WO2018074539A1 - 硬化膜の形成方法、感放射線樹脂組成物、硬化膜を備える表示素子及びセンサー - Google Patents

硬化膜の形成方法、感放射線樹脂組成物、硬化膜を備える表示素子及びセンサー Download PDF

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WO2018074539A1
WO2018074539A1 PCT/JP2017/037808 JP2017037808W WO2018074539A1 WO 2018074539 A1 WO2018074539 A1 WO 2018074539A1 JP 2017037808 W JP2017037808 W JP 2017037808W WO 2018074539 A1 WO2018074539 A1 WO 2018074539A1
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Prior art keywords
forming
cured film
mass
radiation
pattern
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PCT/JP2017/037808
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English (en)
French (fr)
Japanese (ja)
Inventor
仁 浜口
健朗 田中
光弘 和田
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Jsr株式会社
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Priority to CN201780063875.8A priority Critical patent/CN109843452A/zh
Priority to KR1020197004666A priority patent/KR20190071672A/ko
Priority to JP2018546395A priority patent/JP7099323B2/ja
Publication of WO2018074539A1 publication Critical patent/WO2018074539A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Definitions

  • the present invention relates to a method for forming a cured film, a radiation-sensitive resin composition, a display element and a sensor provided with the cured film.
  • a photolithography method using a radiation-sensitive material is widely used for forming a pattern used for a display element, a semiconductor element, or the like.
  • the removal of the unexposed portion of the radiation sensitive material is performed by development if the negative type, and the exposed portion of the radiation sensitive material is removed by development if the positive type.
  • the radiation-sensitive material used for the photolithography method can be used only if it can be removed by a developer.
  • the radiation-sensitive curable composition containing a colorant and the like is widely used for the formation of display elements, image sensors, etc., but in the formation of a colored pattern, from the viewpoint of efficiently realizing a coloring function and the like.
  • a curable composition having a high concentration of colorant and the like there has been a demand for a curable composition having a high concentration of colorant and the like.
  • the coating film formed from the radiation-sensitive curable composition is colored, so that radiation due to exposure is sufficiently transmitted.
  • the coating film formed from the radiation-sensitive curable composition is colored, so that radiation due to exposure is sufficiently transmitted.
  • Such a problem is likely to occur particularly in a curable composition that is sensitive to radiation and contains a high-density black agent that blocks radiation caused by exposure or a high-density refractive agent.
  • each printing method such as ink jet printing, screen printing, and gravure printing used in printed electronics is a simple and low-cost method because a desired pattern can be directly formed on a substrate.
  • a printing method there is a limit to forming a fine pattern because the ink material used flows and wets and spreads.
  • the above-described method performs high-energy laser irradiation to form a region with high wettability to be a pattern, and it is difficult to say that the efficiency is good.
  • a laser for example, as the pattern becomes more complicated, the scanning path becomes more complicated and the working time becomes longer.
  • the above method is limited to patterns using conductive ink, and a specific material whose surface energy is changed by applying energy includes polyimide in the main chain and is hydrophilic by irradiation with ultraviolet rays. Only polymers having side chains capable of generating groups are used.
  • the present invention has been made based on the circumstances as described above, and the purpose thereof is to use a curable composition containing a curable composition having poor developability and an insoluble material such as a colorant. And efficiently forming a cured film pattern. Furthermore, it is providing the display element or sensor which comprises the cured film pattern obtained from the formation method of the said cured film.
  • the invention made in order to solve the above-described problems is a process for forming a layer containing a liquid-repellent surface and a layer containing a lyophilic surface on a substrate, and a curable composition in the layer containing the lyophilic surface.
  • a method for forming a cured film comprising a step of applying a coating, a step of curing the coating film, and a step of removing a layer including a liquid repellent surface.
  • a radiation-sensitive composition containing a polymer having an acid-dissociable group and a radiation-sensitive acid generator is used to form a layer containing a liquid-repellent surface and a layer containing a lyophilic surface.
  • a radiation-sensitive acid generator is used to form a layer containing a liquid-repellent surface and a layer containing a lyophilic surface.
  • This irradiation can be performed by exposure through a photomask without using a laser.
  • the obtained layer containing a lyophilic surface can be removed by development, and a lyophilic substrate surface can be obtained.
  • a cured composition is applied onto a template having a layer containing a liquid repellent surface and a layer containing a lyophilic surface, the cured composition collects in the lyophilic portion due to the difference in wettability, and cures in that state. By curing the composition, a cured product can be formed only on the layer containing the lyophilic surface.
  • the present invention can efficiently form a cured film pattern by using a curable composition in which an insoluble matter such as a curable composition or a colorant having poor developability is dispersed and contained.
  • a curable composition in which an insoluble matter such as a curable composition or a colorant having poor developability is dispersed and contained.
  • FIG. 1 is an explanatory view of a step (A) of forming a layer including a liquid repellent surface and a layer including a lyophilic surface according to an embodiment of the present invention
  • a step of forming a template coating film (A) -1) is an explanatory diagram, an explanatory diagram of a step (A-2) for forming a layer including a lyophilic surface by irradiation with radiation, and an explanatory diagram of a step (A-3) for forming a pattern by development.
  • FIG. 1 is an explanatory view of a step (A) of forming a layer including a liquid repellent surface and a layer including a lyophilic surface according to an embodiment of the present invention
  • a step of forming a template coating film (A) -1) is an explanatory diagram
  • an explanatory diagram of a step (A-2) for forming a layer including a lyophilic surface by irradiation with radiation and an explanatory diagram of
  • FIG. 2 is an explanatory view of a step (A) of forming a layer including a liquid repellent surface and a layer including a lyophilic surface according to an embodiment of the present invention, and a step of forming a template coating film (A) -1), an explanatory diagram of the step (A-2) for forming a layer including a lyophilic surface by irradiation with radiation, and a step (A-4) when there is a residual film by changing exposure conditions, etc. ).
  • FIG. 3 is an explanatory diagram of a step (B) of applying a curable composition to a layer including a lyophilic surface (A-3) according to an embodiment of the present invention.
  • FIG. 4 is an explanatory diagram of the step (B) of applying a curable composition to a layer including a lyophilic surface (A-4) according to an embodiment of the present invention.
  • FIG. 5 is an explanatory view of a step (C) of applying a curable composition to a layer containing a lyophilic surface of (A-3) according to an embodiment of the present invention and curing the coating film.
  • FIG. 6 is an explanatory view of a step (C) of applying a curable composition to a layer including a lyophilic surface of (A-4) according to an embodiment of the present invention and curing the coating film. .
  • FIG. 5 is an explanatory view of a step (C) of applying a curable composition to a layer containing a lyophilic surface of (A-3) according to an embodiment of the present invention and curing the coating film.
  • FIG. 6 is an explanatory view of a step (C) of applying a curable composition to a layer including a
  • FIG. 7 shows a coating of a curable composition on a layer containing a lyophilic surface of (A-3) according to an embodiment of the present invention, curing the coating film, and then including a liquid repellent surface. It is explanatory drawing of the process (D) which removes a layer.
  • FIG. 8 shows a coating of a curable composition on a layer containing a lyophilic surface of (A-4) according to an embodiment of the present invention, the coating film is cured, and then containing a liquid repellent surface. It is explanatory drawing of the process (D) which removes a layer.
  • FIG. 8 shows a coating of a curable composition on a layer containing a lyophilic surface of (A-4) according to an embodiment of the present invention, the coating film is cured, and then containing a liquid repellent surface. It is explanatory drawing of the process (D) which removes a layer.
  • FIG. 9 shows that the layer containing a lyophilic surface (A-3) according to one embodiment of the present invention has a height comparable to the thickness of the layer pattern containing a lyophobic surface. It is explanatory drawing of the process (C) which apply
  • FIG. 10 shows a layer having a lyophilic surface of (A-4) according to an embodiment of the present invention, the curable composition having a height similar to the thickness of a layer pattern including a liquid repellent surface. It is explanatory drawing of the process (C) which apply
  • FIG. 11 shows that the curable composition is added to the layer containing the lyophilic surface of (A-3) according to one embodiment of the present invention so that the thickness is about the same as the thickness of the layer pattern including the liquid repellent surface. It is explanatory drawing of the process (D) of apply
  • FIG. 12 shows that the curable composition is added to the layer containing the lyophilic surface of (A-4) according to an embodiment of the present invention so that the layer pattern has the same height as the layer pattern including the liquid repellent surface.
  • FIG. 13 is a process (C) in which a curable composition is applied to a base film in which a film thickness of a layer pattern including a liquid repellent surface according to an embodiment of the present invention is thin, and the coating film is cured. It is explanatory drawing of the process (D) which makes it harden
  • FIG. 13 is a process (C) in which a curable composition is applied to a base film in which a film thickness of a layer pattern including a liquid repellent surface according to an embodiment of the present invention is thin, and the coating film is cured. It is explanatory drawing of the process (D) which makes it harden
  • FIG. 14 shows a process of applying a curable composition to a template coating film having a thin layer pattern including a liquid repellent surface according to an embodiment of the present invention and curing the coating film (C ) And then removing the layer including the liquid repellent surface (D).
  • FIG. 15 is a diagram showing the process of (A-4) including a lyophilic surface according to an embodiment of the present invention, in which a curable composition is applied, the coating film is cured, and then a liquid repellent surface is included. It is an electron micrograph of the cured film pattern formed in the layer containing a lyophilic surface after removing a layer.
  • FIG. 15 is a diagram showing the process of (A-4) including a lyophilic surface according to an embodiment of the present invention, in which a curable composition is applied, the coating film is cured, and then a liquid repellent surface is included. It is an electron micrograph of the cured film pattern formed in the layer containing a lyophilic surface after removing a layer.
  • FIG. 16 is an electron micrograph according to a perspective view and a cross-sectional view of a layer pattern including a liquid repellent surface according to an embodiment of the present invention.
  • FIG. 17 is a perspective view of the remaining cured film pattern in which a cured film is formed between the layer patterns including the liquid repellent surface according to the embodiment of the present invention, and then the layer including the liquid repellent surface is removed. It is an electron micrograph concerning a sectional view.
  • FIG. 18 is an electron micrograph according to a perspective view and a cross-sectional view of a layer pattern including a liquid repellent surface according to an embodiment of the present invention.
  • 19 is a perspective view of a remaining cured film pattern in which a cured film is formed between layer patterns including a liquid repellent surface according to an embodiment of the present invention, and then the layer including the liquid repellent surface is removed. It is an electron micrograph concerning a sectional view.
  • the object of the present invention has been achieved by the following. 1) forming a layer including a liquid repellent surface and a layer including a lyophilic surface on a substrate; Applying a curable composition to the layer including the lyophilic surface to form a coating film; Curing the coating film; and Developing and removing the layer containing the liquid repellent surface with a developer;
  • the contact angle difference with respect to tetradecane of the layer containing the liquid repellent surface and the layer containing the lyophilic surface is 30 ° or more.
  • a method for forming a cured film according to an embodiment of the present invention includes: A step (A) of forming a layer including a liquid-repellent surface and a layer including a lyophilic surface on a substrate; a step (B) of applying a curable composition to the layer including the lyophilic surface; A step (C) for curing the coating film and a step (D) for removing the layer including the liquid repellent surface are provided.
  • the step (A) of forming a layer including a liquid repellent surface and a layer including a lyophilic surface includes a polymer having an acid dissociable group and a radiation sensitive acid generator on the surface of the substrate.
  • a region not irradiated with radiation is a region having a layer including a liquid repellent surface.
  • the liquid repellent surface means a surface having a contact angle with respect to tetradecane of 30 ° or more
  • the layer containing a liquid repellent surface means a layer having a surface with a contact angle with respect to tetradecane of 30 ° or more.
  • a layer including a surface of 40 ° or more is preferable.
  • the step (A) of forming a layer containing a liquid repellent surface and a layer containing a lyophilic surface is a step (A-1) of forming a template coating film, and a layer containing a lyophilic surface by irradiation with radiation. It is preferable to include a step (A-2) of forming a pattern and a step (A-3) or (A-4) of forming a pattern by development.
  • the patterned region is a layer including a lyophobic surface
  • the portion removed by development is a layer including a lyophilic surface.
  • the step (B) of applying the curable composition in the forming method includes spin coating, ink jet method, dipping method, printing on a substrate on which a layer including a liquid repellent surface and a layer including a lyophilic surface are formed. Etc., and a method for forming a coating film is not limited.
  • the coating film can be cured by heating or light irradiation.
  • the entire coating film may be exposed, exposed through a photomask, or directly irradiated with a laser or the like.
  • the step (D) of removing the layer including the liquid repellent surface is a step of removing a portion other than the cured film formed by the heating or light irradiation to form a cured film pattern.
  • the removal method is not particularly limited, and examples thereof include development and etching.
  • development may be performed with an alkaline developer or with an organic solvent.
  • the region is further exposed to acid dissociation.
  • the functional group dissociates and becomes a lyophilic region.
  • the layer including the region can be removed with an alkaline developer.
  • the formation method will be described in detail in order.
  • the order of the steps is not limited to the following order, and the order of the steps may be different as long as a similar cured film can be formed, and a plurality of steps may be performed simultaneously.
  • Step (A) of forming a layer including a liquid repellent surface and a layer including a lyophilic surface is a step (A-1) of forming a template coating film, and a layer containing a lyophilic surface by irradiation with radiation.
  • A-1 a step of forming a template coating film, and a layer containing a lyophilic surface by irradiation with radiation.
  • the template coating film forming step (A-1) is a step of forming a template coating film having a liquid-repellent surface from the radiation-sensitive composition.
  • the radiation sensitive composition contains a polymer having an acid dissociable group and a radiation sensitive acid generator.
  • the acid dissociable group refers to a group in which a hydrogen atom in an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group is substituted, and refers to a group that dissociates in the presence of an acid.
  • This radiation sensitive composition will be described in detail later.
  • the template coating film 11 is formed by applying a radiation-sensitive composition to the surface of the substrate 10.
  • Examples of the material of the substrate 10 include glass, quartz, silicon, and resin.
  • Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyether sulfone, polycarbonate, polyimide, cyclic olefin ring-opening polymer (ROMP polymer), polyacrylate, ABS resin, AES resin, and the like. it can.
  • the substrate 10 is preferably a conventional resin substrate, glass substrate, or semiconductor substrate. By using such a substrate, the obtained laminated pattern can be used as it is for optical applications and the like.
  • the application method of the radiation-sensitive composition is not particularly limited, and is a coating method using a brush or brush, a dipping method, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar
  • Known methods such as a coating method, flexographic printing, offset printing, ink jet printing, and dispensing method can be exemplified.
  • the template coating film 11 is preferably heated (pre-baked).
  • the heating conditions vary depending on the composition of the radiation-sensitive composition, but are, for example, about 60 ° C. or higher and 120 ° C. or lower and about 1 minute or longer and 10 minutes or shorter.
  • the average thickness of the template coating film 11 to be obtained can be adjusted as appropriate according to the application, etc., but the lower limit is preferably 0.05 ⁇ m, more preferably 0.1 ⁇ m. On the other hand, the upper limit is preferably 20 ⁇ m, and more preferably 10 ⁇ m.
  • the layer forming step (A-2) including a lyophilic surface as shown in FIG. 1, a part of the surface region of the template coating film 11 is irradiated (exposure) with radiation (h ⁇ ). This is a step of forming the layer 12 including the surface.
  • the surface of the coating film 11 for templates obtained from a radiation sensitive composition has liquid repellency, and the area
  • the region not irradiated with radiation is the layer 13 including a liquid repellent surface.
  • the layer containing a lyophilic surface is a region in which the contact angle with respect to tetradecane described later is 30 degrees or more smaller than the contact angle with respect to tetradecane on the liquid repellent surface. If it exists, it is not necessary to be an area derived from the template coating film. That is, when the template coating film is removed by development and the substrate surface is exposed, the substrate surface becomes a layer including a lyophilic surface. Although the entire substrate surface may be exposed, even a part of the substrate surface is preferable because it becomes a lyophilic surface.
  • the reason why the layer 12 including the lyophilic surface is formed by irradiation with radiation is as follows.
  • an acid is generated from the radiation-sensitive acid generator in the radiation-sensitive composition, whereby the acid-dissociable group of the polymer is dissociated. Due to the dissociation of the acid dissociable group, the surface energy of the irradiated region changes, and wettability increases.
  • the acid-dissociable group has a fluorine atom, the expression of this liquid repellency becomes remarkable.
  • the layer 12 including the lyophilic surface becomes a recess (concave pattern). Since the layer 12 including the lyophilic surface becomes a concave portion, the concave portion (the layer 12 including the lyophilic surface) can be filled with the cured film composition without bleeding, as will be described later.
  • Radiation irradiation can be performed through a photomask having a predetermined pattern so that the layer 12 including a lyophilic surface having a shape similar to the pattern shape of the cured product to be formed is formed.
  • Exposure can be performed through a photomask having a predetermined pattern so that the layer 12 including a lyophilic surface having a shape similar to the pattern shape of the cured product to be formed is formed.
  • the radiation irradiated in this step (A-2) visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray or the like can be used.
  • radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet light having a wavelength of 365 nm is more preferable.
  • the exposure dose of radiation in this step (A-2) may be appropriately set within a range in which a sufficient change in wettability and formation of recesses can be formed.
  • the lower limit of the exposure amount is preferably 10 mJ / cm 2 and more preferably 20 mJ / cm 2 as the intensity of radiation at a wavelength of 365 nm.
  • this upper limit 1000 mJ / cm 2 is preferable, and 500 mJ / cm 2 is more preferable.
  • the size and shape of the layer 12 including the lyophilic surface to be formed correspond to the desired size and shape of the pattern, but can be linear with a width of 50 ⁇ m or less, preferably 0.1. It can be a linear shape of ⁇ 30 ⁇ m, more preferably 0.5 ⁇ 10 ⁇ m.
  • the template coating film 11 and the layer 12 including a lyophilic surface may be heated.
  • the heating condition varies depending on the composition of the radiation-sensitive composition, but is, for example, about 50 ° C. to 120 ° C. and about 1 minute to 20 minutes.
  • the development step (A-3) is a step of developing the template coating film 11 irradiated with radiation.
  • the acid dissociable group can be dissociated in the region irradiated with radiation (layer 12 including a lyophilic surface).
  • the part irradiated with the radiation becomes a layer including a lyophilic surface, and can be removed by the developer.
  • the wettability of the layer including the lyophilic surface is further increased by exposing the substrate surface.
  • a layer including a lyophilic surface can be formed by leaving a partial film without exposing the substrate surface.
  • the depth of the layer 12 (concave portion) including the lyophilic surface formed by leaving a part of the film can be, for example, 0.1 ⁇ m or more and 1 ⁇ m or less. Moreover, as a minimum of the depth of the layer 12 (concave part) containing the lyophilic surface with respect to the average thickness of the layer 13 containing the liquid repellent surface in the coating film 11 for templates, 5% is preferable and 10% is more preferable. On the other hand, the upper limit is preferably 70% and more preferably 50%.
  • Examples of the developer used for development include at least one alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like.
  • An aqueous solution in which is dissolved can be used.
  • An appropriate amount of a water-soluble organic solvent such as methanol or ethanol can be added to the aqueous solution of the alkaline compound described above.
  • an organic solvent shown below when an alkaline aqueous solution is used as a developer, a region irradiated with radiation (a layer including a lyophilic surface) remains and a non-radiation region (hydrophobic surface region) is removed by an organic solvent. A reverse pattern can be formed.
  • an organic solvent developer that can be used, development can be performed using an organic solvent such as ethyl acetate, butyl acetate, and isobutyl acetate as the developer.
  • Examples of the developing method include a liquid filling method, a dipping method, a rocking dipping method, and a spray method.
  • the development time varies depending on the composition of the cured film forming composition, but the lower limit of the development time is preferably 5 seconds, and more preferably 10 seconds. Further, the upper limit of the development time is preferably 300 seconds, and more preferably 180 seconds. Subsequent to the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds and then dried with compressed air or compressed nitrogen, whereby a desired cured film pattern is obtained.
  • the contact angle difference between the layer 12 including the lyophilic surface thus formed and the layer 13 including the liquid repellent surface with respect to tetradecane (the contact angle in the layer 13 including the liquid repellent surface minus the lyophilic surface).
  • the contact angle in the containing layer 12) is 30 ° or more, preferably 40 ° or more, and more preferably 50 ° or more.
  • the upper limit of this contact angle difference is, for example, 70 °.
  • a contact angle difference between the layer 12 including the lyophilic surface and the layer 13 including the lyophobic surface with respect to water contact angle in the layer 13 including the lyophobic surface ⁇ contact in the layer 12 including the lyophilic surface
  • the lower limit of (angle) is preferably 20 °, more preferably 25 °.
  • the upper limit of this contact angle difference is, for example, 90 °.
  • the curable composition in contact with the layer 13 including the lyophobic surface can easily move to the layer 12 including the lyophilic surface, A cured film can be suitably formed along the layer 12 including a lyophilic surface.
  • the step (B) of applying the curable composition is a step of forming a coating film of the curable composition by applying the curable composition to the surface of the template coating film or the substrate surface irradiated with radiation. (See FIGS. 3 and 4).
  • the curable composition is not particularly limited.
  • it may be a curable material containing a component that crosslinks with heat or light, and may contain a polymerizable compound, a polymerization initiator, an additive such as a colorant, a fluorescent substance, a metal oxide, a resin, and the like.
  • a functional resin composition can also be preferably used.
  • the additive refers to a component that does not contribute to polymerization.
  • the curable composition is not particularly limited as long as it contains a curable component, but since the pattern can be complicated, the cured film can be used even if it contains a conductive component so as not to interfere with proximity. Insulating is preferable.
  • “insulating” means a material having a volume resistivity of 1 ⁇ ⁇ cm or more. It can be measured according to JISK7194. Examples thereof include curable compositions described in JP 2012-149141 A, JP 2013-237835 A, and the like.
  • the polymerizable compound is preferably a compound having two or more polymerizable groups.
  • the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. be able to.
  • the polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.
  • the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-functional (meth) acrylate and polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid anhydride
  • the polyfunctional (meth) acrylate which has a carboxyl group obtained by making a product react can be mentioned.
  • examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that.
  • hydroxyl group-containing (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester.
  • a methacrylate etc. can be mentioned.
  • polyfunctional isocyanate examples include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.
  • acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid.
  • dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.
  • Examples of caprolactone-modified polyfunctional (meth) acrylates include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955.
  • the alkylene oxide-modified polyfunctional (meth) acrylate is at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide.
  • Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure.
  • the melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof.
  • the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ′′, N ′′ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril, and the like.
  • polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (Meth) acrylate, N, N, N ′, N ′, N ′′, N ′′ -hexa (alkoxymethyl) melamine, N, N, N ′, N′-tetra (alkoxymethyl) benzoguanamine are preferred.
  • polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol Pentaacrylate and dipentaerythritol hexaacrylate are particularly preferred.
  • the content of the polymerizable compound is usually 3 to 200 parts by weight, preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the total amount of the (A) colorant. is there.
  • the content of the polymerizable compound is usually 20 to 300 parts by weight, preferably 50 to 250 parts by weight, and more preferably 100 to 200 parts by weight with respect to 100 parts by weight of the resin (B).
  • the curable composition of the present invention is preferably a curable composition containing a colorant as an additive.
  • additives include color pigments, dyes, carbon black, metal oxides having a high refractive index, and hollow particles.
  • JP 2006-113380 A, JP 2013-134263 A, WO 2009/119622, WO 2009/119622, JP 2014-146029, JP 2008-46330 examples thereof include a curable composition containing a colorant and the like described in JP-A-2013-225091.
  • Examples of the fluorescent material include inorganic fluorescent materials, organic fluorescent materials, quantum dots, and quantum rods.
  • Examples of the curable composition containing these fluorescent materials include Japanese Unexamined Patent Application Publication Nos. 2014-174406 and 2015-018131. And curable compositions such as JP-A-2015-127733, JP-A-2015-125197, and JP-A-2016-35602.
  • the metal oxide examples include a metal oxide containing at least one metal element selected from the group consisting of titanium oxide, cesium, barium, strontium, calcium, magnesium, zirconium and lead. Specific examples of such metal oxides include titanium oxide, barium oxide, cesium tungsten oxide, barium titanate and strontium titanate.
  • Examples of the curable composition containing these metal oxides include Japanese Patent Application Laid-Open Nos. 2016-14849 and 2016-27384.
  • Examples of the carbon material include carbon nanotubes, fullerenes, graphite, and carbon black materials.
  • the hollow particles are not particularly limited as long as they have pores inside, and may be organic hollow particles or inorganic hollow particles. From the viewpoint of easy dispersion in a solvent, organic hollow particles may be used. Particles are preferred.
  • the organic hollow particles commercially available products may be used, and conventionally known methods, for example, JP-A-62-2127336, JP-A-01-315454, JP-A-4-126771, They may be synthesized by the methods described in JP-A No. 2002-241448, JP-A No. 2007-112935, and Japanese Patent No. 5439102.
  • the inorganic hollow particles are not particularly limited, and examples thereof include inorganic particles composed of glass, SiO 2 , CaCO 3 , polyorganosiloxane compounds, and the like.
  • the high concentration is specifically 30% by mass or more when the total amount of components excluding the solvent of the curable composition is 100% by mass. It means that it is 95% by mass or less, preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more.
  • the coating film formed by the curable composition containing a colorant or the like having a high concentration as described above does not sufficiently transmit radiation due to exposure, for example, the composition described in JP2013-134263A As a result of the insufficient developability of the coating film formed by the product, it is difficult to obtain a desired pattern shape.
  • a desired pattern shape can be easily obtained by the curable composition containing a high concentration of colorant and the like. Can do.
  • the photopolymerization initiator is a compound that generates active species capable of initiating polymerization of a polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.
  • a photoinitiator can be used 1 type or in mixture of 2 or more types.
  • photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, acyl compounds.
  • photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, acyl compounds.
  • examples thereof include phosphine oxide compounds, titanocene compounds, ⁇ -diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, onium salt compounds, and the like.
  • at least one selected from O-acyloxime compounds, acetophenone compounds, acylphosphine oxide compounds, and titanocene compounds is preferable.
  • examples of the O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2 -Methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- ⁇ 2-methyl-4- (2 , 2-Dimethyl-1,3-dioxolanyl) methoxybenzoyl ⁇ -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 1-octanone,
  • O-acyloxime compounds include NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), DFI-020, DFI-091 (above, made by Daito Chemix Corporation), Irgacure® OXE-03, Irgacure® OXE-04 (manufactured by BASF) or the like can also be used.
  • O-acyloxime compounds etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 1- Octanone, 1- [4- [3- [4-[[2- (acetyloxy) ethyl] sulfonyl] -2-methylbenzoyl] -6- [1-[(acetyloxy) imino] ethyl] -9H-carbazole ] -9-yl] phenyl, 1- (O-acetyloxime) is preferred.
  • the acetophenone compound is more preferably an ⁇ -aminoalkylphenone compound, such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpho And linophenyl) butan-1-one.
  • 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one
  • 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpho And linophenyl) butan-1-one 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane
  • the acetophenone compounds can be used alone or in combination of two or more.
  • acylphosphine oxide compounds include, for example, isobutyrylmethylphosphinic acid methyl ester, isobutyrylphenylphosphinic acid methyl ester, pivaloylphenylphosphinic acid methyl ester, 2- Ethyl hexanoylphenylphosphinic acid methyl ester, pivaloylphenylphosphinic acid isopropyl ester, p-toluylphenylphosphinic acid methyl ester, o-toluylphenylphosphinic acid methyl ester, 2,4-dimethylbenzoylphenylphosphinic acid methyl ester, p- t-butylbenzoylphenylphosphinic acid isopropyl ester, acryloylphenylphosphinic acid methyl ester, isobutyryldiphenylphosphine oxide,
  • 2,4,6-trimethylbenzoyldiphenylphosphine oxide (for example, Darocur TPO manufactured by BASF) is preferable as the monoacylphosphine oxide, and bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide (for example, Irgacure 819 manufactured by BASF), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphenylphosphine oxide (for example, Irgacure 1700 manufactured by BASF) ) Is preferred, and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide is more preferred.
  • 2,4,6-trimethylbenzoyldiphenylphosphine oxide for example, Darocur TPO manufactured by BASF
  • bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide for example, Irgacure 819 manufactured by BASF
  • the acylphosphine oxide compounds can be used alone or in combination of two or more.
  • titanocene photo compounds include, for example, bis (cyclopentadienyl) -Ti-di-chloride, bis (cyclopentadienyl) -Ti-bis-phenyl, bis ( Cyclopentadienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis ( Cyclopentadienyl) -Ti-bis-2,4,6-trifluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,6-difluorophenyl, bis (cyclopentadienyl) -Ti-bis -2,4-difluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,4,5,
  • titanocene compounds bis (cyclopentadienyl) -bis (2,6-difluoro-3- (py-1-yl) phenyl) titanium is preferable.
  • the titanocene compounds can be used alone or in combination of two or more. Examples of photopolymerization initiators other than the above include those exemplified in paragraphs [0079] to [0095] of JP2010-134419A.
  • the photopolymerization initiator preferably contains at least one selected from acylphosphine oxide compounds and titanocene compounds.
  • the content is preferably 90% by mass or more, particularly 96% by mass or more of the total photopolymerization initiator.
  • the content of the photopolymerization initiator is 5 to 200 parts by mass, preferably 10 to 100 parts by mass, and more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the polymerizable compound.
  • the said desired pattern is a viewpoint which apply
  • a method for providing a layer including a liquid repellent surface to the desired pattern include a method of adding an ink repellent agent described in WO2015 / 190294 to a curable composition.
  • the contact of the curable composition to the surface of the template coating film 11 can be performed by a known method such as coating. Specifically, application method using brush or brush, dipping method, spray method, roll coating method, spin coating method (spin coating method), slit die coating method, bar coating method, flexographic printing, offset printing, inkjet Well-known methods, such as printing and a dispensing method, can be mentioned.
  • a dipping method, a spray method, a spin coating method, a slit die coating method, an offset printing method, an ink jet method, and a dispensing method are preferable.
  • an ink jet method that can save the liquid of the cured composition and easily applies the cured composition to a desired position is preferable.
  • a layer 12 including a lyophilic surface and a layer 13 including a liquid repellent surface are formed on the surface of the template coating film 11. Therefore, when the curable composition is brought into contact with the surface of the template coating film 11, the curable composition is repelled by the layer 13 including the liquid repellent surface, and preferably includes a lyophilic surface that is a recess. It flows into layer 12. Thereby, the coating film of a curable composition is formed along the layer 12 containing the lyophilic surface which is a recessed part.
  • the cured composition is applied not only to the concave portion but also to the convex portion, and patterning of the cured composition cannot be achieved. Therefore, this method using patterning by lyophilicity and liquid repellency is excellent.
  • the radiation irradiation step is a step of irradiating the side on which the curable composition is applied with radiation (h ⁇ ).
  • exposure can be performed through a photomask, but exposure can also be performed without using a photomask.
  • the hydrophilic region to which the curable composition is applied is cured, and the hydrophobic region becomes a hydrophilic region because the acid dissociation property is dissociated.
  • regions other than the cured portion can be removed by developing with an alkaline aqueous solution (see FIGS. 7 and 8).
  • Specific examples and preferred examples of radiation irradiated in this step are the same as those in the layer forming step including a lyophilic surface.
  • the exposure dose of radiation in this step can also be the same as in the layer forming step including a lyophilic surface.
  • the component derived from the acid dissociable group dissociated in the exposed portion (exposed portion) is volatilized, and the exposed portion becomes thinner and more lyophilic.
  • This heating method is not particularly limited, and examples thereof include a method of heating using a hot plate, oven, dryer or the like. In addition, you may heat by vacuum baking.
  • the heating conditions are not particularly limited, but may be, for example, 50 ° C. or higher and 200 ° C. or lower and 1 minute or longer and 120 minutes or shorter.
  • the development process after exposure of the radiation irradiated in this process is, for example, the same as the layer forming process including a lyophilic surface.
  • the exposure dose of radiation in this step can also be the same as in the layer forming step including a lyophilic surface.
  • the cured film obtained in the present invention can be obtained in an inversely tapered shape (referred to as a downward trapezoidal or T-shaped shape with a large top and a small bottom).
  • the radiation-sensitive composition is not particularly limited, but is preferably a composition in which a part of a coating film formed from the composition volatilizes and decomposes upon irradiation and heating with radiation.
  • a composition containing a polymer having a functional group hereinafter also referred to as “[A] polymer” and an acid generator (hereinafter also referred to as “[C] acid generator”) is more preferable.
  • Such a radiation-sensitive composition is used as an underlayer-forming composition for forming a high-definition pattern by suppressing bleeding of the pattern-forming material on the substrate, and improves the adhesion between the pattern and the substrate.
  • the composition for forming an underlayer can be suitably used.
  • the composition may further contain a solvent (hereinafter also referred to as “[B] solvent”).
  • the composition exhibits a liquid state by containing the [B] solvent, and can easily form a coating film by coating.
  • the composition may further contain a sensitizer as an auxiliary material for the [C] acid generator, and may contain a quencher as a material for suppressing the diffusion of acid from the [C] acid generator.
  • the said composition may contain the polymeric compound which has ethylenically unsaturated bonds other than a [A] polymer, and may contain the radiation sensitive polymerization initiator. Furthermore, the said composition may contain another arbitrary component, unless the effect of this invention is impaired.
  • the viscosity (temperature: 20 ° C., shear rate: 10 sec-1) of the composition may be adjusted depending on the desired coating method and the film thickness of the coating film to be formed.
  • the viscosity is preferably 5 cP (0.003 Pa ⁇ s) to 20 cP (0.02 Pa ⁇ 0.02) when a coating film having a film thickness of 0.5 to 2 ⁇ m is formed and the spin coating method is used as the coating method. s), and when the slit die coating method is used as the coating method, it is preferably 1 cP (0.001 Pa ⁇ s) to 20 cP (0.01 Pa ⁇ s).
  • the acid dissociable group is preferably a group containing a fluorine atom. Since the polymer [A] has such a group, a liquid repellent coating film can be formed in the step (i), and the liquid repellent property can be obtained through the subsequent step (ii). Can be easily formed, and a high-definition pattern can be manufactured through subsequent steps (iv) and (v). preferable.
  • the acid-dissociable group is a group having a group containing at least one bond selected from the group consisting of an acetal bond and a hemiacetal ester bond from the viewpoint that a high-definition pattern can be produced. More preferably, such a group is at least one group selected from the group consisting of a group represented by the following formula (1-1) and a group represented by the following formula (1-2). preferable.
  • R1 and R2 each independently represent a hydrogen atom or a methyl group
  • Rf independently represents an organic group having a fluorine atom. * Indicates a binding site.
  • a compound containing an acetal bond can be obtained by reacting an alcohol with a compound having a group CH2 ⁇ C (R1) —O—, and a compound containing a hemiacetal ester bond can be obtained by reacting a carboxylic acid with a group CH2 ⁇ C ( R1) It can be obtained by reacting with a compound having —O—.
  • Rf is preferably a group of the following formulas (1-1) to (1-33), a 2,2,2-trifluoroethyl group or a 1,2,2-trifluorovinyl group.
  • an acid dissociable group derived from a vinyl ether compound represented by the following formula (1) (hereinafter also referred to as “compound (1)”) is introduced into the hydroxyl group of the precursor compound having a hydroxyl group. It is preferable that it is a compound which has the structure formed.
  • the polymer may be a compound having a structure in which an acid-dissociable group derived from the compound (1) is introduced into a carboxyl group of a compound having a carboxyl group as a precursor.
  • a compound having a structure in which these acid dissociable groups are introduced (hereinafter also referred to as “compound (a)”), particularly a compound having a hydroxyl group as a precursor, is unlikely to cause dissociation of the acid dissociable group due to heat.
  • compound (a) since it has the property that the dissociation of the acid-dissociable group by irradiation can be controlled, it can be suitably used as the [A] polymer.
  • the compound (a) is preferable because the dissociation of the acid dissociable group can be controlled with higher accuracy by irradiation with a combination with the [C] acid generator described later.
  • R 0 represents a hydrogen atom or a methyl group.
  • R A independently represents a methylene group, an alkylene group having 2 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms. And a substituted or unsubstituted alicyclic hydrocarbon group having 4 to 12 carbon atoms, or a group in which one or more hydrogen atoms of these groups are substituted with a fluorine atom.
  • R A is preferably a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, a phenylene group, or a vinylene group.
  • R B represents a group in which one or more hydrogen atoms of a hydrocarbon group are substituted with fluorine atoms.
  • R B represents, for example, a group represented by the formulas (1-1) to (1-33) in the Rf, a 2,2,2-trifluoroethyl group, 1,2,2-trimethyl Fluorovinyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group of the above formula (1-1), 4,4,4- Trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group of formula (1-4), 4,4,5,5,6,6,6-hepta of formula (1-16) Fluorohexyl group, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group of formula (1-8), 1,2,2-tri A fluorovinyl group and a 2,3,4,5,6-pentafluorophenyl group of the formula (1-29) are preferred.
  • x represents an integer of 0 to 12, an integer of 0 to 9 is preferable, and 0 is more preferable.
  • the coating film formed in the step (i) exhibits characteristics based on the [A] polymer, [A]
  • the compound (a) When the compound (a) is used as the polymer, it exhibits characteristics derived from the acid-dissociable group of the compound (a).
  • step (i) when a coating film is formed from the radiation-sensitive composition containing the compound (a), first, in step (i), a liquid-repellent coating film is formed, and when this coating film is irradiated with radiation In the exposed part, dissociation of the acid-dissociable group occurs, and in the part where the acid-dissociable group dissociates, the hydroxyl group remains and the liquid repellency due to the acid-dissociable group is lost.
  • a method for obtaining the [A] polymer will be described.
  • a method for obtaining the [A] polymer two methods are possible: a method using a polymer as a compound serving as a precursor and a method using a monomer as a compound serving as a precursor.
  • the precursor polymer contains a hydroxyl group or a carboxyl group in the molecule, and the compound (1) is reacted with the hydroxyl group or carboxyl group of the precursor polymer. By doing so, the [A] polymer can be obtained.
  • the precursor monomer contains a hydroxyl group or a carboxyl group in the molecule, and the compound (1) is reacted with the hydroxyl group or carboxyl group of the precursor monomer. Then, the [A] polymer can be obtained by polymerizing the obtained monomer.
  • the two methods for obtaining the [A] polymer will be described more specifically.
  • a polymer as a compound to be a precursor a monomer having a hydroxyl group or a carboxyl group is polymerized to obtain a polymer having a hydroxyl group or a carboxyl group (precursor), and then the precursor and The [A] polymer can be obtained by reacting the compound (1) with a hydroxyl group or a carboxyl group of the resulting polymer.
  • (meth) acrylic acid ester is preferable.
  • 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Phenyl (meth) acrylate, 4-hydroxybenzyl acrylamide, 3,5-dimethyl-4-hydroxybenzyl acrylamide, etc. can be mentioned.
  • the compound which has hydroxyl groups and unsaturated bonds such as isopropenyl phenol, can also be used besides this compound.
  • the monomer having a hydroxyl group one type may be used alone, or two or more types may be used.
  • Examples of the monomer having a carboxyl group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 4-carboxylphenyl (meth) acrylate, and the like. Can be mentioned.
  • the monomer which has a carboxyl group may be used individually by 1 type, and may use 2 or more types.
  • the polymer having a hydroxyl group or a carboxyl group which is a precursor of the polymer, can be obtained using only the above-mentioned monomer having a hydroxyl group or a carboxyl group. It can be obtained by copolymerizing with a monomer other than a monomer having a hydroxyl group or a carboxyl group.
  • (meth) acrylic acid chain alkyl ester As monomers other than the monomer having a hydroxyl group or a carboxyl group, (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated aromatic compound, conjugated diene, tetrahydrofuran Mention may be made of unsaturated compounds containing skeletons, maleimides and monomers other than these.
  • Monomers other than the monomer having a hydroxyl group or a carboxyl group may be used alone or in combination of two or more. Specifically, unsaturated compounds described in WO2014 / 178279 can be used.
  • a solvent used in a polymerization reaction for synthesizing a polymer having a hydroxyl group or a carboxyl group which is a precursor of a polymer
  • diethylene glycol monoalkyl ether diethylene glycol dialkyl ether
  • the solvent described in WO2014 / 178279 can be used.
  • the solvent may be used alone or in combination of two or more.
  • one or more molecular weight regulators can be used to adjust the molecular weight.
  • the polystyrene-reduced weight average molecular weight (Mw) of the polymer having a hydroxyl group or a carboxyl group by gel permeation chromatography (GPC) is preferably from 1000 to 40000, more preferably from 1000 to 30000, and further preferably from 5000 to 30000.
  • the sensitivity of the radiation sensitive composition containing the [A] polymer which has this molecular weight can be raised by making Mw of the polymer which has a hydroxyl group or a carboxyl group into the above-mentioned range.
  • a method of reacting the compound (1) with a hydroxyl group or a carboxyl group of a polymer having a hydroxyl group or a carboxyl group to obtain a polymer [A] can be polymerized by a polymerization method described in WO2014 / 178279.
  • an acetal bond is formed by the hydroxyl group of the monomer having a hydroxyl group and the vinyl ether group of the compound (1), or the carboxyl group of the monomer having a carboxyl group
  • a hemiacetal ester bond is formed by the vinyl ether group of the compound (1) to form an adduct.
  • [A] polymer can be obtained in the same manner as in the method for producing a polymer having a hydroxyl group or a carboxyl group as described above.
  • Preferred examples of the [A] polymer obtained as described above include a polymer having at least one selected from the group consisting of structural units represented by the following formulas (2) to (6). .
  • R3 independently represents a hydrogen atom or a methyl group.
  • R4 is independently a methylene group, an alkylene group having 2 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms, or 4 to 12 carbon atoms.
  • R5 independently represents a group in which one or more hydrogen atoms of a hydrocarbon group are substituted with a fluorine atom.
  • m represents 0 or 1; n independently represents an integer of 0 to 12.
  • polymer More preferable examples of the polymer include a polymer having at least one selected from the group consisting of structural units represented by the following formula.
  • a polymer may be used individually by 1 type, and may use 2 or more types.
  • Suitable [B] solvents include alcohol solvents, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aliphatic hydrocarbons. , Aromatic hydrocarbons, ketones and esters. [B] solvent mentioned above may be used individually by 1 type, and may use 2 or more types.
  • the amount of the solvent used is preferably 200 to 1600 parts by mass, and more preferably 400 to 1000 parts by mass with respect to 100 parts by mass of the component excluding the solvent of the radiation-sensitive composition.
  • the amount of the solvent used is preferably 200 to 1600 parts by mass, and more preferably 400 to 1000 parts by mass with respect to 100 parts by mass of the component excluding the solvent of the radiation-sensitive composition.
  • the acid generator is a compound that generates an acid at least upon irradiation with radiation.
  • the radiation-sensitive composition contains a [C] acid generator, the acid-dissociable group can be dissociated from the [A] polymer.
  • Examples of the acid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds.
  • the acid generator may be used alone or in combination of two or more.
  • oxime sulfonate compound As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (5) is preferable.
  • R 11 is an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl having 6 to 20 carbon atoms. Or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group are substituted with a substituent.
  • oxime sulfonate compounds include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene).
  • onium salt examples include diphenyliodonium salt, triphenylsulfonium salt, alkylsulfonium salt, benzylsulfonium salt, dibenzylsulfonium salt, substituted benzylsulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt. Of these, triphenylsulfonium salt is particularly preferable.
  • Preferred sulfonimide compounds as acid generators include, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N— (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-tri Fluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) succinimi
  • the content of the [C] acid generator is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the [A] polymer.
  • ⁇ Other optional components As other optional components, a surfactant, a storage stabilizer, an adhesion assistant, a heat resistance improver, and the like can be blended. Specific examples and formulation examples of these optional components can be referred to the specific examples and formulation examples described in WO2014 / 178279.
  • solid content concentration means the ratio of the copolymer mass which occupies for the total mass of a copolymer solution.
  • the obtained reaction solution was added dropwise to a large excess of methanol for reprecipitation purification, and after drying, 230 parts by mass of [A] polymer (P-1) was obtained as a white solid copolymer.
  • the obtained [A] polymer (P-1) was analyzed using 1 H-NMR to confirm that acetalization had progressed (chemical shift: 5.50 ppm, acetal group C—H). .
  • the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing a polymer (P-2) as a copolymer.
  • the polymer (P-2) had a weight average molecular weight (Mw) in terms of polystyrene of 9000.
  • Mw weight average molecular weight
  • the solid content concentration of the polymer solution obtained here was 31.3 mass%.
  • a surfactant 0.1 parts by mass of Polyflow No95 (manufactured by Kyoeisha Chemical Co., Ltd.) is added, and when the total amount of components excluding the solvent is 100% by mass, 30% by mass, respectively. After adding propylene glycol monomethyl ether acetate, the mixture is filtered through a Millipore filter having a pore size of 0.5 ⁇ m to obtain a radiation sensitive composition (X-3 ) Was prepared.
  • a coating film was formed on the substrate using the above radiation sensitive compositions (X-1) to (X-3), and a template was formed through exposure and development steps.
  • the forming method is shown below. It is described as a template pattern (T-1 to T-7).
  • the exposed portion was removed by immersing the substrate in an aqueous 2.38% tetraammonium hydroxide solution for 2 minutes.
  • the finally obtained pattern was dried and baked on a hot plate at 90 ° C. for 15 minutes to obtain a liquid repellent template pattern (T-1).
  • T-1 liquid repellent template pattern
  • the contact angle with respect to tetradecane of the layer containing the remaining liquid repellent surface is 60 °
  • the contact angle with water is 109 °
  • the contact angle with respect to tetradecane of the lyophilic surface without the film is 8 °
  • the contact angle with water is It was 23 °, and it was confirmed that the layer including the liquid repellent surface was sufficiently liquid repellent.
  • the contact angle with respect to tetradecane of the layer including the remaining liquid repellent surface is 61 °
  • the contact angle with water is 110 °
  • the contact angle with respect to tetradecane of the lyophilic surface having no film is 9 °
  • the contact angle with water is It was 25 °, and it was confirmed that the layer including the liquid repellent surface was sufficiently liquid repellent.
  • the contact angle with respect to tetradecane of the layer containing the remaining liquid repellent surface is 61 °
  • the contact angle with water is 110 °
  • the contact angle with respect to tetradecane of the lyophilic surface having no film is 7 °
  • the contact angle with water is It was 23 °, and it was confirmed that the layer including the liquid repellent surface was sufficiently liquid repellent.
  • the contact angle with respect to tetradecane of the layer containing the remaining liquid-repellent surface is 60 °
  • the contact angle with water is 106 °
  • the contact angle with tetradecane of the lyophilic surface where no film is present is 8 °
  • the contact angle with water is It was 25 °, and it was confirmed that the layer including the liquid repellent surface was sufficiently liquid repellent.
  • the contact angle with respect to tetradecane of the layer containing the remaining liquid-repellent surface is 60 °
  • the contact angle with water is 108 °
  • the contact angle with tetradecane of the lyophilic surface without the film is 8 °
  • the contact angle with water is It was 25 °, and it was confirmed that the layer including the liquid repellent surface was sufficiently liquid repellent.
  • the contact angle with respect to tetradecane of the layer containing the remaining liquid repellent surface is 60 °
  • the contact angle with water is 109 °
  • the contact angle with respect to tetradecane of the lyophilic surface without the film is 8 °
  • the contact angle with water is It was 24 °, and it was confirmed that the layer including the liquid repellent surface was sufficiently liquid repellent.
  • the contact angle with respect to tetradecane of the layer containing the remaining liquid-repellent surface is 5 °
  • the contact angle with water is 52 °
  • the contact angle with respect to tetradecane of the lyophilic surface without the film is 6 °
  • the contact angle with water is It was 28 °.
  • a curable composition was prepared as a curable ink composition as follows.
  • ⁇ Preparation of curable ink composition (B-1)> As a polymerizable compound, dipentaerythritol hexaacrylate (30 parts by mass), trimethylolpropane triacrylate (30 parts by mass), isobornyl acrylate (35 parts by mass), 3-acryloxypropyltrimethoxysilane (5 parts by mass), Irgacure 907 (BASF, 8 parts by mass) as a photopolymerization initiator and Basic Blue 7 (TCI, 0.5 parts by mass) as a colorant were stirred until uniform to prepare an ink composition (B-1). .
  • an emulsifier an anionic surfactant (New Coal 707SF manufactured by Nippon Emulsifier Co., Ltd., active ingredient concentration: 30% by mass), 3.3 parts by mass (in terms of active ingredient), and 60 parts by mass of water are added to the composition.
  • An aqueous dispersion of the monomer was prepared by dispersing and mixing with an ultrasonic disperser under ice cooling.
  • hollow organic particles prepared according to the method described in Example ⁇ Production of Hollow Base Particles (A-1)> of Japanese Patent No. 5181565 30% by volume) aqueous dispersion 7.0 parts by weight (in terms of non-volatile content), 28.0 parts in terms of solid organic particle dispersion (in terms of non-volatile content), a fluorosurfactant (Kyoeisha Chemical Co., Ltd.) as a wetting agent ) Produced aftergent 215M) and 0.3 parts by mass of water and water were added so that the non-volatile content was 25% by mass, and the mixture was stirred well to prepare an ink composition (B-2).
  • TMPTA Trimethylolpropane triacrylate 100 parts by mass as a polymerizable compound, Irgacure 907 (BASF, 3 parts by mass) as a photopolymerization initiator, and carbon black MA100R (Mitsubishi Chemical Corporation, 20 parts by mass) as a black pigment,
  • the ink composition (B-3) was prepared by stirring well at room temperature.
  • carbon black Printex 45, average primary particle size 26 nm, manufactured by Orion Engineered Carbons
  • DISPERBYK-168 manufactured by BYK Chemie
  • paramethoxyphenol as a polymerization inhibitor 0.1 parts by mass
  • carbon black Printex 45, average primary particle size 26 nm, manufactured by Orion Engineered Carbons
  • DISPERBYK-161 manufactured by BYK Chemie
  • Solsperse 5000 as a dispersion aid 1 part by mass of Lubrizol
  • 3-methoxybutanol 3-methoxybutanol
  • the black dispersion liquid (V-2) 87.8 parts by mass, EPICLON EXA-4816 (manufactured by DIC) 9.2 parts by mass as a crosslinking agent, N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester 1. 7 parts by mass, 1.2 parts by mass of 3-glycidoxypropyltrimethoxysilane as an adhesion assistant are mixed, and an ink composition (B-5) having a carbon black concentration of 50% by mass with respect to the total amount of components excluding the solvent Was prepared.
  • An ink composition (B-8) having a carbon black concentration of 50% by mass relative to the total amount of the components excluding the components was prepared.
  • the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a polymer (Q-1).
  • ⁇ Preparation of curable ink composition (B-10)> Add 100 parts by weight of trimethylolpropane triacrylate (TMPTA) as a polymerizable compound, Irgacure 907 (BASF, 3 parts by weight) as a photopolymerization initiator, and titanium oxide (20 parts by weight) as a metal oxide material, and stir well at room temperature.
  • TMPTA trimethylolpropane triacrylate
  • Irgacure 907 BASF, 3 parts by weight
  • titanium oxide 20 parts by weight
  • the reaction solution was heated to 80 ° C. with stirring. Then, the polymerization was carried out while maintaining this temperature for 5 hours to obtain a polymerization solution containing 33% by mass of the alkali-soluble resin (P-3).
  • the weight average molecular weight (Mw) in terms of polystyrene by GPC of this alkali-soluble resin C1 was 3,000.
  • V-4 black pigment dispersion
  • 20.0 parts by mass of carbon black Printex 45, average primary particle size 26 nm, manufactured by Orion Engineered Carbons
  • 4.0 parts by mass of DISPERBYK-2001 manufactured by BYK Chemie
  • Black pigment dispersion (V-4) was prepared by mixing with butyl acetate with a bead mill using a solid content of 24% by mass.
  • ⁇ Preparation of black resist composition 150 parts by mass of a black pigment dispersion (V-4), 19 parts by mass of a polymerization solution (solid content concentration: 33% by mass) containing an alkali-soluble resin (P-3), and dipentaerythritol hexaacrylate as a polymerizable oligomer.
  • a white pigment dispersion (V-5) was prepared by mixing with a bead mill using a partial concentration of 45% by mass.
  • ⁇ Preparation of white resist composition 150 parts by weight of a white pigment dispersion (V-5), 19 parts by weight of a polymerization solution (solid content concentration 33% by weight) containing an alkali-soluble resin (P-3), and dipentaerythritol hexaacrylate as a polymerizable oligomer.
  • Example 1 An ink composition (B-1) was formed on a linear liquid-repellent template (T-1) having a thickness of 0.5 ⁇ m and a width of 50 ⁇ m obtained using the radiation-sensitive resin composition (X-1). As a result, the ink composition was not applied on the liquid repellent pattern but was selectively applied onto a 50 ⁇ m development pattern. Then, the exposure amount was set to 1000 mJ / cm 2 using a high-pressure mercury lamp, the whole substrate was irradiated with radiation, and then heated at 70 ° C. for 15 minutes to cure the ink composition.
  • Example 2 The ink composition (B-1) is formed on the 10 ⁇ m-thick line-like liquid-repellent template (T-2) obtained by using the radiation-sensitive resin composition (X-1).
  • T-2 the 10 ⁇ m-thick line-like liquid-repellent template obtained by using the radiation-sensitive resin composition (X-1).
  • X-1 the radiation-sensitive resin composition
  • ink-jet coating was performed using a Mattix Material Printer DMP-2831 (Fujifilm Global Graphic Systems)
  • the ink composition did not remain on the liquid repellent pattern and was selectively coated on a 10 ⁇ m development pattern.
  • the high-pressure mercury lamp was used, the exposure dose was 1000 mJ / cm 2 using the high-pressure mercury lamp, the whole substrate was irradiated with radiation, and then heated at 70 ° C. for 15 minutes to cure the ink composition.
  • the substrate was immersed in an aqueous 2.38% tetramethylammonium hydroxide solution for 2 minutes to remove the liquid repellent template portion, and the cured ink composition (B-1) remained.
  • the obtained pattern width was 10 ⁇ m, and a pattern matched to the template width was formed favorably.
  • Example 3 On the 10 ⁇ m thick, 10 ⁇ m ⁇ 10 ⁇ m square liquid-repellent template (T-3) (FIG. 16) obtained using the radiation sensitive resin composition (X-2), the ink composition (B -1) was applied by inkjet using DMP-2831 (Fujifilm Global Graphic Systems Co., Ltd.), and the ink composition did not remain on the liquid repellent pattern and was selected on a 10 ⁇ m ⁇ 10 ⁇ m development pattern. Applied.
  • the high-pressure mercury lamp was used, the exposure dose was 1000 mJ / cm 2 using the high-pressure mercury lamp, the whole substrate was irradiated with radiation, and then heated at 70 ° C. for 15 minutes to cure the ink composition.
  • the substrate was immersed in an aqueous 2.38% tetramethylammonium hydroxide solution for 2 minutes to remove the liquid repellent template portion, and the cured ink composition (B-1) (FIG. 17) remained.
  • the obtained pattern was 10 ⁇ m ⁇ 10 ⁇ m, and the pattern matched to the template was formed favorably.
  • Example 4 On the line-shaped liquid repellent template (T-4) having a thickness of 2.0 ⁇ m and a width of 50 ⁇ m obtained by using the radiation sensitive resin composition (X-2), the ink composition (B-2) As a result of dip coating, the ink composition did not remain on the liquid repellent pattern but was selectively coated on a 50 ⁇ m development pattern.
  • the high-pressure mercury lamp was used, the exposure dose was 1000 mJ / cm 2 using the high-pressure mercury lamp, the whole substrate was irradiated with radiation, and then heated at 70 ° C. for 15 minutes to cure the ink composition.
  • the substrate was immersed in an aqueous 2.38% tetramethylammonium hydroxide solution for 2 minutes to remove the liquid repellent template portion, and the cured ink composition (B-2) remained.
  • the obtained pattern width was 50 ⁇ m, and a pattern matched to the template width was formed favorably.
  • Example 5 On the liquid repellent template (T-2) obtained by using the radiation sensitive resin composition (X-1), the ink composition (B-3) was added to the Dimamics Material Printer DMP-2831 (Fuji When ink jet coating was performed using Film Global Graphic Systems), the ink composition did not remain on the liquid repellent pattern, but was selectively coated on a 10 ⁇ m wide development pattern.
  • the high-pressure mercury lamp was used, the exposure amount was 1000 mJ / cm 2 using the high-pressure mercury lamp, and the entire substrate was irradiated with radiation to cure the ink composition.
  • the substrate was immersed in an aqueous 2.38% tetramethylammonium hydroxide solution for 2 minutes to remove the liquid repellent template portion, and the cured ink composition (B-3) remained.
  • the obtained pattern width was 10 ⁇ m, and a pattern matched to the template width was formed favorably.
  • Example 6 On the line-shaped liquid repellent template (T-5) (FIG. 18) having a thickness of 10 ⁇ m and a width of 10 ⁇ m obtained using the radiation-sensitive resin composition (X-2), the ink composition (B- When 4) was applied using a microcapillary, the ink composition did not remain on the liquid repellent pattern, but was selectively applied on a 10 ⁇ m development pattern.
  • the high-pressure mercury lamp was used, the exposure dose was 1000 mJ / cm 2 using the high-pressure mercury lamp, the whole substrate was irradiated with radiation, and then heated at 70 ° C. for 15 minutes to cure the ink composition.
  • the substrate was immersed in an aqueous 2.38% tetramethylammonium hydroxide solution for 2 minutes to remove the liquid repellent template portion, and the cured ink composition (B-4) remained.
  • the obtained pattern width was 10 ⁇ m, and a pattern corresponding to the template width was well formed (FIG. 19).
  • Example 7 On the 5 ⁇ m-thickness, 10 ⁇ m-wide line-shaped liquid-repellent template (T-6) obtained using the radiation-sensitive resin composition (X-2), the ink composition (B-5) was micronized. When applied using a capillary, the ink composition did not remain on the liquid repellent pattern, but was selectively applied onto a 10 ⁇ m development pattern.
  • the high-pressure mercury lamp was used, the exposure dose was 1000 mJ / cm 2 using the high-pressure mercury lamp, the whole substrate was irradiated with radiation, and then heated at 70 ° C. for 15 minutes to cure the ink composition.
  • the substrate was immersed in an aqueous 2.38% tetramethylammonium hydroxide solution for 2 minutes to remove the liquid repellent template portion, and the cured ink composition (B-5) remained.
  • the obtained pattern width was 10 ⁇ m, and a pattern matched to the template width was formed favorably.
  • Example 8 The ink composition (B-6) is micro-coated on the 5 ⁇ m-thickness, 10 ⁇ m-width linear liquid-repellent template (T-6) obtained by using the radiation-sensitive resin composition (X-2). When applied using a capillary, the ink composition did not remain on the liquid repellent pattern, but was selectively applied onto a 10 ⁇ m development pattern.
  • the high-pressure mercury lamp was used, the exposure dose was 1000 mJ / cm 2 using the high-pressure mercury lamp, the whole substrate was irradiated with radiation, and then heated at 70 ° C. for 15 minutes to cure the ink composition.
  • the substrate was immersed in an aqueous 2.38% tetramethylammonium hydroxide solution for 2 minutes to remove the liquid repellent template portion, and the cured ink composition (B-6) remained.
  • the obtained pattern width was 10 ⁇ m, and a pattern matched to the template width was formed favorably.
  • Example 9 The ink composition (B-7) was micro-coated on the 5 ⁇ m-thickness, 10 ⁇ m-width linear liquid-repellent template (T-6) obtained using the radiation-sensitive resin composition (X-2). When applied using a capillary, the ink composition did not remain on the liquid repellent pattern, but was selectively applied onto a 10 ⁇ m development pattern.
  • the high-pressure mercury lamp was used, the exposure dose was 1000 mJ / cm 2 using the high-pressure mercury lamp, the whole substrate was irradiated with radiation, and then heated at 70 ° C. for 15 minutes to cure the ink composition.
  • the substrate was immersed in an aqueous 2.38% tetramethylammonium hydroxide solution for 2 minutes to remove the liquid repellent template portion, and the cured ink composition (B-7) remained.
  • the obtained pattern width was 10 ⁇ m, and a pattern matched to the template width was formed favorably.
  • Example 10 On the 5 ⁇ m-thickness, 10 ⁇ m-wide linear liquid-repellent template (T-6) obtained by using the radiation-sensitive resin composition (X-2), the ink composition (B-8) was micronized. When applied using a capillary, the ink composition did not remain on the liquid repellent pattern, but was selectively applied onto a 10 ⁇ m development pattern.
  • the high-pressure mercury lamp was used, the exposure dose was 1000 mJ / cm 2 using the high-pressure mercury lamp, the whole substrate was irradiated with radiation, and then heated at 70 ° C. for 15 minutes to cure the ink composition.
  • the substrate was immersed in an aqueous 2.38% tetramethylammonium hydroxide solution for 2 minutes to remove the liquid repellent template portion, and the cured ink composition (B-8) remained.
  • the obtained pattern width was 10 ⁇ m, and a pattern matched to the template width was formed favorably.
  • Example 11 On the line-shaped liquid repellent template (T-3) having a thickness of 2.0 ⁇ m and a width of 50 ⁇ m obtained by using the radiation sensitive resin composition (X-2), the ink composition (B-9) was applied using a microcapillary, and the ink composition did not remain on the liquid repellent pattern but was selectively applied onto a 50 ⁇ m development pattern.
  • the high-pressure mercury lamp was used, the exposure dose was 1000 mJ / cm 2 using the high-pressure mercury lamp, the whole substrate was irradiated with radiation, and then heated at 70 ° C. for 15 minutes to cure the ink composition.
  • the substrate was immersed in an aqueous 2.38% tetramethylammonium hydroxide solution for 2 minutes to remove the liquid repellent template portion, and the cured ink composition (B-9) remained.
  • the obtained pattern width was 50 ⁇ m, and a pattern matched to the template width was formed favorably.
  • the obtained pattern was further examined for fluorescence quantum yield at 25 ° C. using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics).
  • the fluorescence quantum yield was 38%, and the fluorescence characteristics were judged to be good.
  • Example 12 On the 5 ⁇ m-thickness, 10 ⁇ m-wide line-shaped liquid-repellent template (T-6) obtained by using the radiation-sensitive resin composition (X-2), the ink composition (B-10) was micronized. When applied using a capillary, the ink composition did not remain on the liquid repellent pattern, but was selectively applied onto a 10 ⁇ m development pattern.
  • the high-pressure mercury lamp was used, the exposure dose was 1000 mJ / cm 2 using the high-pressure mercury lamp, the whole substrate was irradiated with radiation, and then heated at 70 ° C. for 15 minutes to cure the ink composition.
  • the substrate was immersed in an aqueous 2.38% tetramethylammonium hydroxide solution for 2 minutes to remove the liquid repellent template portion, and the cured ink composition (B-10) remained.
  • the obtained pattern width was 10 ⁇ m, and a pattern matched to the template width was formed favorably.
  • Example 13 On the 5 ⁇ m-thickness, 10 ⁇ m-wide line-shaped liquid-repellent template (T-6) obtained by using the radiation-sensitive resin composition (X-2), the ink composition (B-11) was micronized. When applied using a capillary, the ink composition did not remain on the liquid repellent pattern, but was selectively applied onto a 10 ⁇ m development pattern.
  • the high-pressure mercury lamp was used, the exposure dose was 1000 mJ / cm 2 using the high-pressure mercury lamp, the whole substrate was irradiated with radiation, and then heated at 70 ° C. for 15 minutes to cure the ink composition.
  • the substrate was immersed in an aqueous 2.38% tetramethylammonium hydroxide solution for 2 minutes to remove the liquid repellent template portion, and the cured ink composition (B-11) remained.
  • the obtained pattern width was 10 ⁇ m, and a pattern matched to the template width was formed favorably.
  • Example 14 On the 5 ⁇ m-thickness, 10 ⁇ m-wide line-shaped liquid-repellent template (T-6) obtained by using the radiation-sensitive resin composition (X-2), the ink composition (B-12) was micronized. When applied using a capillary, the ink composition did not remain on the liquid repellent pattern, but was selectively applied onto a 10 ⁇ m development pattern.
  • the high-pressure mercury lamp was used, the exposure dose was 1000 mJ / cm 2 using the high-pressure mercury lamp, the whole substrate was irradiated with radiation, and then heated at 70 ° C. for 15 minutes to cure the ink composition.
  • the substrate was immersed in an aqueous 2.38% tetramethylammonium hydroxide solution for 2 minutes to remove the liquid repellent template portion, and the cured ink composition (B-12) remained.
  • the obtained pattern width was 10 ⁇ m, and a pattern matched to the template width was formed favorably.
  • the black resist composition (B-13) was applied to a silicon wafer substrate using a spin coater, and then pre-baked on a 90 ° C. hot plate for 150 seconds to form a film having a thickness of 1.7 ⁇ m.
  • the substrate is cooled to room temperature, and each wavelength of 365 nm, 405 nm, and 436 nm is applied to the coating film through a photomask having a width of 50 ⁇ m using an exposure apparatus (trade name “Mask Aligner MA200e”, manufactured by SUSS). Exposed ultraviolet light was exposed.
  • the exposure amount at this time was 500 mJ / cm 2. Thereafter, the substrate was shower-developed for 1 minute using a 0.05% by weight tetramethylammonium hydroxide aqueous solution containing a polyoxyethylene surfactant at 23 ° C.
  • the white resist composition (B-14) was applied to a silicon wafer substrate using a spin coater, and then pre-baked on a 90 ° C. hot plate for 150 seconds to form a film having a thickness of 1.7 ⁇ m.
  • the substrate is cooled to room temperature, and each wavelength of 365 nm, 405 nm, and 436 nm is applied to the coating film through a photomask having a width of 50 ⁇ m using an exposure apparatus (trade name “Mask Aligner MA200e”, manufactured by SUSS). Exposed ultraviolet light was exposed. The exposure amount at this time was 500 mJ / cm 2.
  • the substrate was shower-developed for 1 minute using a 0.05% by mass tetramethylammonium hydroxide aqueous solution containing a polyoxyethylene surfactant at 23 ° C. And it wash
  • post baking was performed on a hot plate at 180 ° C. for 5 minutes to form a patterned film on the substrate.
  • the obtained patterned film was observed with an electron microscope to confirm whether the pattern was formed satisfactorily. As a result, it was found that the white pattern was not confirmed and disappeared during development. This is because the white pigment concentration was too high and photocuring did not proceed sufficiently.
  • a black ink composition (B-3) to (B-7) is coated on a 9.5 cm square non-alkali glass substrate (EAGLE-XG, 0.7 mm thickness, manufactured by Corning)), and a high-pressure mercury lamp The exposure amount was set to 1000 mJ / cm 2 using, and the entire substrate was irradiated with radiation, followed by heating at 70 ° C. for 15 minutes to cure the ink composition to a thickness of 1 ⁇ m. Thereafter, the optical density OD value of the black cured film was measured under an atmosphere of 23 ° C. and 55% RH using X-Rite 361T (manufactured by Sakata Inx Engineering).
  • a black ink composition (B-5), (B-7), (B-8) is entirely coated on a 9.5 cm square alkali-free glass substrate (EAGLE-XG, 0.7 mm thickness, manufactured by Corning). Apply, set the exposure to 1000 mJ / cm 2 using a high-pressure mercury lamp, irradiate the entire substrate with radiation, and then heat at 70 ° C. for 15 minutes to cure the ink composition to a thickness of 1 ⁇ m. It was.
  • the contact angle on the surface of the cured film of the present invention was confirmed.

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019193941A1 (ja) * 2018-04-02 2019-10-10 Jsr株式会社 硬化膜の形成方法及び硬化性組成物
CN110850680A (zh) * 2018-08-21 2020-02-28 Jsr株式会社 硬化性组合物、显示元件及硬化膜的形成方法
TWI696045B (zh) * 2018-05-21 2020-06-11 日商信越化學工業股份有限公司 圖案形成方法
JP6947269B1 (ja) * 2020-09-18 2021-10-13 荒川化学工業株式会社 環状オレフィン樹脂用コーティング剤、コーティング剤キット、硬化物、及び積層物
KR20230046242A (ko) 2021-09-29 2023-04-05 후지필름 가부시키가이샤 조성물, 차광막, 고체 촬상 소자, 화상 표시 장치, 경화막의 제조 방법
CN110850680B (en) * 2018-08-21 2024-10-25 Jsr株式会社 Curable composition, display element, and method for forming cured film

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110459691B (zh) * 2019-08-30 2022-04-08 京东方科技集团股份有限公司 显示基板及其制作方法、和显示装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006349981A (ja) * 2005-06-16 2006-12-28 Jsr Corp 着色層形成用感放射線性組成物およびカラーフィルタ
JP2008256972A (ja) * 2007-04-05 2008-10-23 Toppan Printing Co Ltd 光学素子の製造方法、カラーフィルタの製造方法及び有機エレクトロルミネッセンス素子の製造方法
WO2014178279A1 (ja) * 2013-05-01 2014-11-06 Jsr株式会社 凹パターンを有する基材の製造方法、組成物、導電膜の形成方法、電子回路および電子デバイス
JP2016087602A (ja) * 2014-10-31 2016-05-23 Jsr株式会社 親液部と撥液部を有する基材の製造方法、組成物、導電膜の形成方法、電子回路および電子デバイス

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0147976B1 (ko) * 1995-06-30 1998-10-15 배순훈 박막 헤드의 패턴 평탄화 방법
JP2007178532A (ja) * 2005-12-27 2007-07-12 Seiko Epson Corp カラーフィルタ基板の製造方法および液晶表示装置の製造方法
JP6197418B2 (ja) 2013-07-05 2017-09-20 株式会社リコー 積層配線の形成方法、積層配線、及び電子素子
TWI651593B (zh) * 2014-03-14 2019-02-21 日商Ｊｓｒ股份有限公司 配線的製造方法、感放射線性組成物、電子電路及電子元件
CN105573053B (zh) * 2014-10-31 2020-12-29 Jsr株式会社 具有亲液部与疏液部的基材的制造方法及其应用及组合物
JP6776565B2 (ja) * 2016-03-15 2020-10-28 Jsr株式会社 親撥材を用いたパターン形成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006349981A (ja) * 2005-06-16 2006-12-28 Jsr Corp 着色層形成用感放射線性組成物およびカラーフィルタ
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JP2022051220A (ja) * 2020-09-18 2022-03-31 荒川化学工業株式会社 環状オレフィン樹脂用コーティング剤、コーティング剤キット、硬化物、及び積層物
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