JP2006113161A - Method of forming fine pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of forming a fine pattern that has an intended stable shape on a substrate and that also excels in surface roughness. <P>SOLUTION: The fine pattern is formed by: stacking a substrate 12, a forming layer 13 that is composed of an organic/inorganic composite ionizing radiation-curing resin composition containing oligomers of silicon alkoxide, and a forming die 14 that has a forming pattern 15 comprising grooves of desired depth and width; hardening the forming layer by irradiating it with an ionizing radiation 17 from the forming die 14 end; releasing the forming layer from the die; and thereafter heating and calcining it. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  An object of the present invention is to provide a method for forming a fine pattern which has a stable shape as intended on a substrate and is excellent in terms of surface roughness.

  According to the inventor's study, an organic / inorganic composite ionizing radiation curable resin composition containing a silicon alkoxide oligomer is finely formed instead of forming a pattern by coating film formation, pattern exposure, and dissolution development with a solvent. It is found that the above-mentioned problems can be solved by applying to a mold surface of a mold having a proper mold shape, peeling off by irradiation with ionizing radiation, and then heating or further firing. The invention has been reached.

  The first invention is an organic / inorganic composite ionizing radiation curable resin composition comprising an ionizing radiation curable resin as an organic component and an oligomer of silicon alkoxide as an inorganic component, and having a predetermined width and depth on the mold surface. A coating film prepared by forming a molding die having a molding pattern formed by grooves, and applying the organic / inorganic composite ionizing radiation curable resin composition to the mold surface of the molding die and closely contacting the mold surface The film is formed by irradiating and curing the ionized radiation, the cured film is peeled off, and after the peeling, heating is performed.

  According to a second invention, in the first invention, a substrate is prepared in addition to the organic / inorganic composite ionizing radiation curable resin composition and the molding die, and the organic / inorganic composite ionizing radiation curable resin composition is prepared. Applying the organic / inorganic composite ionizing radiation curable resin composition applied to the substrate to the mold surface of the molding die together with the substrate to form a coating film in close contact with the mold surface The present invention relates to a featured fine pattern forming method.

  According to a third invention, in the first invention, a substrate is prepared in addition to the organic / inorganic composite ionizing radiation curable resin composition and the molding die, and the organic / inorganic composite ionizing radiation curable resin composition is prepared. Applying the applied organic / inorganic composite ionizing radiation curable resin composition to the mold surface of the molding die and overlapping the molding mold on the substrate to form a coating film in close contact with the mold surface. The present invention relates to a method for forming a fine pattern.

  A fourth invention is the invention according to any one of the first to fourth inventions, wherein the coating film is irradiated with ionizing radiation and cured, and instead of peeling the cured coating film, ionizing radiation is applied to the coating film. The present invention relates to a method for forming a fine pattern, characterized in that after irradiation and semi-curing and peeling off the semi-cured coating film, the coating film is cured by irradiating the film with ionizing radiation.

  According to a fifth invention, in any one of the first to fourth inventions, the present invention relates to a fine pattern forming method, wherein the baking is performed following the heating.

  According to the first invention, an organic / inorganic composite ionizing radiation curable resin composition containing an oligomer of silicon alkoxide is applied to a mold surface of a molding die having a molding pattern formed by grooves having a predetermined width and depth. A method for forming a fine pattern that can be applied, irradiated with ionizing radiation, peeled off, and then heated to form a fine pattern of ridges with a reproducible cross-sectional shape is provided. can do.

  According to the second or third invention, in addition to the effect of the first invention, it is possible to provide a method for forming a fine pattern having a fine pattern with a substrate.

  According to the fourth invention, in addition to the effects of any one of the first to third inventions, the irradiation with ionizing radiation is divided into two times for semi-curing before peeling and for hardening after peeling. Therefore, since the coating film is flexible at the time of peeling, it is possible to provide a method for forming a fine pattern that can be peeled more reliably.

  According to the fifth invention, in addition to the effects of any one of the first to fourth inventions, a method for forming a fine pattern capable of removing an organic component contained in a pattern is provided because firing is performed. Can do.

FIG. 1 is a diagram showing an outline of a fine pattern forming method of the present invention.
In the method for forming a fine pattern of the present invention, first, (1) an organic / inorganic composite ionizing radiation curable resin composition containing an ionizing radiation curable resin as an organic component and an oligomer of silicon alkoxide as an inorganic component, and ( 2) A molding die having a molding pattern formed with grooves having a predetermined width and depth on the mold surface is prepared. Further, (3) it is preferable to prepare a substrate.

  Next, the organic / inorganic composite ionizing radiation curable resin composition of (1) is applied to the mold surface of the molding mold of (2) to form a coating film in close contact with the mold surface.

  There are roughly two ways to form this coating film. In the first method, as shown in FIGS. 1A and 1B, a substrate 12 of (3) is prepared, and the substrate 12 is made of an organic / inorganic composite ionizing radiation curable resin composition. In this method, the layer 13 is applied, and the molding layer 13 made of the applied organic / inorganic composite ionizing radiation curable resin composition is overlaid on the mold surface of the molding die 14 together with the substrate 12. In the second method, contrary to the first method, although not shown, a molding layer 13 made of an organic / inorganic composite ionizing radiation curable resin composition is applied to the mold surface of the molding die 14. In this method, the molding layer 13 made of the applied organic / inorganic composite ionizing radiation curable resin composition is overlaid on the substrate 12 together with the molding die 14. In order to reliably perform the superposition, as shown in FIG. 1B, it may be brought into close contact with pressure by pressing means such as a roller 16 or the like. Alternatively, the molding layer 13 made of the organic / inorganic composite ionizing radiation curable resin composition may be applied to the mold surface of the molding die 14 without using the substrate 12.

  The coating film of the organic / inorganic composite ionizing radiation curable resin composition formed as described above is irradiated with ionizing radiation 17. For example, the ionizing radiation 17 is irradiated from the molding die 14 side to cure the coating film. After curing, the cured coating film is peeled off, and after peeling, heating is performed to form a fine pattern.

  The irradiation, peeling, and heating of these ionizing radiations can have the following deformation modes.

First, for ionizing radiation irradiation and peeling, the ionizing radiation irradiation step and the two steps of performing the peeling step in the order of description, the semi-curing step by ionizing radiation irradiation, the peeling step, and the ionizing radiation There are cases where the step of curing by irradiating consists of three steps in the order of description. Irradiation of ionizing radiation, for example, using ultraviolet rays having a wavelength of 365 nm, illuminance; 1~1000mW / cm ^2, irradiation amount; 0.01~5000mJ / cm ^2, so that preferably is about 0.1~1000mJ / cm ² Irradiate and expose. In addition, when ionizing radiation irradiation is performed in two steps for the purpose of both semi-curing and complete curing, taking into consideration the physical and scientific properties of the product obtained, and the workability of demolding, It is preferable to determine the first and second irradiation conditions. In the case of the above two steps, since the coating film is cured before peeling, the flexibility of the coating film is poor, and deformation due to stress at the time of peeling is unlikely to occur, so the coating film may be damaged. There is. On the other hand, when it consists of the above three steps, since it is in a semi-cured state where the curing has not been completed at the stage before peeling, the coating film is flexible, and deformation due to stress during peeling is caused. As a result, it is easy to peel off and, after peeling, returns to its original shape. In particular, as the pattern becomes finer and the aspect ratio becomes larger, the advantage of performing in three steps becomes more significant.

  In the present invention, since the molding layer 13 is made of a coating film of an organic / inorganic composite ionizing radiation curable resin composition, the organic component remains together with the inorganic component in the fine pattern only by heating. It is normal. However, depending on the use of the fine pattern, it may be preferable that the organic component does not remain but only the inorganic component. In such a case, heating is performed at a high temperature that can remove the organic component, so-called baking. Is preferably performed.

  In the fine pattern forming method of the present invention, by adjusting the thickness of the molding layer 13 and the depth and width of the grooves of the molding pattern 15 of the molding die 14, the ridges 18 of the inorganic fine pattern obtained are obtained. The thin portion where the molding layer 13 is cured between the layers can be eliminated, or the thickness can be made extremely 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 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 is irradiated with ionizing radiation from the substrate 12 side. When it does, it is preferable that it is transparent.

The molding die 14 has a molding pattern 15 corresponding to a fine pattern to be obtained. The molding pattern is a pattern in which grooves having a predetermined width and depth are formed. And depth correspond to the width and height of the ridges of the resulting fine pattern, respectively. Here, the ridges are those having a relatively large height H with respect to the width W, protruding from the substrate (12), and having a length in a direction from the near side to the far side of the drawing, Preferably, the ratio represented by W / H (= aspect ratio) is 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 fine pattern forming method of the present invention, the tops of the ridges of the fine pattern to be obtained do not necessarily have to be flat, and may be those that form two sides of an arc shape or a triangle.

  The organic / inorganic composite ionizing radiation curable resin composition contains an ionizing radiation curable resin as an organic component and an oligomer of silicon alkoxide as an inorganic component.

  Silicon alkoxides include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-sec-butoxysilane, tetra Tetraalkoxysilanes such as t-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltri Methoxysilane, i-propyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyl Ethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, 3-glycol Sidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltrimethoxy Trialkoxysilanes such as silane, vinyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and dimethyldimethoxy Silane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, Dialkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane; tetraacyloxysilanes such as tetraacetyloxysilane and tetrapropionyloxysilane; triacyloxysilanes such as methyltriacetyloxysilane and ethyltriacetyloxysilane; dimethyl Diacyloxysilanes such as diacetyloxysilane and diethyldiacetyloxysilane are preferred. Among these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane are preferable.

  Various ionizing radiation curable resins can be used. An ionizing radiation curable resin composition prepared using a monomer, oligomer, or polymer of a so-called (meth) acrylate compound having a (meth) acryloyl group can be used. Preferably, the ionizing radiation curable resin composition preferably contains a monomer having a hydroxyl group.

  Examples of the monomer having a hydroxyl group include pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, glycerol monomethacrylate, glycerol dimethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl. Mention may be made of methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, or 2-hydroxy-3-acryloyloxypropyl methacrylate.

  The organic / inorganic composite ionizing radiation curable resin composition was prepared by mixing an oligomer of silicon alkoxide as an inorganic component and an ionizing radiation curable resin as an organic component with a solvent, if necessary. Thus, an organic / inorganic composite ionizing radiation curable resin composition in which the dispersion of the inorganic component has advanced can be obtained.

  The hydrolyzed condensate solid content / ionizing radiation curable resin composition can be arbitrarily set in the range of about 1/99 to 99/1. However, as a fine pattern to be finally obtained, it has an inorganic or near-inorganic property. If desired, it is preferably 25/75 to 99/1.

  When the mold surfaces of the molding layer 13, the substrate 12, and the molding die 14 are overlapped, in the description with reference to FIG. 1, it is assumed that pressure is applied using the roller 16, but molding can be easily performed if necessary. Therefore, heating may be accompanied during pressurization. As a means for pressurization, or pressurization and heating, a roller 16 or a flat plate press may be used.

  The molding layer 13 is heated, for example, in the temperature range of 50 ° C. to 300 ° C. for 1 minute to 24 hours, and in the case of firing, it is performed in the temperature range of 200 ° C. to 700 ° C. for 1 minute to 24 hours. Perform under the following conditions. However, when baking is performed after heating, it is preferable to set the heating temperature so that the baking of the organic component does not proceed, that is, lower than the baking temperature.

Creation of a fine uneven original plate 150 mm x 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 the entire surface of one side 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 An ultraviolet curable resin composition having the composition shown in the next paragraph is dropped on each mold surface of the above-mentioned fine irregularities 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 (for resin stamper)
・ Urethane acrylate: 35 parts (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gosselak 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 (manufactured by 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)

  In the following manner, the oligomer of the methoxysilicate compound is further hydrolyzed and condensed, and a resin composition is prepared separately, and the resulting hydrolyzed condensate and resin composition are used to form an inorganic material for molding. / Organic composite composition A was prepared.

First, a silicate main component (methoxy silicate compound oligomer) and a silicate curing agent (mainly a metal complex catalyst and ethanol) are mixed and allowed to react for one day according to the following blending ratio, and the methoxy silicate compound oligomer is mixed. A hydrolysis condensate was prepared.
Mixing ratio / silicate base (Mitsubishi Chemical Co., Ltd., MSH1) 35 parts silicate curing agent (Mitsubishi Chemical Co., Ltd., MSH1) ……………… 65 copies

Next, a resin composition having the following blending ratio was prepared.
UV curable resin composition (A for molding)
・ Urethane acrylate: 35 parts (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gosselak UV-7500B)
・ Pentaerythritol triacrylate (Toagosei Co., Ltd.) …… 45 parts ・ Vinylpyrrolidone (Toagosei Co., Ltd.) ………………………………………… 15 parts, 1-hydroxycyclohexyl phenyl ketone ... 2 parts (Ciba Specialty Chemicals Co., Ltd., using "Irgacure 184")
・ Benzophenone (manufactured by Nippon Kayaku Co., Ltd.) ………………………………………………… 2 parts ・ Polyether-modified silicone ………………………………… ………………………… 1 part (GE Toshiba Silicones Co., Ltd., TSF4440)

The hydrolyzed condensate of the oligomer of the methoxysilicate compound obtained above and the ultraviolet curable resin composition (A for molding) were used in a ratio (mass of hydrolysis condensate: UV curable resin composition = 95: 5). The mixture was allowed to stand for 10 days to obtain an inorganic / organic composite composition A for molding.
The hydrolyzed condensate is obtained as a liquid, and the solid content thereof is 16% on a mass basis, so hydrolyzed condensate solid content / ultraviolet curable resin composition = 75/25.

  The above-mentioned inorganic / organic composite composition for molding is dropped on the surface (mold surface) of the resin stamper obtained above, and the spinner is used for 10 seconds at 300 rpm, 10 seconds at 1000 rpm, and 30 seconds at 4000 rpm. The coating film was formed on the resin stamper by sequentially rotating under each of the conditions.

A roll press apparatus in which a soda glass plate having a thickness of 1.1 mm is stacked on the coating film of the resin stamper on which the coating film is formed, and the stacked rollers are placed on a transfer table. The sample was placed on a work table and rolled with a rubber roller having a hardness of 80 degrees under the conditions of speed: 15 mm / s, roll pressure: 5 kg / cm ² .

After the roll press, the coating film was cured by irradiating with ultraviolet rays under the condition of 1500 mJ / cm ² (365 nm) using an ultraviolet light source (H-bulb manufactured by Fusion UV Systems) from the resin stamper side in a stacked state. Thereafter, the resin stamper was peeled in a direction parallel to the grooves on the mold surface. After peeling, heated for 1 hour in an atmosphere at a temperature of 150 ° C. to react with silicate, and then heated in a clean oven at a temperature of 500 ° C. for 30 minutes to remove only organic components leaving only inorganic components. The width of the first fine uneven original plate A: 0.2 μm, 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 was faithfully reproduced. The thickness of the entire molded product was 1 μm.

The following resin compositions were prepared.
UV curable resin composition (for molding B)
・ Urethane acrylate: 35 parts (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gosselak 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 (manufactured by Toagosei Co., Ltd.) ………………………………………… 15 parts 1-hydroxycyclohexyl phenyl ketone ………………………………………… 2nd part (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)

  The hydrolyzed condensate of the same methoxysilicate compound oligomer as obtained in Example 1 and the above-mentioned UV curable resin composition (molding B) were hydrolyzed condensate: UV curable resin composition = 80. : 20 ratio (mass basis) and left to stand for 10 days to obtain an inorganic / organic composite composition B for molding. In addition, it is hydrolytic condensate solid content / ultraviolet curable resin composition = 39/61.

The resulting inorganic / organic composite composition B for molding was used in the same manner as in Example 1 except that the spinner conditions were set to 500 rpm for 5 seconds and 4000 rpm for 30 seconds in this order, roll press After that, the condition of irradiating with ultraviolet rays is set to 300 mJ / cm ² (365 nm), and heating after peeling is performed only in an atmosphere at a temperature of 150 ° C. for 1 hour, and organic components are not removed. Made the changes consisting of:
In the obtained molded product, the width of the first fine uneven original plate A: 0.2 μm, depth: 0.5 μm, pitch: 0.4 μm groove, and fine uneven original plate width: 0.3 μm, depth; Grooves of 0.5 μm and pitch; 0.6 μm were faithfully reproduced. The thickness of the molded product was 3 μm.

  The same as in Example 2, except that the blending ratio of the inorganic / organic composite composition B for molding was set to hydrolysis condensate: UV curable resin composition = 70: 30. The effect was obtained. The hydrolysis condensate solid content / ultraviolet curable resin composition = 27/73.

(Measurement of glass transition point and flexural modulus)
The same inorganic / organic molding composition B for molding as used in Example 2 was dropped on a soda glass having a thickness of 1.1 mm, applied at 500 rpm under a spinner condition of 35 seconds, and at room temperature for 5 minutes. After placing, the coating film side was irradiated with ultraviolet rays under the condition of 700 mJ / cm ² (365 nm) using an ultraviolet light source (manufactured by Fusion UV Systems, H bulb), and then the coating film was cured. Peel from soda glass, cut the peeled piece into 5 mm width, and after cutting, use the same UV light source as above, and irradiate with ultraviolet rays under the condition of 2000 mJ / cm ² (365 nm), and after irradiation, further temperature: 150 ° C. A test piece A was prepared by heating for 1 hour in the atmosphere.
Further, it is composed of the same components as used in Example 2 and is composed of hydrolysis condensate: UV curable resin composition = 70: 30 inorganic / organic composite composition for molding (hydrolysis condensate solids / UV curable). The test piece B and C were obtained in the same manner using a resin composition comprising a mold resin composition = 27/73 and a composition comprising only an ultraviolet curable resin composition.

Each test piece obtained above was measured with a dynamic viscoelasticity measurement apparatus (RSA-II, manufactured by Rheometric Scientific Co., Ltd.), and a glass transition point and a flexural modulus were obtained. The results obtained are shown in Table 1 below. The test piece C does not contain an inorganic component, and the test piece A contains more inorganic components than the test piece B, but as the inorganic component increases, both the glass transition point and the flexural modulus can be improved. It was confirmed.

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

Explanation of symbols

12 ... Substrate 13 ... Molding layer 14 ... Mold 15 ... Molding pattern 16 ... Roller 17 ... Ionizing radiation 18 ... Projection

Claims (5)

  An organic / inorganic composite ionizing radiation curable resin composition containing an ionizing radiation curable resin as an organic component and an oligomer of silicon alkoxide as an inorganic component, and molding formed with grooves of a predetermined width and depth on the mold surface Forming a coating mold in close contact with the mold surface by applying the organic / inorganic composite ionizing radiation curable resin composition to the mold surface of the molding mold. A method of forming a fine pattern, comprising: curing the coating film by irradiating with ionizing radiation, peeling the cured coating film, and heating after peeling.   In addition to the organic / inorganic composite ionizing radiation curable resin composition and the mold, a substrate is prepared, and the organic / inorganic composite ionizing radiation curable resin composition is applied to the substrate. 2. The fine pattern according to claim 1, wherein a coating film in close contact with the mold surface is formed by overlaying the inorganic composite ionizing radiation curable resin composition together with the substrate on the mold surface of the molding die. Method.   In addition to the organic / inorganic composite ionizing radiation curable resin composition and the mold, a substrate is prepared, and the organic / inorganic composite ionizing radiation curable resin composition is applied to the mold surface of the mold and applied. 2. The fine pattern according to claim 1, wherein the coated organic / inorganic composite ionizing radiation curable resin composition is laminated on the substrate together with the molding die to form a coating film in close contact with the mold surface. Forming method. Instead of peeling the cured coating film by irradiating the coating film with ionizing radiation and curing it,
The coating film is irradiated with ionizing radiation to be semi-cured, and after the semi-cured coating film is peeled off, the coating film is irradiated with ionizing radiation to cure the coating film. The method for forming a fine pattern according to claim 3. The method for forming a fine pattern according to any one of claims 1 to 4, wherein baking is performed following the heating.

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