KR20220012890A - A method for producing a composition for forming a protective layer, a method for preserving a composition for forming a protective layer, and application of the preservation method - Google Patents

Abstract

A method for producing 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, after stirring a composition containing a water-soluble resin and a solvent, after stirring the composition A composition for forming a protective layer, comprising continuously exposing a container to an environment in a temperature range of 0 to 18 ° C. for 24 hours or more, wherein the start time of the period of exposure to the environment is within 72 hours after the end of the stirring manufacturing method, preservation method of a composition for forming a protective layer, and application of this preservation method.

Description

A method for producing a composition for forming a protective layer, a method for preserving a composition for forming a protective layer, and application of the preservation method

The present invention relates to a method for producing a composition for forming a protective layer, a method for preserving a composition for forming a protective layer, and application of the preservation method.

DESCRIPTION OF RELATED ART In recent years, the electronic device (organic-semiconductor device) using an organic semiconductor is used widely. The organic semiconductor device has a merit that it can be manufactured by a simple process compared with the conventional electronic device using inorganic semiconductors, such as silicon|silicone. In addition, an organic semiconductor can easily change material properties by changing its molecular structure. Moreover, it is thought that it becomes possible to implement|achieve the function and element similar to what could not be achieved with an inorganic semiconductor because there are abundant material variations. The organic semiconductor is, for example, an organic solar cell, an organic electroluminescent display, an organic photodetector, an organic field effect transistor, an organic electroluminescent device, a gas sensor, an organic rectifying device, an organic inverter, an information recording device, etc. It has the potential to be applied to electronic devices of

Although the main patterning method of an organic semiconductor includes, for example, a printing method and a lithography method, the lithographic method is advantageous from a 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 a photolithographic method, and then the protective layer and dry etching the organic semiconductor layer to pattern the organic semiconductor layer. Here, the protective layer serves to reduce damage to the organic semiconductor layer by protecting the organic semiconductor layer from a chemical solution (eg, a developer for developing a photosensitive layer) used during patterning.

Patent Document 1: International Publication No. 2016/175220

As described above, a composition for forming a protective layer 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. If left, microorganisms such as mold may be generated and the quality of the composition may be deteriorated.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a composition for forming a protective layer and a method for preserving a composition for forming a protective layer in which the quality is hardly deteriorated even when stored for a long period of time.

The above problem could be solved by promptly storing the stirred composition in a specific temperature range after the stirring of the raw material of the composition for forming a protective layer was completed. Specifically, by the following means <1>, Preferably, by the following means <2>, the said subject was solved.

<1>

A method for producing 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, comprising:

After stirring the composition containing the water-soluble resin and the solvent, the container containing the composition after stirring is continuously exposed to an environment in a 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 start time of the period of exposure to the environment is within 72 hours after the end of stirring.

<2>

The production method according to <1>, wherein the start time of the period of exposure to the environment is within 24 hours after the end of stirring.

<3>

The production method according to <1> or <2>, wherein the period of continuous exposure to the environment is 1 month or more.

<4>

The manufacturing method according to any one of <1> to <3>, wherein the temperature range when exposing the container to the environment is 0 to 10°C.

<5>

The production method according to any one of <1> to <4>, which includes filtering the composition after completion of stirring and before exposing to the environment.

<6>

The manufacturing method in any one of <1>-<5> in which the said composition at the time of stirring contains a fungicide.

<7>

The composition for forming a protective layer is an isothiazolinone compound, 2-bromo-2-nitropropane-1,3-diol, methylsulfonyltetrachloropyridine, 2-(dichloro- The production method according to <6>, comprising at least one of fluoromethyl)sulfanylisoindole-1,3-dione, sodium diacetate, and diiodomethylparatolylsulfone.

<8>

The production method according to any one of <1> to <7>, wherein the water-soluble resin contains at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble polysaccharides.

<9>

A water-soluble resin comprising a high molecular weight substance and a low molecular weight substance having a weight average molecular weight smaller than the weight average molecular weight of the high molecular weight substance;

The manufacturing method in any one of <1>-<8> whose weight average molecular weight of a low molecular weight body is half or less of the weight average molecular weight of a high molecular weight body.

<10>

The manufacturing method as described in <9> whose content of a high molecular weight body is 30 mass % or less with respect to all the water-soluble resins.

<11>

The manufacturing method as described in <9> or <10> containing polyvinyl alcohol which has a weight average molecular weight of 20,000 or more as a high molecular weight body.

<12>

The production method according to any one of <9> to <11>, wherein the polyvinylpyrrolidone having a weight average molecular weight of 300,000 or more is included as the high molecular weight body.

<13>

The production method according to any one of <9> to <12>, wherein the high molecular weight substance contains a water-soluble polysaccharide having a weight average molecular weight of 300,000 or more.

<14>

The production method according to <13>, wherein the water-soluble polysaccharide is cellulose.

<15>

In the molecular weight distribution of the water-soluble resin, there are two or more peak tops,

The production method according to any one of <1> to <14>, wherein a molecular weight corresponding to one peak top among two or more peak tops is half or less of a molecular weight corresponding to another peak top.

<16>

A method of preserving 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, comprising:

After stirring the composition containing the water-soluble resin and the solvent, the container containing the composition after stirring is continuously exposed to an environment in the temperature range of 0 to 18 ° C. for 24 hours or more, including preservation,

A method for preserving a composition for forming a protective layer, wherein the start time of the period of exposure to the environment is within 72 hours after the end of stirring.

<17>

A method for producing a laminate, comprising applying the composition for forming a protective layer saved by the storage method according to <16> on the organic layer.

<18>

The manufacturing method of a semiconductor element including the manufacturing method of the laminated body as described in <17> as a process.

<19>

A protective layer obtained from the composition for forming a protective layer preserved 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 the composition for forming a protective layer of the present invention, a composition for forming a protective layer in which the quality is hardly deteriorated even when stored for a long period of time can be obtained.

1 is a cross-sectional view schematically illustrating a processing process of a laminate to which a composition for forming a protective layer is applied.

EMBODIMENT OF THE INVENTION Hereinafter, typical embodiment of this invention is 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, the numerical range indicated by using the symbol "to" means a range including the numerical value described before and after "to" as a lower limit and an upper limit, respectively.

As used herein, the term "process" is meant to include not only an independent process, but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.

With respect to the description of the group (atomic group) in the present specification, the description not describing substituted or unsubstituted means not having a substituent and includes a group having a substituent. For example, when simply described as "alkyl group", this is meant to include both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). In addition, when simply described as "alkyl group", this may be linear or cyclic, and in the case of chain, it may be linear or branched. These have the same meaning for other groups such as "alkenyl group", "alkylene group" and "alkenylene group".

In this specification, "exposure" is a meaning including not only writing using light, but writing using particle beams, such as an electron beam and an ion beam, unless otherwise indicated. Examples of the energy rays used for drawing include active rays such as a bright spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), and X-rays, and particle rays such as electron beams and ion rays.

In the present specification, "light" includes not only light and electromagnetic waves of wavelengths in the region of ultraviolet, near-ultraviolet, far-ultraviolet, visible, infrared, etc. unless otherwise specified, but also radiation. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet (EUV) and X-rays. Moreover, laser beams, such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser, can also be used. Monochrome light (single-wavelength light) that has passed through an optical filter may be used for these lights, or light including a plurality of wavelengths (composite light) may be used.

In this specification, "(meth)acrylate" means both, or either of "acrylate" and "methacrylate", and "(meth)acryl" is "acryl" and "methacrylic" It means both, or either of ", and "(meth)acryloyl" means both, or either of "acryloyl" and "methacryloyl".

In the present specification, the solid content in the composition means other components except for the solvent, and the content (concentration) of the solid content in the composition is, unless otherwise specified, the mass of other components excluding the solvent with respect to the total mass of the composition. It is expressed as a percentage.

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

In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are shown as polystyrene conversion values according to gel permeation chromatography (GPC measurement) unless otherwise indicated. This weight average molecular weight (Mw) and number average molecular weight (Mn) use, for example, HLC-8220 (manufactured by Tosoh Corporation), and as a column, a guard column HZ-L, TSKgel Super HZM-M, TSKgel Super It can obtain|require by using HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (made by Tosoh Corporation). In addition, unless otherwise indicated, it shall be measured using THF (tetrahydrofuran) as an eluent. In addition, it shall be assumed that the wavelength 254nm detector of UV rays (ultraviolet rays) is used for detection in a GPC measurement unless it demonstrates in particular.

In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", the Another layer may exist on the upper side or the lower side. That is, a 3rd layer or element may be further interposed between the layer used as a reference|standard and the said other layer, and the layer used as a reference|standard and the said other layer do not need to be in contact. In addition, unless otherwise specified, the direction in which the layers are laminated with respect to the base material is referred to as "upper", or in the case where the photosensitive layer is present, the direction from the base to the photosensitive layer is referred to as "upper". and the opposite direction is called "lower". In addition, the setting of such an up-down direction is for convenience in this specification, and in an actual aspect, the "upward" direction in this specification may differ from a vertically upward direction in some cases.

<Method for producing a composition for forming a protective layer and a method for preserving it>

A 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 laminated on an organic layer and used for forming a water-soluble protective layer for protecting the organic layer from a chemical, the composition comprising a water-soluble resin and a solvent After stirring the composition, the container containing the composition after stirring is continuously exposed to an environment in a temperature range of 0 to 18 ° C. (hereinafter, also referred to as a “low temperature environment”) for 24 hours or more. It is characterized in that the start time of the exposure period is within 72 hours after the end of the stirring.

Further, the method for preserving the composition for forming a protective layer of the present invention is a method of preserving 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, a water-soluble resin and a solvent After stirring the composition containing , characterized in that within 72 hours after the end of the stirring.

In the two methods of the present invention, there is no difference in the act of exposing the container to the low-temperature environment itself, but in the manufacturing method, the composition for forming a protective layer is preserved while exposing it to the low-temperature environment according to the storage method, It is different from the point which can include the process of taking out the composition for protective layer formation from a low-temperature environment, the process of packing for conveyance or shipment, etc.

In the present invention, after the respective raw materials of the composition for forming a protective layer are combined and stirred, the composition is exposed to a low-temperature environment quickly and for a predetermined period or longer as described above (hereinafter, also referred to as “low temperature storage”) for a long period of time. It is possible to obtain a composition for forming a protective layer in which the quality is hardly deteriorated even when stored. Although the reason for this is not certain, the dissolved amount of oxygen mixed into the composition for forming a protective layer during production (for example, the step of mixing or stirring each raw material) is reduced by promptly storing the raw materials at the low temperature after stirring. It is thought that this is because the proliferation of microorganisms is suppressed.

Generally, from a viewpoint of suppressing the deterioration of the quality of the composition containing a water-soluble resin, the below-mentioned antiseptic|preservative and antifungal agent are used. However, it turned out that even if it uses a preservative or a fungicide, the quality of the composition for protective layer formation may not fully be able to be maintained over a long period of time, for example on an annual basis.

ADVANTAGE OF THE INVENTION According to this invention, the quality of the composition for protective layer formation can fully be maintained over a long period of time irrespective of the presence or absence of use of a preservative or antifungal agent. Moreover, in this invention, when an antiseptic|preservative and a fungicide are used together, it becomes possible to extend the period which can maintain the quality of the composition for protective layer formation further.

The composition for forming a protective layer obtained by the production method of the present invention contains at least a water-soluble resin and a solvent, and is laminated on the organic layer as described above and is used for forming a water-soluble protective layer for protecting the organic layer from a chemical solution. Such a protective layer is used for formation of the laminated body which contains a base material, an organic layer, a protective layer, and a photosensitive layer in this order. The detail regarding the use of the raw material of the composition for protective layer formation, and a laminated body is mentioned later.

<<(a) Agitation and other treatment of the composition containing the raw material>>

In the manufacturing method of this invention, the method in particular of stirring the composition containing the raw material of the composition for protective layer formation is not restrict|limited, You may carry out manually or you may use a stirring apparatus. It is preferable to stir the composition with a stirring device from the viewpoint of uniformly stirring in a short time. 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, PTFE jet type stirring rods manufactured by Flon Chemicals, etc.) can be used.

One step may be sufficient as the process of stirring, and two or more steps may be sufficient as it. That is, all the raw materials of the composition for forming a protective layer may be mixed at once and stirring may be completed once, or after mixing and stirring some of the raw materials, other raw materials may be added and the second stage and subsequent stirring may be performed. . Moreover, with respect to all or some raw materials, you may prepare a dilution liquid by injecting|throwing-in the raw material in advance to a solvent and stirring, and then mixing the diluent with another raw material or another diluent and stirring may be performed. From the viewpoint of stirring efficiency, the number of steps of stirring is preferably 1 to 4 steps, more preferably 1 to 3 steps, and still more preferably 1 step or 2 steps.

The conditions at the time of stirring are not especially restrict|limited either.

For example, an atmospheric atmosphere may be sufficient as the atmosphere at the time of stirring, and the atmosphere substituted with inert gas, such as nitrogen, may be sufficient as it. The temperature (stirring temperature) of the composition at the time of stirring is not restrict|limited in particular in the range which does not interfere with the stirring of a raw material, For example, it is 1-99 degreeC. It is preferable that it is 80 degrees C or less, and, as for the upper limit of this numerical range from a viewpoint of stirring efficiency, it is more preferable that it is 70 degrees C or less. Moreover, it is preferable that it is 25 degreeC or more, and, as for the lower limit of this numerical range, it is more preferable that it is 30 degreeC or more. Although the difference in particular between stirring temperature and the temperature of the low-temperature environment mentioned later is not restrict|limited, For example, in the range of 7-80 degreeC, it adjusts suitably as needed. It is preferable that it is 60 degrees C or less, and, as for the upper limit of this numerical range from a viewpoint of uniformity of stirring and cooling efficiency, it is more preferable that it is 40 degrees C or less. Moreover, it is preferable that it is 15 degreeC or more, and, as for the lower limit of this numerical range, it is more preferable that it is 25 degreeC or more.

The stirring method may be mechanical stirring in which raw materials are directly mixed and stirred with a stirring member such as a stirring rod or stirring blade, or ultrasonic or electromagnetic stirring in which the stirring is performed in a non-contact manner. From the viewpoint of productivity, etc., mechanical stirring is preferable as the stirring method. The rotation speed of the stirring member is, for example, in the range of 10 to 1000 rpm, and is appropriately adjusted according to the viscosity of the raw material. It is preferable that it is 900 rpm or less, and, as for the upper limit of this numerical range from a viewpoint of the uniformity of stirring and stirring efficiency, it is more preferable that it is 800 rpm or less. Moreover, it is preferable that it is 30 rpm or more, and, as for the lower limit of this numerical range, it is more preferable that it is 50 rpm or more. Stirring time is, for example, in the range of 30 minutes - 72 hours, and is suitably adjusted according to raw material viscosity and desired uniformity. It is preferable that it is 48 hours or less, and, as for the upper limit of this numerical range from a viewpoint of the uniformity of stirring and stirring efficiency, it is more preferable that it is 24 hours or less. Moreover, it is preferable that it is 60 minutes or more, and, as for the lower limit of this numerical range, it is more preferable that it is 120 minutes or more.

Moreover, when performing stirring multiple times, you may perform other processing of a raw material other than addition of a raw material in the period between each stirring. As such other treatment, for example, degassing of the raw material and the like can be given. In the production method of the present invention, after the stirring is finished and before exposing the composition for forming a protective layer to a low-temperature environment, an additional treatment such as degassing of the composition for forming a protective layer may be further performed. In addition, in this specification, "end|finish" of stirring is performed based on the stop of application of the external force for stirring. The stop of external force application is, for example, in the case of mechanical stirring, operation stop of the stirring rod or stirring blade, and in the case of non-contact stirring, application of ultrasonic waves or electromagnetic force is stopped. In addition, when stirring is performed multiple times, "finish" of stirring means completion|finish of stirring performed last.

It is preferable that filtration of the composition for protective layer formation is filtration using a filter.

Although filtration is effective also in the filtration by a one-stage filter, the filtration by two or more stages of filters is more preferable. Filtration by two or more stages of filters means filtration by arranging two or more filters in series. In this invention, the filtration by the filter of 1-4 stages is preferable, and the filtration by the filter of 2-4 stages is more preferable.

It is preferable that the component (material component) which comprises the material of a filter contains resin. It does not restrict|limit especially as resin, A well-known thing can be used as a material of a filter. As a preferable embodiment of the component (material component) constituting the material of the filter, a polymer (grafted polymer) in which at least one type of neutral group is grafted is exemplified. It is preferable that it is at least 1 sort(s) chosen from a hydroxyl group and a carboxy group, and, as for a neutral group, it is more preferable that it is a hydroxyl group. The grafted polymer is preferably a grafted polyolefin, and more preferably a grafted polyethylene. For the description of the grafted polymer, reference may be made to the description of International Publication No. 2016/081729, the contents of which are incorporated herein by reference.

The pore diameter of the filter used in the present invention is preferably 5 µm or less, more preferably 3 µm or less, still more preferably 1 µm or less, still more preferably 0.5 µm or less, and may be 0.2 µm or less. By making the hole diameter of a filter into said range, an impurity can be reduced more effectively. Moreover, although the lower limit of the pore diameter of a filter is not specifically defined, For example, 1 nm or more is preferable. When the pore diameter of the filter is 1 nm or more, an unnecessarily large pressure is not applied at the time of filtration, productivity is improved, and destruction of the filter can be effectively suppressed. When filtration is performed in stages, the filtration in the first stage uses a filter having a pore diameter of 0.2 to 5 µm (preferably a filter having a pore diameter of 0.2 to 1 µm), and the filtration in the second stage has a pore diameter of 7 nm It is possible to use a smaller filter (preferably a filter having a pore diameter of less than 7 nm and 1 nm or more). Moreover, it is preferable that the difference of the hole diameter of the stage immediately preceding, such as a 1st stage and a 2nd stage, a 2nd stage, and a 3rd stage, is 0.1-2 micrometers.

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

<<(b) Filling of the composition for forming a protective layer into a container >>

The container is not particularly limited as long as the quality of the composition for forming a protective layer can be maintained, and for example, glass (soda-lime glass), metal (stainless steel, aluminum, nickel, etc.), and plastic (polypropylene, polyethylene (especially high-density polyethylene), etc.) can be used. It is preferable that a container is a glass container from a viewpoint of maintaining quality more stably. A container is normally comprised with the container main body and the lid for sealing the container main body. The material of each of the container body and the lid may be the same as or different from each other.

The container is preferably made of a material having a thermal conductivity of 0.1 W/(m·K) or more from the viewpoint of cooling efficiency. The thermal conductivity of the container material is more preferably 0.3 W/(m·K) or more, still more preferably 0.8 W/(m·K) or more, and particularly preferably 1.0 W/(m·K) or more. Although the upper limit in particular of the thermal conductivity of a container material is not restrict|limited, 250 W/(m*K) or less is practical, 100 W/(m*K) or less may be sufficient, and 50 W/(m*K) or less may be sufficient.

It is preferable that the container has a light-shielding function so that the deterioration of the composition for protective layer formation by light may be suppressed more effectively. In particular, the container can block ultraviolet light (e.g., light with a wavelength of 290 to 380 nm), visible light (e.g., light with a wavelength of 380 to 750 nm) and infrared light (e.g., light with a wavelength of 750 to 1100 nm). It is preferable to have Here, blocking means that the transmittance|permeability of the light of each wavelength is 50% or less. In particular, with respect to ultraviolet rays, the maximum transmittance is preferably 20% or less, and more preferably 5% or less. With respect to ultraviolet rays, the minimum transmittance in particular is not restrict|limited, It is preferable that it is 0 %, and about 1 % may be sufficient. Moreover, it is preferable that it is 90 % or less, and, as for each maximum transmittance with respect to visible light and infrared rays, it is more preferable that it is 80 % or less. For visible light and infrared light, the minimum transmittance may be 0% or more. The container may be opaque, but in order to facilitate confirmation of the contents, it is preferably transparent, more preferably colored and transparent, and still more preferably brown, blue or green.

The volume in particular of a container is not restrict|limited, For example, it is 10 mL - 50 L. It is preferable that it is 10 L or less from viewpoints, such as handling easiness, and, as for the upper limit of this numerical range, it is more preferable that it is 5 L or less. Moreover, 25 mL or more may be sufficient as the lower limit of this numerical range, and 50 mL or more may be sufficient as it. Generally, 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, the maximum transmittance of ultraviolet rays is 5% or less, and it is preferably a transparent container made of glass or plastic, among them, colored transparent glass made of glass It is more preferable that it is a container.

The filling rate (%) of the container (= the amount of the composition for forming a protective layer filled in the container/volume of the container x 100) is not particularly limited, but is preferably 50 to 98%. It is more preferable that it is 95 % or less, and, as for the upper limit of this numerical range, it is more preferable that it is 93 % or less. Moreover, as for the lower limit of this numerical range, it is more preferable that it is 60 % or more, and it is still more preferable that it is 65 % or more. By setting the filling rate to 98% or less, the space in the container not filled with the composition for forming a protective layer becomes a region where oxygen exceeding the saturated dissolution amount in the composition for forming a protective layer is released, and in the composition for forming a protective layer. Reduction of oxygen concentration is accelerated|stimulated. In addition, by setting the filling rate to 50% or more, it is possible to suppress the mixing of foreign substances and microorganisms in the atmosphere into the composition for forming a protective layer, and the production efficiency is further improved. As a result, the proliferation of microorganisms can be further suppressed, and the convenience at the time of taking out the composition for forming a protective layer from a container and the manufacturing efficiency of the composition for forming a protective layer 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 gas species in the portion of the container interior space that is not filled with the composition for forming a protective layer is not particularly limited, and may be air derived from the atmosphere or an inert gas such as nitrogen. By sealing the container in the atmosphere filled with the 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 the incorporation of microorganisms into the composition for forming a protective layer, it is preferable that the container be sterilized in advance. Sterilization treatment can be performed, for example, by UV ozone treatment or heat treatment of the container. In addition, from the viewpoint of preventing re-adhesion of microorganisms to the container, the sterilization treatment is preferably performed within 48 hours before filling the container with the composition for forming a protective layer, and more preferably within 24 hours.

From the viewpoint of preventing the incorporation of microorganisms into the composition for forming a protective layer, filling the container with the composition for forming a protective layer is preferably carried out within 72 hours after the stirring of the composition for forming a protective layer is completed, and for 48 hours. It is more preferable to carry out within.

<<(c) Low-temperature storage of the composition for forming a protective layer>>

In the manufacturing method of this invention, a refrigerator can be used for formation of a low-temperature environment, for example. 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 less, more preferably 10°C or less, and still more preferably 8°C or less. Moreover, it is preferable that it is 1 degreeC or more, and, as for the lower limit of the said temperature range, it is more preferable that it is 2 degreeC or more, and it is still more preferable that it is 3 degreeC or more. Moreover, you may change suitably the temperature of a low-temperature environment stepwise or continuously within the range of 0-18 degreeC during a storage period. As an aspect of temperature change, for example, from a viewpoint of cooling efficiency, etc., in the initial stage of a storage period, low temperature storage is started at low temperature, The atmosphere of a low temperature environment which raises temperature gradually after that is not restrict|limited in particular, The atmospheric Although the atmosphere (atmosphere temperature-controlled from the air) may be used, or an atmosphere substituted with an inert gas such as nitrogen may be used, it is preferably an atmosphere derived from the air from the viewpoint of convenience.

By setting the length of the period during which the container is exposed to the low-temperature environment (hereinafter, also referred to as "preservation period") to 24 hours or more, it is possible to sufficiently cool the inside of the composition for forming a protective layer. From the viewpoint of further suppressing the growth of microorganisms in the composition for forming a protective layer, the lower limit of the length of the storage period is preferably 1 week or more, more preferably 1 month or more, still more preferably 6 months or more, and 1 year or more. It is particularly preferred. Although the upper limit in particular of the length of a storage period is not restrict|limited, It is practical that it is 2 years or less, It is preferable that it is 1 year and 6 months or less.

In addition, by setting the start time of the storage period to within 72 hours after the end of the stirring, the growth of microorganisms mixed in the composition for forming a protective layer can be suppressed. From the viewpoint of further suppressing the growth of microorganisms, the start time of the storage period is preferably within 60 hours, more preferably within 40 hours, more preferably within 30 hours, and 24 hours after the end of the stirring. It is especially preferable that it is within In addition, it is practical that the start time of a storage period shall be 6 hours or more after completion|finish of the said stirring, and 12 hours or more may be sufficient.

<Composition for forming a protective layer>

The composition for forming a protective layer obtained by the manufacturing method of this invention is demonstrated. The composition for forming a protective layer contains a water-soluble resin and a solvent, and may contain other components as needed.

<<Water-soluble resin>>

A water-soluble resin means resin which melt|dissolves 1g or more with respect to 100g of water in 23 degreeC. And it is preferable that it is resin which melt|dissolves 5 g or more with respect to 100 g of water in 23 degreeC, water-soluble resin is more preferable that it is resin which melt|dissolves 10 g or more, It is more preferable that it is resin which melt|dissolves 30 g or more. Although there is no upper limit in particular of a dissolution amount, it is practical that it is about 100 g.

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

Specific examples of the water-soluble resin include polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), water-soluble polysaccharides (water-soluble cellulose (methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxy ethylmethylcellulose, hydroxypropylmethylcellulose, propylmethylcellulose, etc.), pullulan or pullulan derivatives, starch (hydroxypropyl starch, carboxymethyl starch, etc.), chitosan, cyclodextrin), polyethylene oxide, polyethyloxazoline, Methylolmelamine, polyacrylamide, phenol resin, styrene/maleic acid half ester, etc. are mentioned. Moreover, you may select and use 2 or more types among these, and may use it 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 is preferable to contain at least 1 sort(s) selected from the group which consists of polyvinylpyrrolidone, polyvinyl alcohol, and water-soluble polysaccharide. It is preferable that it is especially cellulose, and, as for a water-soluble polysaccharide, it is more preferable that it is hydroxyethyl cellulose.

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

[Formula 1]

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, and R ^P3 is (CH ₂ CH ₂ O) _ma H, CH ₂ COONa or a hydrogen atom, and ma represents 1 or 2.

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

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

The resin including the repeating unit represented by the formula (P1-1) may further include a repeating unit different from the repeating unit represented by the formula (P1-1). It is preferable that resin containing the repeating unit represented by Formula (P1-1) contains 65 mass % - 90 mass % of the repeating unit represented by Formula (P1-1) with respect to the total mass of resin, and 70 mass % It is more preferable to contain -88 mass %.

As resin containing the repeating unit represented by Formula (P1-1), resin containing two repeating units represented by following formula (P1-2) is mentioned.

[Formula 2]

In the 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 a constituent ratio in a molecule on a mass basis.

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

In formula (P1-2), as R ^P12 , the group represented by -L ^P -T ^P is exemplified. L ^P is a single bond or a linking group L described later. T ^P is a substituent, and the example of the substituent T mentioned later is given. Among them, R ^P12 is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and still more preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). , 2-3 are more preferable), an alkynyl group (C2-C12 is preferable, 2-6 are more preferable, and 2-3 are more preferable), an aryl group (C6-C22 is preferable, 6-18 are more preferable, and 6-10 are more preferable), or a hydrocarbon group, such as an arylalkyl group (C7-C23 is preferable, 7-19 are more preferable, and 7-11 are still more preferable.) desirable. These alkyl group, alkenyl group, alkynyl group, aryl group, and arylalkyl group may further have group prescribed|regulated by the substituent T within the range which shows the effect of this invention.

In formula (P1-2), np1 and np2 represent the constituent ratio in a molecule|numerator on a mass basis, and are each independently 10 mass % or more and less than 100 mass %. However, np1+np2 does not exceed 100 mass % in any case. When np1+np2 is less than 100 mass %, it means that water-soluble resin is a copolymer containing another repeating unit.

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

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

Resin containing the repeating unit represented by Formula (P2-1) may further contain the repeating unit different from the repeating unit represented by Formula (P2-1). It is preferable that resin containing the repeating unit represented by Formula (P2-1) contains 50 mass % - 98 mass % of the repeating unit represented by Formula (P2-1) with respect to the total mass of resin, and 70 mass % It is more preferable to contain -98 mass %.

As resin containing the repeating unit represented by Formula (P2-1), resin containing two repeating units represented by following formula (P2-2) is mentioned.

[Formula 3]

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

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

In formula (P2-2), as R ^P22 , the group represented by -L ^P -T ^P is exemplified. L ^P is a single bond or a linking group L described later. T ^P is a substituent, and the example of the substituent T mentioned later is given. Among them, R ^P22 is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and still more preferably 1 to 3), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). , 2-3 are more preferable), an alkynyl group (C2-C12 is preferable, 2-6 are more preferable, and 2-3 are more preferable), an aryl group (C6-C22 is preferable, 6-18 are more preferable, and 6-10 are more preferable), or a hydrocarbon group, such as an arylalkyl group (C7-C23 is preferable, 7-19 are more preferable, and 7-11 are still more preferable.) desirable. These alkyl group, alkenyl group, alkynyl group, aryl group, and arylalkyl group may further have group prescribed|regulated by the substituent T within the range which shows the effect of this invention.

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

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

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

The resin including the repeating unit represented by the formula (P3-1) may further include a repeating unit different from the repeating unit represented by the formula (P3-1). It is preferable that resin containing the repeating unit represented by Formula (P3-1) contains 10 mass % - 90 mass % of the repeating unit represented by Formula (P3-1) with respect to the total mass of resin, 30 mass % It is more preferable to contain -80 mass %.

Moreover, the hydroxyl group of Formula (P3-1) may be suitably substituted by the group which combined the substituent T or it and the coupling group L. When a plurality of substituents T exist, 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 a repeating unit represented by formula (P4-1)]

The resin including the repeating unit represented by the formula (P4-1) may further include a repeating unit different from the repeating unit represented by the formula (P4-1). It is preferable that resin containing the repeating unit represented by Formula (P4-1) contains 8 mass % - 95 mass % of the repeating unit represented by Formula (P4-1) with respect to the total mass of resin, 20 mass % It is more preferable to contain -88 mass %.

Moreover, the hydroxyl group described in Formula (P4-1) may be suitably substituted by the group which combined the substituent T or it and the coupling group L. When a plurality of substituents T exist, 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.

As substituent T, an alkyl group (C1-C24 is preferable, 1-12 are more preferable, and 1-6 are still more preferable), an arylalkyl group (C7-C21 is preferable, 7-15 are more preferable, 7-11 are more preferable), an alkenyl group (C2-C24 is preferable, 2-12 are more preferable, and 2-6 are still more preferable), an alkynyl group (C2-C12 are preferable, 2 -6 are more preferable, 2-3 are more preferable), a hydroxyl group, an amino group (C0-24 are preferable, 0-12 are more preferable, 0-6 are still more preferable), a thiol group, a carboxy group , aryl group (C6-22 are preferable, 6-18 are more preferable, 6-10 are still more preferable), alkoxyl group (C1-C12 are preferable, 1-6 are more preferable, 1- 3 is more preferable), an aryloxy group (C6-C22 is preferable, 6-18 are more preferable, and 6-10 are still more preferable), an acyl group (C2-C12 are preferable, 2-6 are preferable. This is more preferable, and 2-3 are more preferable), an acyloxy group (C2-C12 is preferable, 2-6 are more preferable, and 2-3 are still more preferable), an aryloyl group (C7-C12 are preferable. 23 are preferable, 7-19 are more preferable, 7-11 are still more preferable), aryloyloxy group (C7-23 are preferable, 7-19 are more preferable, 7-11 are still more preferable. ), a carbamoyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, more preferably 1 to 3), a sulfamoyl group (preferably having 0 to 12 carbon atoms, more preferably 0 to 6 carbon atoms) , 0-3 are more preferable), a sulfo group, an alkylsulfonyl group (C1-C12 is preferable, 1-6 are more preferable, and 1-3 are more preferable), an arylsulfonyl group (C6-C22 is preferable) is preferable, 6-18 are more preferable, 6-10 are more preferable), heteroaryl group (C1-C12 are preferable, 1-8 are more preferable, 2-5 are still more preferable, 5 It is preferable to include a ring or 6-membered ring), (meth)acryloyl group, (meth)acryloyloxy group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), oxo group (=O), imino group (=NR ^N ), alkylidene group (=C(R ^N ) ₂ ), etc. can be heard R ^N is a hydrogen atom or an alkyl group (C1-C12 is preferable, 1-6 are more preferable, and 1-3 are still more preferable), and a hydrogen atom, a methyl group, an ethyl group, or a propyl group is preferable. The alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be linear or cyclic, and may be linear or branched. When the said substituent T is group which can take a substituent, you may have the substituent T further. For example, an alkyl group may become a halogenated alkyl group, and may become 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 linking group L, an alkylene group (C1-C24 is preferable, 1-12 are more preferable, and 1-6 are still more preferable), an alkenylene group (C2-C12 is preferable, 2-6 are more preferable. and 2 to 3 are more preferable), an alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, and still more preferably 2 to 3), an (oligo)alkyleneoxy group (one The number of carbon atoms of the alkylene group in the repeating unit is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 3; the number of repeats is preferably 1 to 50, more preferably 1 to 40, and 1 -30 is more preferable), an arylene group (C6-22 is preferable, 6-18 are more preferable, 6-10 are still more preferable), an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, thioca. and a linking group relating to a bornyl group, —NR ^N —, and combinations thereof. In the present specification, the "(oligo)alkyleneoxy group" means a divalent linking group having one or more "alkyleneoxy" structural units. Carbon number of the alkylene chain in a structural unit may be same or different for every structural unit. The alkylene group may have a substituent T. For example, the alkylene group may have a hydroxyl group. 1-50 are preferable except a hydrogen atom, as for the number of atoms contained in the coupling group L, 1-40 are more preferable, and 1-30 are still more preferable. The number of connecting atoms refers to the number of atoms located in the shortest path among atomic groups involved in the connection. For example, if -CH ₂ -(C=O)-O-, the number of atoms involved in the connection is 6, and 4 is also excluded from the hydrogen atom. On the other hand, the shortest atom involved in the connection is -CCO-, and there are three. As this number of connection atoms, 1-24 are preferable, 1-12 are more preferable, and 1-6 are still more preferable. In addition, the said alkylene group, an alkenylene group, an alkynylene group, and the (oligo)alkyleneoxy group may be linear or cyclic|annular, and may be linear or a branch may be sufficient as them. When a linking group is a group capable of forming a salt such as -NR ^N -, the group may form a salt.

Moreover, as a water-soluble resin, you may use a commercial item, As a commercial item, Daiichi Kogyo Seiyaku Co., Ltd. Fitzcall series (K-30, K-50, K-80, K-90, V-7154, etc.), BASF LUVITEC series (VA64P, VA6535P, etc.) manufactured by the company, PXP-05, JL-05E, JP-03, JP-04 manufactured by Nippon Sakubi Poval Co., Ltd., Nanoclay manufactured by Aldrich, etc. are mentioned.

Among these, it is preferable to use Fitzcall K-90, PXP-05, or Fitzcall V-7154, and it is more preferable to use Fitzcall V-7154.

About the water-soluble resin, the resin of International Publication No. 2016/175220 is cited, and it is integrated in this specification.

The weight average molecular weight of water-soluble resin is suitably selected according to the kind of water-soluble resin. In this specification, let the weight average molecular weight (Mw) and number average molecular weight (Mn) of water-soluble resin be polyetheroxide conversion value by GPC measurement. In particular, when the water-soluble resin is polyvinyl alcohol (PVA), the weight average molecular weight is preferably 10,000 to 100,000. It is preferable that it is 80,000 or less, and, as for the upper limit of this numerical range, it is more preferable that it is 60,000 or less. Moreover, it is preferable that it is 13,000 or more, and, as for the lower limit of this numerical range, it is more preferable that it is 15,000 or more. When water-soluble resin is polyvinylpyrrolidone (PVP), it is preferable that weight average molecular weights are 20,000-2,000,000. It is preferable that it is 1,800,000 or less, and, as for the upper limit of this numerical range, it is more preferable that it is 1,500,000 or less. Moreover, it is preferable that it is 30,000 or more, and, as for the lower limit of this numerical range, it is more preferable that it is 40,000 or more. When water-soluble resin is a water-soluble polysaccharide, it is preferable that weight average molecular weights are 50,000-2,000,000. It is preferable that it is 1,500,000 or less, and, as for the upper limit of this numerical range, it is more preferable that it is 1,300,000 or less. Moreover, it is preferable that it is 70,000 or more, and, as for the lower limit of this numerical range, it is more preferable that it is 90,000 or more.

1.0-5.0 are preferable and, as for the molecular weight dispersion degree (weight average molecular weight/number average molecular weight, also simply "dispersion degree") of water-soluble resin, 2.0-4.0 are more preferable.

Further, in the present invention, the composition for forming a protective layer is a water-soluble resin, which has a high molecular weight material (for example, a water-soluble resin having a weight average molecular weight of 10,000 or more) and a weight average molecular weight smaller than the weight average molecular weight of the high molecular weight material. It is preferable that the weight average molecular weight of a low molecular weight body is half or less of the weight average molecular weight of a high molecular weight body including a low molecular weight body. In this way, the low molecular weight substance is rapidly eluted into the removal solution (especially water), and the high molecular weight substance is also easily removed starting from the portion where the low molecular weight substance was eluted. lose Moreover, when forming a protective layer using the composition for protective layer formation, it can suppress that a crack arises in a 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 is determined by, for example, taking the molecular weight distribution of the composition for forming a protective layer or the water-soluble resin, the peak top (maximum value) of 2 It can be judged based on whether or not more than one can be confirmed.

It is preferable that it is 20,000 or more, and, as for the weight average molecular weight of a high molecular weight body, it is preferable that it is 45,000 or more. Moreover, it is preferable that it is 2,000,000 or less, and, as for the weight average molecular weight of a high molecular weight body, 1,500,000 or less may be sufficient. It is preferable that the molecular weight ratio (= weight average molecular weight of low molecular weight body/weight average molecular weight of high molecular weight body) of the low molecular weight body to a high molecular weight body is 0.4 or less. As for the upper limit of this molecular weight ratio, it is more preferable that it is 0.3 or less, and it is still more preferable that it is 0.2 or less. Moreover, although the lower limit in particular of the said molecular weight ratio is not restrict|limited, It is preferable that it is 0.001 or more, and 0.01 or more may be sufficient.

In addition, in the molecular weight distribution of the entire water-soluble resin used in the present invention, two or more peak tops exist, and among these two or more peak tops, a molecular weight corresponding to one peak top corresponds to another peak top. It is also preferable that it is half or less of the molecular weight to be used. Thereby, the same effect as the case where the weight average molecular weight of a low molecular weight body is half or less of the weight average molecular weight of a high molecular weight body is acquired. The water-soluble resin which has the above molecular weight distribution is obtained by mixing the said high molecular weight substance and the said low molecular weight substance. When a plurality of peaks are identified in the molecular weight distribution, two sets of peak tops are selected from among those peak tops, and with respect to at least one set of peak tops, the molecular weight corresponding to one peak top is the other peak top. It may be less than half of the molecular weight corresponding to .

It is preferable that it is 20,000 or more, and, as for the larger one of the molecular weights (peak top molecular weight) to which the said peak top corresponds, it is preferable that it is 45,000 or more. Moreover, it is preferable that it is 2,000,000 or less, and the one with the larger said peak top molecular weight may be 1,500,000 or less. It is preferable that the molecular weight ratio of the smaller one with respect to the one with the larger peak top molecular weight (= the one with the smaller peak top molecular weight/the one with the larger peak top molecular weight) is 0.4 or less. As for the upper limit of this molecular weight ratio, it is more preferable that it is 0.3 or less, and it is still more preferable that it is 0.2 or less. Moreover, although the lower limit in particular of the said molecular weight ratio is not restrict|limited, It is preferable that it is 0.001 or more, and 0.01 or more may be sufficient.

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

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 a high molecular weight substance. In this case, as for a weight average molecular weight, it is more preferable that it is 30,000 or more, and it is still more preferable that it is 40,000 or more. Moreover, in this invention, it is also preferable that the water-soluble resin contains PVP with a weight average molecular weight of 300,000 or more as a high molecular weight substance. In this case, as for a weight average molecular weight, it is more preferable that it is 400,000 or more, and it is still more preferable that it is 500,000 or more. Further, in the present invention, the water-soluble resin preferably contains a water-soluble polysaccharide having a weight average molecular weight of 300,000 or more as a high molecular weight substance. In this case, as for a weight average molecular weight, it is more preferable that it is 400,000 or more, and it is still more preferable that it is 500,000 or more.

A preferable combination of the high molecular weight substance and the low molecular weight substance is, for example, as follows. Although the water-soluble resin may satisfy only one requirement of the following combinations, the aspect which satisfy|fills the requirements of two or more combinations simultaneously may be sufficient as it.

- Combination of PVA (high molecular weight body) whose weight average molecular weight Mw is 30,000-100,000, and PVA (low molecular weight body) whose Mw is 10,000-40,000.

Combination of PVP (high molecular weight substance) having Mw of 500,000 to 1,500,000 and PVP (low molecular weight substance) having Mw of 30,000 to 600,000.

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

Combination of PVP (high molecular weight body) having Mw of 500,000 to 1,500,000 and PVA (low molecular weight body) having Mw of 10,000 to 100,000.

Combination of water-soluble polysaccharides (high molecular weight substances) having a Mw of 500,000 to 1,500,000 and PVA (low molecular weight substances) having an Mw of 10,000 to 100,000.

Combination of a PVP (high molecular weight substance) having a Mw of 500,000 to 1,500,000 and a water-soluble polysaccharide (a low molecular weight substance) having an Mw of 50,000 to 600,000.

Combination of water-soluble polysaccharides (high molecular weight substances) having a Mw of 500,000 to 1,500,000 and PVP (low molecular weight substances) having an Mw of 30,000 to 600,000.

It is preferable that content of a high molecular weight body is 50 mass % or less with respect to all the water-soluble resins. It is more preferable that it is 40 mass % or less, and, as for the upper limit of this numerical range, it is more preferable that it is 30 mass % or less. Moreover, it is more preferable that it is 5 mass % or more, and, as for the lower limit of this numerical range, it is still more preferable that it is 10 mass % or more.

In addition, the aspect which does not contain a low molecular-weight body substantially may be sufficient as water-soluble resin. In the present invention, "it does not contain a low molecular weight substance substantially" means that content of a low molecular weight substance is 3 mass % or less with respect to all the water-soluble resins. In this aspect, it is preferable that content of a low molecular-weight body is 1 mass % or less with respect to all the water-soluble resins.

The content of the total water-soluble resin in the composition for forming a protective layer is preferably 30 mass % or less, more preferably 25 mass % or less, and still more preferably 20 mass % or less, in solid content, which may be appropriately adjusted as necessary. As a minimum, it is preferable that it is 1 mass % or more, It is more preferable that it is 2 mass % or more, It is more preferable that it is 4 mass % or more.

The composition for forming a protective layer may contain only 1 type of water-soluble resin, and may contain 2 or more types. When 2 or more types of water-soluble resin are contained, it is preferable that those total amounts become the said range.

<<Other Ingredients>>

In the present invention, the composition for forming a protective layer includes, as other components, a resin soluble in a water-soluble solvent (alcohol, etc.) to be described later, a surfactant containing an acetylene group, other surfactants, preservatives, fungicides, light-shielding agents, and; As another solvent, a water-soluble solvent may be included.

[Resin soluble in water-soluble solvent]

Resin soluble in a water-soluble solvent means resin which melt|dissolves 1 g or more with respect to 100 g of water-soluble solvents in 23 degreeC. The water-soluble resin is preferably a resin that dissolves 5 g or more with respect to 100 g of the water-soluble solvent at 23°C, more preferably a resin that dissolves 10 g or more, and still more preferably a resin that dissolves 20 g or more. Although there is no upper limit in particular of a dissolution amount, it is practical that it is about 30 g.

It is preferable that it is alcohol-soluble resin soluble in the alcohol which is a water-soluble solvent, and, as for resin soluble in a water-soluble solvent, it is more preferable that it is polyvinyl acetal.

[Surfactant containing an acetylene group]

When the composition for forming a protective layer contains a surfactant containing an acetylene group, generation of a residue can be further suppressed.

Although the number in particular of the acetylene group in a molecule|numerator in surfactant containing an acetylene group is not restrict|limited, 1-10 are preferable, 1-5 are more preferable, 1-3 are still more preferable, 1-2 are more preferably.

The molecular weight of the surfactant containing an acetylene group is preferably relatively small, preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 1,000 or less. Although there is no particular lower limit, it is preferable that it is 200 or more.

-Compound represented by Formula (9)-

It is preferable that surfactant containing an acetylene group is a compound represented by following formula (9).

[Formula 4]

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. 1-12 are preferable, as for carbon number of an aromatic heteroaryl group, 2-6 are more preferable, 2-4 are still more preferable. The aromatic heterocycle is preferably a 5-membered ring or a 6-membered ring. The hetero atom contained in the aromatic heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom.

R ⁹¹ and R ⁹² each independently may have a substituent, and examples of the substituent include the substituent T described above.

-Compound represented by Formula (91)-

As a compound represented by Formula (9), it is preferable that it is a compound represented by following formula (91).

[Formula 5]

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 that of n9, n10 is an integer of 1 to 6, m10 is an integer twice as large as n10, and 19 and 11 are each independently a number of 0 or more and 12 or less.

Although R ⁹³ to R ⁹⁶ are hydrocarbon groups, among them, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms), 2-6 are more preferable, 2-3 are more preferable), an alkynyl group (C2-C12 are preferable, 2-6 are more preferable, and 2-3 are still more preferable), an aryl group (the number of carbon atoms) 6-22 are preferable, 6-18 are more preferable, 6-10 are more preferable), an arylalkyl group (C7-23 are preferable, 7-19 are more preferable, 7-11 are still more preferable. ) is preferred. An alkyl group, an alkenyl group, and an alkynyl group may be linear or cyclic|annular may be sufficient as them, and linear or branched may be sufficient as them. R ⁹³ to R ⁹⁶ may have a substituent T within the range showing the effects of the present invention. In addition, R ⁹³ to R ⁹⁶ may be bonded to each other or may form a ring through the above-described linking group L. When a plurality of substituents T exist, they may be bonded to each other, or may be bonded to a hydrocarbon group in the formula with or without the following linking group L to form a ring.

It is preferable that R ⁹³ and R ⁹⁴ are an alkyl group (C1-C12 are preferable, 1-6 are more preferable, and 1-3 are more preferable). Among them, a methyl group is preferable.

It is preferable that R ⁹⁵ and R ⁹⁶ are an alkyl group (C1-C12 is preferable, 2-6 are more preferable, and 3-6 are still more preferable). Among them, -(C _n11 R ⁹⁸ _m11 )-R ⁹⁷ is preferable. It is preferable that R ⁹⁵ and R ⁹⁶ are especially isobutyl groups.

n11 is an integer of 1-6, and the integer of 1-3 is preferable. m11 is a number twice n11.

It is preferable that R ⁹⁷ and R ⁹⁸ are each independently a hydrogen atom or an alkyl group (C1-C12 are preferable, 1-6 are more preferable, and it is preferable that 1-3 are still more preferable).

n9 is an integer of 1-6, and the integer of 1-3 is preferable. m9 is an integer twice n9.

n10 is an integer of 1-6, and the integer of 1-3 is preferable. m10 is an integer twice n10.

19 and 11 are each independently a number of 0-12. However, as for l9+l10, it is preferable that it is the number of 0-12, It is more preferable that it is the number of 0-8, The number of 0-6 is still more preferable, The number of more than 0 and less than 6 is still more preferable, The number of more than 0 and 3 or less It is even more preferable. In addition, with respect to l9 and l10, the compound of formula (91) may be a mixture of compounds different in the number, in that case, the number of l9 and l10, or l9+l10, is an award including a decimal point. do.

-Compound represented by Formula (92)-

It is preferable that the compound represented by Formula (91) is a compound represented by following formula (92).

[Formula 6]

R ⁹³ , R ⁹⁴ , and R ⁹⁷ to R ¹⁰⁰ are each independently a hydrocarbon group having 1 to 24 carbon atoms, and 11 and 11 are each independently a number of 0 or more and 12 or less.

Among them, R ⁹³ , R ⁹⁴ , R ⁹⁷ to R ¹⁰⁰ are an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms). , 2-6 are more preferable, 2-3 are more preferable), an alkynyl group (C2-12 are preferable, 2-6 are more preferable, and 2-3 are more preferable), an aryl group ( C6-C22 is preferable, 6-18 are more preferable, 6-10 are still more preferable), an arylalkyl group (C7-C23 is preferable, 7-19 are more preferable, 7-11 are still more preferable. ) is preferable. The alkyl group, the alkenyl group, and the alkynyl group may be linear or cyclic, and may be linear or branched. R ⁹³ , R ⁹⁴ , and R ⁹⁷ to R ¹⁰⁰ may have a substituent T within the range showing the effect of the present invention. Further, R ⁹³ , R ⁹⁴ , and R ⁹⁷ to R ¹⁰⁰ may be bonded to each other or may form a ring through a linking group L. When a plurality of substituents T exist, 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 to form a ring.

It is preferable that R ⁹³ , R ⁹⁴ , and R ⁹⁷ -R ¹⁰⁰ are each independently an alkyl group (C1-C12 is preferable, 1-6 are more preferable, and 1-3 are still more preferable). Among them, a methyl group is preferable.

l11+l12 is preferably a number from 0 to 12, more preferably a number from 0 to 8, more preferably a number from 0 to 6, still more preferably a number from more than 0 to less than 6, and still more from a number from more than 0 to 5 and less. Preferably, the number of more than 0 and 4 or less is still more preferable, and the number of more than 0 and 3 or less may be awarded, and the number of more than 0 and 1 or less may be awarded. In addition, 11 and 112 may be a mixture of compounds in which the compound of Formula (92) differs in the number, and in that case, the number of 111 and 112 or 11+112 may be a number including a decimal point. .

Examples of the surfactant containing an acetylene group include Surfynol 104 series (trade name, Nisshin Chemical Industry Co., Ltd.), Acetyrenol E00, Copper E40, Copper E13T, Copper 60 (all trade names, manufactured by Kawaken Fine Chemicals) Among them, surfinol 104 series, acetylenol E00, copper E40, and copper E13T are preferable, and acetylenol E40 and copper E13T are more preferable. In addition, Surfinol 104 series and acetylenol E00 are surfactants with the same structure.

[Other Surfactants]

The composition for forming a protective layer may contain other surfactants other than the surfactant containing an acetylene group for the purpose of improving the applicability.

As another surfactant, any type, such as a nonionic type, an anionic type, an amphoteric fluorine type, may be sufficient as long as it reduces surface tension.

As another surfactant, For example, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octylphenyl ether, polyoxy Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, and sorbitan monool Ratio of oligomers containing fluorine or silicon, such as sorbitan alkyl esters such as ate, sorbitan sesquioleate, and sorbitan trioleate, and monoglyceride alkyl esters such as glycerol monostearate and glycerol monooleate ionic surfactants; Alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, sodium pentylnaphthalenesulfonate, sodium hexylnaphthalenesulfonate, and sodium octylnaphthalenesulfonate, sodium lauryl sulfate, etc. Anionic surfactants, such as alkylsulfonates, such as alkyl sulfates, sodium dodecylsulfonate, and sulfosuccinic acid ester salts, such as sodium dilaurylsulfosuccinate; Amphoteric surfactants, such as alkyl betaines, such as lauryl betaine and stearyl betaine, and amino acids, can be used.

When the composition for forming a protective layer contains a surfactant containing an acetylene group and another surfactant, the amount of the surfactant added in the total amount of the surfactant containing an acetylene group and the other surfactant is the amount of the composition for forming a protective layer. To the total mass, Preferably it is 0.05-20 mass %, More preferably, it is 0.07-15 mass %, More preferably, it is 0.1-10 mass %. One type may be used for these surfactant, and several things may be used for it. When using a plurality of things, their total amount falls within the above range.

Moreover, in this invention, it can also be set as the structure which does not contain another surfactant substantially. Substantially not included means that the content of the other surfactant is 5 mass% or less of the content of the surfactant containing an acetylene group, preferably 3 mass% or less, and more preferably 1 mass% or less.

In the composition for forming a protective layer, the content of the other surfactant is preferably 0.05 mass % or more, more preferably 0.07 mass % or more, still more preferably 0.1 mass % or more with respect to the total mass of the protective layer. Moreover, an upper limit becomes like this. Preferably it is 20 mass % or less, More preferably, it is 15 mass % or less, More preferably, it is 10 mass % or less. As another surfactant, 1 type may be used and several things may be used for it. When using plural things, it is preferable that those total amounts become said range.

It is preferable that the surface tension of the 0.1 mass % aqueous solution in 23 degreeC of other surfactant is 45 mN/m or less, It is more preferable that it is 40 mN/m or less, It is still more preferable that it is 35 mN/m or less. As a lower limit, it is preferable that it is 5 mN/m or more, It is more preferable that it is 10 mN/m or more, It is more preferable that it is 15 mN/m or more. What is necessary is just to select the surface tension of surfactant suitably according to the kind of other surfactant selected.

[Preservatives and fungicides]

When the composition for forming a protective layer contains a preservative and an antifungal agent, the quality of the composition for forming a protective layer can be maintained for a longer period of time.

As the preservative and antifungal agent, it is preferable to include at least one selected from water-soluble or water-dispersible organic compounds as an additive having an antibacterial or antifungal action. Examples of such additives include organic antiseptics and fungicides, inorganic antiseptics and fungicides, and natural antiseptics and fungicides. For example, as an antiseptic and mold inhibitor, those described in "Antibacterial and antifungal technology" published by Toray Research Center can be used.

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

Preservatives and fungicides include phenol ether compounds, imidazole compounds, sulfone compounds, N haloalkylthio compounds, anilide compounds, pyrrole compounds, quaternary ammonium salts, arsine compounds, pyridine compounds, A triazine type compound, a benzisothiazoline type compound, an isothiazoline type compound, etc. are mentioned. Specifically, for example, methyl isothiazolinone, 2(4-thiocyanomethyl)benzimidazole, 1,2-benzothiazolone, 1,2-benzisothiazolin-3-one, N-Fluorodichloromethylthio-phthalimide, 2,3,5,6-tetrachloroisophthalonitrile, N-trichloromethylthio-4-cyclohexene-1,2-dicarboxyimide , 8-quinoline copper, bis (tributyl tin) oxide, 2- (4-thiazolyl) benzimidazole, 2-benzimidazole carbamate methyl, 10,10'-oxybisphenoxyarcin, 2 ,3,5,6-tetrachloro-4-(methylsulfone)pyridine, bis(2-pyridylthio-1-oxide) zinc, N,N-dimethyl-N'-(fluorodichloromethylthi Oh) -N'-phenylsulfamide, poly-(hexamethylenebiguanide) hydrochloride, dithio-2-2'-bis, 2-methyl-4,5-trimethylene-4-isothiazoline -3-one, 2- (dichloro-fluoromethyl) sulfanylisoindole-1,3-dione, 2-bromo-2-nitropropane-1,3-diol, methylsulfonyltetra Chloropyridine, hexahydro-1,3-tris-(2-hydroxyethyl)-S-triazine, p-chloro-m-xyleneol, 1,2-benzisothiazolin-3-one, methylphenol , sodium dioxide, diiodomethylparatolylsulfone, and the like.

In the present invention, it is preferable that the composition for forming a protective layer contains a fungicide from the viewpoint of suppressing the occurrence of mold in the composition for forming a protective layer. In particular, the fungicide is, among the compounds described above, isothiazolinone compounds, 2-bromo-2-nitropropane-1,3-diol, methylsulfonyltetrachloropyridine, 2-(dichloro- It is preferable to include at least one of fluoromethyl)sulfanylisoindole-1,3-dione, sodium diacetate, and diiodomethylparatolylsulfone, and it is more preferable to include an isothiazoline-based compound. And, it is more preferable to include methyl isothiazolinone.

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

The content of the antiseptic agent and the antifungal agent in the composition for forming a protective layer is preferably 0.005 to 5 mass%, more preferably 0.01 to 3 mass%, and 0.05 to about the total mass of the composition for forming a protective layer. It is more preferable that it is 2 mass %, and it is still more preferable that it is 0.1-1 mass %. As an antiseptic|preservative and a fungicide, 1 type may be used and several things may be used. When using plural things, it is preferable that those total amounts become said range.

[Light-shielding agent]

The composition for forming a protective layer preferably contains a light-shielding agent. By mix|blending a light-shielding agent, the influence, such as damage by light to an organic layer etc., is suppressed more.

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

To [ content of the light-shielding agent / total mass of the composition for protective layer formation ], Preferably it is 1-50 mass %, More preferably, it is 3-40 mass %, More preferably, it is 5-25 mass %. As a light-shielding agent, 1 type may be used and several things may be used. When using plural things, it is preferable that those total amounts become said range.

〔solvent〕

It is preferable that the solvent used for the composition for protective layer formation contains water. Moreover, a solvent can contain a water-soluble solvent as another solvent other than water. Further, the composition for forming a protective layer may be in an embodiment in which a water-soluble solvent is not included (that is, the solvent in the composition for forming a protective layer is only water).

It is preferable that the water-soluble solvent added to the composition for protective layer formation is an organic solvent whose solubility with respect to water in 23 degreeC is 1 g or more. As for the solubility with respect to the water in 23 degreeC of an organic solvent, 10 g or more are more preferable, and 30 g or more are still more preferable.

As such a water-soluble solvent, For example, alcohol solvents, such as methanol, ethanol, a propanol, ethylene glycol, glycerol; ketone solvents such as acetone; Amide solvents, such as formamide, etc. are mentioned.

<Laminate>

The composition for forming a protective layer obtained by the production method of the present invention is used for forming a laminate including a base material, an organic layer, a protective layer, and a photosensitive layer in this order as described above. And the laminated body can be used for patterning of the organic layer contained in a laminated body.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows typically the processing process of a laminated body. With respect to the laminate, an organic layer 3 (eg, an organic semiconductor layer) is disposed on the substrate 4 as in the example shown in FIG. 1A . Moreover, the protective layer 2 which protects the organic layer 3 is arrange|positioned on the surface in the form in contact. Although another layer may be provided between the organic layer 3 and the protective layer 2, it is preferable that the organic layer 3 and the protective layer 2 are in direct contact from a viewpoint of protecting an organic layer appropriately. Moreover, the photosensitive layer 1 is arrange|positioned on this protective layer. The photosensitive layer 1 and the protective layer 2 may be in direct contact with each other, and another layer may be provided between the photosensitive layer 1 and the protective layer 2 .

An example of the state in which a part of the photosensitive layer 1 was exposed and developed is shown in FIG.1(b). For example, by partially exposing the photosensitive layer 1 to light by a method such as using a predetermined mask, etc., and developing using a developer such as an organic solvent after exposure, the photosensitive layer ( 1) is removed, and the photosensitive layer 1a after exposure development is formed. At this time, the protective layer 2 remains because it is difficult to remove by the developer, and the organic layer 3 is protected from damage by the developer by the remaining protective layer 2 .

An example of the state in which the protective layer 2 and the organic layer 3 were partially removed is shown in FIG.1(c). For example, by removing the protective layer 2 and the organic layer 3 in the removal portion 5 without the photosensitive layer (resist) 1a after development by dry etching treatment or the like, the protective layer 2 and A removal portion 5a is formed in the organic layer 3 . In this way, the organic layer 3 can be removed in the removal part 5a. That is, the organic layer 3 can be patterned.

Fig. 1D shows an example of a state in which the photosensitive layer 1a and the protective layer 2 are removed after the patterning. For example, the organic layer 3a after processing by washing the photosensitive layer 1a and the protective layer 2 in the laminate of the state shown in FIG. 1C with a stripper containing water, for example. ) on the photosensitive layer 1a and the protective layer 2 are removed.

As described above, a desired pattern is formed on the organic layer 3 using a laminate including a substrate, an organic layer, a protective layer, and a photosensitive layer in this order, and the photosensitive layer 1 serving as a resist, and the organic layer 3 ), the protective layer 2 serving as the protective film can be removed. The details of these steps will be described later.

<<Report>>

As the substrate used for the laminate, for example, a substrate formed of various materials such as a polyester film such as silicon, quartz, ceramic, glass, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), and a polyimide film , and any substrate may be selected according to the use. For example, when using for a flexible element, the base material formed with the flexible material can be used. Further, the substrate may be a composite substrate formed of a plurality of materials or a laminate substrate in which a plurality of materials are laminated. Moreover, the shape of a base material is also not specifically limited, What is necessary is just to select according to a use, For example, a plate-shaped base material (it is also referred to as "substrate" hereafter) is mentioned. It does not specifically limit also about the thickness of a board|substrate, etc.

<<Organic Layer>>

The organic layer is a layer containing an organic material. A specific organic material is suitably selected according to the use and function of an organic layer. Examples of the functions assumed for the organic layer include semiconductor properties, light emission properties, photoelectric conversion properties, light absorption properties, electrical insulation properties, ferroelectric properties, transparency, and insulation properties. In the laminate, the organic layer may be included above the substrate, the substrate and the organic layer may be in contact, and another layer may be further included between the organic layer and the substrate.

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

Hereinafter, in particular, 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 the organic material which shows the characteristic of a semiconductor.

An organic semiconductor layer is an organic layer containing an organic semiconductor, and an organic semiconductor is an organic compound which shows the characteristic of a semiconductor. Similar to the case of semiconductors made of inorganic compounds, organic semiconductors include p-type semiconductors that conduct with holes (holes) as carriers and n-type semiconductors that conduct with electrons as carriers. The ease of flow of carriers in the organic semiconductor layer is indicated by the carrier mobility μ. Although it varies depending on the application, in general, the carrier mobility is preferably high, preferably 10 ^-7 cm ² /Vs or more, more preferably 10 ^-6 cm ² /Vs or more, and 10 ^-5 cm ² /Vs or more. it is more preferable Carrier mobility can be calculated|required based on the characteristic at the time of producing a field effect transistor (FET) element, and the measured value of the time-of-flight measurement (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 transport property. The p-type organic semiconductor is preferably any one of a p-type ?-conjugated polymer, a condensed polycyclic compound, a triarylamine compound, a hetero 5-membered ring compound, a phthalocyanine compound, a porphyrin compound, a 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 hetero 5-membered ring compound, a phthalocyanine compound, and a porphyrin compound, more preferably , at least one of a p-type π-conjugated polymer and a condensed polycyclic compound.

The p-type π-conjugated polymer is, for example, a substituted or unsubstituted polythiophene (for example, poly(3-hexylthiophene) (P3HT, manufactured by Sigma-Aldrich Japan Co., Ltd.), etc.), polyselenophene, polypyrrole, polyparaphenylene, polyparaphenylenevinylene, polythiophenevinylene, polyaniline, and the like. The condensed polycyclic compound is, for example, a substituted or unsubstituted anthracene, tetracene, pentacene, anthradithiophene, hexabenzocoronene or the like.

The triarylamine compound is, 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.

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

The phthalocyanine compound is a substituted or unsubstituted phthalocyanine, naphthalocyanine, anthracyanine, tetrapyrazinopopyrazine, etc. which have various central metals. The porphyrin compound is a substituted or unsubstituted porphyrin having various central metals. Further, the carbon nanotube may be a carbon nanotube in which a semiconductor polymer is modified on the surface.

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 transport 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) phosphorus compound), polythiophene-based compound, benzidine-based compound, carbazole-based compound, phenanthroline-based compound, pyridinephenyl ligand iridium-based compound, quinolinol ligand aluminum-based compound, n-type π-conjugated polymer, 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, particularly preferably a fullerene compound, a condensed polycyclic compound and at least one of n-type π-conjugated polymers.

The 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 Any one of fullerenes represented by ₁₁₆ , C ₁₈₀ , C ₂₄₀ , C ₅₄₀ and the like may be sufficient. The fullerene compound is preferably a substituted or unsubstituted C ₆₀ , C ₇₀ , C ₈₆ fullerene, particularly preferably PCBM ([6,6]-phenyl-C61-butyric acid methyl ester, Sigma-Aldrich Japan Joint Association manufactured by the company, etc.) and analogs thereof (for example, those in which the C ₆₀ moiety is substituted with C ₇₀ , C ₈₆ , etc., the benzene ring of the substituent is substituted with another aromatic ring or a hetero ring, methyl ester is substituted with n-butyl ester, i-butyl ester, etc.).

The electron-deficient phthalocyanine compound refers to a substituted or unsubstituted phthalocyanine, naphthalocyanine, anthracyanine, tetrapyrazinopopyrazine, etc. having four or more electron withdrawing groups bonded thereto and having various central metals. to be. The electron-deficient phthalocyanine compound is, for example, a fluorinated phthalocyanine (F ₁₆ MPc), a chlorinated phthalocyanine (Cl ₁₆ MPc), or the like. Here, M represents the central metal and Pc represents phthalocyanine.

The naphthalenetetracarbonyl compound may be any, but preferably naphthalenetetracarboxylic anhydride (NTCDA), naphthalenebisimide compound (NTCDI), and perinone pigments (Pigment Orange 43, Pigment Red 194, etc.).

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

The TCNQ compound is a compound in which substituted or unsubstituted TCNQ and the benzene ring portion of TCNQ are substituted with other aromatic rings or heterocycles. TCNQ compounds are, 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).

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

A benzidine-type compound is a compound which has a benzidine structure in a molecule|numerator. The benzidine-based compound is, 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-type compound is a compound which has a carbazole ring structure in a molecule|numerator. The carbazole-based compound is, for example, 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP) or the like.

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

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

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

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

[Formula 7]

[Formula 8]

The number of organic semiconductors contained in an organic-semiconductor layer may be one, and 2 or more types may be sufficient as them. The organic semiconductor layer may be a lamination or mixed layer of a p-type layer and an n-type layer.

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

On the other hand, in the case of a liquid phase method, an organic material is mix|blended in a solvent normally, and turns into a composition (composition for organic layer formation) which forms an organic layer. Then, the composition is supplied on the substrate and dried to form an organic layer. As a supply method, application|coating is preferable. Examples of the application method include a slit coating method, a casting method, a blade coating method, a wire bar coating method, a spray coating method, a dipping (dipping) coating method, a bead coating method, an air knife coating method, a curtain coating method, an inkjet method, a spin coating method method, the Langmuir-Blodgett (LB) method, the edge casting method (for details, Japanese Patent Application Laid-Open No. 6179930), etc. are mentioned. It is more preferable to use the casting method, the spin coating method, and the inkjet method. By such a process, it becomes possible to produce the organic layer of a large area with a smooth surface at low cost.

Moreover, as a solvent used for the composition for organic layer formation, an organic solvent is preferable. Examples of the organic solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, and 1,2-dichlorobenzene; For example, Ketone solvents, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; For example, halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene and chlorotoluene; For example, Ester solvents, such as ethyl acetate, a butyl acetate, and an amyl acetate; For example, alcohol solvents, such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol; For example, Ether solvents, such as dibutyl ether, tetrahydrofuran, dioxane, anisole; For example, polarity of N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, dimethyl sulfoxide, etc. A solvent etc. are mentioned. These solvents may use only 1 type, and may use 2 or more types. Preferably the ratio of the organic material in the composition for organic layer formation is 1-95 mass %, More preferably, it is 5-90 mass %, Thereby, the film|membrane of arbitrary thickness can be formed.

Moreover, you may mix|blend a resin binder with the composition for organic layer formation. In this case, the film-forming material and the binder resin are dissolved or dispersed in the above-mentioned suitable solvent to obtain a coating solution, and a thin film can be formed by various coating methods. Examples of the resin binder include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, polypropylene Insulating polymers, such as these, and these copolymers, photoconductive polymers, such as polyvinylcarbazole and polysilane, conductive polymers, such as polythiophene, polypyrrole, polyaniline, polyparaphenylene vinylene, etc. are mentioned. A resin binder may be used independently and may use two or more together. In consideration of the mechanical strength of the thin film, a resin binder having a high glass transition temperature is preferable, and in consideration of charge mobility, a resin binder made of a photoconductive polymer or a conductive polymer having a structure not including a polar group is preferable.

When mix|blending a resin binder, the compounding quantity is in an organic layer, Preferably it is used in 0.1-30 mass %. Only 1 type may be used for a resin binder, and 2 or more types may be used for it. When using 2 or more types of resin binders, it is preferable that those total amounts become the said range.

The organic layer may be a blend film composed of a plurality of material types, either individually or in a mixed solution to which various organic materials or additives are added, depending on the application. For example, when producing the photoelectric conversion layer, it is possible to use a mixed solution using a plurality of types of semiconductor materials.

Further, during film formation, the substrate may be heated or cooled, and by changing the temperature of the substrate, it is possible to control the film quality and the packing of molecules in the film. Although there is no restriction|limiting in particular as temperature of a base material, Preferably it is -200 degreeC - 400 degreeC, More preferably, it is -100 degreeC - 300 degreeC, More preferably, it is 0 degreeC - 200 degreeC.

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

<<Protective Layer>>

A protective layer is a layer formed with the composition for protective layer formation. A protective layer can be formed by applying the composition for protective layer formation on an organic layer, and drying, for example.

As an application method of the composition for forming a protective layer, application|coating is preferable. Examples of the application method include a slit coating method, a casting method, a blade coating method, a wire bar coating method, a spray coating method, a dipping (dipping) coating method, a bead coating method, an air knife coating method, a curtain coating method, an inkjet method, a spin coating method method, and the Langmuir-Blodgett (LB) method. It is more preferable to use the casting method, the spin coating method, and the inkjet method. By such a process, it becomes possible to produce a protective layer with a smooth surface and a large area at low cost.

When drying the coating film of the composition for protective layer formation, it is preferable to heat a base material. Heating temperature is suitably selected from the range of 50-200 degreeC, for example.

In addition, the composition for forming a protective layer is formed by a method of transferring a coating film formed in advance on a provisional support by the above application method or the like, onto an application target (eg, an organic layer). You may. Regarding the transcription|transfer method, description of Paragraphs 0023, 0036-0051 of Unexamined-Japanese-Patent No. 2006-023696, Paragraph 0096-0108 of Unexamined-Japanese-Patent No. 2006-047592, etc. can be referred.

It is preferable that it is 0.1 micrometer or more, and, as for the thickness of a protective layer, it is more preferable that it is 0.5 micrometer or more, It is more preferable that it is 1.0 micrometer or more, and its 2.0 micrometers or more are still more preferable. As an upper limit of the thickness of a protective layer, 10 micrometers or less are preferable, 5.0 micrometers or less are more preferable, and 3.0 micrometers or less are still more preferable.

It is preferable that it is a layer whose dissolution amount with respect to a developing solution is 10 nm/s or less in 23 degreeC, and, as for a protective layer, it is more preferable that it is a layer of 1 nm/sg/L or less. The lower limit of the amount of dissolution is not particularly limited, and may be 0 nm/s or more.

The protective layer is provided for removal using a stripper. A method of removing the protective layer using a stripper will be described later.

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

It is preferable that it is 90-100 mass %, and, as for content of water with respect to the total mass of the said peeling liquid, it is preferable that it is 95-100 mass %. Moreover, the peeling liquid which consists only of water may be sufficient as the said peeling liquid.

Moreover, in order to improve the removability of a protective layer, the peeling liquid may contain surfactant. Although a well-known compound can be used as surfactant, A nonionic surfactant is mentioned preferably.

<<Photosensitive layer>>

The photosensitive layer is a layer provided for development using a developer. It is preferable that the said development is negative type development. As a photosensitive layer, a well-known photosensitive layer (for example, a photoresist layer) used in this technical field can be used suitably. The laminate WHEREIN: A negative photosensitive layer may be sufficient as a photosensitive layer, and a positive photosensitive layer may be sufficient as it.

It is preferable that the photosensitive layer is poorly soluble with respect to the developing solution in which the exposure part contains the organic solvent. A poorly soluble means that an exposed part is hard to melt|dissolve in a developing solution. It is preferable that the dissolution rate of the photosensitive layer with respect to the developing solution in an exposed part becomes smaller (it becomes difficult to soluble) than the dissolution rate with respect to the developing solution of the photosensitive layer in an unexposed part. Specifically, the polarity changes by exposing light of at least one wavelength among wavelength 365 nm (i-line), wavelength 248 nm (KrF line), and wavelength 193 nm (ArF line) with an irradiation dose of 50 mJ/cm ² or more, so that the sp value (solubility) parameter) is preferably poorly soluble to a solvent of less than 19.0 (MPa) ^1/2 , more preferably poorly soluble to a solvent of 18.5 (MPa) ^1/2 or less, and 18.0 (MPa) ^1/2 or less It is more preferable that it becomes poorly soluble with respect to a solvent.

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

In addition, by exposing light of at least one wavelength of wavelength 365 nm (i-line), wavelength 248 nm (KrF line), and wavelength 193 nm (ArF line) with an irradiation dose of 50 to 250 mJ/cm ² , the polarity changes as described above more preferably.

It is preferable that the photosensitive layer has photosensitivity with respect to irradiation of i line|wire. Photosensitivity means that the rate of dissolution in an organic solvent (preferably butyl acetate) changes with irradiation of at least one of actinic ray and radiation (irradiation of i-ray when photosensitive to i-ray irradiation) say that

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").

It is preferable that the change of the dissolution rate in specific resin for photosensitive layers is a fall of a dissolution rate.

As for the dissolution rate of specific resin for photosensitive layers with respect to the organic solvent whose sp value is 18.0 (MPa) ^1/2 or less before the dissolution rate changes, it is more preferable that it is 40 nm/sec or more.

As for the dissolution rate with respect to the organic solvent whose sp value is 18.0 (MPa) ^1/2 or less after the dissolution rate of specific resin for photosensitive layers changes, it is more preferable that it 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 after the dissolution rate changes, the sp value is 18.0 (MPa) It is preferable that it is resin which is hardly soluble in the organic solvent of ^1/2 or less.

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

As a photosensitive layer, the photosensitive layer etc. containing the photosensitive layer containing specific resin for photosensitive layers, and a photo-acid generator, a polymeric compound, a photoinitiator, etc. are mentioned, for example.

Moreover, it is preferable that a photosensitive layer is a chemically amplified photosensitive layer from a viewpoint of making high storage stability and fine pattern formation compatible.

Hereinafter, the example of the photosensitive layer containing the specific resin for photosensitive layers and a photo-acid generator is demonstrated.

[Specific resin for photosensitive layer]

It is preferable that specific resin for photosensitive layers is an acrylic polymer.

"Acrylic polymer" is an addition polymerization type resin, is a polymer containing repeating units derived from (meth)acrylic acid or an ester thereof, and repeating units other than repeating units derived from (meth)acrylic acid or an ester thereof, e.g. For example, the repeating unit derived from styrene, the repeating unit derived from a vinyl compound, etc. may be included. The acrylic polymer preferably contains 50 mol% or more, more preferably 80 mol% or more, of repeating units derived from (meth)acrylic acid or an ester thereof, with respect to all repeating units in the polymer, ( It is especially preferable that it is a polymer which consists only of repeating units derived from meth)acrylic acid or its ester.

As the specific resin for the photosensitive layer, a resin having a repeating unit having a structure in which an acid group is protected by an acid-decomposable group is preferably mentioned. Examples of the structure in which the acid group is protected by the acid-decomposable group include a structure in which a carboxy group is protected by an acid-decomposable group, a structure in which a phenolic hydroxyl group is protected by an acid-decomposable group, and the like.

Further, examples of the repeating unit having a structure in which an acid group is protected by an acid-decomposable group include 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-hydroxystyrene; and a repeating unit having a structure in which the phenolic hydroxyl group in a monomer unit derived from hydroxystyrene such as α-methyl-p-hydroxystyrene is protected by an acid-decomposable group.

Examples of the repeating unit having a structure in which an acid group is protected by an acid-decomposable group include a repeating unit having an acetal structure, and a repeating unit having a cyclic etherester structure in its side chain is preferable. As the cyclic ether ester structure, the oxygen atom in the cyclic ether structure and the oxygen atom in the ester bond are preferably bonded to the same carbon atom to form an acetal structure.

Moreover, as a repeating unit which has a structure in which an acidic radical is protected by the acid-decomposable group, the repeating unit represented by following formula (1) is preferable.

Hereinafter, "repeating unit represented by Formula (1)" etc. is also called "repeating unit (1)" or the like.

[Formula 9]

In formula (1), ^R8 represents a hydrogen atom or an alkyl group (C1-C12 is preferable, 1-6 are more preferable, and 1-3 are more preferable), L< ¹ > represents a carbonyl group or a phenylene group. and R ¹ to R ⁷ each independently represent a hydrogen atom or an alkyl group.

In formula (1), it is preferable that it is a hydrogen atom or a methyl group, and, as for R< ⁸ >, it is more preferable that it is a methyl group.

In Formula (1), L ¹ represents a carbonyl group or a phenylene group, and is preferably a carbonyl group.

^In Formula ( ¹ ), R1-R7 each independently represents a hydrogen atom or an alkyl group. ^The alkyl group in ^R1 -R7 has the same meaning as ^R8 , and a preferable aspect is also the same. Moreover, ^it is preferable that one or more of ^R1 -R7 is a hydrogen atom, and ^it is more preferable that all of ^R1 -R7 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.

[Formula 10]

A commercially available thing may be used for the radically polymerizable monomer used in order to form the repeating unit (1), and what was synthesize|combined by a well-known method can also be used. For example, it can be synthesized by reacting (meth)acrylic acid with a dihydrofuran compound in the presence of an acid catalyst. Alternatively, after polymerization with a precursor monomer, it can also be formed by reacting a carboxy group or a phenolic hydroxyl group with a dihydrofuran compound.

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

[Formula 11]

In the formula (2), A represents a hydrogen atom or a group detached by the action of an acid. Examples of the group detached by the action of an acid include an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms), an alkoxyalkyl group (preferably 2 to 12 carbon atoms, 2 to 6 is more preferable, and 2-3 are more preferable), an aryloxyalkyl group (7-40 carbon atoms in total are preferable, 7-30 are more preferable, and 7-20 are still more preferable), an alkoxycarbonyl group (the number of carbon atoms) 2-12 are preferable, 2-6 are more preferable, 2-3 are more preferable), aryloxycarbonyl group (C7-23 are preferable, 7-19 are more preferable, 7-11 are more preferred) is preferred. A may further have a substituent, and the example of the said substituent T is mentioned as a substituent.

In formula (2), R ¹⁰ represents a substituent, and examples of the substituent T are given. R ⁹ represents a group having the same meaning as R ⁸ in Formula (1).

In Formula (2), nx represents the integer of 0-3.

As the group that is released by the action of an acid, a repeating unit containing a group that is released by an acid among the compounds described in Paragraph Nos. 0039 to 0049 of JP 2008-197480 A is also preferable. The compounds described in Paragraph Nos. 0052 to 0056 of 159830 (Japanese Patent Publication No. 5191567) are also preferable, the contents of which are incorporated herein by reference.

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

[Formula 12]

[Formula 13]

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

Specific resin for photosensitive layers may contain the repeating unit containing a crosslinkable group. For the detail of a crosslinkable group, Paragraph No. 0032 of Unexamined-Japanese-Patent No. 2011-209692 - description of 0046 can be considered into consideration, and these content is integrated in this specification.

Although it is also preferable that the specific resin for photosensitive layers contains a repeating unit (repeating unit (3)) containing a crosslinkable group, it is preferable to set it as the structure which does not contain the repeating unit (3) containing a crosslinkable group substantially. . By setting it as such a structure, it becomes possible to remove a photosensitive layer more effectively after patterning. Here, "not substantially included" means 3 mol% or less of all the repeating units of the specific resin for photosensitive layers, for example, Preferably it says 1 mol% or less.

Specific resin for photosensitive layers may contain another repeating unit (repeating unit (4)). As a radically polymerizable monomer used in order to form the repeating unit (4), the compound of Paragraph Nos. 0021 - 0024 of Unexamined-Japanese-Patent No. 2004-264623 is mentioned, for example. 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. Among these, benzyl (meth)acrylate, (meth)acrylic acid tricyclo[5.2.1.0 ^2,6 ]decan-8-yl, (meth)acrylic acid tricyclo[5.2.1.0 ^2,6 ]decan-8-yloxy (meth)acrylic acid esters containing an alicyclic structure such as ethyl, (meth)acrylic acid isobornyl, (meth)acrylic acid cyclohexyl, (meth)acrylic acid 2-methylcyclohexyl, or hydrophobic monomers such as styrene are preferable do.

The repeating unit (4) can be used 1 type or in combination of 2 or more types. Among all the monomer units constituting the specific resin for photosensitive layer, the content rate of the monomer unit forming the repeating unit (4) in the case of containing the repeating unit (4) is preferably 1 to 60 mol%, and 5 to 50 mol%. mol% is more preferable, and 5-40 mol% is still more preferable. When two or more types of the said repeating unit are contained, it is preferable that their total amount becomes the said range.

Various methods are known about the method of synthesizing the specific resin for the photosensitive layer, but for example, a radically polymerizable monomer mixture containing at least a radically polymerizable monomer used to form the repeating unit (1), the repeating unit (2), etc. , it can synthesize|combine by superposing|polymerizing using a radical polymerization initiator in an organic solvent.

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 unsaturated polyhydric carboxylic acid anhydrides, in the absence of an acid catalyst, at room temperature (25°C) to 100°C. The copolymer obtained is also preferable.

The following resin is also mentioned as a preferable example of specific resin for photosensitive layers.

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

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

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

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

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

Moreover, as specific resin for photosensitive layers used for positive image development, the thing of Unexamined-Japanese-Patent No. 2013-011678 is illustrated, and these content is integrated in this specification.

From the viewpoint of improving the pattern formability at the time of development, the content of the specific resin for the photosensitive layer is preferably 20 to 99 mass%, more preferably 40 to 99 mass%, with respect to the total mass of the photosensitive layer, It is more preferable that it is 70-99 mass %. The specific resin for photosensitive layers may contain only 1 type, and may contain it 2 or more types. When using 2 or more types of specific resin for photosensitive layers, it is preferable that those total amounts become the said range.

Moreover, it is preferable that it is 10 mass % or more, and, as for content of the specific resin for photosensitive layers, it is more preferable that it is 50 mass % or more, It is more preferable that it is 90 mass % or more with respect to the total mass of the resin component contained in the photosensitive layer.

It is preferable that it is 10,000 or more, as for the weight average molecular weight of specific resin for photosensitive layers, 20,000 or more are more preferable, 35,000 or more are still more preferable. Although it does not specifically set as an upper limit, It is preferable that it is 100,000 or less, and it is good also as 70,000 or less, and is good also as 50,000 or less.

Moreover, it is preferable that it is 10 mass % or less, and, as for the quantity of the component with a weight average molecular weight of 1,000 or less contained in the specific resin for photosensitive layers with respect to the total mass of the specific resin for photosensitive layers, it is more preferable that it is 5 mass % or less.

1.0-4.0 are preferable and, as for the molecular weight dispersion degree (weight average molecular weight/number average molecular weight) of specific resin for photosensitive layers, 1.1-2.5 are more preferable.

[Mine generator]

It is preferable that the photosensitive layer further contains a photo-acid generator. The photo-acid generator is preferably a photo-acid generator that decomposes by 80 mol% or more when the photosensitive layer is exposed at an exposure amount of 100 mJ/cm ² at a wavelength of 365 nm.

The decomposition degree of a photo-acid generator can be calculated|required with the following method. Details of the composition for forming the photosensitive layer will be described later.

Using the composition for forming a photosensitive layer, a photosensitive layer is formed on a silicon wafer substrate, heated at 100° C. for 1 minute, and after heating, the photosensitive layer is exposed at an exposure dose of 100 mJ/cm ² using light having a wavelength of 365 nm. . The thickness of the photosensitive layer after heating is set to 700 nm. Thereafter, the silicon wafer substrate on which the photosensitive layer is formed is immersed in a methanol/tetrahydrofuran (THF)=50/50 (mass ratio) solution while applying ultrasonic waves for 10 minutes. After the said immersion, the decomposition rate of a photo-acid generator is computed from the following formula by analyzing the extract extracted into the said solution using HPLC (high-performance liquid chromatography).

Decomposition rate (%) = amount of decomposition product (mol) / amount of photoacid generator contained in the photosensitive layer before exposure (mol) x 100

The photo-acid generator is preferably one that decomposes by 85 mol% or more when the photosensitive layer is exposed at an exposure amount of 100 mJ/cm ² at a wavelength of 365 nm.

-Oximesulfonate compound-

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

Although there will be no restriction|limiting in particular as long as an oxime sulfonate compound has an oxime sulfonate group, The following formula (OS-1), a formula (OS-103) mentioned later, a formula (OS-104), or a formula (OS-105) It is preferable that it is an oxime sulfonate compound which appears.

[Formula 14]

In formula (OS-1), X ³ represents an alkyl group, an alkoxyl group, or a halogen atom. When two or more X< ³ > exists, respectively, it may be same or different. The alkyl group and the alkoxyl group in X ³ may have a substituent. As the alkyl group for X ³ , a linear or branched alkyl group having 1 to 4 carbon atoms is preferable. As an alkoxyl group in said X< ³ >, a C1-C4 linear or branched alkoxyl group is preferable. As a halogen atom in said X< ³ >, a chlorine atom or a fluorine atom is preferable.

In formula (OS-1), m3 represents the integer of 0-3, 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X ³ 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, or halogen having 1 to 5 carbon atoms. It is preferable that it is an alkoxyl group, the phenyl group which may be substituted with W, the naphthyl group which may be substituted with W, or the anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms. , an aryl group having 6 to 20 carbon atoms or a halogenated aryl group having 6 to 20 carbon atoms.

In formula (OS-1), m3 is 3, X ³ is a methyl group, the substitution position of X ³ is ortho, R ³⁴ is a linear alkyl group having 1 to 10 carbon atoms, and 7,7-dimethyl-2- A compound which is an oxonobonylmethyl group or a p-tolyl group is especially preferable.

As a specific example of the oxime sulfonate compound represented by Formula (OS-1), Paragraph No. 0064 - 0068 of Unexamined-Japanese-Patent No. 2011-209692, Paragraph No. 0158 - 0167 of Unexamined-Japanese-Patent No. 2015-194674 The following compounds are illustrated and these contents are incorporated herein by reference.

[Formula 15]

In formulas (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group, or a heteroaryl group, and R ^s2 that may be present in a plurality is each independently a hydrogen atom, an alkyl group, an aryl group, or a Represents a rosen atom, and R ^s6 , which may be present in plurality, each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer of 0-6.

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 (having 4 to 30 carbon atoms) represented by R ^s1 This is preferable) 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), and hydrogen It is more preferable that it is an atom or an alkyl group. Among R ^s2 that may exist in two or more in the compound, one or two of them are preferably an alkyl group, an aryl group, or a halogen atom, more preferably one is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group , and it is particularly preferable that the remainder is a hydrogen atom. 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, and it is preferable that it is O. In the formulas (OS-103) to (OS-105), the ring containing Xs as a reduction is a 5-membered ring or a 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 desirable.

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

In formula (OS-103) - formula (OS-105), ms represents the integer of 0-6, It is preferable that it is an integer of 0-2, It is more preferable that it is 0 or 1, It is especially preferable that it is 0.

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

[Formula 16]

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, and has 1 to 8 represents an alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ^t2 is A hydrogen atom or a methyl group is represented.

In formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and is 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, halogen atom or phenyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group desirable.

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

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

Moreover, the said oxime sulfonate compound WHEREIN: About the three-dimensional structure (E, Z) of an oxime, either may be sufficient and a mixture may be sufficient.

As a specific example of the oxime sulfonate compound represented by the said Formula (OS-103) - Formula (OS-105), Paragraph No. 0088-0095 of Unexamined-Japanese-Patent No. 2011-209692, Paragraph No. 0168- of Unexamined-Japanese-Patent No. 2015-194674 0194 is exemplified, the contents of which are incorporated herein by reference.

As another suitable aspect of the oxime sulfonate compound containing at least 1 oxime sulfonate group, the compound represented by a following formula (OS-101) and a formula (OS-102) is mentioned.

[Formula 17]

In formula (OS-101) or formula (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, or a cyano group group, an aryl group or a heteroaryl group. An embodiment in which R ^u9 is a cyano group or an aryl group is more preferable, and an embodiment in which R ^u9 is a cyano group, a phenyl group or a naphthyl group is still more preferable.

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

In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, -CR ^u6 H- or CR ^u6 R ^u7 represents -, 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 amide group, a sulfo group, a cyano group, or an aryl group is represented. Two of R ^u1 to R ^u4 may combine with each other to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom or an alkyl group is preferable, and an embodiment in which at least two of R ^u1 to R ^u4 combine with each other to form an aryl group is also preferable. Among these, the aspect in which R ^u1 to R ^u4 are all hydrogen atoms is preferable. All of the above-described substituents may further have a substituent.

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

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

As a specific example of the compound represented by Formula (OS-101), Paragraph No. 0102 - 0106 of Unexamined-Japanese-Patent No. 2011-209692, Paragraph No. 0195 - 0207 of Unexamined-Japanese-Patent No. 2015-194674 are illustrated, These contents are It is incorporated herein by reference.

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

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

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

On the other hand, in the oxime sulfonate compound, since the acid generated in response to actinic light acts as a catalyst for the deprotection of the protected acid group, the acid generated by the action of one photon contributes to a number of deprotection reactions, The yield exceeds 1, for example, becomes a large value such as a number square of 10, and it is estimated that high sensitivity is obtained as a result of so-called chemical amplification.

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

By using a tetrahydrofuranyl group as an acid-decomposable group in the photosensitive layer, an acid-decomposable property equivalent to or higher than that of acetal or ketal can be obtained. Thereby, an acid-decomposable group can be consumed reliably by post-baking for a shorter time. Moreover, by using in combination the oxime sulfonate compound which is a photo-acid generator, since the sulfonic acid generation rate increases, generation|occurrence|production of an acid is accelerated|stimulated, and decomposition|disassembly of the acid-decomposable group of resin is accelerated|stimulated. Moreover, since the acid obtained by decomposing|disassembling an oxime sulfonate compound is a sulfonic acid with a small molecule|numerator, the diffusivity in a cured film is also high, and it can make it highly sensitive.

It is preferable to use 0.1-20 mass % of a photo-acid generator with respect to the total mass of a photosensitive layer, It is more preferable to use 0.5-18 mass %, It is more preferable to use 0.5-10 mass %, 0.5- It is still more preferable to use 3 mass %, and it is still more preferable to use 0.5-1.2 mass %.

A photo-acid generator may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types of photo-acid generators, it is preferable that those total amounts become the said range.

[Basic compound]

It is preferable that a photosensitive layer contains a basic compound from a viewpoint of the liquid storage stability of the composition for photosensitive layer formation mentioned later.

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

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanol An amine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, etc. are mentioned.

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

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8 -Oxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, cyclohexylmorpholinoethylthiourea, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabi Cyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.3.0]-7-undecene, etc. are mentioned.

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

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

When a photosensitive layer contains a basic compound, it is preferable that it is 0.001-1 mass part with respect to 100 mass parts of specific resin for photosensitive layers, and, as for content of a basic compound, it is more preferable that it is 0.002-0.5 mass part.

A basic compound may be used individually by 1 type, and may use 2 or more types together, It is preferable to use 2 or more types together, It is more preferable to use 2 types together, Using 2 types of heterocyclic amines together more preferably. When using 2 or more types of basic compounds, it is preferable that those total amounts become the said range.

〔Surfactants〕

It is preferable that a photosensitive layer contains surfactant from a viewpoint of improving the applicability|paintability of the composition for photosensitive layer formation mentioned later.

As the surfactant, any of anionic, cationic, nonionic, and amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants.

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

As surfactant, it is more preferable that a fluorochemical surfactant or silicone type surfactant is included.

As these fluorine-based surfactants or silicone-based surfactants, for example, Japanese Patent Application Laid-Open No. 62-036663, Japanese Unexamined Patent Publication No. 61-226746, Japanese Unexamined Patent Publication No. 61-226745, and Japanese Patent Application Laid-Open Nos. No. 62-170950, Japanese Unexamined Patent Publication No. 63-034540, Japanese Unexamined Patent Publication No. Hei 07-230165, Japanese Unexamined Patent Publication No. Hei 08-062834, Japanese Unexamined Patent Publication No. Hei 09-054432, Japanese Unexamined Patent Publication No. The surfactant described in each publication of Hei 09-005988 and Unexamined-Japanese-Patent No. 2001-330953 is mentioned, A commercially available surfactant can also be used.

As commercially available surfactants that can be used, for example, EFTOP EF301, EF303 (above, manufactured by Shin-Akita Chemical Co., Ltd.), Fluorad FC430, 431 (above, manufactured by Sumitomo 3M Co., Ltd.), Megapac F171, F173, F176, F189, R08 (above, manufactured by DIC Corporation), Sufflon S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by AGC Semi Chemical Co., Ltd.), PF-6320 and fluorine-based surfactants or silicone-based surfactants such as PolyFox series (manufactured by OMNOVA). Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone type surfactant.

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

[Formula 18]

In the 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 or more and 4 or less carbon atoms, and R ⁴⁴ is a hydrogen atom or a C 1 or more and 4 or less group. represents an alkyl group, L ⁴ represents an alkylene group having 3 or more and 6 or less carbon atoms, p4 and q4 are mass percentages representing the polymerization ratio, p4 represents a numerical value of 10 mass% or more and 80 mass% or less, q4 is 20 mass% A numerical value of 90 mass % or more is shown, r4 shows an integer of 1 or more and 18 or less, n4 shows an integer of 1 or more and 10 or less.

^In formula (41), it is preferable that L4 is a branched alkylene group represented by following formula (42). R ⁴⁵ in the formula (42) represents an alkyl group having 1 to 4 carbon atoms, and from the viewpoint of wettability to the surface to be coated, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 2 or 3 carbon atoms is more preferable. do.

-CH ₂ -CH(R ⁴⁵ )- (42)

As for the weight average molecular weight of the said copolymer, it is more preferable that they are 1,500 or more and 5,000 or less.

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

Surfactant can be used individually by 1 type or in mixture of 2 or more types. When using 2 or more types of surfactant, it is preferable that those total amounts become the said range.

[Other ingredients]

The photosensitive layer further contains, if necessary, known additives such as antioxidants, plasticizers, thermal radical generators, thermal acid generators, acid proliferators, ultraviolet absorbers, thickeners, and organic or inorganic precipitation inhibitors, respectively. , one type or two or more types may be added. For these details, Paragraph No. 0143 of Unexamined-Japanese-Patent No. 2011-209692 - description of 0148 can be considered into consideration, and these content is integrated in this specification.

From the viewpoint of improving the resolution, 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. As an upper limit of the thickness of a photosensitive layer, 10 micrometers or less are preferable, 5.0 micrometers or less are more preferable, and 2.0 micrometers or less are still more preferable.

It is preferable that it is 0.2 micrometer or more, and, as for the sum total of the thickness of a photosensitive layer and a protective layer, it is more preferable that it is 1.0 micrometer or more, It is more preferable that it is 2.0 micrometers or more. As an upper limit, it is preferable that it is 20.0 micrometers or less, It is more preferable that it is 10.0 micrometers or less, It is more preferable that it is 5.0 micrometers or less.

〔developer〕

The photosensitive layer is provided for development using a developer.

As a developing solution, the developing solution containing an organic solvent is preferable.

It is preferable that it is 90-100 mass %, and, as for content of the organic solvent with respect to the total mass of a developing solution, it is more preferable that it is 95-100 mass %. Moreover, the developing solution which consists only of an organic solvent may be sufficient as a developing solution.

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

-Organic solvent-

It is preferable that it is less than 19 MPa ^1/2 , and, as for the sp value of the organic solvent contained in a developing solution, it is more preferable that it is 18 MPa ^1/2 or less.

As an organic solvent contained in a developing solution, polar solvents, such as a ketone type solvent, an ester type solvent, an amide type solvent, and a hydrocarbon type solvent are mentioned.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methylamyl ketone), 4-heptanone, 1-hexanone, 2 -hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, aceto phenone, methyl naphthyl ketone, isophorone, propylene carbonate, and the like.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether. Acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, and the like.

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

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

One type may be sufficient as the said organic solvent, and 2 or more types may be used for it. Moreover, you may use it, mixing with organic solvents other than the above. However, it is preferable that content of water with respect to the total mass of a developing solution is less than 10 mass %, and it is more preferable that it does not contain water substantially. Here, "substantially not containing water" means, for example, that the content of water with respect to the total mass of the developer is 3% by mass or less, and more preferably it is less than the measurement limit.

That is, it is preferable that it is 90 mass % or more and 100 mass % or less, and, as for the usage-amount of the organic solvent with respect to an organic developing solution, it is more preferable that they are 95 mass % or more and 100 mass % or less with respect to the whole quantity of a developing solution.

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

Moreover, the organic developing solution may contain the basic compound in an appropriate amount as needed. As an example of a basic compound, what was demonstrated in the term of said basic compound is mentioned.

The vapor pressure of the organic developer is preferably 5 kPa or less at 23°C, more preferably 3 kPa or less, and still more preferably 2 kPa or less. By setting the vapor pressure of the organic developer to 5 kPa or less, 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, as a result, the dimensional uniformity of the photosensitive layer after development This is improved.

Specific examples of the solvent having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methylamylketone), 4-heptanone, 2-hexanone. , diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, ketone solvents such as 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 monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, Ester solvents such as 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and amide-based solvents such as N,N-dimethylformamide, aromatic hydrocarbon-based solvents such as toluene and xylene, and aliphatic hydrocarbon-based solvents such as octane and decane.

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

-Surfactants-

The developing solution may contain surfactant.

Although it does not specifically limit as surfactant, For example, the surfactant demonstrated in the term of the said protective layer is used preferably.

When mix|blending surfactant with a developing solution, the compounding quantity is 0.001-5 mass % normally with respect to the whole quantity of a developing solution, Preferably it is 0.005-2 mass %, More preferably, it is 0.01-0.5 mass %.

[Composition for photosensitive layer formation]

The composition for photosensitive layer formation is a composition used for formation of the photosensitive layer contained in a laminated body.

A laminate WHEREIN: The photosensitive layer can be formed by applying the composition for photosensitive layer formation on a protective layer, and drying, for example. As an application method, the description about the application method of the composition for protective layer formation in the protective layer mentioned later can be referred, for example.

It is preferable that the composition for forming a photosensitive layer contains a component (for example, a specific resin for a photosensitive layer, a photo-acid generator, a basic compound, a surfactant, and other components, etc.) contained in the above-mentioned photosensitive layer, and a solvent do. It is preferable to melt|dissolve or disperse|distribute to the solvent, and, as for the component contained in these photosensitive layers, it is more preferable to melt|dissolve.

As for content of the component contained in the composition for photosensitive layer formation, it is preferable to substitute content with respect to the total mass of the photosensitive layer of each component mentioned above with the -flow rate with respect to the solid content of the composition for photosensitive layer formation.

-Organic solvent-

As an organic solvent used for the composition for photosensitive layer formation, a well-known organic solvent can be used, Ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, Propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates , dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like can be exemplified.

As an organic solvent, for example,

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

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

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

(4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;

(5) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether and propylene glycol diethyl ether;

(6) Propylene glycol monoalkyl, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate ether acetates;

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

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

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

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

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

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

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

(14) Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, other esters such as 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, and ethyl pyruvate;

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

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

(17) Lactones, such as (gamma)-butyrolactone, etc. are 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 ter, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate, etc. An organic solvent may also be added.

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

When the composition for photosensitive layer formation contains an organic solvent, it is preferable that content of the organic solvent is 1-3,000 mass parts per 100 mass parts of specific resin for photosensitive layers, It is more preferable that it is 5-2,000 mass parts, It is more preferable, 10-1,500 It is more preferable that it is a mass part.

These organic solvents can be used individually by 1 type or in mixture of 2 or more types.

When using 2 or more types of organic solvents, it is preferable that those total amounts become the said range.

<Kit for forming a laminate>

The kit for forming a laminate includes, for example, the above-described composition for forming a protective layer and a composition for forming a photosensitive layer. Moreover, the kit for laminated body formation may further contain the composition for organic layer formation mentioned above.

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

The manufacturing method of a laminated body includes the following process (1) at least. Moreover, the patterning method of an organic layer includes the following processes (1)-(5) at least.

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

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

(3) exposing the photosensitive layer;

(4) a process of producing a mask pattern by developing the photosensitive layer using a developer containing an organic solvent;

(5) a step of removing the protective layer and the organic layer of the non-mask portion;

(6) a step of removing the protective layer using a stripper;

<<(1) Step of forming a protective layer into a film on the organic layer >>

The patterning method of the organic layer of this embodiment includes the process of forming a protective layer into a film on the organic layer. Usually, after forming an organic layer into a film on a base material, this process is performed. In this case, a protective layer is formed into a film on the surface on the opposite side to the surface on the side of a base material of an organic layer. 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 spirit of the present invention. As another layer, a fluorine-type undercoat layer etc. are mentioned. Moreover, only one layer of a protective layer may be provided, and two or more layers may be provided. The protective layer is preferably formed using the composition for forming a protective layer as described above.

For the detail of a formation method, the application method of the composition for protective layer formation in the laminated body mentioned above can be referred.

<<(2) Step of forming a photosensitive layer on the side opposite to the organic layer of the protective layer >>

After the step (1) above, a photosensitive layer is formed on the side opposite to the surface of the protective layer on the organic layer side (preferably on the surface). The photosensitive layer is preferably formed using the composition for photosensitive layer formation as described above. For the detail of a formation method, the application method of the composition for photosensitive layer formation in the laminated body mentioned above can be referred.

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

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

The exposure is preferably performed so as to form a predetermined pattern. Moreover, exposure may be performed through a photomask, and a predetermined|prescribed pattern may be drawn directly.

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

As the light source of the actinic ray, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a laser generator, a light emitting diode (LED) light source, or the like can be used.

When a mercury lamp is used as the light source, actinic rays having a wavelength such as g-line (436 nm), i-line (365 nm), or h-line (405 nm) can be preferably used, and i-ray is more preferably used.

When a laser generator is used as the light source, actinic rays having wavelengths of 343 nm and 355 nm are suitably used for solid-state (YAG) lasers, and for excimer lasers, 193 nm (ArF line), 248 nm (KrF line), 351 nm (Xe) Actinic ray having a wavelength of line) is suitably used, and in a semiconductor laser, actinic ray having a wavelength of 375 nm or 405 nm is suitably used. Among these, the actinic ray which has a wavelength of 355 nm or 405 nm from points, such as stability and cost, is more preferable. The laser can be irradiated to the photosensitive layer once or divided into a plurality of times.

40-120 mJ is preferable and, as for an exposure amount, 60-100 mJ is more preferable.

The energy density per pulse of the laser is preferably 0.1 mJ/cm ² or more and 10,000 mJ/cm ² or less. In order to sufficiently harden the coating film, 0.3 mJ/cm ² or more is more preferable, and 0.5 mJ/cm ² or more is still more preferable. From a viewpoint of suppressing decomposition|disassembly of the photosensitive layer etc. by an ablation phenomenon, it is preferable to make an exposure amount into 1,000 mJ/cm< ² > or less, and 100 mJ/cm< ² > or less is more preferable.

Moreover, it is preferable that a pulse width is 0.1 nanosecond (henceforth "ns") or more and 30,000 ns or less. In order not to decompose the color coating film by the ablation phenomenon, 0.5 ns or more is more preferable, and 1 ns or more is still more preferable. In order to improve the alignment precision at the time of scan exposure, 1,000 ns or less is more preferable, and 50 ns or less is still more preferable.

When using a laser generator as a light source, 1 Hz or more and 50,000 Hz or less are preferable and, as for the frequency of a laser, 10 Hz or more and 1,000 Hz or less are more preferable.

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

Compared with a mercury lamp, a laser is easy to focus, and it is preferable also from the point which can abbreviate|omit use of a photomask in pattern formation in an exposure process.

Although there is no restriction|limiting in particular as an exposure apparatus, As what is marketed, Callisto (made by V Technology Co., Ltd.), AEGIS (made by V Technology Co., Ltd.), DF2200G (made by Dainippon Screen Seijo Co., Ltd.) etc. It is possible to use Moreover, devices other than the above are also used suitably.

Moreover, the amount of irradiation light can also be adjusted through a spectral filter like a long wavelength cut off filter, a short wavelength cut off filter, and a band pass filter as needed.

Moreover, after the said exposure, you may perform a post-exposure heating process (PEB) as needed.

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

After exposing the photosensitive layer through a photomask in the step (3), the photosensitive layer is developed using a developer.

As for development, negative type is preferable. The details of the developer are as described above in the description of the photosensitive layer.

As the developing method, for example, a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method), a method of developing by raising the developer on the surface of the substrate by surface tension and stopping for a certain period of time (puddle method); A method of spraying a developer on the surface of a substrate (spray method), a method of continuously discharging a developer while scanning a developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method), etc. can be applied.

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

Although the details of this mechanism are not certain, it is probably because by setting the discharge pressure within the above range, the pressure applied by the developer to the photosensitive layer is reduced, and the resist pattern on the photosensitive layer is suppressed from being inadvertently scraped or collapsed. . The discharge pressure (mL/sec/mm ² ) of the developer is a value at the outlet of the developing nozzle in the developing device.

As a method of adjusting the discharge pressure of a developing solution, the method of adjusting the discharge pressure with a pump etc., the method of changing by adjusting the pressure by supply from a pressurization tank, etc. are mentioned, for example.

Moreover, you may implement the process of stopping image development, replacing with another organic solvent after the process of developing using the developing solution containing an organic solvent.

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

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

The etching treatment may be performed in a plurality of steps. For example, the protective layer and the organic layer may be removed by one etching process, and after at least a part of the protective layer is removed by the etching process, the organic layer (and, if necessary, the remainder of the protective layer) is etched. It may be removed by treatment.

Moreover, dry etching process or wet etching process may be sufficient as the said etching process, and the aspect which divides etching into a plurality of times to perform dry etching process and wet etching process may be sufficient as it. For example, the protective layer may be removed by dry etching or wet etching.

As a method of removing the protective layer and the organic layer, for example, method A in which the protective layer and the organic layer are removed by a single dry etching treatment, at least a part of the protective layer is removed by a wet etching treatment, Methods, such as method B, which removes the said organic layer (and the remainder of the said protective layer as needed) by dry etching after that, are mentioned.

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

Hereinafter, the detail of one aspect of the said method A is demonstrated. As a specific example of the said method B, the description of Unexamined-Japanese-Patent No. 2014-098889, etc. can be referred.

In the said method A, specifically, the protective layer and organic layer of a non-mask part can be removed by dry etching using a resist pattern as an etching mask (mask pattern). As a representative example of dry etching, Japanese Patent Application Laid-Open No. 59-126506, Japanese Patent Application Laid-Open No. 59-046628, Japanese Unexamined Patent Publication No. 58-009108, Japanese Unexamined Patent Publication No. 58-002809, Japanese Patent Laid-Open No. There is a method described in So 57-148706 and Japanese Patent Laid-Open No. 61-041102.

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

A first step etching in which etching is performed to a region (depth) where the organic layer is not exposed using a mixed gas of a fluorine-based gas and oxygen gas (O ₂ ), and after the first step etching, nitrogen gas (N ₂ ) and oxygen It is preferable to use a gas mixture of a gas (O ₂ ) to etch a second-stage etching in which the organic layer is preferably etched to the vicinity of the exposed region (depth), and an over-etching performed after the organic layer is exposed. Hereinafter, the specific method of dry etching, and 1st step etching, 2nd step etching, and over etching are demonstrated.

It is preferable to perform etching conditions in dry etching, calculating etching time by the following method.

(A) The etching rate (nm/min) in 1st-step etching and the etching rate (nm/min) in 2nd-step etching are computed, respectively.

(B) The time for etching the desired thickness in the first step etching and the time for etching the desired thickness in the second step etching are respectively calculated.

(C) The first step etching is performed according to the etching time calculated in (B) above.

(D) A second step 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 step etching may be performed according to the determined etching time.

(E) Over-etching is performed by calculating over-etching time with respect to the total time of said (C) and (D).

The mixed gas used in the first-step etching preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing an organic material as a film to be etched into a rectangular shape. Moreover, in a 1st-step etching, the laminated body is etched to the area|region to which an organic layer is not exposed. Therefore, at this stage, the organic layer is not receiving any damage, or it is considered that the damage is slight.

Moreover, in the said 2nd step etching and the said over-etching, it is preferable to perform an etching process using the mixed gas of nitrogen gas and oxygen gas from a viewpoint of avoiding damage to an organic layer.

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

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

Moreover, it is preferable that etching includes an over-etching process. It is preferable to perform an over-etching process by setting an over-etching ratio. Although the over-etching ratio can be set arbitrarily, it is preferable that it is 30% or less of the whole etching processing time in an etching process from the point of the etching resistance of a photoresist and the point of maintaining the rectangularity of a pattern to be etched (organic layer), 5-25% It is more preferable that it is, and it is especially preferable that it is 10 to 15 %.

<<(6) Step of removing the protective layer using a stripper >>

After etching, the protective layer is removed using a stripper (eg, water). The details of the stripper are as described above in the description of the protective layer.

As a method of removing a protective layer with a stripper, the method of removing a protective layer by spraying stripping liquid to a resist pattern from a spray type or shower type spray nozzle, for example is mentioned. As the stripper, pure water can be preferably used. Moreover, as a spray nozzle, the spray nozzle in which the whole base material is contained within the spraying range, It is a movable spray nozzle, and the spray nozzle whose movable range contains the whole base material is mentioned. As another aspect, after mechanically peeling a protective layer, the aspect which melt|dissolves and removes the residue of the protective layer which remain|survives on an organic layer is mentioned.

When the spray nozzle is of a movable type, the resist pattern can be removed more effectively by moving the stripping solution from the center of the substrate to the end of the substrate twice or more during the process of removing the protective layer.

It is also preferable to perform a process, such as drying, after removing a protective layer. As a drying temperature, it is preferable to set it as 80-120 degreeC.

<Use>

The 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 containing a semiconductor, having two or more electrodes, and controlling the current flowing between the electrodes or the voltage generated by electricity, light, magnetism, a chemical substance, or the like, or It is a device which generates light, an electric field, a magnetic field, etc. by voltage or current.

Examples include an organic photoelectric conversion element, an organic field effect transistor, an organic electroluminescent element, a gas sensor, an organic rectifying element, an organic inverter, and an information recording element. The organic photoelectric conversion element can be used for any of an optical sensor application and an energy conversion application (solar cell). Among these, as a use, Preferably they are an organic field effect transistor, an organic photoelectric conversion element, and an organic electroluminescent element, More preferably, they are an organic field effect transistor and an organic photoelectric conversion element, Especially preferably, they are an organic field effect transistor.

Example

Hereinafter, the present invention will be more specifically described by way of Examples. Materials, amounts of use, ratios, processing contents, processing procedures, etc. shown in the Examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In Examples, unless otherwise specified, "parts" and "%" are based on mass, and the environmental temperature (room temperature) of each process is 23°C.

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

The weight average molecular weight (Mw) of water-insoluble resins, such as (meth)acrylic resin, was computed as polystyrene conversion 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 mmID x 15.0 cm) was used as a column.

<Preparation and storage of the composition for forming a protective layer>

For the compositions for forming a protective layer (S-1 to S-24), the following raw materials were mixed, respectively. After mixing, the composition for forming a protective layer was each stirred under the following stirring conditions using a stirrer (hot magnet stirrer, C-MAG HS4, manufactured by IKA Corporation). After the stirring was completed, a PVDF (polyvinylidene fluoride) membrane filter (Durapore, Merck) with a pore diameter of 5 μm was installed in a stainless steel pressure filter holder (manufactured by Sartorius), and pressurized to 2 MPa using this. While filtering each composition. After this filtration, each of the compositions was filled in glass containers (volume of 250 mL) under the atmosphere so that the filling rate was 80%, and the containers were sealed with screw caps. Then, under each storage condition shown in following Table 1 and Table 2, the container with which the composition was filled was each preserve|saved in a refrigerator (Examples 1-36 and Comparative Examples 1-5).

<<Stirring conditions>>

・Atmosphere: Atmosphere

・Stirring time: 240 minutes

・Stirring temperature: 50℃

· Rotational speed of the stirring member: 500 rpm

<<Composition for forming a protective layer S-1, S-10, S-20, S-24>>

・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

· 84.992 parts by mass of water

<<Composition for forming a protective layer 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 fungicide listed in the table

· 84.990 parts by mass of water

<<Composition for forming a protective layer S-8, S-9, S-11 to S-19, S-21 to S-23>>

· 15.000 parts by mass of each high molecular weight substance listed in the table × each ratio listed in the table

· 15.000 parts by mass of each low molecular weight substance listed in the table × each ratio listed in the table

· 0.008 parts by mass of each surfactant listed in the table

· 0.002 parts by mass of each fungicide listed in the table

· 84.990 parts by mass of water

[Table 1]

[Table 2]

The specifications of each raw material are as follows. In addition, for 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 (= weight average molecular weight of low molecular weight substance / weight average molecular weight of high molecular weight substance) is shown in Tables 1 and 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: Daiichi High School Seiyaku Co., Ltd. Fitzcall K-30, Mw = 45,000.

·PVP-2: Daiichi High School Seiyaku Co., Ltd. Fitzcall K-50, Mw=250,000.

·PVP-3: Daiichi High School Seiyaku Co., Ltd. Fitzcall K-80, Mw = 900,000.

·PVP-4: Daiichi High School Seiyaku Co., Ltd. Fitzcall K-90, Mw=1200,000.

<<2-Hydroxyethylcellulose (HEC)>>

·HEC-1: Fujifilm Wako Junyaku Co., Ltd., Mw=90,000.

·HEC-2: Fujifilm Wako Junyaku Co., Ltd., Mw=380,000.

·HEC-3: Fujifilm Wako Junyaku Co., Ltd., Mw=720,000.

·HEC-4: Fujifilm Wako Junyaku Co., Ltd., Mw=1300,000.

<<PVA (GRA) grafted to PVP>>

・GRA-1: Fitzcall V-7154 manufactured by Daiichi High School Seiyaku.

<Surfactant>

· Surfactant E-1: A compound having the following structure. Acetyleneol E00 manufactured by Kawaken Fine Chemicals.

· Surfactant E-2: polyoxyethylene lauryl ether. EMALEX710 made by Nippon Emulsion Corporation.

[Formula 19]

<Anti-fungal agent>

-F-1: methyl isothiazolinone.

• 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: diiodomethylparatolylsulfone.

<Evaluation>

In order to evaluate the effect of the production method of the present invention, for each composition for forming a protective layer in Examples and Comparative Examples, the number of defects and the residual ratio of the protective layer formed using the composition for forming a protective layer after storage were measured.

<<Formation of laminate >>

When measuring the number of defects and the residual ratio of the protective layer, using the respective protective layer-forming compositions of Examples and Comparative Examples, laminates were prepared as follows. On a rectangular glass substrate having a side of 5 cm, a composition for forming an organic layer of the following composition containing an organic semiconductor material as an organic material was spin-coated and dried at 80° C. for 10 minutes to form an organic semiconductor layer having a thickness of 150 nm. Next, on the said organic semiconductor layer, each composition for protective layer formation of an Example and a comparative example was spin-coated, and by drying at 80 degreeC for 1 minute, the protective layer with a thickness of 2 micrometers was formed. At this time, as a composition for forming a protective layer, a composition having passed one year and a composition having been three years from the start of storage were used, respectively. Moreover, on the said protective layer, the photosensitive resin composition of the following composition was spin-coated, and the 2 micrometers-thick photosensitive resin layer was formed by drying at 80 degreeC for 1 minute. By the above, the laminated body which has a glass substrate, an organic-semiconductor layer (150 nm in thickness), a protective layer (2 micrometers in thickness), and the photosensitive resin layer (2 micrometers in thickness) in order is obtained.

<<<Composition for forming an organic layer >>>

・P3HT (manufactured by Sigma-Aldrich Japan Co., Ltd.) 10% by mass

・PCBM (manufactured by Sigma-Aldrich Japan Co., Ltd.) 10% by mass

・Chloroform (manufactured by Fujifilm Wako Junyaku Co., Ltd.) 80% by mass

<<<photosensitive resin composition >>>

· 25.09 parts by mass of photosensitive resin A-1 synthesized by the following method

The following photoacid generator X 0.26 parts by mass

0.08 parts by mass of the following basic compound Y

0.08 parts by mass of the following surfactant B

74.50 parts by mass of PGMEA

A method for synthesizing the 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 put into a three-necked flask equipped with a nitrogen inlet tube and a cooling tube, and the temperature was raised to 86° C., and the PGMEA solution was added dropwise thereto for 2 hours. Then, the solution was 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, the weight average molecular weight Mw obtained photosensitive resin A-1 whose weight average molecular weight Mw is 45000.

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

[Formula 20]

Basic compound Y: a thiourea derivative having the following structure. DSP Gokyo Foods & Chemicals.

[Formula 21]

- Surfactant B: OMNOVA company make, PF-6320.

<<Measurement of defect function>>

During the formation process of the laminate, after the formation of the protective layer and before the formation of the photosensitive resin layer, using an optical microscope, the surface of the protective layer was applied to the entire area on the substrate with a field of view of 2.6 mm × 3.8 mm (magnification 5). The number of colonies of visible microorganisms was counted over observation.

<<Measurement of residual rate>>

The residual ratio when the protective layer was removed was evaluated for the laminate in the case of using the composition for forming a protective layer after one year from the start of storage. Specifically, it is as follows.

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

Next, with respect to this laminated body, puddle development for 30 second using nBA (n-butyl acetate) was performed twice, and the photosensitive resin layer was removed. Then, with respect to this laminated body, the puddle image development for 30 second using water was performed twice, and also shower washing was performed with water, and the protective layer was removed. Thereby, the laminated body in which the organic layer remained on the glass substrate is obtained.

And again using TOF-SIMS apparatus, the surface of this organic layer was measured and the signal intensity I derived from water-soluble resin was measured. The residual ratio of the composition for forming a protective layer was defined by the following formula. It can be said that generation|occurrence|production of a residue is suppressed, so that an evaluation value is small.

Residual rate (%) =

(Signal intensity I derived from the water-soluble resin on the surface of the organic layer after carrying out the protective layer removal treatment) / (Signal intensity I ₀ derived from the water-soluble resin on the surface of the protective layer) x 100

<Evaluation result>

The respective results of Examples and Comparative Examples are shown in Tables 1 and 2 above. From this result, it was found that, by the method for producing the composition for forming a protective layer of the present invention, a composition for forming a protective layer in which the quality hardly deteriorates even after long-term storage can be obtained.

Moreover, with respect to the residual rate of Example 21, the process of water peeling of "performing the puddle development for 30 seconds using water twice, and shower washing with water further" was "putting water on the laminated body, In the case of changing to the process of "leaving still for 5 minutes as it is, and then further shower washing with water", the residual ratio was 0.18%, which was a very good result.

Furthermore, organic semiconductor elements were respectively produced using the laminated body containing the protective layer obtained from the composition for protective layer formation which concerns on each Example. None of the organic semiconductor elements had a problem in performance.

1 photosensitive layer
1a Photosensitive layer after exposure development
2 protective layer
3 organic layer
3a Organic layer after processing
4 description
5 remover
5a Removal after etching

Claims (20)

A method for producing 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, comprising:
After stirring the composition containing the water-soluble resin and the solvent, the container containing the composition after stirring is continuously exposed to an environment in a 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 start time of the period of exposure to the environment is within 72 hours after the end of the stirring. The method according to claim 1,
The method for producing a composition for forming a protective layer, wherein the start time of the period of exposure to the environment is within 24 hours after the end of the stirring. The method according to claim 1 or 2,
A method for producing a composition for forming a protective layer, wherein the period of continuous exposure to the environment is 1 month or more. 4. The method according to any one of claims 1 to 3,
A method for producing a composition for forming a protective layer, wherein the temperature range when exposing the container to the environment is 0 to 10°C. 5. The method according to any one of claims 1 to 4,
After completion of the stirring, before exposing to the environment, the method for producing a composition for forming a protective layer comprising filtering the composition. 6. The method according to any one of claims 1 to 5,
The manufacturing method of the composition for protective layer formation in which the said composition at the time of the said stirring contains a fungicide. 7. The method of claim 6,
The composition for forming a protective layer, as the fungicide, isothiazolinone-based compound, 2-bromo-2-nitropropane-1,3-diol, methylsulfonyltetrachloropyridine, 2-(di A method for producing a composition for forming a protective layer, comprising at least one of chloro-fluoromethyl)sulfanylisoindole-1,3-dione, sodium diacetate and diiodomethylparatolylsulfone. 8. The method according to any one of claims 1 to 7,
The method for producing a composition for forming a protective layer, wherein the water-soluble resin includes at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and water-soluble polysaccharides. 9. The method according to any one of claims 1 to 8,
As the water-soluble resin, it contains a high molecular weight material and a low molecular weight material having a weight average molecular weight smaller than the weight average molecular weight of the high molecular weight material,
The method for producing a composition for forming a protective layer, wherein the weight average molecular weight of the low molecular weight material is half or less of the weight average molecular weight of the high molecular weight material. 10. The method of claim 9,
The content of the high molecular weight substance is 30 mass % or less with respect to all the water-soluble resins, the manufacturing method of the composition for protective layer formation. 11. The method according to claim 9 or 10,
As the high molecular weight material, a method for producing a composition for forming a protective layer comprising polyvinyl alcohol having a weight average molecular weight of 20,000 or more. 12. The method according to any one of claims 9 to 11,
As the high molecular weight material, a method for producing a composition for forming a protective layer comprising polyvinylpyrrolidone having a weight average molecular weight of 300,000 or more. 13. The method according to any one of claims 9 to 12,
A method for producing a composition for forming a protective layer, comprising, as the high molecular weight material, a water-soluble polysaccharide having a weight average molecular weight of 300,000 or more. 14. The method of claim 13,
The method for producing a composition for forming a protective layer, wherein the water-soluble polysaccharide is cellulose. 15. The method according to any one of claims 1 to 14,
In the molecular weight distribution of the water-soluble resin, two or more peak tops exist, and among the two or more peak tops, the molecular weight corresponding to one peak top is half or less of the molecular weight corresponding to the other peak top, protection, A method for producing a composition for forming a layer. A method of preserving 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, comprising:
After stirring the composition containing the water-soluble resin and the solvent, the container containing the composition after stirring is continuously exposed to an environment in a temperature range of 0 to 18 ° C. for 24 hours or more, including storing,
The method for preserving the composition for forming a protective layer, wherein 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 laminate, comprising applying the composition for forming a protective layer preserved by the preservation method according to claim 16 on an organic layer. A method for manufacturing a semiconductor device comprising the method for manufacturing the laminate according to claim 17 as a process. A protective layer obtained from the composition for forming a protective layer preserved by the storage method according to claim 16 . A laminate comprising the protective layer according to claim 19 and an organic layer.

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