JP2006106449A - Inorganic micropattern organizer and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic micropattern organizer having an inorganic micropattern which is stable in the cross-sectional shape and as intended, on a substrate, and a method for forming such an inorganic micropattern. <P>SOLUTION: A molding type 14 having a molding pattern 15 of the predetermined width and depth, and a substrate for molding 11 in which a layer for molding 13 consisting of a hardened material of the radiation hardening resin composition containing polysiloxane of which a phenyl group content is 40-90% is laminated on the substrate 12 are prepared. The inorganic micropattern is formed by the molding which is done by making the molding pattern 15 abut on the layer for molding 13, by making the layer for molding hardened by irradiating an ionizing radiation 17 from the side of the molding type 14, and by removing the formwork. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an inorganic fine pattern formed body and a method for forming an inorganic fine pattern. Preferably, the inorganic fine pattern is a glass-like one having a width of 1 μm or less and an aspect ratio of 1 or more, and the pattern formed body on which such an inorganic fine pattern is formed is used for a recording device, a liquid crystal device, and an optical lens. It can be used for a glass stamper, a liquid crystal device, an optical device, an optical lens, or the like, and is suitable for an optical waveguide, for example.

There is a demand for a fine pattern formed of an inorganic material as an optical waveguide, a fine optical component, or a replication mold for producing them. Taking an optical waveguide as an example, instead of forming a thin film on a substrate by a reactive ion etching method, a polysiloxane-based coating film is exposed to a pattern, and uncured portions are dissolved and removed. Therefore, it is proposed to make a pattern. (Reference 1).
JP 2004-85646 A.

  According to the method described in Patent Document 1, formation of an inorganic fine pattern itself is possible, but the thickness of the coating film is limited, and when the cross section of the pattern obtained by dissolution and removal is viewed, The joint portion between the side surface and the joint portion between the side surface and the substrate may be rounded, and the intended precise shape may not be obtained. In particular, when the obtained pattern is baked to obtain an inorganic-only fine pattern, it is more difficult to obtain the intended precise shape because the pattern with a round cross-section originally has a tendency to further deform. Become. In optical applications, it is desired that the cross-sectional shape is reproduced as intended and stably, and the surface roughness of the resulting pattern is extremely small.

  In the present invention, it is possible to provide an inorganic fine pattern forming body having an inorganic fine pattern having a stable shape as intended on a substrate and having an excellent surface roughness, and formation of such an inorganic fine pattern. It is an object to provide a method.

  According to the inventor's study, after forming a coating film using a molding die having a fine mold shape, instead of forming a pattern by forming a coating film, pattern exposure, and dissolving and developing with a solvent, The inventors have found that the above-mentioned problems can be solved by curing or further firing, and have reached the present invention.

  According to a first aspect of the present invention, there is provided a molding die having a molding pattern formed with grooves of a predetermined width and depth on a mold surface, and a polycrystal having a phenyl group content of 40 to 90% laminated on a substrate. A molding layer comprising a cured product of a radiation curable resin composition containing siloxane and having a silanol concentration of 10 mmol / g or less is prepared, and molding is performed by applying the mold surface of the molding die to the molding layer. The present invention relates to a method for forming an inorganic fine pattern comprising performing the molding and then curing the molding layer.

  According to a second invention, in the first invention, the molding layer is prepared using a composition containing a solvent in addition to the inorganic component and the curable organic component. Then, it is related with the formation method of the inorganic fine pattern characterized by performing by removing a solvent.

  According to a third invention, in the first or second invention, the molding layer is semi-cured before the mold surface of the molding die is applied to the layer of the molding layer, and the molding is performed. In addition, the present invention relates to a method for forming an inorganic fine pattern, wherein the molding layer is completely cured after a while.

  According to a fourth invention, in any one of the first to third inventions, the molding layer is cured after the molding is performed while the molding die is applied to the molding layer. The present invention relates to a method for forming an inorganic fine pattern.

  5th invention is a hardened | cured material of the radiation curable resin composition containing polysiloxane whose phenyl group content is 40 to 90% on a board | substrate, Comprising: From the thing whose silanol concentration is 10 mmol / g or less An inorganic fine pattern composed of ridges having a predetermined width and height is laminated, and the curvature radius of the cross section of the skirt near the substrate of the ridges is 0.02 μm or less. The present invention relates to an inorganic fine pattern formed body.

  A sixth invention is characterized in that, in the fifth invention, a cross section of the ridge is a quadrangle, and a radius of curvature of an angle formed by a top surface and a side surface of the ridge is 0.5 μm or less. 1 relates to an inorganic fine pattern formed body according to 1.

  According to 1st invention, it consists of hardened | cured material of the radiation curable resin composition containing the polysiloxane which is laminated | stacked on the board | substrate and whose phenyl group content is 40-90%, Silanol concentration is 10 mmol / g or less. A molding pattern having a molding pattern formed with a groove having a predetermined width and depth is applied to the molding layer, and then molded, and then cured to form a fine pattern formed with ridges. It is possible to provide a method for forming an inorganic fine pattern capable of forming the cross-sectional shape with good reproducibility.

  According to the second invention, in addition to the effect of the first invention, the composition containing the solvent is used to prepare the molding layer, and the solvent is removed after the application, so that a pattern obtained by evaporation of the solvent is obtained. It is possible to provide a method for forming an inorganic fine pattern that does not deform or shrink.

  According to the third invention, in addition to the effects of the first or second invention, the molding layer is semi-cured before molding with the molding die and completely cured after molding. In addition, it is possible to provide a method for forming an inorganic fine pattern in which the handling of the layer at the time is easy and the shrinkage due to curing can be reduced.

  According to the fourth invention, in addition to the effects of any one of the first to third inventions, the molding layer is cured with the molding die applied thereto, so that deformation during curing can be suppressed. A method for forming an inorganic fine pattern can be provided.

  According to 5th invention, it is a hardened | cured material of the radiation curable resin composition containing polysiloxane whose phenyl group content is 40 to 90% on a board | substrate, Comprising: Silanol concentration is 10 mmol / g or less. An inorganic fine pattern composed of ridges having a predetermined width and height is laminated, and the radius of curvature of the cross section of the bottom of the inorganic fine pattern formed of ridges is small. That is, an inorganic fine pattern formed body in which the shape of the bottom surface is accurately reproduced can be provided.

  According to the sixth invention, in addition to the effect of the fifth invention, there is provided an inorganic fine pattern forming body in which the radius of curvature formed by the top and side surfaces of the ridge is small, that is, the shape of the upper surface is accurately reproduced. can do.

  FIG. 1 is a diagram schematically showing a cross-sectional shape of a pattern forming body of the present invention, and FIG. 2 is a diagram showing an outline of a method for forming an inorganic pattern of the present invention.

  The inorganic fine pattern forming body 1 of the present invention basically has a laminated structure in which ridges 3 are laminated on a substrate 2 as illustrated in a cross section in FIG. Here, the ridge 3 has a relatively large height H with respect to the width W, protrudes from the substrate 2, and has a length in a direction from the near side to the far side of the drawing. Has a ratio expressed by W / H (= aspect ratio) of 1 or 1 or more. Note that having a length in the direction from the near side to the far side of the drawing includes not only a straight line but also a curved line.

  In the inorganic fine pattern forming body 1 of the present invention, an angle (corner) formed by the side surface 3b of the ridge and the upper surface of the substrate 2 (in a circle surrounded by a circle A in FIGS. 1A and 1B) 1 and the arrow indicating the radius of curvature Ra in FIG. 1 (b).) In other words, the occurrence of roundness at the bottom is suppressed, and the radius of curvature at the bottom of the ridge 3 is suppressed. Ra is 0.02 μm or less, more preferably 0.015 μm or less. The practical lower limit of Ra is about 0.01 μm.

  In the inorganic pattern forming body 1 of the present invention, the top 3a of the ridge 3 does not necessarily have to be a flat surface, and may be one that forms two sides of an arc shape or a triangle.

  When the top 3a of the ridge 3 is a flat surface, the angle formed by the top surface 3a and the side surface 3b (indicated by a circle B in FIGS. 1 (a) and 1 (c) is shown in FIG. (C) is the tip pointed by the arrow indicating the radius of curvature Rb.), That is, the radius of curvature Rb in this portion is 0.5 μm or less, more preferably 0. .1 μm or less. The practical lower limit of Rb is about 0.015 μm.

  The pattern of the ridges 3 in the inorganic fine pattern forming body 1 of the present invention is basically formed by using a mold, not by patterning the coating film photolithography or patterning by a printing method. For example, it is formed as follows.

  As shown in FIG. 2A, first, a forming substrate 11 having a forming layer 13 laminated on a substrate 12 and a forming die 14 having a predetermined forming pattern are prepared.

  The substrate 12 is a substrate of the inorganic fine pattern forming body 1 finally obtained (the same as that indicated by reference numeral 2 in FIG. 1). The molding layer 13 is a layer to be molded using the molding die 14 and is made of a material suitable for the use of the inorganic fine pattern forming body 1, preferably mainly composed of an inorganic substance, more preferably If it is a glass-like thing comprised with the inorganic substance and for optical uses, it is transparent, More preferably, it is a colorless and transparent thing. As described later, for example, it consists of a cured product of a radiation curable resin composition containing polysiloxane having a phenyl group content of 40 to 90%.

  The molding die 14 has a molding pattern 15 corresponding to a desired pattern of the ridges 3 of the inorganic fine pattern forming body 1, and the molding pattern has a groove shape having a predetermined width and depth. The width and depth of the grooves correspond to the width and height of the ridges of the pattern forming body 1 to be obtained, respectively.

  Whether the molding die 14 is overlaid on the molding substrate so that the molding pattern 15 side faces the molding layer 13 side, and is pressed by using a roller 16 as shown in FIG. Alternatively, pressurization and heating are performed as necessary to form the molding layer 13 with the molding pattern 15. As a means for pressurization or pressurization and heating, a flat press may be used.

  After molding, for example, as shown in FIG. 2C, ionizing radiation 17 is irradiated from the molding die 14 side to cure the molded molding layer 13. Curing may be by heating as well as by irradiation with ionizing radiation. According to the method of the present invention, since the molding layer 13 is molded and then cured, the cross-sectional shape of the ridge at this stage is a predetermined shape obtained by molding the cross-sectional shape of the molding pattern of the molding die 14. Have In addition, before or after irradiating with ionizing radiation, demolding is performed, that is, the molding die 14 is separated from the molding layer 13, and the molding layer 13 is formed on the substrate 12 as shown in FIG. Is formed and an inorganic fine pattern having ridges 18 produced by curing is obtained.

  When the ridges 3 in the inorganic fine pattern-formed body 1 may have an organic component, if the ionizing radiation is irradiated and the molding die 14 is separated as described above, the final product may be obtained. However, when a harder one is desired as the ridge 3 of the final product, heating or the like may be further performed.

  The above is a basic method for forming an inorganic fine pattern, but there may be a modified form such as adding several steps.

  First, when preparing a laminate of the molding layer 13 on the substrate 12, the molding layer 13 may be formed by application or the like using a composition containing a solvent. In this case, a solvent is contained in the molding layer 13 immediately after it is applied, and handling it as it is is inconvenient because it is sticky, and the solvent evaporates even if molding can be performed. Since the shrinkage of the molding layer 13 due to this is inevitable, the reproducibility of the molding pattern 15 of the molding die 14 is lowered.

  Therefore, when forming the molding layer 13 using a composition containing a solvent, it is preferable to remove the solvent by forming a film of the composition by coating or the like and then taking a drying means. May be performed by cold air drying or hot air drying.

  Secondly, the molding layer is cured by irradiation with ionizing radiation not only after molding but also before molding. Since the molding layer 13 includes a component sensitive to ionizing radiation, if a completely uncured molding layer is cured, shrinkage during curing is unavoidable. This is because reproducibility is lowered. However, since molding cannot be performed if it is completely cured before molding, it is preferable to perform so-called semi-curing to leave room for molding while eliminating the disadvantages of uncured.

  In the case where the molding layer is cured by irradiation with ionizing radiation 17, when the semi-curing is performed, about 1% to 50% of the irradiation dose necessary for complete curing is preferable.

  Third, it is preferable that the molding layer is cured after molding while the molding die 14 is applied to the molding layer 13 as shown in FIG. Regardless of whether the molding layer is uncured or semi-cured, if the mold is released after the molding is separated from the molding layer 13 after molding, the molded shape is lost at the time of demolding. This is because there is a fear, deformation may occur during curing, or oxygen in the air may inhibit curing. Further, if completely cured, the adhesive property between the molded layer 14 that has been molded and cured and the molding die 14 is lost at the time of demolding. Because.

  Therefore, in the formation method of the inorganic fine pattern of the present invention, in addition to the basic formation method, when the molding layer contains a solvent, the solvent is removed in advance and semi-cured before molding. It is more preferable to perform the molding and to cure the molding die while it is applied to the molding layer.

  In the method for forming an inorganic fine pattern according to the present invention, by adjusting the thickness of the molding layer 13 and the depth and width of the groove of the molding pattern 15 of the molding die 14, the ridges 18 of the inorganic fine pattern obtained can be obtained. It is possible to eliminate the thin portion where the molding layer 13 is cured, or to make the thickness very thin. In the case of using an inorganic fine pattern as an optical waveguide, it is desirable to more reliably eliminate the portion between the ridges 18. By covering the top surface and side surfaces of the ridges 18 with a mask and performing plasma treatment or the like, the portion between the ridges 18 can be surely eliminated.

  The substrate 2 (or 12) in the present invention is an inorganic plate such as glass, quartz glass, or silicon wafer, a plastic plate, or a plastic film, and may be transparent or opaque, but from the substrate 2 side. When irradiating with ionizing radiation, it is preferably transparent.

  A preferred molding layer 13 is composed of a radiation curable resin composition containing polysiloxane having a preferred phenyl group content, and the ridge 3 is a cured product of this radiation curable resin composition, more preferably. A radiation curable resin composition containing a polysiloxane component (A) having a phenyl group content of 40 to 90 mol%. This radiation curable resin composition is described in, for example, Japanese Patent Application Laid-Open No. 2004-85646. However, this radiation curable resin composition is intended to create an optical waveguide by pattern exposure after application to a substrate. In the invention, the photosensitivity of the radiation curable resin composition is used for curing, but the patterning is not used at all, and the patterning itself is performed by pressing without using light.

The polysiloxane component (A) having a phenyl group content of 40 to 90 mol% is obtained by condensing a hydrolyzable silane compound represented by the following general formula (1), a hydrolyzate thereof, or a mixture thereof. can get.
(Chemical formula 1) R ¹ _m Si (X) _4-m (1)
Here, in the general formula (1), the subscript m of R ¹ and m in 4-m which is the subscript of (X) are 0 to 3, and each R ¹ is independently selected from ^{1 to} 3 carbon atoms. 12 non-hydrolyzable cyclic, branched, and linear alkyl groups, aryl groups, and aralkyl groups, and some or all of the hydrogen atoms on the substituent are substituted with deuterium, fluorine, or chlorine. May be.

As the alkyl group for R ¹ , methyl, ethyl, propyl, butyl, octyl, or dodecyl, or a deuterium substituted thereof, and as the aryl group, phenyl, biphenyl, or naphthyl, or their deuterium, fluorine, Alternatively, each substituent of chlorine can be exemplified, and examples of the aralkyl group include tolyl, xylyl, or mesityl, or their respective deuterium, fluorine, or chlorine substituents. Preferred alkyl groups include a methyl group, 3, 3,3-trifluoropropyl group or trideuteriomethyl group, and preferable aryl group may include phenyl group, pentafluorophenyl group, or pentadeuteriophenyl basis, particularly preferably as aryl group Mention may be made of phenyl. Preferred aralkyl groups include trifluoromethylphenyl group and bis (trifluoromethyl) phenyl group.

  Examples of the hydrolyzable group X include a hydrogen atom, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, an amino group, or an alkyl carboxylate group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an octyloxy group, or a dodecyloxy group, a halogen atom is fluorine or chlorine, an amino group is an amino group, a dimethylamino group, or Examples of the diethylamino group and the alkylcarboxylate group include an acetoxy group or a propiolate group. Among these, preferred X is an alkoxy group, and more preferred is a methoxy group or an ethoxy group.

  The hydrolyzable silane compound represented by the general formula (1) is divided into a hydrolyzable silane compound (a) containing no phenyl group and a hydrolyzable silane compound (b) containing no phenyl group. . In addition, (a) and (b) are mixed and used so that the phenyl group content of component (A) may be a predetermined value. Furthermore, (a) and (b) may be used as a mixture of plural kinds.

  Examples of the phenyl group-containing hydrolyzable silane compound (a) include benzyltrimethoxysilane, phenyltrimethoxysilane, phenylsilane, phenyltriacetoxysilane, phenyltriaminosilane, phenyltrichlorosilane, phenyltriethoxysilane, and pentafluorophenyltrimethoxy. Silane, pentafluorophenyltrichlorosilane, pentadeuteriophenyltrimethoxysilane, pentadeuteriophenyltriacetoxysilane, pentadeuteriophenyltrichlorosilane, pentadeuteriophenyltriethoxysilane, xylyltrimethoxysilane, trifluoromethylphenyltochi Methoxysilane, biphenyltrimethoxysilane, biphenyltrichlorosilane, diphenyldimethoxysilane, diph Such alkenyl dichlorosilane can be exemplified. Among these, preferred examples include phenyltrimethoxysilane.

  Examples of the hydrolyzable silane compound (b) containing no phenyl group include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra (2-methacryloxyethoxy) silane, tetra (2-acryloxyethoxy) silane, and tetrachlorosilane. , Tetraacetoxysilane, tetraaminosilane, methyltrimethoxysilane, methyltrichlorosilane, methyldichlorosilane, methyldimethoxysilane, methyltriacetoxysilane, trideuteriomethyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, 3, 3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, bis (trideuteriomethyl) dimethoxysilane, dimethyldimethoxysilane Emissions, dimethyldichlorosilane, trimethylchlorosilane, mention may be made of trimethyl methoxy silane, triethylsilane, or triethylchlorosilane like. Among these, preferred specific examples include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, methyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, or dimethyldimethoxysilane. .

When the hydrolyzable group is an alkoxy group, the hydrolysis or condensation of the hydrolyzable silane compound that is a raw material for producing polysiloxane can be carried out without adding a solvent in the hydrolysis and condensation process.
On the other hand, if the hydrolyzable group is a raw material that does not produce a by-product that becomes a diluting solvent such as a halogen group, and is a by-product of an acid that becomes an autocatalyst, after diluting by adding an organic solvent described later in advance It is desirable to carry out hydrolysis and condensation reactions. In that case, the generated acid remains after the reaction and impairs the stability as the curable composition. For example, neutralization with a basic substance, washing with water, and addition of an ion exchange resin are added. It is preferable to make it a stable curable composition.

The hydrolysis and condensation step of the silane compound when the hydrolyzable group is an alkoxy group is 1)
The hydrolyzable silane compound is accommodated in a container, 2) a predetermined amount of water and a catalyst are then added dropwise with stirring, 3) and then heated and stirred at a predetermined temperature for a predetermined time. 4) as required Then, a predetermined solvent is added and diluted.

Dilution solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, cyclohexanone, acetylacetone and diacetone alcohol, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol diethyl ether, and hydrocarbons such as toluene and xylene. Alcohol, methanol, ethanol, butanol, octanol, furfuryl alcohol, etc., ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. Ether-containing alcohol System solvent, ethyl acetate, butyl acetate, amyl acetate, octyl acetate, ethyl lactate, selected in combination a single or two or more ester-based solvents such as butyl lactate. Preferred solvents are ketone-based, alcohol-based, ether-containing alcohol-based and ester-based solvents, more preferably methyl isobutyl ketone, cyclohexanone, diacetone alcohol, butyl alcohol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate. Butyl lactate can be mentioned, and the diluent solvent is used in a ratio (mass basis) of 0 to 1000, preferably 40 to 250, based on 100 of the amount of the hydrolyzable silane compound charged.

(A) The phenyl group content in the polysiloxane needs to be 40 to 90 mol%, preferably 50 to 80 mol%. When the phenyl group content is less than 40 mol%, the optical properties at a wavelength of 1.55 μm are deteriorated, which is not preferable. On the other hand, if it exceeds 90 mol%, the resolution at the time of pattern formation decreases, which is not preferable. In addition, the value of phenyl group content of a component (A) is phenyl group content (charge amount) about the mixture of each hydrolysable silane compound before condensation reaction. The molecular weight of the component (A) is a weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (hereinafter abbreviated as GPC), and is preferably in the range of 500 to 50,000, preferably 1000 to 20,000. If it is less than 500, the durability of the resulting inorganic fine pattern is lowered, and if it exceeds 50,000, the storage stability is lowered.
In addition to the component (A), components (B) to (H) described later or other components can be contained as necessary. That is, (B) photoacid generator, (C) acid diffusion controller, (D) surface tension reducing agent, (E) photosensitizer, (F) crosslinkable organic compound, (G) inorganic fine particles, (H ) Metal alkoxide.

When a radiation curable resin composition containing polysiloxane having a phenyl group content in the above range is used, application to a substrate can be performed by a known method, for example, by spin coating. It is preferable to dry or pre-bake after application. If necessary, it may be further semi-cured by heating or ionizing radiation irradiation. Drying or pre-baking is performed, for example, at a temperature range of 50 ° C. to 300 ° C. for 1 minute to 24 hours, and ionizing radiation irradiation is performed using, for example, ultraviolet light having a wavelength of 365 nm, and illuminance: 1-1000 mW / cm ² . the amount; 0.01~5000mJ / cm ^2, preferably by irradiation so as to be approximately 0.1~1000mJ / cm ^2, exposure. In addition, when ionizing radiation irradiation is performed twice for the purpose of both semi-curing and complete curing, the conditions for semi-curing are also obtained in consideration of handling in the state before molding and moldability. It is preferable to determine the conditions for complete curing in consideration of the physical and scientific properties of the product to be obtained and the workability of demolding.

  The layer of the radiation curable resin composition formed as described above is formed by stacking and pressing a molding die and using a roll press or a flat plate press. Thereby, the molding pattern of the molding die is formed on the layer of the radiation curable resin composition, but at this stage, the layer of the radiation curable resin composition is in an uncured or semi-cured state, Since it is in a deformable state, it is preferable that the radiation-curable resin composition layer be irradiated with radiation in the stacked state without removing the molding die so that the shape of the molding pattern mold is accurate. It is preferable to cure in the state as reproduced.

The silanol concentration in the molding layer in the present invention is 10 mmol / g or less, preferably 5 mmol / g or less. When the silanol concentration exceeds 10 mmol / g, the optical transmission loss at a wavelength of 1.55 μm exceeds 1.0 dB / cm. In particular, when the inorganic fine pattern of the present invention is used as an optical waveguide, the wavelength 1. This is because the silanol concentration in the core layer is preferably 10 mmol / g or less in order to reduce transmission loss at 55 μm. Further, by using an ionizing radiation curable resin composition containing a polysiloxane component (A) and a photoacid generator (B) for forming the core layer, excellent productivity and pattern accuracy can be obtained.
The silanol concentration (mol / g) is defined as a value obtained by a solid ²⁹ Si-NMR method and obtained by multiplying the silanol concentration (mol / total Si mole) and the total Si concentration (mol / g).

Preparation of fine concave / convex original plate A 150 mm × 150 mm square, 9 mm thick quartz substrate with a width of 0.2 μm, a depth of 0.5 μm, a pitch of 0.4 μm, and dry etching on one surface of a quartz substrate. A fine uneven original plate A was prepared by forming a mold surface by the method. Similarly, a groove with a width of 0.3 μm, a depth of 0.5 μm, and a pitch of 0.6 μm was formed by a dry etching method to form a mold surface, thereby producing a fine uneven original plate B.

Preparation of resin stamper The ultraviolet curable resin composition having the composition shown in the next paragraph is dropped on the mold surfaces of the above-described fine uneven original plates A and B, and a polycarbonate sheet having a thickness of 0.4 mm is laminated thereon. Then, ultraviolet rays were irradiated using an ultraviolet light source (H bulb, manufactured by Fusion UV Systems, Inc.) under the condition of 170 mJ / cm ² (365 nm) to cure the ultraviolet curable resin composition. Then, when the cured ultraviolet curable resin composition is peeled in the direction parallel to the groove on the mold surface together with the polycarbonate sheet, the surface of the cured ultraviolet curable resin composition has irregularities on the mold surface of each fine uneven original plate. Was reproduced and a replica lined with a polycarbonate sheet was obtained. A 3000 mJ / cm ² (365 nm) ultraviolet ray was further irradiated from the uneven side of the duplicate to obtain a resin stamper.

UV curable resin composition / urethane acrylate 35 parts (Nippon Synthetic Chemical Industry Co., Ltd., GOSELAC UV-7500B)
・ 1,6-Hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd.) …… 35 parts ・ Pentaerythritol triacrylate (manufactured by Toagosei Co., Ltd.) ……………… 10 parts ・ Vinyl Pyrrolidone (Toagosei Co., Ltd.) ……………………………………………… 15 parts, 1-hydroxycyclohexyl phenyl ketone ………………………………………… Part 2 (Ciba Specialty Chemicals Co., Ltd., “Irgacure 184” is used)
・ Benzophenone (manufactured by Nippon Kayaku Co., Ltd.) ………………………………………………… 2 parts ・ Polyether-modified silicone ………………………………… ………………………… 1 part (GE Toshiba Silicones Co., Ltd., TSF4440)

Duplicate using resin stamper 150 mm × 150 mm square, 0.7 mm thick alkali-free glass plate on one side of a substrate containing a phenyl group-containing hydrolyzable silane compound (manufactured by JSR Corporation, “OPSTAR PJ5029 "was dropped, and the spinner was rotated at 300 rpm for 10 seconds, and then at 1000 rpm for 30 seconds to form a uniform coating film having a thickness of 10 μm and having no defects. Heating in an atmosphere at 120 ° C. for 5 minutes to remove the solvent in the coating film.

After the heating described above, the resin stamper obtained above is stacked on the surface of the coating film on the substrate so that the mold surface is in contact with the coating film. It was placed on a transport table of an installed roll press apparatus, and roll press was performed with a rubber roller having a hardness of 80 degrees under conditions of speed: 15 mm / s, roller pressure: 5 kg / cm ² .

After roll pressing, the resin stamper is irradiated from the resin stamper side with the ultraviolet light source (H-bulb manufactured by Fusion UV Systems Co., Ltd.) under the condition of 40 mJ / cm ² (365 nm), and then the resin stamper is molded. The surface of the cured coating film was peeled in a direction parallel to the groove of the film, and the fine unevenness on the surface of the cured coating film was exposed. Then, from the exposed fine unevenness side, using the same ultraviolet light source, the condition of 1500 mJ / cm ² (365 nm) was further applied. The coating film on which the fine irregularities were formed was completely cured by irradiating with ultraviolet rays to obtain a molded product.

  The molded product obtained by complete curing was heated in a clean oven at a temperature of 300 ° C. for 30 minutes, and the organic component was removed leaving only the inorganic component. , Depth: 0.5 μm, pitch: 0.4 μm groove, and fine uneven original plate width: 0.3 μm, depth: 0.5 μm, pitch: 0.6 μm groove were faithfully reproduced. Also, the surface of the pattern was highly smooth, and a product suitable for optical use was obtained.

It is a figure which shows an inorganic pattern formation body. It is a figure which illustrates the formation method of an inorganic fine pattern formation body.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Inorganic fine pattern formation body 2, 12 ... Board | substrate 3 ... Projection 13 ... Molding layer 14 ... Molding type | mold 15 ... Molding pattern 16 ... Roller 17 ... Ionizing radiation

Claims (6)

  Radiation curing containing a molding die having a molding pattern formed with grooves having a predetermined width and depth on the mold surface and polysiloxane laminated on the substrate and having a phenyl group content of 40 to 90% And forming a molding layer having a silanol concentration of 10 mmol / g or less. The molding layer was molded by applying the mold surface of the molding die to the molding layer. A method for forming an inorganic fine pattern, comprising later curing the molding layer.   The molding layer is prepared by forming the molding layer using a composition containing a solvent in addition to the inorganic component and the curable organic component, and then removing the solvent. The method for forming an inorganic fine pattern according to claim 1.   The method includes semi-curing the molding layer before applying the mold surface of the molding die to the layer of the molding layer, and completely curing the molding layer after performing the molding. The formation method of the inorganic fine pattern of Claim 1 or Claim 2.   The inorganic fine pattern according to any one of claims 1 to 3, wherein the molding layer is cured after the molding is performed while the molding die is applied to the molding layer. Forming method.   A cured product of a radiation curable resin composition containing a polysiloxane having a phenyl group content of 40 to 90% on a substrate and having a silanol concentration of 10 mmol / g or less, and having a predetermined width In addition, an inorganic fine pattern composed of ridges having a height is laminated, and a curvature radius of a cross section of a skirt near the substrate of the ridges is 0.02 μm or less. Inorganic fine pattern forming body. 6. The inorganic fine pattern forming body according to claim 5, wherein a cross section of the ridge is a quadrangle, and a radius of curvature of an angle formed by a top surface and a side surface of the ridge is 0.5 μm or less.

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