable. The carrier mobility can be obtained based on the characteristics of a field effect transistor (FET) device when it is manufactured and the measured value of time of flight (TOF) method.

As the p-type organic semiconductor that can be used for the organic semiconductor layer, any material may be used as long as it has a hole-transporting property. The p-type organic semiconductor is preferably any one of p-type π-conjugated polymer, condensed polycyclic compound, triarylamine compound, five-membered heterocyclic compound, phthalocyanine compound, porphyrin compound, carbon nanotube, and graphene. Moreover, you may use combining multiple types of compounds among these compounds as a p-type organic semiconductor. The p-type organic semiconductor is more preferably at least one of a p-type π-conjugated polymer, a condensed polycyclic compound, a triarylamine compound, a five-membered heterocyclic compound, a phthalocyanine compound, and a porphyrin compound, and more preferably, It is at least one of a p-type π-conjugated polymer and a condensed polycyclic compound.

Examples of p-type π-conjugated polymers include substituted or unsubstituted polythiophene (e.g., poly(3-hexylthiophene) (P3HT, manufactured by Sigma-Aldrich Japan G.K.), etc.), polyselenophene, polypyrrole, polyparaphenylene, poly Examples include paraphenylene vinylene, polythiophene vinylene, and polyaniline. Examples of condensed polycyclic compounds include substituted or unsubstituted anthracene, tetracene, pentacene, anthradithiophene, and hexabenzocoronene.

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

Hetero 5-membered ring compounds are, for example, substituted or unsubstituted oligothiophene, TTF (Tetrathiafulvalene), and the like.

Phthalocyanine compounds include substituted or unsubstituted phthalocyanines, naphthalocyanines, anthracyanines, tetrapyrazinoporphyrazines, etc., having various central metals. Porphyrin compounds are substituted or unsubstituted porphyrins having various central metals. Alternatively, the carbon nanotube may be a carbon nanotube whose surface is modified with a semiconducting polymer.

As the n-type organic semiconductor that can be used for the organic semiconductor layer, any material may be used as long as it has an electron-transporting property. The n-type organic semiconductor is preferably a fullerene compound, an electron-deficient phthalocyanine compound, a condensed polycyclic compound (naphthalenetetracarbonyl compound, perylenetetracarbonyl compound, etc.), a TCNQ compound (tetracyanoquinodimethane compound), a polythiophene compound. , benzidine-based compounds, carbazole-based compounds, phenanthroline-based compounds, pyridinephenyl ligand iridium-based compounds, quinolinol-ligand aluminum-based compounds, n-type π-conjugated polymers, and graphene. Moreover, you may use combining multiple types of compounds among these compounds as an n-type organic semiconductor. The n-type organic semiconductor is more 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 particularly preferably a fullerene compound and a condensed polycyclic It is at least one of a compound and an n-type π-conjugated polymer.

A fullerene compound means a substituted or unsubstituted fullerene, and the fullerene is C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₀ , C ₈₂ , C ₈₄ , C ₈₆ , C ₈₈ , C ₉₀ , C ₉₆ , C ₁₁₆ , C ₁₈₀ , C ₂₄₀ , C ₅₄₀ , and the like. The fullerene compound is preferably a substituted or unsubstituted C ₆₀ , C ₇₀ , or C ₈₆ fullerene, and particularly preferably PCBM ([6,6]-phenyl-C61-butyric acid methyl ester, manufactured by Sigma-Aldrich Japan LLC. etc.) and analogues thereof ₍ e.g., those in which the C60 moiety is substituted with _C70 , _C86 , etc., those in which the benzene ring of the substituent is substituted with another aromatic ring or heterocyclic ring, methyl ester to n-butyl ester, i-butyl ester, etc.).

Electron-deficient phthalocyanine compounds include substituted or unsubstituted phthalocyanines, naphthalocyanines, anthracyanines, tetrapyrazinoporphyrazines, etc. having four or more electron-withdrawing groups bonded together and various central metals. Electron-deficient phthalocyanine compounds include, for example, fluorinated phthalocyanines (F ₁₆ MPc) and chlorinated phthalocyanines (Cl ₁₆ MPc). Here, M represents a central metal and Pc represents a phthalocyanine.

Any naphthalenetetracarbonyl compound may be used, but naphthalenetetracarboxylic acid anhydride (NTCDA), naphthalenebisimide compound (NTCDI), and perinone pigments (Pigment Orange 43, Pigment Red 194, etc.) are preferred.

Any perylene tetracarbonyl compound may be used, but perylene tetracarboxylic anhydride (PTCDA), perylene bisimide compound (PTCDI), and condensed benzimidazole (PV) are preferred.

A TCNQ compound is a substituted or unsubstituted TCNQ, or a TCNQ in which the benzene ring portion is replaced with another aromatic ring or heterocyclic ring. TCNQ compounds include, for example, TCNQ, TCNAQ (tetracyanoanthraquinodimethane), TCN3T (2,2′-((2E,2″E)-3′,4′-Alkyl substituted-5H,5″H -[2,2′:5′,2″-terthiophene]-5,5″-diylidene) dimalononitrile derivatives), and the like.

A polythiophene-based compound is a compound having a polythiophene structure such as poly(3,4-ethylenedioxythiophene). Polythiophene-based compounds include, for example, PEDOT:PSS (a composite of poly(3,4-ethylenedioxythiophene) (PEDOT) and polystyrene sulfonic acid (PSS)).

A benzidine-based compound is a compound having a benzidine structure in its molecule. Benzidine compounds include, for example, N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD), N,N'-di-[(1-naphthyl)-N,N'- diphenyl]-1,1′-biphenyl)-4,4′-diamine (NPD) and the like.

A carbazole-based compound is a compound having a carbazole ring structure in the molecule. Examples of carbazole compounds include 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP).

A phenanthroline-based compound is a compound having a phenanthroline ring structure in the molecule, such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).

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

A quinolinol ligand aluminum-based compound is a compound having an aluminum complex structure with a quinolinol structure as a ligand, such as tris(8-quinolinolato)aluminum.

Particularly preferred examples of n-type organic semiconductor materials are shown below. In addition, R in the formula may be any one, but a hydrogen atom, a substituted or unsubstituted branched or straight-chain alkyl group (preferably having 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 8) or a substituted or unsubstituted aryl group (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 14 carbon atoms). Me in the structural formula represents a methyl group, and M represents a metal atom.

The number of organic semiconductors contained in the organic semiconductor layer may be one, or two or more. Also, the organic semiconductor layer may be a laminate or mixed layer of a p-type layer and an n-type layer.

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

On the other hand, in the case of the liquid phase method, the organic material is usually blended in a solvent to form a composition for forming an organic layer (composition for forming an organic layer). Then, this composition is supplied onto a substrate and dried to form an organic layer. As a supply method, coating is preferred. Examples of supply methods include slit coating method, casting method, blade coating method, wire bar coating method, spray coating method, dipping (immersion) coating method, bead coating method, air knife coating method, curtain coating method, inkjet method, A spin coating method, a Langmuir-Blodgett (LB) method, an edge casting method (details are disclosed in Japanese Patent No. 6179930), and the like can be mentioned. It is more preferable to use a casting method, a spin coating method, and an inkjet method. Such a process makes it possible to produce organic layers with smooth surfaces and large areas at low cost.

Moreover, as a solvent used for the composition for organic layer formation, an organic solvent is preferable. Examples of organic solvents include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, and 1,2-dichlorobenzene; Ketone solvents; Halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene; Esters such as ethyl acetate, butyl acetate, and amyl acetate system solvents; alcohol solvents such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, and ethylene glycol; ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, and anisole; , N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, and dimethylsulfoxide. Only one of these solvents may be used, or two or more thereof may be used. The proportion of the organic material in the organic layer-forming composition is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, whereby a film of any thickness can be formed.

Moreover, you may mix|blend a resin binder with the composition for organic layer formation. In this case, the material for forming the film and the binder resin are dissolved or dispersed in the suitable solvent described above to form a coating liquid, and the thin film can be formed by various coating methods. Resin binders include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, polypropylene, and copolymers thereof. Examples include photoconductive polymers such as coalescence, polyvinylcarbazole, and polysilane, and conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyparaphenylene vinylene. A single resin binder may be used, or a plurality of resin binders may be used in combination. Considering the mechanical strength of the thin film, a resin binder having a high glass transition temperature is preferable, and considering charge mobility, a resin binder composed of a photoconductive polymer or a conductive polymer having a structure containing no polar groups is preferable.

When a resin binder is blended, its blending amount is preferably 0.1 to 30% by mass in the organic layer. Only one kind of resin binder may be used, or two or more kinds thereof may be used. When two or more resin binders are used, the total amount thereof is preferably within the above range.

Depending on the application, the organic layer may be a blend film composed of a plurality of material species using a single material or a mixed solution containing various organic materials and additives. For example, when producing a photoelectric conversion layer, a mixed solution using a plurality of semiconductor materials can be used.

In addition, the substrate may be heated or cooled during film formation, and the film quality and molecular packing in the film can be controlled by changing the temperature of the substrate. The temperature of the substrate is not particularly limited, but is preferably -200°C to 400°C, more preferably -100°C to 300°C, still more preferably 0°C to 200°C.

The properties of the formed organic layer can be adjusted by post-treatment. For example, properties can be enhanced by altering the morphology of the film and the packing of molecules in the film by heat treatment or exposure to vaporized solvents. Also, by exposing the film to an oxidizing or reducing gas, solvent, substance, or the like, or by using these techniques together, an oxidation or reduction reaction can be induced to adjust the carrier density and the like in the film.

<<Protective layer>>
The protective layer is a layer formed from a protective layer-forming composition. The protective layer can be formed, for example, by applying a protective layer-forming composition onto the organic layer and drying it.

As a method for applying the composition for forming a protective layer, coating is preferred. Examples of application methods include slit coating method, casting method, blade coating method, wire bar coating method, spray coating method, dipping (immersion) coating method, bead coating method, air knife coating method, curtain coating method, inkjet method, A spin coating method, a Langmuir-Blodgett (LB) method, and the like can be mentioned. It is more preferable to use a casting method, a spin coating method, and an inkjet method. Such a process makes it possible to produce protective layers with smooth surfaces and large areas at low cost.

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

The composition for forming a protective layer can also be formed by a method of transferring a coating film formed by applying the protective layer-forming composition onto a temporary support in advance by the above applying method or the like onto an application target (for example, an organic layer). Regarding the transfer method, paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can be referred to.

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

The protective layer preferably has a solubility in a developer of 10 nm/s or less at 23° C., more preferably 1 nm/sg/L or less. The lower limit of the dissolution amount is not particularly limited, and may be 0 nm/s or more.

The protective layer is subjected to removal using a stripping solution. A method for removing the protective layer using a stripping solution will be described later.

Examples of the stripping solution include water, a mixture of water and a water-soluble solvent, and a water-soluble solvent. Water or a mixture of water and a water-soluble solvent is preferable. The water-soluble solvent is the same as the water-soluble solvent added to the protective layer-forming composition.

The content of water in the stripping solution is preferably 90 to 100% by mass, more preferably 95 to 100% by mass. Further, the stripping solution may be a stripping solution containing only water.

Moreover, the stripping solution may contain a surfactant in order to improve the removability of the protective layer. A known compound can be used as the surfactant, and nonionic surfactants are preferred.

<<Photosensitive layer>>
The photosensitive layer is a layer that is subjected to development using a developer. The development is preferably negative development. As the photosensitive layer, a known photosensitive layer (for example, a photoresist layer) used in this technical field can be appropriately used. In the laminate, the photosensitive layer may be either a negative photosensitive layer or a positive photosensitive layer.

It is preferable that the exposed portion of the photosensitive layer is sparingly soluble in a developer containing an organic solvent. The term "sparingly soluble" means that the exposed portion is hardly soluble in a developer. It is preferable that the dissolution rate of the photosensitive layer in the exposed area in the developer is lower than the dissolution rate of the photosensitive layer in the unexposed area in the developer (slightly soluble). Specifically, the polarity is changed by exposure to light having at least one wavelength of 365 nm (i-line), 248 nm (KrF line), and 193 nm (ArF line) at a dose of 50 mJ/cm ² or more. , Sp value (solubility parameter) is preferably poorly soluble in solvents of less than 19.0 (MPa) ^1/2 , and poorly soluble in solvents of 18.5 (MPa) ^1/2 or less is more preferable, and it is even more preferable that it is sparingly soluble in a solvent of 18.0 (MPa) ^1/2 or less.

The solubility parameter (sp value) is a value [unit: (MPa) ^1/2 ] determined by the Okitsu method. The Okitsu method is one of the conventionally well-known methods of calculating the sp value. 29, No. 6 (1993) 249-259.

Further, by exposing at least one wavelength of light having a wavelength of 365 nm (i-line), 248 nm (KrF line) and 193 nm (ArF line) at a dose of 50 to 250 mJ/cm ² , the polarity is changed as described above. Change is more preferable.

The photosensitive layer preferably has photosensitivity to i-line irradiation. Photosensitivity means that the rate of dissolution in an organic solvent (preferably butyl acetate) changes due to irradiation of at least one of actinic rays and radiation (irradiation of i-rays when having photosensitivity to irradiation of i-rays). It means to

Examples of the photosensitive layer include a photosensitive layer containing a resin whose dissolution rate in a developer is changed by the action of an acid (hereinafter also referred to as "specific resin for photosensitive layer").
The change in dissolution rate of the specific resin for photosensitive layer is preferably a decrease in 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/sec or more.
More preferably, 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 after the dissolution rate changes is less than 1 nm/sec.
The specific resin for the photosensitive layer 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 the dissolution rate changes. It is preferable that the resin is sparingly soluble in an organic solvent having an sp value of 18.0 (MPa) ^1/2 or less.

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

Examples of the photosensitive layer include a photosensitive layer containing a specific resin for photosensitive layer and a photoacid generator, a photosensitive layer containing a polymerizable compound, a photopolymerization initiator, and the like.
Further, the photosensitive layer is preferably a chemically amplified photosensitive layer from the viewpoint of achieving both high storage stability and fine pattern formability.

Examples of the photosensitive layer containing the specific resin for the photosensitive layer and the photoacid generator are described below.

[Specific resin for photosensitive layer]
The specific resin for the photosensitive layer is preferably an acrylic polymer.
"Acrylic polymer" is an addition polymerization type resin, a polymer containing repeating units derived from (meth)acrylic acid or its ester, other than repeating units derived from (meth)acrylic acid or its ester may contain repeating units such as repeating units derived from styrenes and repeating units derived from vinyl compounds. The acrylic polymer preferably contains 50 mol% or more, more preferably 80 mol% or more, of repeating units derived from (meth)acrylic acid or its ester, relative to the total repeating units in the polymer. A polymer consisting only of repeating units derived from meth)acrylic acid or its ester is particularly preferred.

The specific resin for the photosensitive layer is preferably a resin having a repeating unit having a structure in which the acid group is protected by an acid-decomposable group. A structure protected by an acid-decomposable group, a structure in which a phenolic hydroxyl group is protected by an acid-decomposable group, and the like can be mentioned.

Further, as the repeating unit having a structure in which an acid group is protected by an acid-decomposable group, a repeating unit having a structure in which a carboxy group in a monomer unit derived from (meth)acrylic acid is protected by an acid-decomposable group, p Examples include repeating units having a structure in which the phenolic hydroxyl group in monomer units derived from hydroxystyrenes such as -hydroxystyrene and α-methyl-p-hydroxystyrene is protected by an acid-decomposable group.

Examples of repeating units having a structure in which an acid group is protected by an acid-decomposable group include repeating units containing an acetal structure, and repeating units containing a cyclic ether ester structure in a side chain are preferred. As for the cyclic ether ester structure, it is preferable 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.

Moreover, as the repeating unit having a structure in which an acid group is protected by an acid-decomposable group, a repeating unit represented by the following formula (1) is preferable.
Hereinafter, the "repeating unit represented by formula (1)" and the like are also referred to as "repeating unit (1)" and the like.

In formula (1), R ⁸ represents a hydrogen atom or an alkyl group (having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), and L ¹ represents a carbonyl group or a phenylene group. , R ¹ to R ⁷ each independently represent a hydrogen atom or an alkyl group.
In formula (1), R ⁸ is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
In formula (1), L ¹ 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 groups for R ¹ to R ⁷ are synonymous with R ⁸ and preferred embodiments are also the same. At least one of R ¹ to R ⁷ is preferably a hydrogen atom, and more preferably all of R ¹ to R ⁷ are hydrogen atoms.

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

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

Moreover, as a repeating unit having a structure in which an acid group is protected by an acid-decomposable group, a repeating unit represented by the following formula (2) is also preferably exemplified.

In formula (2), A represents a hydrogen atom or a group that leaves under the action of an acid. Examples of groups that leave by the action of an acid include alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), alkoxyalkyl groups (preferably 2 to 12 carbon atoms, 2 to 6 are more preferred, and 2 to 3 are even more preferred), aryloxyalkyl groups (preferably 7 to 40 total carbon atoms, more preferably 7 to 30, and even more preferably 7 to 20), alkoxycarbonyl groups (2 carbon atoms to 12 are preferred, 2 to 6 are more preferred, and 2 to 3 are even more preferred), and an aryloxycarbonyl group (having preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11) is preferred. A may further have a substituent, and examples of the substituent include the substituent T described above.
In formula (2), R ¹⁰ represents a substituent, and examples of the substituent T are given. R9 represents the same group as R8 ⁱⁿ formula ( ¹ ).
In formula (2), nx represents an integer of 0-3.

As the group that leaves by the action of an acid, among the compounds described in paragraphs 0039 to 0049 of JP-A-2008-197480, repeating units containing a group that leaves by an acid are also preferred, and JP-A-2012- Also preferred are the compounds described in paragraphs 0052-0056 of JP 159830 (Patent No. 5191567), the contents of which are incorporated herein.

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

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-decomposable group, contained in the specific resin for photosensitive layer, is 5 to 80 mol. %, more preferably 10 to 70 mol %, even more preferably 10 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 of the above repeating units are included, the total amount thereof preferably falls within the above range.

The specific resin for photosensitive layer may contain a repeating unit containing a crosslinkable group. For details of the crosslinkable group, the description of paragraphs 0032 to 0046 of JP-A-2011-209692 can be referred to, and the contents thereof are incorporated herein.
The specific resin for the photosensitive layer preferably contains a repeating unit (repeating unit (3)) containing a crosslinkable group, but preferably does not substantially contain the repeating unit (3) containing a crosslinkable group. . With such a configuration, the photosensitive layer can be removed more effectively after patterning. Here, "substantially free" means, for example, 3 mol % or less, preferably 1 mol % or less, of the total repeating units of the specific resin for photosensitive layer.

The specific resin for photosensitive layer may contain other repeating units (repeating unit (4)). Examples of the radically polymerizable monomer used to form the repeating unit (4) include compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623. Preferred examples of the repeating unit (4) include repeating units derived from at least one selected from the group consisting of hydroxyl group-containing unsaturated carboxylic acid esters, alicyclic structure-containing unsaturated carboxylic acid esters, styrene, and N-substituted maleimides. are mentioned. Among these, benzyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate, tricyclo[5.2.1.0 ^{2, (meth)acrylate, 6} ] alicyclic structure-containing (meth)acrylic acid esters such as decane-8-yloxyethyl, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-methylcyclohexyl (meth)acrylate, or Hydrophobic monomers such as styrene are preferred.
The repeating unit (4) can be used singly or in combination of two or more. When the repeating unit (4) is included, the content of the monomer unit forming the repeating unit (4) in the total monomer units constituting the specific resin for the photosensitive layer is preferably 1 to 60 mol%, more preferably 5 to 50 mol. %, more preferably 5 to 40 mol %. When two or more of the above repeating units are included, the total amount thereof preferably falls within the above range.

Various methods are known for synthesizing the specific resin for the photosensitive layer. can be synthesized by polymerizing a mixture of radically polymerizable monomers containing the polymer in an organic solvent using a radical polymerization initiator.
As the specific resin for the photosensitive layer, 2,3-dihydrofuran is added to the acid anhydride group in the precursor copolymer obtained by copolymerizing the unsaturated polycarboxylic acid anhydrides at room temperature in the absence of an acid catalyst. Copolymers obtained by addition at a temperature of about (25° C.) to 100° C. are also preferred.
The following resins are also preferred examples of the specific resin for the photosensitive layer.
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 t-butyl methacrylate, THFAA is tetrahydrofuran-2-yl acrylate, THPMA is tetrahydro-2H -pyran-2-yl methacrylate and PEES is p-ethoxyethoxystyrene.

Further, examples of the specific resin for photosensitive layer used in positive development are those described in JP-A-2013-011678, the contents of which are incorporated herein.

From the viewpoint of improving the pattern formability during development, the content of the specific resin for the photosensitive layer is preferably 20 to 99% by mass, more preferably 40 to 99% by mass, based on the total mass of the photosensitive layer. is more preferred, and 70 to 99% by mass is even more preferred. Only one kind of the specific resin for the photosensitive layer may be contained, or two or more kinds thereof may be contained. When two or more kinds of specific resins for the photosensitive layer are used, the total amount thereof is preferably within the above range.
The content of the specific resin for the photosensitive layer is preferably 10% by mass or more, more preferably 50% by mass or more, and 90% by mass or more with respect to the total mass of the resin components contained in the photosensitive layer. is more preferable.

The weight-average molecular weight of the specific resin for photosensitive layer is preferably 10,000 or more, more preferably 20,000 or more, even more preferably 35,000 or more. Although the upper limit is not particularly defined, it is preferably 100,000 or less, may be 70,000 or less, or may be 50,000 or less.
The amount of the component having a weight-average molecular weight of 1,000 or less contained in the specific resin for the photosensitive layer is preferably 10% by mass or less, and preferably 5% by mass or less, relative to the total mass of the specific resin for the photosensitive layer. is more preferable.
The molecular weight distribution (weight average molecular weight/number average molecular weight) of the specific resin for the photosensitive layer is preferably 1.0 to 4.0, more preferably 1.1 to 2.5.

[Photoacid generator]
The photosensitive layer preferably further contains a photoacid generator. The photoacid generator is preferably a photoacid generator that decomposes by 80 mol % or more when the photosensitive layer is exposed at a wavelength of 365 nm with an exposure amount of 100 mJ/cm ² .

The degree of decomposition of the photoacid generator can be obtained by the following method. The details of the photosensitive layer-forming composition will be described later.
Using the composition for forming a photosensitive layer, a photosensitive layer was formed on a silicon wafer substrate and heated at 100° C. for ¹ minute. expose. The thickness of the photosensitive layer after heating is 700 nm. Thereafter, the silicon wafer substrate with the photosensitive layer formed thereon is immersed in a methanol/tetrahydrofuran (THF)=50/50 (mass ratio) solution for 10 minutes while applying ultrasonic waves. After the immersion, the extract extracted in the solution is analyzed using HPLC (high performance liquid chromatography) to calculate the decomposition rate of the photoacid generator from the following formula.
Decomposition rate (%) = amount of decomposed product (mol)/amount of photoacid generator contained in photosensitive layer before exposure (mol) x 100
The photoacid generator preferably decomposes by 85 mol % or more when the photosensitive layer is exposed at a wavelength of 365 nm with an exposure amount of 100 mJ/cm ² .

-Oxime sulfonate compound-
The photoacid generator is preferably a compound containing an oximesulfonate group (hereinafter also simply referred to as "oximesulfonate compound").
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group. 105) is preferably an oxime sulfonate compound.

In formula (OS- ¹ ), X3 represents an alkyl group, an alkoxyl group, or a halogen atom. When there ^are multiple X3's, they may be the same or different. The alkyl group and alkoxyl group in X ³ above may have a substituent. The alkyl group for X ³ above is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxyl group for X ³ above is preferably a linear or branched alkoxyl group having 1 to 4 carbon atoms. As the halogen atom for X3 ^, a chlorine atom or a fluorine atom is preferable.
In formula (OS-1), m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or ³ , multiple X3's may be the same or different.
In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a carbon It is preferably a halogenated alkoxyl group of number 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxyl group having 1 to 5 carbon atoms; group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.

In formula (OS-1), m3 is 3, X ³ is a methyl group, the substitution position of X ³ is the ortho position, R ³⁴ is a linear alkyl group having 1 to 10 carbon atoms, 7, Compounds with a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group are particularly preferred.

Specific examples of the oxime sulfonate compound represented by formula (OS-1) are described in paragraph numbers 0064 to 0068 of JP-A-2011-209692 and paragraph numbers 0158-0167 of JP-A-2015-194674. The following compounds are exemplified, the contents of which are incorporated herein.

In formulas (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and each R ^s2 , which may be present in plurality, is independently a hydrogen atom, an alkyl group, or an aryl represents a group or a halogen atom, and each R ^s6 which may be present in plurality independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and Xs represents O or S. , ns represents 1 or 2, and ms represents an integer of 0-6.
In formulas (OS-103) to (OS-105), an alkyl group (preferably having 1 to 30 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms) or a heteroaryl group (preferably having 6 to 30 carbon atoms) represented by R ^s1 Numbers 4 to 30 are preferred) may have a substituent T.

In formulas (OS-103) to (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). , a hydrogen atom or an alkyl group. One or two of ^Rs2 , which may be present in the compound at least 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. , 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 the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5- or 6-membered ring.

In formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is 2 is preferred.
In formulas (OS-103) to (OS-105), an alkyl group (preferably having 1 to 30 carbon atoms) and an alkyloxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 are substituents. may have.
In formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0 is particularly preferred.

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

In formulas (OS-106) to (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, the number of carbon atoms 1 to 8 alkyl group, halogen atom, chloromethyl group, bromomethyl group, bromoethyl group, methoxymethyl group, phenyl group or chlorophenyl group; R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group; ^t2 represents a hydrogen atom or a methyl group.
In formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

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

In formulas (OS-106) to (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 the above oxime sulfonate compound, the oximes may have either one of the three-dimensional structures (E, Z) or may be a mixture.
Specific examples of the oxime sulfonate compounds represented by the formulas (OS-103) to (OS-105) include paragraphs 0088 to 0095 of JP-A-2011-209692 and paragraphs of JP-A-2015-194674. Compounds described in numbers 0168-0194 are exemplified, the contents of which are incorporated herein.

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

In formula (OS-101) or (OS-102), R ^u9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, It represents an aryl group or a heteroaryl group. An aspect in which ^Ru9 is a cyano group or an aryl group is more preferred, and an aspect in which ^Ru9 is a cyano group, a phenyl group or a naphthyl group is even more preferred.
In formula (OS-101) or (OS-102), R ^u2a represents an alkyl group or an aryl group.
In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, -CR ^u6 H- or CR ^u6 R ^u7 —, and R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group. , an arylcarbonyl group, an amido group, a sulfo group, a cyano group or an aryl group. Two of R ^u1 to R ^u4 may each combine to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring. R ^u1 to R ^u4 are preferably hydrogen atoms, halogen atoms or alkyl groups, and an aspect in which at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group is also preferable. Among them, an aspect in which all of R ^u1 to R ^u4 are hydrogen atoms is preferable. Any of the substituents described above may further have a substituent.

The compound represented by formula (OS-101) is more preferably a compound represented by formula (OS-102).
In the above oxime sulfonate compound, the stereostructures (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture.
Specific examples of the compound represented by formula (OS-101) include compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-209692 and paragraph numbers 0195-0207 of JP-A-2015-194674. and the contents of which are incorporated herein.
Among the above compounds, b-9, b-16, b-31 and b-33 are preferred.
Examples of commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Chemical Co., Ltd.), and the like. can be done.

As a photoacid generator sensitive to actinic rays, one containing no 1,2-quinonediazide compound is preferred. The reason for this is that 1,2-quinonediazide compounds generate carboxyl groups through sequential photochemical reactions, but their quantum yield is 1 or less, and they are less sensitive than oxime sulfonate compounds.
On the other hand, oxime sulfonate compounds act as a catalyst for the deprotection of the acid groups in which the acid generated in response to actinic rays is protected. , and the quantum yield exceeds 1, for example, a large value such as a power of 10. It is speculated that high sensitivity is obtained as a result of so-called chemical amplification.
In addition, since the oxime sulfonate compound has a wide π-conjugated system, it has absorption up to the long wavelength side, and not only far ultraviolet rays (DUV), ArF rays, KrF rays, i rays, It also exhibits very high sensitivity to the g-line.

By using a tetrahydrofuranyl group as the acid-decomposable group in the photosensitive layer, acid-decomposability equivalent to or higher than that of acetal or ketal can be obtained. As a result, the acid-decomposable groups can be reliably consumed by post-baking for a shorter time. Furthermore, the combined use of an oxime sulfonate compound, which is a photoacid generator, increases the rate of sulfonic acid generation, thereby promoting the generation of acid and the decomposition of the acid-decomposable groups of the resin. In addition, since the acid obtained by decomposing the oxime sulfonate compound is a sulfonic acid with a small molecule, it has high diffusibility in the cured film, and higher sensitivity can be achieved.

The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and more preferably 0.5 to 10% by mass, based on the total mass of the photosensitive layer. It is more preferable to use 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.
A photo-acid generator may be used individually by 1 type, or may use 2 or more types together. When two or more photoacid generators are used, the total amount thereof preferably falls within the above range.

[Basic compound]
The photosensitive layer preferably contains a basic compound from the viewpoint of the liquid storage stability of the composition for forming a photosensitive layer, which will be described later.

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

Examples of aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine and dicyclohexylamine. , dicyclohexylmethylamine, and the like.
Examples of aromatic amines include aniline, benzylamine, N,N-dimethylaniline, diphenylamine and the like.
Heterocyclic amines include, for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, cyclohexylmorpholinoethylthiourea, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.3 .0]-7-undecene and the like.
Quaternary ammonium hydroxides include, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide and the like.
Examples of quaternary ammonium salts of carboxylic acids include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.

When the photosensitive layer contains a basic compound, the content of the basic compound is preferably from 0.001 to 1 part by mass, and from 0.002 to 0.1 part by mass, based on 100 parts by mass of the specific resin for the photosensitive layer. It is more preferably 5 parts by mass.

The basic compound may be used alone or in combination of two or more, preferably two or more in combination, more preferably two in combination, heterocyclic amine It is more preferable to use two kinds of together. When two or more kinds of basic compounds are used, the total amount thereof is preferably within the above range.

[Surfactant]
The photosensitive layer preferably contains a surfactant from the viewpoint of improving the applicability of the composition for forming a photosensitive layer, which will be described later.

Any of anionic, cationic, nonionic, or amphoteric surfactants can be used as surfactants, and nonionic surfactants are preferred.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based surfactants, and silicone-based surfactants. .

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

Examples of these fluorine-based surfactants or silicone surfactants include JP-A-62-036663, JP-A-61-226746, JP-A-61-226745, -170950, JP-A-63-034540, JP-A-07-230165, JP-A-08-062834, JP-A-09-054432, JP-A-09-005988, JP-A-2001- Surfactants described in each publication of JP-A-330953 can be mentioned, and commercially available surfactants can also be used.

Commercially available surfactants that can be used include, for example, F-top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (manufactured by Sumitomo 3M Co., Ltd.), and Megafac F171, F173 and F176. , F189, R08 (manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox series such as PF-6320 ( OMNOVA) or other fluorine-based surfactants or silicone-based surfactants. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

Further, as a surfactant, it contains a repeating unit A and a repeating unit B represented by the following formula (41), and a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. Preferred examples include copolymers having (Mw) of 1,000 or more and 10,000 or less.

In formula (41), R ⁴¹ and R ⁴³ each independently represent a hydrogen atom or a methyl group, R ⁴² represents a linear alkylene group having 1 to 4 carbon atoms, R ⁴⁴ represents a hydrogen atom or 1 carbon atom Represents an alkyl group of ⁴ or less, L4 represents an alkylene group having 3 to 6 carbon atoms, p4 and q4 are mass percentages representing the polymerization ratio, and p4 is a numerical value of 10 mass% to 80 mass%. q4 represents a numerical value of 20 mass % or more and 90 mass % or less, r4 represents an integer of 1 or more and 18 or less, and n4 represents an integer of 1 or more and 10 or less.

In formula (41), L ⁴ is preferably a branched alkylene group represented by formula (42) below. R ⁴⁵ in formula (42) represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of wettability to the surface to be coated, and an alkyl group having 2 or 3 carbon atoms. groups are more preferred.
—CH ₂ —CH(R ⁴⁵ )— (42)

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

When the photosensitive layer contains a surfactant, the amount of the surfactant added is preferably 10 parts by mass or less, and 0.01 to 10 parts by mass, with respect to 100 parts by mass of the specific resin for the photosensitive layer. is more preferable, and 0.01 to 1 part by mass is even more preferable.
Surfactant can be used individually by 1 type or in mixture of 2 or more types. When two or more surfactants are used, the total amount thereof is preferably within the above range.

[Other ingredients]
The photosensitive layer may further contain an antioxidant, a plasticizer, a thermal radical generator, a thermal acid generator, an acid multiplier, an ultraviolet absorber, a thickener, and an organic or inorganic suspending agent, if necessary. 1 type or 2 types or more can be added, respectively. Details thereof can be referred to paragraphs 0143 to 0148 of Japanese Patent Laid-Open No. 2011-209692, and the contents thereof are incorporated herein.

The thickness of the photosensitive layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 0.75 μm or more, and particularly preferably 0.8 μm or more, from the viewpoint of improving resolution. The upper limit of the thickness of the photosensitive layer is preferably 10 μm or less, more preferably 5.0 μm or less, and even more preferably 2.0 μm or less.

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

[Developer]
The photosensitive layer is subjected to development using a developer.
As the developer, a developer containing an organic solvent is preferable.
The content of the organic solvent with respect to the total weight of the developer is preferably 90 to 100% by mass, more preferably 95 to 100% by mass. Further, the developer may be a developer containing only an organic solvent.

A method for developing the photosensitive layer using a developer will be described later.

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

Ketone solvents include, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, Methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate and the like.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl. ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. can be mentioned.

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

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

The above organic solvents may be used alone or in combination of two or more. Moreover, you may use it, mixing with organic solvents other than the above. However, the content of water relative to the total mass of the developer is preferably less than 10% by mass, more preferably substantially no water. Here, "substantially free of water" means, for example, that the content of water is 3% by mass or less with respect to the total mass of the developer, and more preferably below the limit of measurement.
That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, relative to the total amount of the developer.

In particular, the organic developer preferably contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents and amide solvents.
Moreover, the organic developer may contain an appropriate amount of a basic compound as necessary. Examples of the basic compound include those mentioned in the section on the basic compound above.

The vapor pressure of the organic developer at 23° C. is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less. By setting the vapor pressure of the organic developer to 5 kPa or less, the evaporation of the developer on the photosensitive layer or in the developing cup is suppressed, and the temperature uniformity in the surface of the photosensitive layer is improved. Dimensional uniformity of the layer is improved.

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

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

-Surfactant-
The developer may contain a surfactant.
Although the surfactant is not particularly limited, for example, the surfactants described in the section on the protective layer above are preferably used.
When a surfactant is blended in the developer, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0, based on the total amount of the developer. 0.01 to 0.5% by mass.

[Composition for forming photosensitive layer]
The composition for forming a photosensitive layer is a composition used for forming the photosensitive layer included in the laminate.
In the laminate, the photosensitive layer can be formed, for example, by applying a composition for forming a photosensitive layer onto the protective layer and drying it. As the application method, for example, the description of the application method of the composition for forming a protective layer in the protective layer described later can be taken into consideration.

The composition for forming a photosensitive layer includes the components contained in the photosensitive layer described above (e.g., the specific resin for the photosensitive layer, the photoacid generator, the basic compound, the surfactant, and other components), a solvent, is preferably included. These components contained in the photosensitive layer are preferably dissolved or dispersed in a solvent, more preferably dissolved.

The content of the components contained in the composition for forming a photosensitive layer can be read by replacing the content of each component with respect to the total weight of the photosensitive layer described above with the content with respect to the solid content of the composition for forming a photosensitive layer. preferable.

-Organic solvent-
As the organic solvent used in the photosensitive layer-forming composition, known organic solvents can be used, including 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 ethers Acetates, esters, ketones, amides, lactones and the like can be exemplified.

Examples of organic solvents include
(1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
(2) ethylene glycol 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, ethylene glycol monobutyl ether acetate;
(4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
(5) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether and propylene glycol diethyl ether;
(6) propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
(7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether;
(8) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate;
(9) dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether;
(10) Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether;
(11) dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate;
(12) lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate and isoamyl lactate;
(13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, propionate Aliphatic carboxylic acid esters such as isobutyl acid, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, and isobutyl butyrate;
(14) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl Other esters such as butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;
(15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone;
(16) amides such as N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone;
(17) Lactones such as γ-butyrolactone can be mentioned.
In addition to these organic solvents, if necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1- Organic solvents such as nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate can also be added.

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

When the composition for forming a photosensitive layer contains an organic solvent, the content of the organic solvent is preferably 1 to 3,000 parts by mass, preferably 5 to 2,000 parts by mass, per 100 parts by mass of the specific resin for the photosensitive layer. It is more preferably 10 to 1,500 parts by mass.
These organic solvents can be used individually by 1 type or in mixture of 2 or more types.
When two or more organic solvents are used, the total amount thereof is preferably within the above range.

<Laminate forming kit>
The laminate-forming kit includes, for example, the protective layer-forming composition and the photosensitive layer-forming composition described above. Moreover, the laminate-forming kit may further include the above-described organic layer-forming composition.

<Laminate manufacturing method and organic layer patterning method>
A method for manufacturing a laminate includes at least the following step (1). Also, the patterning method for the organic layer includes at least the following steps (1) to (5).
(1) forming a protective layer on the organic layer on the substrate;
(2) forming a photosensitive layer on the side of the protective layer opposite to the organic layer;
(3) exposing the photosensitive layer;
(4) developing the photosensitive layer with a developer containing an organic solvent to prepare a mask pattern;
(5) removing the protective layer and the organic layer in the non-masked portion;
(6) removing the protective layer using a stripping solution;

<<(1) Step of forming a protective layer on the organic layer>>
The organic layer patterning method of the present embodiment includes a 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 substrate side. The protective layer is preferably formed so as to be in direct contact with the organic layer, but other layers may be provided therebetween without departing from the gist of the present invention. Other layers include a fluorine-based undercoat layer and the like. Also, only one protective layer may be provided, or two or more layers may be provided. As described above, the protective layer is preferably formed using the protective layer-forming composition.
For the details of the formation method, the application method of the composition for forming the protective layer in the laminate can be referred to.

<<(2) Step of forming a photosensitive layer on the opposite side of the protective layer to the organic layer>>
After the step (1) above, a photosensitive layer is formed on the side of the protective layer opposite to the side facing the organic layer (preferably on the surface). The photosensitive layer is preferably formed using the composition for forming a photosensitive layer, as described above. For the details of the forming method, the application method of the composition for forming the photosensitive layer in the laminate can be referred to.

<<(3) Step of exposing photosensitive layer>>
After forming the photosensitive layer in step (2), the photosensitive layer is exposed. Specifically, for example, at least part of the photosensitive layer is irradiated (exposed) with actinic rays.
It is preferable that the exposure is performed so as to form a predetermined pattern. Also, exposure may be performed through a photomask, or a predetermined pattern may be directly drawn.
The wavelength of the actinic ray during exposure is preferably 180 nm or more and 450 nm or less, more preferably 365 nm (i-line), 248 nm (KrF line) or 193 nm (ArF line). can.

Low-pressure mercury lamps, high-pressure mercury lamps, extra-high pressure mercury lamps, chemical lamps, laser generators, light-emitting diode (LED) light sources, and the like can be used as light sources for actinic rays.
When a mercury lamp is used as the light source, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm) and h-line (405 nm) can be preferably used, and i-line is more preferably used.

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

The exposure dose is preferably 40-120 mJ, more preferably 60-100 mJ.
The energy density per pulse of the laser is preferably 0.1 mJ/cm ² or more and 10,000 mJ/cm ² or less. 0.3 mJ/cm ² or more is more preferable, and 0.5 mJ/cm ² or more is even more preferable in order to sufficiently cure the coating film. From the viewpoint of suppressing decomposition of the photosensitive layer and the like due to an ablation phenomenon, the exposure dose is preferably 1,000 mJ/cm ² or less, more preferably 100 mJ/cm ² or less.

Also, the pulse width is preferably 0.1 nanoseconds (hereinafter referred to as "ns") or more and 30,000 ns or less. In order not to decompose the color coating film due to the abrasion phenomenon, it is more preferably 0.5 ns or more, and even more preferably 1 ns or more. 1,000 ns or less is more preferable, and 50 ns or less is even more preferable, in order to improve alignment accuracy during scanning exposure.

When a laser generator is used as the light source, the laser frequency is preferably 1 Hz or more and 50,000 Hz or less, more preferably 10 Hz or more and 1,000 Hz or less.
Furthermore, the laser frequency is more preferably 10 Hz or higher, more preferably 100 Hz or higher, in order to shorten the exposure processing time. ,000 Hz or less is more preferable.
A laser is easier to focus than a mercury lamp, and is also preferable in that the use of a photomask can be omitted in the pattern formation in the exposure process.

The exposure apparatus is not particularly limited, but commercially available ones include Callisto (manufactured by V Technology Co., Ltd.), AEGIS (manufactured by V Technology Co., Ltd.), DF2200G (Dainippon Screen Mfg. Co., Ltd.). ) etc. can be used. Apparatuses other than those described above are also suitably used.
Also, if necessary, the irradiation light amount can be adjusted through a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, or a bandpass filter.
After the exposure, a post-exposure baking step (PEB) may be performed as necessary.

<<(4) Step of developing a photosensitive layer with a developer containing an organic solvent to prepare a mask pattern>>
After the photosensitive layer is exposed through a photomask in step (3), the photosensitive layer is developed using a developer.
Negative development is preferred. The details of the developer are as described in the description of the photosensitive layer above.
As the development method, for example, a method of immersing the base material in a tank filled with a developer for a certain period of time (dip method), or a method of developing by standing still for a certain period of time while the developer is heaped up on the surface of the base material by surface tension. (paddle method), method of spraying the developer onto the substrate surface (spray method), method of continuously ejecting the developer while scanning the developer ejection nozzle at a constant speed on the substrate rotating at a constant speed ( dynamic dispensing method) and the like can be applied.

When the above-described various developing methods include a step of discharging the developer from the developing nozzle of the developing device toward the photosensitive layer, the discharge pressure of the discharged developer (flow velocity per unit area of the discharged developer) is , preferably 2 mL/sec/mm ² or less, more preferably 1.5 mL/sec/mm ² or less, and even more preferably 1 mL/sec/mm ² or less. Although there is no particular lower limit for the discharge pressure, it is preferably 0.2 mL/sec/mm ² or more in consideration of throughput. By setting the ejection pressure of the ejected developer within the above range, pattern defects caused by resist residues after development can be significantly reduced.

Although the details of this mechanism are not clear, it is probable that by setting the discharge pressure within the above range, the pressure exerted by the developer on the photosensitive layer is reduced, and the resist pattern on the photosensitive layer is inadvertently scraped or collapsed. This is thought to be due to the suppression of The developer discharge pressure (mL/sec/mm ² ) is the value at the outlet of the developing nozzle in the developing device.
Examples of methods for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure supplied from a pressurized tank.

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

<<(5) Step of removing protective layer and organic layer from non-masked portion>>
After the photosensitive layer is developed to form a mask pattern, at least the protective layer and the organic layer on the non-masked portion are removed by etching. The non-masked portion refers to a region that is not masked by a mask pattern formed by developing the photosensitive layer (region from which the photosensitive layer is removed by development).

The etching process may be performed in a plurality of stages. For example, the protective layer and the organic layer may be removed by a single etching process, or after at least a portion of the protective layer is removed by an etching process, the organic layer (and, if necessary, the protective layer) are removed. remainder) may be removed by an etching process.

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

Methods for removing the protective layer and the organic layer include, for example, method A in which the protective layer and the organic layer are removed by dry etching treatment once, removal of at least part of the protective layer by wet etching treatment, A method such as method B in which the organic layer (and, if necessary, the remainder of the protective layer) is then removed by dry etching.

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

Details of one aspect of method A are described below. As a specific example of the method B, the description of Japanese Patent Application Laid-Open No. 2014-098889 can be referred to.

Specifically, in the method A, dry etching is performed using the resist pattern as an etching mask (mask pattern), thereby removing the protective layer and the organic layer in the non-masked portion. Typical examples of dry etching include JP-A-59-126506, JP-A-59-046628, JP-A-58-009108, JP-A-58-002809, JP-A-57. -148706 and JP-A-61-041102.

Dry etching is preferably carried out in the following manner from the viewpoint of forming the cross section of the pattern of the formed organic layer to be more rectangular and from the viewpoint of further reducing damage to the organic layer.
A mixed gas of a fluorine-based gas and an oxygen gas (O ₂ ) is used to perform a first-stage etching to a region (depth) where the organic layer is not exposed, and after the first-stage etching, a nitrogen gas ( N ₂ ) and oxygen gas (O ₂ ) are used to perform second-stage etching, preferably to the vicinity of the region (depth) where the organic layer is exposed, and over-etching is performed after the organic layer is exposed. A form containing and is preferred. A specific method of dry etching, the first stage of etching, the second stage of etching, and the overetching will be described below.

Etching conditions for dry etching are preferably performed while calculating the etching time according to the following method.
(A) Calculate the etching rate (nm/min) in the first-stage etching and the etching rate (nm/min) in the second-stage etching.
(B) Calculate the time required to etch the desired thickness in the first stage etching and the time required to etch the desired thickness in the second stage etching.
(C) Perform the first stage etching according to the etching time calculated in (B) above.
(D) The second stage etching is performed according to the etching time calculated in (B) above. Alternatively, the etching time may be determined by endpoint detection, and the second-stage etching may be performed according to the determined etching time.
(E) Calculate the over-etching time with respect to the total time of (C) and (D) above, and perform over-etching.

The mixed gas used in the etching of the first stage preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material, which is the film to be etched, into a rectangular shape. Also, in the first-stage etching, the laminate is etched up to a region where the organic layer is not exposed. Therefore, it is considered that the organic layer is not damaged or the damage is slight at this stage.

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

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

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

Also, the etching preferably includes an over-etching process. The over-etching process is preferably performed by setting an over-etching ratio. Although the over-etching ratio can be set arbitrarily, it is preferably 30% or less of the total etching time in the etching process from the viewpoint of the etching resistance of the photoresist and the rectangularity of the pattern to be etched (organic layer). 25% is more preferred, and 10 to 15% is particularly preferred.

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

Examples of the method of removing the protective layer with a stripping solution include a method of spraying the stripping solution onto the resist pattern from a spray nozzle or a shower nozzle to remove the protective layer. Pure water can be preferably used as the stripping liquid. Further, examples of the injection nozzle include an injection nozzle whose injection range includes the entire substrate, and a movable injection nozzle whose movable range includes the entire substrate. In another embodiment, after the protective layer is mechanically peeled off, the residue of the protective layer remaining on the organic layer is removed by dissolution.
When the injection nozzle is of a movable type, the resist pattern is removed more effectively by moving from the center of the base material to the edge of the base material two or more times during the process of removing the protective layer and injecting the stripping solution. be able to.
It is also preferable to carry out a step such as drying after removing the protective layer. The drying temperature is preferably 80 to 120°C.

<Application>
A laminate to which the composition for forming a protective layer is applied can be used for manufacturing a semiconductor element (electronic device) using an organic semiconductor. Here, the electronic device is a device that contains a semiconductor, has two or more electrodes, and controls the current flowing between the electrodes and the voltage generated by electricity, light, magnetism, chemical substances, etc., or A device that generates light, an electric field, a magnetic field, etc. by applying voltage or current.

Examples include organic photoelectric conversion elements, organic field effect transistors, organic electroluminescence elements, gas sensors, organic rectifying elements, organic inverters, and information recording elements. Organic photoelectric conversion elements can be used for both optical sensor applications and energy conversion applications (solar cells). Among these, the use thereof is preferably an organic field effect transistor, an organic photoelectric conversion device, or an organic electroluminescence device, more preferably an organic field effect transistor, an organic photoelectric conversion device, and particularly preferably an organic field effect transistor. .

EXAMPLES The present invention will be described in more detail below with reference to examples. Materials, usage amounts, proportions, treatment details, treatment procedures, etc. shown in the examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In the examples, "parts" and "%" are based on mass unless otherwise specified, and the environmental temperature (room temperature) in each step is 23°C.

The weight average molecular weight (Mw) of the water-soluble resin such as polyvinyl alcohol was calculated as a polyether oxide conversion value by GPC measurement. HLC-8220 (manufactured by Tosoh Corporation) was used as an apparatus, and SuperMultipore PW-N (manufactured by Tosoh Corporation) was used as a column.

The weight-average molecular weight (Mw) of the water-insoluble resin such as (meth)acrylic resin was calculated as a polystyrene-equivalent value by GPC measurement. HLC-8220 (manufactured by Tosoh Corporation) was used as an apparatus, and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID×15.0 cm) was used as a column.

<Preparation and Storage of Composition for Forming Protective Layer>
For the protective layer-forming compositions (S-1 to S-24), the following raw materials were mixed. After mixing, using a stirrer (hot magnet stirrer, C-MAG HS4, manufactured by IKA), the protective layer-forming composition was stirred under the following stirring conditions. After stirring was completed, a PVDF (polyvinylidene fluoride) membrane filter (Durapore, manufactured by Merck) with a pore size of 5 μm was placed on a stainless steel pressure filter holder (manufactured by Sartorius), and pressure was applied at 2 MPa using this. Each composition was filtered while After this filtration, glass containers (volume: 250 mL) were each filled with the above compositions to a filling rate of 80% under air, and the containers were sealed with screw caps. Thereafter, the container filled with the composition was stored in a refrigerator under the storage conditions shown in Tables 1 and 2 below (Examples 1 to 36 and Comparative Examples 1 to 5).
<<Stirring conditions>>
・Atmosphere: air ・Stirring time: 240 minutes ・Stirring temperature: 50°C
・Rotating speed of stirring member: 500 rpm
<<Protective Layer Forming Compositions S-1, S-10, S-20, S-24>>
・Each water-soluble resin listed in the table: 15.000 parts by mass ・Each surfactant listed in the table: 0.008 parts by mass ・Water: 84.992 parts by mass <<Protective layer forming compositions S-2 to S-7 >>
・15.000 parts by mass of each water-soluble resin listed in the table ・0.008 parts by mass of each surfactant listed in the table ・0.002 parts by mass of each antifungal agent listed in the table ・84.990 parts by mass of water <<Protective Layer Forming Compositions S-8, S-9, S-11 to S-19, S-21 to S-23>>
・ Each high molecular weight substance listed in the table 15.000 parts by mass × each ratio described in the table ・ Each low molecular weight substance listed in the table 15.000 parts by weight × each ratio described in the table ・ Each surface activity described in the table Agent 0.008 parts by mass 0.002 parts by mass of each antifungal agent listed in the table Water 84.990 parts by mass

The specifications of each raw material are as follows. Further, for the examples and comparative examples in which the water-soluble resin contains a high molecular weight substance and a low molecular weight substance, the molecular weight ratio of the low molecular weight substance (= the weight average molecular weight of the low molecular weight substance/the weight average molecular weight of the high molecular weight substance) is shown in Table 1. and shown in Table 2.

<Water-soluble resin>
<<polyvinyl alcohol (PVA)>>
· PVA-1: PVA-203 manufactured by Kuraray Co., Ltd., Mw = 15,000.
· PVA-2: PVA-205 manufactured by Kuraray Co., Ltd., Mw = 24,000.
· PVA-3: PVA-210 manufactured by Kuraray Co., Ltd., Mw = 50,000.
<<Polyvinylpyrrolidone (PVP)>>
· PVP-1: Pitzcol K-30 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Mw = 45,000.
· PVP-2: Pitzcol K-50 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Mw = 250,000.
· PVP-3: Pitzcol K-80 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Mw = 900,000.
· PVP-4: Pitzcol K-90 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Mw = 1200,000.
<<2-hydroxyethyl cellulose (HEC)>>
· HEC-1: manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Mw = 90,000.
· HEC-2: manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Mw = 380,000.
· HEC-3: manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Mw = 720,000.
· HEC-4: manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Mw = 1300,000.
<<PVA (GRA) grafted with PVP>>
· GRA-1: Pitzcol V-7154 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

<Surfactant>
• Surfactant E-1: a compound having the following structure. Acetylenol E00 manufactured by Kawaken Fine Chemicals.
• Surfactant E-2: polyoxyethylene lauryl ether. EMALEX710 manufactured by Nippon Emulsion Co., Ltd.;

<Antifungal agent>
· F-1: Methylisothiazolinone.
- F-2: 2-bromo-2-nitropropane-1,3-diol.
· F-3: Methylsulfonyltetrachloropyridine.
- F-4: 2-(dichloro-fluoromethyl)sulfanylisoindole-1,3-dione.
· F-5: Sodium diacetate.
· F-6: diiodomethyl p-tolylsulfone.

<Evaluation>
In order to evaluate the effect of the production method of the present invention, the number of defects and the residue ratio of the protective layer formed using the protective layer-forming composition after storage for each protective layer-forming composition of Examples and Comparative Examples were measured. was measured.

<<Formation of laminate>>
When measuring the number of defects and residue ratio of the protective layer, each protective layer-forming composition of Examples and Comparative Examples was used to prepare laminates as follows. An organic layer-forming composition having the following composition containing an organic semiconductor material as an organic material was spin-coated on a 5 cm square glass substrate and dried at 80° C. for 10 minutes to form an organic semiconductor layer having a thickness of 150 nm. . Next, each protective layer forming composition of Examples and Comparative Examples was spin-coated on the organic semiconductor layer and dried at 80° C. for 1 minute to form a protective layer having a thickness of 2 μm. At this time, a composition that had been stored for one year and a composition that had been stored for three years were used as protective layer-forming compositions. Furthermore, a photosensitive resin composition having the following composition was spin-coated on the protective layer and dried at 80° C. for 1 minute to form a photosensitive resin layer having a thickness of 2 μm. As described above, a laminate having a glass substrate, an organic semiconductor layer (thickness of 150 nm), a protective layer (thickness of 2 μm) and a photosensitive resin layer (thickness of 2 μm) in this order is obtained.

<<<composition for forming organic layer>>>
・P3HT (manufactured by Sigma-Aldrich Japan LLC) 10% by mass
・PCBM (manufactured by Sigma-Aldrich Japan LLC) 10% by mass
・ Chloroform (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 80% by mass

<<<photosensitive resin composition>>>
・25.09 parts by mass of photosensitive resin A-1 synthesized by the following method ・0.26 parts by mass of photoacid generator X below ・0.08 parts by mass of basic compound Y below ・Surfactant B below 0.08 parts by mass PGMEA 74.50 parts by mass

Synthesis method of photosensitive resin A-1.
First, BzMA (benzyl methacrylate, 16.65 g), THFMA (tetrahydrofurfuryl methacrylate, 21.08 g), t-BuMA (t-butyl methacrylate, 5.76 g), and V-601 (0.4663 g, Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in PGMEA (32.62 g) to prepare a PGMEA solution. Next, PGMEA (32.62 g) was placed in a three-necked flask equipped with a nitrogen inlet tube and a cooling tube, heated to 86° C., and the above PGMEA solution was added dropwise thereto over 2 hours. The solution was then stirred for 2 hours after which the reaction was terminated. The solution after completion of the reaction was poured into heptane to reprecipitate the polymer component, and the resulting white powder was collected by filtration. As a result, a photosensitive resin A-1 having a weight average molecular weight Mw of 45,000 was obtained.

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

Basic compound Y: a thiourea derivative having the following structure. Manufactured by DSP Gokyo Food & Chemical.

Surfactant B: PF-6320 manufactured by OMNOVA.

<<Measure the number of defects>>
In the process of forming the laminate, after forming the protective layer and before forming the photosensitive resin layer, using an optical microscope, the surface of the protective layer in a field of view of 2.6 mm × 3.8 mm (magnification 5 times) was observed over the entire area of the substrate, and the number of visible microbial colonies was counted.

<<Measurement of residue ratio>>
The residue rate when the protective layer was removed was evaluated for the laminate using the protective layer-forming composition one year after the start of storage. Specifically, it is as follows.

When forming the laminate, after forming the protective layer and before forming the photosensitive resin layer, a TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) device (TOF.SIMS5 manufactured by ION-TOF) was used. Then, the surface of the protective layer was measured using a water-soluble resin, and the signal intensity _I0 derived from the water-soluble resin was measured. For example, when the water-soluble resin contains PVA, the signal derived from C ₄ H ₅ O ^- is measured, and when the water-soluble resin contains PVP, the signal derived from C ₆ H ₁₀ NO ⁺ (112) is measured. , and when the water-soluble resin contains HEC, the signal from [C ₆ H ₁₀ O ₅ ][H ⁺ ] (163) is measured to give the signal intensity I ₀ from the water-soluble resin.

Next, this laminate was subjected to puddle development for 30 seconds using nBA (n-butyl acetate) twice to remove the photosensitive resin layer. After that, this laminate was subjected to puddle development with water for 30 seconds twice, and then subjected to shower cleaning with water to remove the protective layer. As a result, a laminate in which the organic layer remains on the glass substrate is obtained.

Then, using the TOF-SIMS device again, the surface of this organic layer was measured, and the signal intensity I derived from the water-soluble resin was measured. The residue rate of the composition for forming a protective layer was defined by the following formula. It can be said that the smaller the residue ratio, the more suppressed the generation of residues.
Residue rate (%) =
(Signal intensity I derived from water-soluble resin on organic layer surface after protective layer removal treatment)
/(Signal intensity I ₀ derived from the water-soluble resin on the surface of the protective layer) × 100

<Evaluation results>
The results of Examples and Comparative Examples are shown in Tables 1 and 2 above. From these results, it was found that the method for producing a composition for forming a protective layer of the present invention yields a composition for forming a protective layer whose quality is less likely to deteriorate even after long-term storage.

In addition, regarding the residue rate of Example 21, the water peeling process of "performing puddle development with water for 30 seconds twice and then performing shower cleaning with water" was replaced by "putting water on the laminate, When the process was changed to the process of leaving it as it is for 5 minutes, and then further performing shower cleaning with water, the residue rate was 0.18%, which was an extremely good result.

Furthermore, organic semiconductor elements were produced using laminates including a protective layer obtained from the protective layer-forming composition according to each example. None of the organic semiconductor devices had any problem in performance.

1 Photosensitive layer 1a Photosensitive layer 2 after exposure and development Protective layer 3 Organic layer 3a Organic layer 4 after processing Substrate 5 Removed portion 5a Removed portion after etching

Claims (19)

A method for producing a protective layer-forming composition laminated on an organic layer and used for forming a water-soluble protective layer for protecting the organic layer from a chemical solution,
After stirring a composition containing a water-soluble resin and a solvent, the container containing the stirred composition is continuously exposed to an environment in the temperature range of 0 to 18 ° C. for 24 hours or more,
The start time of the period of exposure to the environment is within 72 hours after the end of the stirring ,
A method for producing a composition for forming a protective layer, comprising filtering the composition after completion of the stirring and before exposing to the environment . The start of the period of exposure to the environment is within 24 hours after the end of the stirring.
A method for producing the composition for forming a protective layer according to claim 1 . The period of continuous exposure to the environment is 1 month or more,
A method for producing the composition for forming a protective layer according to claim 1 or 2. The temperature range when exposing the container to the environment is 0 to 10 ° C.
A method for producing the composition for forming a protective layer according to any one of claims 1 to 3. wherein the composition during the agitation comprises an antifungal agent;
A method for producing the composition for forming a protective layer according to any one of claims 1 to 4 . The protective layer-forming composition contains, as the antifungal agent, an isothiazolinone compound, 2-bromo-2-nitropropane-1,3-diol, methylsulfonyltetrachloropyridine, 2-(dichloro-fluoromethyl)sulfanyliso at least one of indole-1,3-dione, sodium diacetate and diiodomethylparatolylsulfone;
A method for producing the composition for forming a protective layer according to claim 5 . The water-soluble resin contains at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and water-soluble polysaccharides,
A method for producing the composition for forming a protective layer according to any one of claims 1 to 6 . The water-soluble resin includes a high molecular weight body and a low molecular weight body having a weight average molecular weight smaller than the weight average molecular weight of the high molecular weight body,
The weight-average molecular weight of the low-molecular-weight substance is not more than half the weight-average molecular weight of the high-molecular-weight substance,
A method for producing the composition for forming a protective layer according to any one of claims 1 to 7 . The content of the high molecular weight substance is 30% by mass or less with respect to the total water-soluble resin,
A method for producing the composition for forming a protective layer according to claim 8 . As the high molecular weight material, polyvinyl alcohol having a weight average molecular weight of 20,000 or more,
A method for producing the composition for forming a protective layer according to claim 8 or 9 . As the high molecular weight material, polyvinylpyrrolidone having a weight average molecular weight of 300,000 or more,
A method for producing the composition for forming a protective layer according to any one of claims 8 to 10 . As the high molecular weight body, a water-soluble polysaccharide having a weight average molecular weight of 300,000 or more,
A method for producing the composition for forming a protective layer according to any one of claims 8 to 11 . wherein the water-soluble polysaccharide is cellulose;
A method for producing the protective layer-forming composition according to claim 12 . Two or more peak tops exist in the molecular weight distribution of the water-soluble resin,
Of the two or more peak tops, the molecular weight corresponding to one peak top is half or less than the molecular weight corresponding to the other one peak top.
A method for producing the composition for forming a protective layer according to any one of claims 1 to 13 . A method for storing a composition for forming a protective layer laminated on an organic layer and used for forming a water-soluble protective layer for protecting the organic layer from a chemical solution,
After stirring a composition containing a water-soluble resin and a solvent, storing the container containing the stirred composition while continuously exposing it to an environment within a temperature range of 0 to 18 ° C. for 24 hours or longer. ,
The start time of the period of exposure to the environment is within 72 hours after the end of the stirring ,
A method for preserving a composition for forming a protective layer, comprising filtering the composition after completion of the stirring and before exposing to the environment . A method for producing a laminate, comprising applying a protective layer-forming composition stored by the storage method according to claim 15 onto an organic layer. A method for manufacturing a semiconductor device, comprising the method for manufacturing a laminate according to claim 16 as a process. A protective layer obtained from a protective layer-forming composition stored by the storage method according to claim 15 . A laminate comprising the protective layer according to claim 18 and an organic layer.

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