JP2021099476A - Method of manufacturing article with moth-eye structure, article with moth-eye structure, moth-eye structure-forming composition for oxygen ion beam processing, method of manufacturing article with protrusions, and structure for forming article with moth-eye structure - Google Patents

Abstract

To provide a method of manufacturing an article with a moth-eye structure having superior light-transmissivity, an article with a moth-eye structure, a moth-eye structure-forming composition for oxygen ion beam processing, and a method of manufacturing an article with protrusions.SOLUTION: A method of manufacturing an article with a moth-eye structure is provided, comprising preparing an article containing an aromatic ring-containing resin on at least part of a surface, and subjecting at least part of the area with the aromatic ring-containing resin to ion-beam processing using a gas containing oxygen.SELECTED DRAWING: Figure 3

Description

The present disclosure relates to a method for producing an article having a moth-eye structure, an article having a moth-eye structure, a moth-eye structure forming composition for oxygen ion beam processing, a method for producing an article having a protrusion group, and a structure for forming an article having a moth-eye structure.

In recent years, high-density semiconductor devices, magnetic recording devices, MEMS, next-generation recording media, and the like may be required to be subjected to micro-order or nano-order fine processing (see, for example, Patent Document 1). There are various purposes for performing microfabrication, and for example, in a display, a lens, or the like, prevention of surface reflection can be mentioned. An antireflection structure (moss eye structure) having micro-order or nano-order irregularities is provided on the surface of such an article.

As a nano-order microfabrication method, nanoimprint lithography using a mold is attracting attention (see, for example, Non-Patent Document 1). In nanoimprint lithography, a mold on which a nanometer-sized uneven pattern is drawn is pressed against a resist on a substrate to transfer the pattern, and the resist is cured to form a fine uneven pattern.

The nanoimprint mold is usually processed from a substrate such as a hard ceramic such as glassy carbon (glassy carbon) or titanium oxide (TiO ₂ ) (see, for example, Patent Document 2). A method of forming a fine concavo-convex structure on glassy carbon is generally to form a mask corresponding to the concavo-convex structure on the surface of glassy carbon and etch in this state.

JP-A-2002-192500 Japanese Unexamined Patent Publication No. 2010-0133337

S. Y. Chou, P. R. Krauss, and P. J. Renstrom, “Imprint of sub-25 nm vias and trenches in polymers”, Appl. Phys. Lett. 67 pp.3114-3116 (1995) 3114

However, since the mold formed from glassy carbon has low light transmittance, there is a problem that curing does not proceed easily when a transfer pattern is formed using a photocurable resist.
Therefore, the present invention relates to a method for producing an article with a moth-eye structure having excellent light transmission, an article with a moth-eye structure, a moth-eye structure forming composition for oxygen ion beam processing, a method for producing an article with a protrusion group, and an article having a moth-eye structure. The purpose is to provide a structure.

Means for solving the above problems include the following embodiments.
<1> A step of preparing an article containing an aromatic ring-containing resin on at least a part of the surface, and
A step of performing ion beam processing using a gas containing oxygen on at least a part of the region containing the aromatic ring-containing resin, and
A method for manufacturing an article with a moth-eye structure.
<2> The aromatic ring-containing resin is at least one selected from the group consisting of aromatic polyimide, a resin having a structural unit derived from a compound having a styrene skeleton, an aromatic ring-containing acrylic resin, and an aromatic ring-containing epoxy resin. The method for producing an article having a styrene structure according to <1>, which includes.
<3> The aromatic ring-containing resin is composed of an aromatic polyimide, a dehydrated ring-closed product of an aromatic polyamic acid, a cured product of a compound having a styrene skeleton, a cured product of an aromatic ring-containing acrylic compound, and a cured product of an aromatic ring-containing epoxy compound. The method for producing an article having a styrene structure according to <1> or <2>, which comprises at least one selected from the group.
<4> The method for producing an article having a moth-eye structure according to <3>, wherein the aromatic ring-containing acrylic compound contains a radically polymerized aromatic ring-containing acrylic compound.
<5> The method for producing an article with a moth-eye structure according to <3>, wherein the aromatic ring-containing epoxy compound contains a cationically polymerized aromatic ring-containing epoxy compound.
<6> In the step of preparing the article, at least one selected from the group consisting of a compound having the styrene skeleton on at least a part of the surface of the substrate, the aromatic ring-containing acrylic compound, and the aromatic ring-containing epoxy compound is selected. Then, at least one selected from the group consisting of the compound having the styrene skeleton, the aromatic ring-containing acrylic compound and the aromatic ring-containing epoxy compound is cured, and the cured product of the compound having the styrene skeleton, the fragrance. Item 2. The moth eye according to any one of <3> to <5>, which forms a film containing at least one selected from the group consisting of a cured product of a ring-containing acrylic compound and a cured product of the aromatic ring-containing epoxy compound. A method for manufacturing structural articles.
<7> In the step of preparing the article, after applying the aromatic polyamic acid to at least a part of the surface of the substrate, the aromatic polyamic acid is dehydrated and ring-closed to form a film containing the aromatic polyimide. , <3>. The method for manufacturing an article with a moth-eye structure.
<8> An article having a moth-eye structure having a moth-eye structure having a plurality of protrusions on at least a part of the surface, and the moth-eye structure contains an aromatic ring-containing resin.
<9> The aromatic ring-containing resin is at least one selected from the group consisting of aromatic polyimide, a resin having a structural unit derived from a compound having a styrene skeleton, an aromatic ring-containing acrylic resin, and an aromatic ring-containing epoxy resin. The article with a styrene structure according to <8>, which includes.
<10> The article with a moth-eye structure according to <8> or <9>, wherein the average diameter of the plurality of protrusions in the moth-eye structure is 5 μm or less.
<11> The article with a moth-eye structure according to any one of <8> to <10>, wherein the average value of the height ratio (aspect ratio) to the diameters of the plurality of protrusions in the moth-eye structure is 2 or more. ..
<12> The article with a moth-eye structure according to any one of <8> to <11>, wherein at least a part of the surface is a curved surface and at least a part of the curved surface has a moth-eye structure.
<13> The item according to any one of <8> to <12>, wherein the article includes a lens, a curved display, an instrument panel of an automobile having a curved surface, a showcase having a curved surface, and a signage having a curved surface. Goods with moth-eye structure.
<14> The article having a moth-eye structure according to any one of <8> to <13>, which is a nanoimprint mold.
<15> The article with a moth-eye structure according to any one of <8> to <13>, which is a replica mold for nanoimprint.
<16> A moth-eye structure forming composition for oxygen ion beam processing, which comprises at least one selected from the group consisting of an aromatic ring-containing resin and an aromatic ring-containing compound which is a precursor of the aromatic ring-containing resin.
<17> At least one selected from the group consisting of the aromatic ring-containing resin and the aromatic ring-containing compound which is a precursor of the aromatic ring-containing resin is an aromatic polyimide, a dehydrated ring-closed product of an aromatic polyamic acid, and a styrene skeleton. The moth-eye structure-forming composition according to <16>, which comprises at least one selected from the group consisting of a compound having an aromatic ring, an aromatic ring-containing acrylic compound, and an aromatic ring-containing epoxy compound.
<18> The moth-eye structure-forming composition according to <17>, wherein the aromatic ring-containing acrylic compound contains a radically polymerized aromatic ring-containing acrylic compound.
<19> The moth-eye structure-forming composition according to <17>, wherein the aromatic ring-containing epoxy compound contains a cationically polymerized aromatic ring-containing epoxy compound.
<20> A step of preparing an article containing an aromatic ring-containing resin on at least a part of the surface, and
A step of performing ion beam processing using a gas containing oxygen on at least a part of the region containing the aromatic ring-containing resin, and
A method for manufacturing an article with a group of protrusions.
<21> The aromatic ring-containing resin is at least one selected from the group consisting of aromatic polyimide, a resin having a structural unit derived from a compound having a styrene skeleton, an aromatic ring-containing acrylic resin, and an aromatic ring-containing epoxy resin. The method for producing an article with a protrusion group according to <20>, which includes.
<22> The aromatic ring-containing resin is composed of an aromatic polyimide, a dehydrated ring-closed product of an aromatic polyamic acid, a cured product of a compound having a styrene skeleton, a cured product of an aromatic ring-containing acrylic compound, and a cured product of an aromatic ring-containing epoxy compound. The method for producing an article with a protrusion group according to <20> or <21>, which comprises at least one selected from the group.
<23> The method for producing an article with a protrusion group according to <22>, wherein the aromatic ring-containing acrylic compound contains a radical polymerization type aromatic ring-containing acrylic compound.
<24> The method for producing an article with a protrusion group according to <22>, wherein the aromatic ring-containing epoxy compound contains a cationically polymerized aromatic ring-containing epoxy compound.
<25> In the step of preparing the article, at least one selected from the group consisting of a compound having the styrene skeleton on at least a part of the surface of the substrate, the aromatic ring-containing acrylic compound, and the aromatic ring-containing epoxy compound is selected. Then, at least one selected from the group consisting of the compound having the styrene skeleton, the aromatic ring-containing acrylic compound and the aromatic ring-containing epoxy compound is cured, and the cured product of the compound having the styrene skeleton, the fragrance. Item 2. The protrusion according to any one of <22> to <24>, which forms a film containing at least one selected from the group consisting of a cured product of a ring-containing acrylic compound and a cured product of the aromatic ring-containing epoxy compound. A method for manufacturing a group of articles.
<26> In the step of preparing the article, after applying the aromatic polyamic acid to at least a part of the surface of the substrate, the aromatic polyamic acid is dehydrated and ring-closed to form a film containing the aromatic polyimide. , <22>. The method for producing an article with a protrusion group.
<27> A structure for forming an article with a moth-eye structure, which has a region containing an aromatic ring-containing resin for forming a moth-eye structure by oxygen ion beam processing on at least a part of the surface.

According to the present invention, a method for producing an article with a moth-eye structure having excellent light transmission, an article with a moth-eye structure, a moth-eye structure forming composition for oxygen ion beam processing, a method for producing an article with a protrusion group, and an article having a moth-eye structure. Structures can be provided.

It is a schematic block diagram which shows the ECR type ion beam processing apparatus. It is an electrograph of a processed product (article with a moth-eye structure) obtained in Example 1. It is an electrograph of a processed product (article with a moth-eye structure) obtained in Example 2. It is an electrograph of the transfer product (replica mold) obtained in Example 3. It is an electrograph of a master mold (article with a moth-eye structure) after the re-transfer of Example 4. (A) is an electrograph of a processed product (article with a moth-eye structure) processed into a curved surface, and (B) to (D) are electrographs in which (A) is partially enlarged. It is a graph which shows the reflectance of a resin convex lens (before applying an aromatic polyimide film, without a moth-eye structure), an article with an aromatic polyimide film (after applying a film), and a processed product (after processing). It is a graph which shows the haze of the convex lens made of resin (before applying an aromatic polyimide film, without a moth-eye structure), the article with an aromatic polyimide film (after applying a film), and the processed product (after processing). (A) is an electrograph of the processed product (article with a moth-eye structure) obtained in Example 6, and (B) is an electrograph of (A) partially enlarged. (A) is an electrograph of the processed product (article with a moth-eye structure) obtained in Example 7, and (B) is an electrograph of (A) partially enlarged. It is a graph which shows the reflectance in the work piece (a glass convex lens with a moth-eye structure) obtained in Example 7 and a glass convex lens (after a film is applied and without a moth-eye structure) with an aromatic polyimide film. It is a graph which shows the reflectance of the transfer product (replica mold, with a moth-eye structure) obtained in Example 8, and the structure without a moth-eye structure. (A) is an electrograph of the processed product (aromatic ring-containing epoxy resin film having a moth-eye structure) obtained in Example 9, and (B) and (C) partially enlarge the moth-eye structure in (A). It is an electronic photograph. It is a graph which shows the reflectance in the processed product (aromatic ring-containing epoxy resin film with a moth-eye structure) obtained in Example 9 and the aromatic ring-containing epoxy resin film without a moth-eye structure, and (A) is condition 1. B) is the case of processing under the condition 2. It is an appearance photograph of the concave lens before ion beam processing in Example 10. It is a graph which shows the reflectance in the work piece (concave lens with a moth-eye structure) obtained in Example 10 and the concave lens without a moth-eye structure.

Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
In the present disclosure, the term "process" includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if the process cannot be clearly distinguished from the other process. ..
The numerical range indicated by using "~" in the present disclosure includes the numerical values before and after "~" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.

<Manufacturing method of articles with moth-eye structure>
The method for producing an article with a moth-eye structure of the present disclosure includes a step of preparing an article containing an aromatic ring-containing resin on at least a part of the surface (hereinafter, also referred to as an “article preparation step”) and a region containing the aromatic ring-containing resin. It has a step of performing ion beam processing using a gas containing oxygen on at least a part of the above (hereinafter, also referred to as “ion beam processing step”).

In the method for producing an article with a moth-eye structure of the present disclosure, since glassy carbon is not used as the workpiece and an aromatic ring-containing resin is used, an article with a moth-eye structure having excellent light transmission (for example, a nanoimprint mold) can be obtained. it can. Further, since the material of the article with the moth-eye structure is an aromatic ring-containing resin, the shape of the article with the moth-eye structure can be various shapes such as a curved surface as well as a flat surface.

Then, a fine moth-eye structure can be formed by performing ion beam processing using a gas containing oxygen in at least a part of the region containing the aromatic ring-containing resin. The reason is not clear, but it is presumed as follows.
It is considered that in the ion beam processing using a gas containing oxygen, the portion where the aromatic ring exists remains and the other portion is easily removed. As a result, it is presumed that the remaining portion becomes a convex portion and the removed portion becomes a concave portion, and fine uneven processing is realized.

(1) Article preparation step In the article preparation step, an article containing an aromatic ring-containing resin on at least a part of the surface is prepared.

The article is not particularly limited as long as it has a region containing an aromatic ring-containing resin on at least a part of its surface. For example, diamond, glass, sapphire, resin or the like may be used as a substrate to form a film containing an aromatic ring-containing resin on at least a part of the surface of the substrate. Further, the entire substrate may be formed of an aromatic ring-containing resin.

The shape of the article may be any of a plate shape, a curved surface shape, an uneven shape, and the like. Further, at least a part of the surface of the article is a curved surface, and a moth-eye structure may be formed on at least a part of the curved surface. Further, the article is provided with an uneven shape on at least a part of the surface thereof, and a moth-eye structure may be formed on at least a part of the uneven shape.

Examples of articles that are at least partially curved include lenses, curved displays, automobile instrument panels with curved surfaces, showcases with curved surfaces, and signage with curved surfaces.

The aromatic ring-containing resin may be any resin having an aromatic ring, and two or more kinds may be used in combination. Since the resin has an aromatic ring, it is possible to form a fine uneven shape in the next ion beam processing step.

The aromatic ring-containing resin may be used in combination with a resin that does not have an aromatic ring (hereinafter, also referred to as “aromatic ring-free resin”). Further, two or more kinds of aromatic ring-free resins may be contained.
When the aromatic ring-free resin is used in combination, the content of the aromatic ring-free resin with respect to the total amount of the aromatic ring-containing resin and the aromatic ring-free resin may be 5% by mass or more, or 10% by mass or more. It may be 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more. The content may be 90% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, and 65% by mass or less. It may be 60% by mass or less.

The aromatic ring-containing resin is selected from the group consisting of aromatic polyimide, a dehydrated ring-closed product of aromatic polyamic acid, a resin having a structural unit derived from a compound having a styrene skeleton, an aromatic ring-containing acrylic resin, and an aromatic ring-containing epoxy resin. At least one selected from the group consisting of aromatic polyimide, a resin having a structural unit derived from a compound having a styrene skeleton, an aromatic ring-containing acrylic resin, and an aromatic ring-containing epoxy resin. May include. From the viewpoint of adhesion to an article, it is preferable to contain at least one selected from the group consisting of an aromatic ring-containing acrylic resin and an aromatic ring-containing epoxy resin.

The aromatic polyimide may be any polyimide having an aromatic ring, and two or more kinds may be used in combination.

Examples of the aromatic polyimide include polyimide having the following structural unit (A).

From the viewpoint of improving the adhesion to the article, the structural formula (A) may have at least one functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, an ester group, and an amide group. The carboxylic acid group, ester group, and amide group may be added by reacting with the carbonyl group in the structural formula (A). Further, a structural unit to which at least one functional group selected from the group consisting of a carboxylic acid group, an ester group and an amide group is imparted by reacting the carbonyl group in the structural formula (A) and these functional groups are imparted. It may be a copolymer with a structural unit that has not been used. The copolymer may be a random copolymer or a block copolymer.

The aromatic polyimide may be used in combination with a polyimide having no aromatic ring (hereinafter, also referred to as “aromatic ring-free polyimide”). Further, two or more kinds of polyimides containing no aromatic ring may be contained.

When the aromatic ring-free polyimide is used in combination, the content of the aromatic ring-free polyimide with respect to the total amount of the aromatic polyimide and the aromatic ring-free polyimide may be 5% by mass or more, or 10% by mass or more. It may be 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more. The content may be 90% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, and 65% by mass or less. It may be 60% by mass or less.

When aromatic polyimide is used as the aromatic ring-containing resin, it is preferable to impart aromatic polyimide to at least a part of the surface of the substrate to form an aromatic polyimide film. An aromatic polyamic acid, which is a precursor of an aromatic polyimide, may be applied to at least a part of the surface of the substrate and then heated to form an aromatic polyimide film by a dehydration ring closure reaction (hereinafter, “post-imide imide”). Also called "chemical method").

From the viewpoint of easily obtaining a coating film, a method of applying a coating liquid containing an aromatic polyimide to at least a part of the surface of the substrate may be used.
On the other hand, the aromatic polyamic acid used in the post-imidization method has higher solubility in a solvent than the aromatic polyimide. Therefore, the coating liquid containing the aromatic polyamic acid used in the post-imidization method is superior to the coating liquid containing the aromatic polyimide in the smoothness of the surface of the film to be formed, the followability to the surface shape of the substrate, and the like. .. Therefore, it can be applied to a substrate having various surface shapes, and for example, it can be applied to an article having a curved surface or a surface having a confined structure. Further, in the coating liquid containing the aromatic polyamic acid used in the post-imidization method, the viscosity of the coating liquid is reduced, and the thickness of the coating film can be finely adjusted.

The aromatic polyamic acid is not particularly limited as long as it has an aromatic ring. The aromatic polyamic acid can be obtained, for example, by polymerizing an organic acid dianhydride and a diamine compound in a solvent. At least one of the organic acid dianhydride and the diamine compound may have an aromatic ring, and it is preferable that both have an aromatic ring.

Examples of the organic acid dianhydride having an aromatic ring include pyromellitic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride, and 3,3', 4,4'-biphenylsulfonetetra. Carboxyl dianhydride, 1,4,5,8-naphthalenetetracarboxylic hydride, 2,3,6,7-naphthalenetetracarboxylic hydride, 3,3', 4,4'-biphenyl ether Tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2 , 3,4-Frantetracarboxylic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl Symphonic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4'-perfluoroisopropyridene diphthalic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenyl) Examples thereof include phthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, and bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride.

Examples of the organic acid dianhydride having no aromatic ring include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2, 3,4-Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tri Carboxanolbonane-2-acetic acid dianhydride, 2,3,4,5-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, Examples thereof include 2-dicarboxylic dianhydride and tetracarboxylic dianhydride such as bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride.

Examples of the diamine compound having an aromatic ring include 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl. Etan, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5 -Amino-1- (4'-aminophenyl) -1,3,3-trimethylindan, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindan, 4,4'- Diaminobenzanilide, 3,5-diamino-3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 2,7-diaminofluorene, 2,2-bis (4-amino) Phenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4 , 4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2 , 2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) -biphenyl, 1,3-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-(p-phenylene) Isopropyridene) bisaniline, 4,4'-(m-phenylene isopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, metaxylylene diamine , 4,4'-Bis [4- (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl and the like.

Examples of the diamine compound having no aromatic ring include 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoin daniline methylenediamine, and tricyclo [6,2]. 1,0 ^2.7 ] -Undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine) and the like can be mentioned.

Examples of the solvent used in the reaction for producing aromatic polyamic acid include sulfoxide-based solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide-based solvents such as N, N-dimethylformamide and N, N-diethylformamide, and N, N. Acetamide-based solvents such as -dimethylacetamide, N, N-diethylacetamide, pyrrolidone-based solvents such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, phenol, o-, m-, or p-cresol, Phenol-based solvents such as xylenol, halogenated phenol, and catechol, ether-based solvents such as tetrahydrofuran, dioxane, and dioxolane, alcohol-based solvents such as methanol, ethanol, and butanol, cellosolve-based solvents such as butyl cellosolve, hexamethylphospholamide, and γ-butyrolactone. And so on. Two or more kinds of solvents may be used in combination.

The polystyrene-equivalent weight average molecular weight of the aromatic polyamic acid is preferably several thousand or more and several hundred thousand or less. When the molecular weight is in the above range, the smoothness of the film surface, the followability to the surface shape of the substrate, and the like tend to be excellent.

The method for applying the aromatic polyimide or its precursor to the substrate may be any method, and examples thereof include a dipping method, a spin coating method, a vapor deposition method, a spray method, and a doctor blade method. The aromatic polyimide film may be formed on the entire surface of the substrate or may be formed on a part of the surface of the substrate. Even if it is partially formed, it falls under the category of "membrane" in this disclosure. The same applies hereinafter.

When applying the aromatic polyimide or its precursor to the substrate, a coating liquid diluted with a solvent may be used. As the solvent, an organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide can be applied. When a precursor of aromatic polyimide is used, dimethyl sulfoxide, N, N-dimethylformamide or the like may be used as the solvent.

When an aromatic polyamic acid, which is a precursor of an aromatic polyimide, is applied to a substrate, it is used for a polymerization reaction between a reaction solution obtained by synthesizing an aromatic polyamic acid, that is, an organic acid dianhydride and a diamine compound. A liquid containing the existing solvent and aromatic polyamic acid may be used as the coating liquid. Further, the viscosity may be adjusted by adding a solvent to the reaction solution obtained by synthesizing the aromatic polyamic acid. The solvent used for adjusting the viscosity may be the same as or different from the solvent used for synthesizing the aromatic polyamic acid.

The viscosity of the coating liquid containing the aromatic polyimide or its precursor is preferably designed appropriately according to the shape of the substrate, the thickness of the coating film to be formed, etc., and from the viewpoint of coatability, storage stability, etc., 25 At ° C., it is preferably 100 mPa · s to 10,000 mPa · s, more preferably 100 mPa · s to 5,000 mPa · s, and even more preferably 500 mPa · s to 1,000 mPa · s.

When a solvent is used, it is preferable to bake the coating film to remove the solvent. The baking temperature is preferably adjusted as appropriate depending on the type of resin and solvent, and may be baked at, for example, 190 ° C. to 350 ° C. for 10 minutes to 30 minutes.

When an aromatic polyamic acid solution is applied to a substrate, it is then heated to form a film containing aromatic polyimide by a dehydration ring closure reaction. The heating temperature for the dehydration ring closure reaction is preferably adjusted as appropriate depending on the type of aromatic polyamic acid, and can be, for example, 190 ° C to 250 ° C. Further, the heating time is also preferably adjusted as appropriate depending on the type of aromatic polyamic acid, and can be, for example, 10 minutes to 30 minutes.

The average thickness of the film containing the aromatic polyimide can be appropriately set according to the height of the unevenness desired in the mold, and may be 20 nm to 50 μm or 100 nm to 20 μm.

The resin having a structural unit derived from the compound having a styrene skeleton may be a homopolymer of the compound having a styrene skeleton or a copolymer with another monomer.

Examples of the compound having a styrene skeleton include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene and chloromethylstyrene. , Trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromo Examples thereof include styrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene and the like.

The other monomer is not particularly limited as long as it can be copolymerized with a compound having a styrene skeleton. In the case of a copolymer with another monomer, the proportion of the structural unit derived from the other monomer contained in the copolymer may be 5% by mass or more, or 10% by mass or more. It may be 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more. Further, the ratio may be 90% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, or 65% by mass or less. It may be present, and may be 60% by mass or less.

The aromatic ring-containing acrylic resin may be any acrylic resin having an aromatic ring, and two or more kinds may be used in combination. The aromatic ring-containing acrylic resin may be used in combination with an acrylic resin having no aromatic ring (hereinafter, also referred to as “aromatic ring-free acrylic resin”). Further, two or more kinds of acrylic resins containing no aromatic ring may be contained.

When the aromatic ring-free acrylic resin is used in combination, the content of the aromatic ring-free acrylic resin with respect to the total amount of the aromatic ring-containing acrylic resin and the aromatic ring-free acrylic resin may be 5% by mass or more, and may be 10% by mass. It may be more than or equal to 15% by mass, may be 20% by mass or more, may be 25% by mass or more, and may be 30% by mass or more. The content may be 90% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, and 65% by mass or less. It may be 60% by mass or less.

The aromatic ring-containing acrylic resin preferably contains a cured product of the following aromatic ring-containing acrylic compound, and preferably contains a cured product of a radically polymerized aromatic ring-containing acrylic compound. Two or more kinds of aromatic ring-containing acrylic compounds may be used in combination.

Examples of the aromatic ring-containing acrylic compound include an aromatic ring-containing mono (meth) acrylate compound having one (meth) acryloyl group and an aromatic ring-containing poly (meth) acrylate compound having two or more (meth) acryloyl groups. Therefore, from the viewpoint of curability, it is preferable to use an aromatic ring-containing poly (meth) acrylate compound, and from the viewpoint of handleability, it is more preferable to use an aromatic ring-containing di (meth) acrylate compound.
In the present disclosure, "(meth) acryloyl group" means at least one of an acryloyl group and a methacryloyl group, and "(meth) acrylate" means at least one of acrylate and methacrylate.

Examples of the aromatic ring-containing mono (meth) acrylate compound include ethylene glycol monophenyl ether (meth) acrylate and 3-phenoxy-2-hydroxypropyl (meth) acrylate. Specific example compounds include the following compounds.

Examples of the aromatic ring-containing di (meth) acrylate resin include compounds represented by the following general formula (1).

In formula (1), R independently represents a hydrogen atom or a methyl group, and X represents a divalent group having an aromatic ring.

The divalent group having an aromatic ring represented by X in the formula (1) may have a substituent. Examples of the substituent include a hydroxyl group and the like. The divalent group having an aromatic ring may have a (poly) alkyleneoxy group.

X in the formula (1) may contain one alkyleneoxy group or two or more. The number of alkyleneoxy groups in X is not limited. Examples of the (poly) alkyleneoxy group include a (poly) ethyleneoxy group and a (poly) propyleneoxy group.

Among the compounds represented by the general formula (1), the following compounds can be mentioned as a compound (epoxy ester) in which X contains an alkyleneoxy group.

Commercially available epoxy esters are available, for example, as trade names of Kyoeisha Chemical Co., Ltd .: Epoxy Ester M-600A, Epoxy Ester 3002M (N), Epoxy Ester 3002A (N), Epoxy Ester 3000MK, and Epoxy Ester 3000A. is there.

The aromatic ring-containing epoxy resin may be any epoxy resin having an aromatic ring. When an aromatic ring-containing epoxy resin is used, yellowing after the next ion beam processing step is suppressed, and the transparency is excellent.
Further, since the aromatic ring-containing epoxy resin has extremely little curing shrinkage, it is possible to form a mold with high dimensional accuracy. Therefore, when an aromatic ring-containing epoxy resin is used, the entire substrate may be formed of the aromatic ring-containing epoxy resin. In this case, an article having a desired shape (for example, a lens or the like) is molded from an aromatic ring-containing epoxy resin, and a moth-eye structure is formed therein to form a final product, which simplifies the manufacturing process. If the resin used in the final product has low dimensional accuracy, a master mold with a moth-eye structure is once made of another resin and then transferred to the final resin, which increases the number of manufacturing steps.
Two or more kinds of aromatic ring-containing epoxy resins may be used in combination.

The aromatic ring-containing epoxy resin may be used in combination with an epoxy resin having no aromatic ring (hereinafter, also referred to as “aromatic ring-free epoxy resin”). Further, two or more kinds of epoxy resins containing no aromatic ring may be contained.

When the aromatic ring-free epoxy resin is used in combination, the content of the aromatic ring-free epoxy resin with respect to the total amount of the aromatic ring-containing epoxy resin and the aromatic ring-free epoxy resin may be 5% by mass or more, and may be 10% by mass. It may be more than or equal to 15% by mass, may be 20% by mass or more, may be 25% by mass or more, and may be 30% by mass or more. The content may be 90% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, and 65% by mass or less. It may be 60% by mass or less.

The aromatic ring-containing epoxy resin preferably contains a cured product of the following aromatic ring-containing epoxy compound, and preferably contains a cured product of a cationically polymerized aromatic ring-containing epoxy compound. When a cationically polymerized aromatic ring-containing epoxy compound is used, the curing reaction is not inhibited by oxygen, so that the curing reaction can be carried out in the atmosphere. In addition, the shrinkage rate during curing is small and the shape transferability is excellent. Two or more kinds of aromatic ring-containing epoxy compounds may be used in combination.

Examples of the aromatic ring-containing epoxy compound include glycidyl ether type, glycidyl ester type, glycidyl amine type, and modified products of these compounds.
Examples of the aromatic ring-containing epoxy compound include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, brominated bisphenol A type epoxy compound, biphenyl type epoxy compound, naphthalene type epoxy compound, and fluorene type epoxy compound. Bisphenol alkanes epoxy compound, phenol novolac type epoxy compound, orthocresol novolac type epoxy compound, brominated cresol novolac type epoxy compound, tetraphenylol ethane type epoxy compound, phenylglycidyl ether compound, cresol glycidyl ether compound, toluidine type epoxy compound , Aniline type epoxy compound, aminophenol type epoxy compound, tetraglycidyl diaminodiphenylmethane compound, diphenyl ether type epoxy compound, silicone-modified aromatic ring-containing epoxy compound, silicon-containing aromatic ring-containing epoxy compound, urethane-modified aromatic ring-containing epoxy compound, NBR-modified aromatic It is preferably at least one compound selected from the group consisting of a ring-containing epoxy compound and a CTBN-modified aromatic ring-containing epoxy compound.

When a cationically polymerized aromatic ring-containing epoxy compound is used, it is preferable to use a photocationic polymerization initiator in combination. Examples of the photocationic polymerization initiator include onium salts. Examples of onium salts include aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts and the like.
Many of the onium salts, halogen metal complex anion _{^{(BF 4 -, PF 6 -}} , AsF 6 -, SbF 6 -, B (C 6 F 5) 4 -), (RF) n PF 6-n - ( wherein , N represents an integer of 1 to 5) and the like as counterions. Furthermore, [{C5 (R ¹ ) _n } ₂ mM _m ] _l + [{B (R ² ) ₄ } ⁻ ] _l (In the formula, M is the central nuclear transition metal; C5 represents cyclopentadienyl; R ¹ is an electron donating substituent attached to the carbon of cyclopentadienyl; n is 4 or 5; m is 1 or 2; l is 1 or 2; R ² is a boron atom ( a ligand coordinating to B), mentioned as the four R ² is represented by the same), metallocene and borate compounds and ion associate crystalline material, such as also cationic photopolymerization initiator which is a combination of ..

The aromatic ring-containing epoxy compound may be used in combination with an epoxy compound having no aromatic ring (hereinafter, also referred to as “aromatic ring-free epoxy compound”). Further, two or more kinds of epoxy compounds containing no aromatic ring may be contained.

When the aromatic ring-free epoxy compound is used in combination, the content of the aromatic ring-free epoxy compound with respect to the total amount of the aromatic ring-containing epoxy compound and the aromatic ring-free epoxy compound may be 5% by mass or more, and may be 10% by mass. It may be more than or equal to 15% by mass, may be 20% by mass or more, may be 25% by mass or more, and may be 30% by mass or more. The content may be 90% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, and 65% by mass or less. It may be 60% by mass or less.

When at least one selected from the group consisting of a resin having a structural unit derived from a compound having a styrene skeleton, an aromatic ring-containing acrylic resin, and an aromatic ring-containing epoxy resin is used as the aromatic ring-containing resin, the surface of the substrate is used. At least one selected from the group consisting of a compound having a styrene skeleton, an aromatic ring-containing acrylic compound and an aromatic ring-containing epoxy compound is added to at least a part thereof, and a compound having a styrene skeleton, an aromatic ring-containing acrylic compound and an aromatic ring-containing compound are added. At least one selected from the group consisting of epoxy compounds is cured and selected from the group consisting of a cured product of a compound having a styrene skeleton, a cured product of an aromatic ring-containing acrylic compound, and a cured product of an aromatic ring-containing epoxy compound. A film containing at least one type may be formed (hereinafter, also referred to as "post-impartment curing method").

That is, in the post-application curing method, a monomer, oligomer or prepolymer having a small molecular weight is applied to at least a part of the surface of the substrate, and after the application is applied, it is cured to increase the molecular weight. The post-application curing method is superior to the method of applying a resin having a large molecular weight in advance, in that it imparts a compound having a small molecular weight, and is excellent in following the surface shape of the substrate. Therefore, it can be applied to a substrate having various surface shapes, and for example, it can be applied to an article having a curved surface or a surface having a confined structure.
Further, in the post-applying curing method, the viscosity of the coating liquid is lowered, and the thickness of the coating film can be finely adjusted.

The method for applying the compound having a styrene skeleton, the aromatic ring-containing acrylic compound, and the aromatic ring-containing epoxy compound may be any method, and examples thereof include a dipping method, a spin coating method, a vapor deposition method, a spray method, and a doctor blade method. be able to.

When imparting at least one selected from the group consisting of a compound having a styrene skeleton, an aromatic ring-containing acrylic compound and an aromatic ring-containing epoxy compound, a coating solution diluted with a solvent may be used, and the coating solution may be used without dilution with a solvent. You may use it.

When at least one selected from the group consisting of a compound having a styrene skeleton, an aromatic ring-containing acrylic compound and an aromatic ring-containing epoxy compound is used, examples of the solvent include aromatic hydrocarbons, aliphatic hydrocarbons and alcohols. Examples thereof include solvents selected from ether acetal esters, ketones, and nitrogen compounds. Specifically, as the solvent, toluene, xylene, hexane, cyclohexane, styrene, octane, decane, petroleum ether, petroleum naphtha, ethyl alcohol, isopropyl alcohol, propanol, ethylene glycol, propylene glycol, γ-butyrolactone, ethyl acetate, butyl acetate. , Acetone, methyl ethyl ketone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether Examples thereof include acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether.

At least one selected from the group consisting of a resin having a structural unit derived from a compound having a styrene skeleton, an aromatic ring-containing acrylic resin and an aromatic ring-containing epoxy resin, or a compound having a styrene skeleton, an aromatic ring-containing acrylic compound and an aromatic ring. The viscosity of the coating liquid containing at least one selected from the group consisting of the contained epoxy compounds is preferably appropriately designed according to the shape of the substrate, the desired thickness of the coating film, etc. From this point of view, it is preferably 100 mPa · s to 10,000 mPa · s at 25 ° C., more preferably 100 mPa · s to 5,000 mPa · s, and 500 mPa · s to 1,000 mPa · s. Is even more preferable.

When a solvent is used, the coating film may be heated to remove the solvent. The heating temperature is preferably adjusted as appropriate depending on the type of resin and solvent.
When a coating liquid containing an aromatic polyimide is used, it is necessary to bake at a relatively high temperature in order to remove the solvent after applying the coating liquid to the substrate.
On the other hand, a compound having a styrene skeleton, an aromatic ring-containing acrylic compound, or an aromatic ring-containing epoxy compound has a lower viscosity than an aromatic polyimide, so that it is not necessary to use a solvent, and even if it is used, the amount used is small. You may. Therefore, the heating step can be omitted, or the baking time required when the aromatic polyimide is used can be shortened, and the production energy can be reduced.
Further, since the precursor of aromatic polyimide, the compound having a styrene skeleton, the aromatic ring-containing acrylic compound, or the aromatic ring-containing epoxy compound has higher solubility in the solvent than the aromatic polyimide, the solvent to be used for the coating liquid can be selected. It also has the advantage of being wider. Then, it is possible to select a solvent having a low boiling point, and the heating temperature can be set to be lower than the baking temperature required when the aromatic polyimide is used. Therefore, it can also be applied to articles having a lower glass transition temperature.

At least one curing selected from the group consisting of a compound having a styrene skeleton, an aromatic ring-containing acrylic compound, and an aromatic ring-containing epoxy compound may be photo-curing or thermosetting, but it is convenient and article-based. From the viewpoint of suppressing the influence on the above, photocuring is preferable, and UV curing is preferable.

In the case of photocuring, the cover film may be brought into contact with the coating film to average the thickness of the coating film. The average thickness of the coating film can be appropriately set according to the height of the unevenness desired by the mold, and may be 20 nm to 100 μm or 100 nm to 50 μm.
If the cover film is transparent, the coating film may be cured by irradiating light with the cover film placed. The curing conditions are preferably set as appropriate according to the type and thickness of the resin.
The average thickness of the film containing a resin having a structural unit derived from a compound having a styrene skeleton, the film containing an aromatic ring-containing acrylic resin, and the film containing an aromatic ring-containing epoxy resin may be 20 nm to 100 μm, and may be 100 nm. It may be ~ 50 μm.

(2) Ion beam processing step In the ion beam processing step, at least a part of the region containing the aromatic ring-containing resin is subjected to ion beam processing using a gas containing oxygen.

As an example of the ion beam processing apparatus, FIG. 1 schematically shows the configuration of an ECR (electron cycloton resonance) type ion beam processing apparatus (plasma etching apparatus) 10. The ion beam processing device 10 includes a holder 12 for holding the work piece 26, a gas introduction pipe 14 for performing ion beam processing on the surface of the work piece 26, a plasma generation chamber 16, and an extractor 18. It includes an electromagnet 20, an ion beam extraction electrode 22, a Faraday cup 24, and the like. Since the current density becomes small at a low acceleration voltage of 500 V or less, for example, an extractor 18 arranged on the plasma side of the extraction electrode 22 is used in order to increase the current density. If the extractor 18 is used, the current density can be increased and the processing speed can be increased even if the acceleration voltage is low.

In the ion beam processing step, an article containing an aromatic ring-containing resin on at least a part of the surface of the workpiece 26 is set in the holder 12. After that, a gas containing oxygen is introduced, and a predetermined acceleration voltage is applied to process the surface of the workpiece 26 with an ion beam.

If the ECR type ion beam processing apparatus 10 is used, even a relatively large surface can be processed all at once, so that the surface can be easily processed. In addition, in the region containing the aromatic ring-containing resin, a mask may be placed in a portion where ion beam processing is not desired, and only a part of the region containing the aromatic ring-containing resin may be ion beam processed.

By performing ion beam processing on the surface of an article containing an aromatic ring-containing resin in at least a part of the surface, a fine protrusion group (microstructure) having a shape such as a needle shape whose diameter is reduced toward the tip is formed. Can be done. Then, in particular, by controlling the acceleration voltage, the processing time, and the gas flow rate, the shape (size, width, angle, etc.) and pitch of the protrusions can be controlled. Specifically, the shape and pitch of the protrusions formed on the surface of the base material can be controlled by controlling at least one of the acceleration voltage, the processing time, and the gas flow rate. In addition, by adjusting the acceleration voltage, processing time, gas flow rate, etc., fine protrusions of various shapes such as needle-shaped, conical, polygonal pyramid, truncated cone, polygonal pyramid, and radial shape can be formed. It can also be formed.

The gas containing oxygen may include oxygen, and may be a gas obtained by mixing oxygen, air, or oxygen with a CF-based gas such as CF _4. The oxygen flow rate can be 1 sccm to 20 sccm, 1 sccm to 10 sccm, and 1 sccm to 5 sccm.

The degree of vacuum ^{is preferably 1.0 × 10 -1} Pa or less, and preferably 1.0 × 10 ^-2 Pa or less. The lower limit of the degree of vacuum is not particularly limited as long as it is feasible.

The beam diameter may be 200 mm or less, 50 mm or less, or 10 mm or less. The lower limit of the beam diameter is not particularly limited as long as it is feasible.

The acceleration voltage of the ion beam can be appropriately designed depending on the material, thickness, etc. of the workpiece, and 1V to 100kV can be applied, but it is preferably 1V to 10kV, and more preferably 1V to 8kV. More preferably, it is 1 V to 1 kV.

The irradiation time of the ion beam can be appropriately designed depending on the material, thickness, etc. of the part to be processed. For example, it can be 1 minute to 15 minutes, 1 minute to 10 minutes, 1 minute to 1 minute. It can be 8 minutes.

The moth-eye structure obtained through the ion beam process has a plurality of protrusions. The average diameter of the plurality of protrusions can be 5 μm or less, 1 μm or less, 200 nm or less, and 10 nm or less. The lower limit of the average diameter is not particularly limited as long as it is feasible.

The average height of the plurality of protrusions in the moth-eye structure can be 50 nm or more, 100 nm or more, and 500 nm or more. It can be 1 μm or more. The lower limit of the average height is not particularly limited as long as it is feasible.

The average value of the height ratio (aspect ratio) to the diameters of the plurality of protrusions in the moth-eye structure can be 2 or more, 5 or more, and 10 or more. The upper limit of the aspect ratio is not particularly limited as long as it is feasible.

<Article with moss eye structure>
The article with a moth-eye structure of the present disclosure has a moth-eye structure having a plurality of protrusions on at least a part of the surface, and the moth-eye structure contains an aromatic ring-containing resin.
The "article", "protrusion", "moss eye structure" and "aromatic ring-containing resin" in the article with a moth-eye structure are the "article", "protrusion", "moth-eye structure" and "moth-eye structure" described in the method for manufacturing an article with a moth-eye structure. It is the same as "aromatic ring-containing resin". As for other products, a method for manufacturing an article having a moth-eye structure can be appropriately applied.

The average diameter of the plurality of protrusions in the article with the moth-eye structure can be 5 μm or less, 1 μm or less, 200 nm or less, and 10 nm or less.

The average height of the plurality of protrusions in the article with the moth-eye structure can be 50 nm or more, 100 nm or more, and 500 nm or more. It can be 1 μm or more.

The average value of the height ratio (aspect ratio) to the diameters of a plurality of protrusions in an article having a moth-eye structure can be 2 or more, 5 or more, and 10 or more.

In an article having a moth-eye structure, at least a part of the surface thereof may be a curved surface, and at least a part of the curved surface may have a moth-eye structure. Further, the article may be a lens, a curved display, an instrument panel of an automobile having a curved surface, a showcase having a curved surface, or a signage having a curved surface.

The article with a moth-eye structure may be used as a mold for nanoimprint. Further, the article having a moth-eye structure may be used as a replica mold for nanoimprint.

The article with the moth-eye structure of the present disclosure has low reflectance and excellent antireflection property. Further, the article with a moth-eye structure of the present disclosure can have a low reflectance even for light in an ultraviolet light region such as 300 nm to 550 nm or a short wavelength visible light region. Further, it is possible to obtain a low reflectance even for light on the long wavelength side such as 550 nm to 700 nm (or up to 800 nm or 1000 nm). Therefore, the article with the moth-eye structure of the present disclosure can have a low reflectance with little wavelength dependence for incident light having a wide range of wavelengths.

<Mosseye structure forming composition for oxygen ion beam processing>
The moth-eye structure forming composition for oxygen ion beam processing of the present disclosure (hereinafter, may be abbreviated as "moth-eye structure forming composition") is for forming a moth-eye structure by oxygen ion beam processing and contains an aromatic ring. It contains at least one selected from the group consisting of a resin and an aromatic ring-containing compound which is a precursor of an aromatic ring-containing resin.

The "aromatic ring-containing resin" in the moth-eye structure forming composition is the same as the "aromatic ring-containing resin" described in the method for producing an article having a moth-eye structure. The "aromatic ring-containing compound" is a precursor of the "aromatic ring-containing resin", and is the "aromatic polyamic acid", the "compound having a styrene skeleton", and the "aromatic ring-containing acrylic" described in the method for producing an article having a moth-eye structure. Examples thereof include "compounds" and "aromatic ring-containing epoxy compounds". As for other items, the matters described in the method for manufacturing an article having a moth-eye structure can be appropriately applied.

At least one selected from the group consisting of an aromatic ring-containing compound and an aromatic ring-containing resin is a group consisting of an aromatic polyimide, an aromatic polyamic acid, a compound having a styrene skeleton, an aromatic ring-containing acrylic compound, and an aromatic ring-containing epoxy compound. It is preferable to contain at least one selected from the above. The aromatic ring-containing acrylic compound preferably contains a radically polymerized aromatic ring-containing acrylic compound, and the aromatic ring-containing epoxy compound preferably contains a cationically polymerized aromatic ring-containing epoxy compound.

<Manufacturing method of articles with protrusions>
The method for producing an article with a protrusion group of the present disclosure includes a step of preparing an article containing an aromatic ring-containing resin on at least a part of the surface and a gas containing oxygen for at least a part of the region containing the aromatic ring-containing resin. It has a step of performing ion beam processing using the above.

In the method for manufacturing an article with a protrusion group, the "moss eye structure" in the above-mentioned method for manufacturing an article with a moth-eye structure can be read as "protrusion group". As for other products, a method for manufacturing an article having a moth-eye structure can be appropriately applied.

The aromatic ring-containing resin preferably contains at least one selected from the group consisting of aromatic polyimide, a resin having a structural unit derived from a compound having a styrene skeleton, an aromatic ring-containing acrylic resin, and an aromatic ring-containing epoxy resin. , At least one selected from the group consisting of an aromatic polyimide, a dehydrated ring-closed product of an aromatic polyamic acid, a cured product of a compound having a styrene skeleton, a cured product of an aromatic ring-containing acrylic compound, and a cured product of an aromatic ring-containing epoxy compound. It is more preferable to include. The "compound having a styrene skeleton", the "aromatic ring-containing acrylic compound" and the "aromatic ring-containing epoxy compound" in the method for producing an article with a protrusion group are the "compound having a styrene skeleton" described in the method for producing an article with a moth-eye structure. , "Aromatic ring-containing acrylic compound" and "Aromatic ring-containing epoxy compound", respectively.

The aromatic ring-containing acrylic compound preferably contains a radically polymerized aromatic ring-containing acrylic compound, and the aromatic ring-containing epoxy compound preferably contains a cationically polymerized aromatic ring-containing epoxy compound.

In the step of preparing the article, at least one selected from the group consisting of a compound having a styrene skeleton, an aromatic ring-containing acrylic compound and an aromatic ring-containing epoxy compound is applied to at least a part of the surface of the substrate to have a styrene skeleton. A cured product of a compound having a styrene skeleton, a cured product of an aromatic ring-containing acrylic compound, and an aromatic ring-containing epoxy are cured by curing at least one selected from the group consisting of a compound, an aromatic ring-containing acrylic compound, and an aromatic ring-containing epoxy compound. A film containing at least one selected from the group consisting of cured products of the compound may be formed.

Further, in the step of preparing the article, after applying an aromatic polyamic acid to at least a part of the surface of the substrate, the aromatic polyamic acid may be dehydrated and ring-closed to form a film containing the aromatic polyimide. ..

The average diameter of the plurality of protrusions in the protrusion group can be 5 μm or less, 1 μm or less, 200 nm or less, and 10 nm or less.

The average height of the plurality of protrusions in the protrusion group can be 50 nm or more, 100 nm or more, and 500 nm or more. It can be 1 μm or more.

The average value of the height ratio (aspect ratio) to the diameters of a plurality of protrusions in the protrusion group can be 2 or more, 5 or more, and 10 or more.

<Structure for forming articles with moth-eye structure>
The article-forming structure with a moth-eye structure of the present disclosure has a region containing an aromatic ring-containing resin for forming a moth-eye structure by oxygen ion beam processing on at least a part of the surface. The "aromatic ring-containing resin" in the structure for forming an article with a moth-eye structure is the same as the "aromatic ring-containing resin" described in the method for producing an article with a moth-eye structure. The structure for forming an article with a moth-eye structure of the present disclosure can be used as an article prepared in an article preparation step in the above-mentioned method for producing an article with a moth-eye structure.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

[Example 1]
<Goods preparation process>
An aromatic polyimide varnish (PI Technical Laboratory Co., Ltd., Q-PILON (registered trademark)) was applied to the surface of a 10 mm square primer-treated silicon substrate with a spin coater. The coating conditions were 4000 times per minute (rpm) for 45 seconds. The obtained coating film was baked on a hot plate at 300 ° C. for 15 minutes to obtain an article with an aromatic polyimide film having a thickness of 1.8 μm.

<Ion beam processing process>
An article with an aromatic polyimide film was placed in a holder of an ECR type ion beam processing apparatus (manufactured by Elionix Inc., trade name: EIS-200ER). The distance L between the beam extraction electrode and the surface of the plate-like body was 17 cm, and ion beam processing was performed under the following conditions.

Acceleration voltage: 400V
Vacuum degree: 1.3 x 10 ^-2 Pa
Beam diameter: 20 mm
Reaction gas: Oxygen gas flow rate: 3.50 sccm
Processing time: 10 minutes

<Result>
An electrograph of the obtained processed product (article with a moth-eye structure) is shown in FIG. The height of the convex portion was about 800 nm to 1 μm, and an unprocessed aromatic polyimide film remained at the bottom of the concave portion. The thickness of the unprocessed aromatic polyimide film was 500 nm.

[Example 2]
Using the same method as in Example 1, however, the thickness of the coating film is changed to 1.1 μm by changing the coating conditions of the aromatic polyimide varnish to prepare an article with an aromatic polyimide film, and an ion beam processing step is performed. It was.

An electrograph of the obtained processed product (article with a moth-eye structure) is shown in FIG. The height of the convex portion was about 1 μm. Since the thickness of the coating film was thinner than that of Example 1, almost no residue of the unprocessed aromatic polyimide film was observed.
In Example 1 and Example 2, the height and shape of the convex portion were the same, and the reproducibility of production was confirmed.

[Example 3]
<Making a replica mold>
A replica mold was produced using the article with a moth-eye structure produced in Example 2 as a master mold.
First, the processed surface (the surface on which the moth-eye structure was formed) of the article with the moth-eye structure produced in Example 2 was coated with platinum using a sputtering device (ESC101 manufactured by Elionix Inc.). Further, it was coated with a fluorine-based resin coating agent (Optur (registered trademark), manufactured by Daikin Industries, Ltd., 0.1% by mass) as a release agent. A photocurable resin (PAK-01CL, manufactured by Toyo Gosei Co., Ltd.) was spin-coated on this. Transfer was performed by pressing the slide glass against the surface coated with the photocurable resin and irradiating the slide glass side with ultraviolet light to cure the photocurable resin under the following conditions.
Pressing pressure: 0.83 MPa
Pressurization maintenance time: 60 seconds UV irradiation amount: ^{2 J / cm 2}

<Measurement of reflectance>
The cured photocurable resin was peeled off, and the reflectance of the transfer surface was measured. The silicon mirror substrate was used as a reference.

<Result>
An electrograph of the obtained transfer product (replica mold) is shown in FIG. The height of the convex portion was about 500 nm to 600 nm, and a cured layer of a photocurable resin was present at the bottom of the concave portion by 15.5 μm. It was confirmed by Example 3 that the transferability was good.
Moreover, the reflectance was 1%, and it was confirmed that it functions as an antireflection structure (moss eye structure).

[Example 4]
<Confirmation of damage to the master mold after two transfers>
Using the master mold used in Example 3, transfer was performed again in the same manner as in Example 3.
An electrograph of the master mold after retransfer is shown in FIG. No major damage was observed on the convex part of the master mold even after the second transfer. Therefore, it was confirmed that the article with the moth-eye structure of this example can be used as a master mold.

[Example 5]
<Curved article preparation process>
Aromatic polyimide varnish (PI Technical Laboratory Co., Ltd., Q-PILON (registered trademark)) was applied on a resin convex lens with a spin coater. The coating conditions were 5000 rpm and 45 seconds. The obtained coating film was baked on a hot plate at 300 ° C. for 15 minutes to obtain an article with an aromatic polyimide film having a thickness of 1 μm.

The reflectance and haze of the resin convex lens before the aromatic polyimide film was applied were measured. Haze was measured according to JIS K 7136: 2000. After that, haze was measured by the same method. In addition, the reflectance and haze of the obtained article with an aromatic polyimide film were also measured.

<Ion beam processing process>
Ion beam processing was performed in the same manner as in Example 1 except that the article was changed to an article with a curved surface aromatic polyimide film. The reflectance and haze of the obtained processed product (article with a moth-eye structure) were measured.

<Result>
An electrograph of the obtained processed product (article with a moth-eye structure) is shown in FIG. A moth-eye structure was formed on the curved surface. In addition, a moth-eye structure was formed at each of the observation points.
The processed product (article with a moth-eye structure) was slightly yellowish, but its transparency was maintained. Therefore, when the photocurable resin is cured by using this article with a moth-eye structure as a mold, it is possible to cure the photocurable resin by irradiating light from the mold side to perform transfer.

FIG. 7 shows the reflectances of a resin-made convex lens (before applying an aromatic polyimide film, without a moth-eye structure), an article with an aromatic polyimide film (after applying a film), and a processed product (after processing). FIG. 8 shows each haze. The reflectance for each 550 nm light is shown in Table 1 below.

From the results of FIGS. 7, 8 and 1, it was confirmed that the effect of antireflection by adding the moth-eye structure was confirmed. From the results shown in FIG. 7, it was confirmed that the addition of the moth-eye structure effectively reduced the reflectance with respect to light in the wavelength range of 300 nm to 1000 nm.

[Example 6]
<Preparation of aromatic polyamic solution>
Piromellitic dianhydride and 4,4'-diaminodiphenyl ether were dissolved in dimethyl sulfoxide in equimolar amounts, and the obtained solution was heated at 85 ° C. for 10 minutes to prepare an aromatic polyamic solution.

<Goods preparation process>
An aromatic polyamic solution was applied to the surface of a 10 mm square primer-treated silicon substrate with a spin coater. The coating conditions were 4000 times per minute (rpm) for 45 seconds. The obtained coating film was heated on a hot plate at 190 ° C. for 10 minutes to undergo a dehydration ring closure reaction to obtain an article with an aromatic polyimide film having a thickness of 2.86 μm.

<Ion beam processing process>
In the same manner as in Example 1, however, an ion beam processing step was performed in place of the article with the aromatic polyimide film produced above.

<Result>
An electrograph of the obtained processed product (article with a moth-eye structure) is shown in FIG. The height of the convex portion was about 510 nm, and an unprocessed aromatic polyimide film remained at the bottom of the concave portion. It has been confirmed that the height of the convex portion can be adjusted to some extent by changing the processing time of the ion beam.

[Example 7]
By the same method as in Example 6, however, a curved article was prepared in place of the convex lens made of glass for the silicon substrate, and a processed product (article with a moth-eye structure) was obtained.
An electrograph of the obtained processed product (article with a moth-eye structure) is shown in FIG. A moth-eye structure was formed on the curved surface.

FIG. 11 shows the reflectances of the processed product (glass convex lens having a moth-eye structure) obtained in Example 7 and the glass convex lens having an aromatic polyimide film without a moth-eye structure. From the results of FIG. 11, it was confirmed that the reflectance was reduced with respect to light having a wavelength of 300 nm to 700 nm by adding the moth-eye structure.

[Example 8]
A replica mold (concave lens) was produced by the same method as in Example 3, except that the article with a moth-eye structure produced in Example 7 was used as a master mold. For comparison, a glass convex lens without a moth-eye structure was used as a master mold to obtain a concave lens without a moth-eye structure.
FIG. 12 shows the reflectances of the obtained replica mold (concave lens with a moth-eye structure) and the concave lens without a moth-eye structure. From the results shown in FIG. 12, it was confirmed that the transfer material also had a reduced reflectance with respect to light having a wavelength of 300 nm to 800 nm due to the addition of the moth-eye structure.

[Example 9]
<Goods preparation process>
A resin composition was prepared by adding CPI-100P (photocationic polymerization initiator, triarylsulfonium salt type, San-Apro Co., Ltd.) to bisphenol A type diglycidyl ether so as to be 20% by mass. The resin composition was applied to the surface of a silicon substrate (20 mm square) treated with HMDS (hexamethyldisilazane) with a spin coater to form a resin composition layer. A glass substrate treated with a fluororesin coating agent (Optur (registered trademark), manufactured by Daikin Industries, Ltd., 0.1% by mass) as a mold release agent is placed on the resin composition layer, and ultraviolet rays are emitted from the glass substrate side. The resin composition layer was cured by irradiation for 60 seconds, and the glass substrate was removed to obtain an article with an aromatic ring-containing epoxy resin film.

<Ion beam processing process>
An article with an aromatic ring-containing epoxy resin film was placed in a holder of an ICP (inductively coupled plasma) apparatus (manufactured by Elionix Inc., trade name: EIS-700), and ion beam processing was performed under the following conditions.

Output: 500W
Bias output: 50W
Vacuum pressure: 5.0 x 10 ^-3 Pa
Reaction gas: Oxygen gas flow rate: 50 sccm
Processing time: 120 seconds (condition 1) or 150 seconds (condition 2)

<Result>
FIG. 13 (A) shows an electrograph of the obtained processed product (aromatic ring-containing epoxy resin film having a moth-eye structure). 13 (B) and 13 (C) are partially enlarged electrographs of the moth-eye structure in (A). The maximum height of the convex portion was about 1 μm, and an unprocessed aromatic ring-containing epoxy resin film remained at the bottom of the concave portion.

FIG. 14 shows the reflectances of the processed product (aromatic ring-containing epoxy resin film having a moth-eye structure) obtained in Example 9 and the aromatic ring-containing epoxy resin film without a moth-eye structure. FIG. 14 (A) shows the result of processing under condition 1, and FIG. 14 (B) shows the result of processing under condition 2. The reflectance of the work piece was measured three times for the work piece under condition 1 and four times for the work piece under condition 2.
From the results of FIG. 14, it was confirmed that the reflectance was reduced with respect to light having a wavelength of 300 nm to 1000 nm by adding the moth-eye structure. Further, there was no significant difference in the reflectance between the condition 1 and the condition 2 in which the processing times differed by 30 seconds.

[Example 10]
In the same manner as in Example 9, however, the glass substrate placed on the resin composition layer is replaced with a convex lens having a diameter of 9 mm treated with Optool ((registered trademark), manufactured by Daikin Industries, Ltd.), and the convex side is made of resin. An article (concave lens) with an aromatic ring-containing epoxy resin film was obtained by arranging the mixture so as to be in contact with the composition layer. FIG. 15 shows an external photograph of the obtained concave lens. The article with the aromatic ring-containing epoxy resin film was subjected to ion beam processing in the same manner as in Example 9.

FIG. 16 shows the reflectances of the workpiece (concave lens with the moth-eye structure) obtained in Example 10 and the concave lens without the moth-eye structure. The reflectance was measured three times for each of the concave lens before processing and the concave lens after processing.
From the results of FIG. 16, it was confirmed that the effect of antireflection by adding the moth-eye structure to the light having a wavelength of 300 nm to 1000 nm was confirmed. The work product with the moth-eye structure (after processing) showed a decrease in reflectance of about 4% to 8% as compared with that before processing.
In Example 10, the aromatic ring-containing resin is molded by UV curing so as to have a lens shape, and then the surface of the lens shape can be directly moth-eyed.

10 ... ECR type ion beam processing device 12 ... Holder 14 ... Reaction gas introduction tube 16 ... Plasma generation chamber 18 ... Extractor 20 ... Electromagnet 22 ... Beam extraction electrode 24 ...・ ・ Faraday cup 26 ・ ・ ・ Work piece

Claims (27)

The process of preparing an article containing an aromatic ring-containing resin on at least a part of the surface,
A step of performing ion beam processing using a gas containing oxygen on at least a part of the region containing the aromatic ring-containing resin, and
A method for manufacturing an article with a moth-eye structure. Claimed that the aromatic ring-containing resin contains at least one selected from the group consisting of aromatic polyimide, a resin having a structural unit derived from a compound having a styrene skeleton, an aromatic ring-containing acrylic resin, and an aromatic ring-containing epoxy resin. Item 3. The method for manufacturing an article having a styrene structure according to Item 1. The aromatic ring-containing resin is composed of a group consisting of an aromatic polyimide, a dehydrated ring-closed product of an aromatic polyamic acid, a cured product of a compound having a styrene skeleton, a cured product of an aromatic ring-containing acrylic compound, and a cured product of an aromatic ring-containing epoxy compound. The method for producing an article with a styrene structure according to claim 1 or 2, which comprises at least one selected. The method for producing an article with a moth-eye structure according to claim 3, wherein the aromatic ring-containing acrylic compound contains a radically polymerized aromatic ring-containing acrylic compound. The method for producing an article with a moth-eye structure according to claim 3, wherein the aromatic ring-containing epoxy compound contains a cationically polymerized aromatic ring-containing epoxy compound. In the step of preparing the article, at least one selected from the group consisting of the compound having the styrene skeleton, the aromatic ring-containing acrylic compound and the aromatic ring-containing epoxy compound is applied to at least a part of the surface of the substrate. At least one selected from the group consisting of the compound having a styrene skeleton, the aromatic ring-containing acrylic compound and the aromatic ring-containing epoxy compound is cured to obtain a cured product of the compound having a styrene skeleton, and the aromatic ring-containing acrylic. The article with a moth-eye structure according to any one of claims 3 to 5, which forms a film containing at least one selected from the group consisting of a cured product of the compound and a cured product of the aromatic ring-containing epoxy compound. Manufacturing method. Claimed in the step of preparing the article, after applying the aromatic polyamic acid to at least a part of the surface of the substrate, the aromatic polyamic acid is dehydrated and ring-closed to form a film containing the aromatic polyimide. 3. The method for manufacturing an article having a moth-eye structure according to 3. An article having a moth-eye structure having a moth-eye structure having a plurality of protrusions on at least a part of the surface, wherein the moth-eye structure contains an aromatic ring-containing resin. Claimed that the aromatic ring-containing resin contains at least one selected from the group consisting of aromatic polyimide, a resin having a structural unit derived from a compound having a styrene skeleton, an aromatic ring-containing acrylic resin, and an aromatic ring-containing epoxy resin. Item 8. The article having a styrene structure according to Item 8. The article with a moth-eye structure according to claim 8 or 9, wherein the average diameter of the plurality of protrusions in the moth-eye structure is 5 μm or less. The article with a moth-eye structure according to any one of claims 8 to 10, wherein the average value of the height ratio (aspect ratio) to the diameters of the plurality of protrusions in the moth-eye structure is 2 or more. The article with a moth-eye structure according to any one of claims 8 to 11, wherein at least a part of the surface is a curved surface and at least a part of the curved surface has a moth-eye structure. The moth-eye structure according to any one of claims 8 to 12, wherein the article includes a lens, a curved display, an instrument panel of an automobile having a curved surface, a showcase having a curved surface, and a signage having a curved surface. Goods. The article with a moth-eye structure according to any one of claims 8 to 13, which is a mold for nanoimprint. The article with a moth-eye structure according to any one of claims 8 to 13, which is a replica mold for nanoimprint. A moth-eye structure forming composition for oxygen ion beam processing, which comprises at least one selected from the group consisting of an aromatic ring-containing resin and an aromatic ring-containing compound which is a precursor of the aromatic ring-containing resin. At least one selected from the group consisting of the aromatic ring-containing resin and the aromatic ring-containing compound which is a precursor of the aromatic ring-containing resin is an aromatic polyimide, a dehydrated ring-closed product of an aromatic polyamic acid, and a compound having a styrene skeleton. The moth-eye structure-forming composition according to claim 16, which comprises at least one selected from the group consisting of an aromatic ring-containing acrylic compound and an aromatic ring-containing epoxy compound. The moth-eye structure-forming composition according to claim 17, wherein the aromatic ring-containing acrylic compound contains a radically polymerized aromatic ring-containing acrylic compound. The moth-eye structure-forming composition according to claim 17, wherein the aromatic ring-containing epoxy compound contains a cationically polymerized aromatic ring-containing epoxy compound. The process of preparing an article containing an aromatic ring-containing resin on at least a part of the surface,
A step of performing ion beam processing using a gas containing oxygen on at least a part of the region containing the aromatic ring-containing resin, and
A method for manufacturing an article with a group of protrusions. Claimed that the aromatic ring-containing resin contains at least one selected from the group consisting of aromatic polyimide, a resin having a structural unit derived from a compound having a styrene skeleton, an aromatic ring-containing acrylic resin, and an aromatic ring-containing epoxy resin. Item 20. The method for producing an article with a protrusion group. The aromatic ring-containing resin is composed of a group consisting of an aromatic polyimide, a dehydrated ring-closed product of an aromatic polyamic acid, a cured product of a compound having a styrene skeleton, a cured product of an aromatic ring-containing acrylic compound, and a cured product of an aromatic ring-containing epoxy compound. The method for producing an article with a protrusion group according to claim 20 or 21, which comprises at least one selected. The method for producing an article with a protrusion group according to claim 22, wherein the aromatic ring-containing acrylic compound contains a radically polymerized aromatic ring-containing acrylic compound. The method for producing an article with a protrusion group according to claim 22, wherein the aromatic ring-containing epoxy compound contains a cationically polymerized aromatic ring-containing epoxy compound. In the step of preparing the article, at least one selected from the group consisting of the compound having the styrene skeleton, the aromatic ring-containing acrylic compound and the aromatic ring-containing epoxy compound is applied to at least a part of the surface of the substrate. At least one selected from the group consisting of the compound having a styrene skeleton, the aromatic ring-containing acrylic compound and the aromatic ring-containing epoxy compound is cured to obtain a cured product of the compound having a styrene skeleton, and the aromatic ring-containing acrylic. The article with a protrusion group according to any one of claims 22 to 24, which forms a film containing at least one selected from the group consisting of a cured product of the compound and a cured product of the aromatic ring-containing epoxy compound. Manufacturing method. In the step of preparing the article, the aromatic polyamic acid is applied to at least a part of the surface of the substrate, and then the aromatic polyamic acid is dehydrated and ring-closed to form a film containing the aromatic polyimide. 22. The method for producing an article with a protrusion group. A structure for forming an article with a moth-eye structure, which has a region containing an aromatic ring-containing resin for forming a moth-eye structure by oxygen ion beam processing on at least a part of the surface.

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