JP2001072442A - Method for producing article having uneven surface and article produced by the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an article having an uneven surface by which a coating film that has high heat resistance, is not peeled from a substrate, has high dimensional accuracy, and a fine uneven surface can be obtained by subjecting a raw material solution containing two kinds of silane compounds to a dehydrative condensation reaction to produce the coating film-forming liquid, leaving the silane compounds in the non-hydrolyzed forms in specific amounts, and controlling the weight average mol. wt. of the product to a specific value. SOLUTION: In the coating film-forming liquid, the contents of the non-hydrolyzed silane compounds of the formulas: RSiX3 and SiX'4 are 0.5 to 40 wt.%, and 0.5 to 60 wt.%, respectively. The produced condensate has a weight-average mol.wt. of 300 to 1,900. In the formula: RSiX3, R is a non-hydrolyzed organic group, such as an alkyl group, phenyl group or vinyl group, and X is a hydrolyzable group such as an alkoxyl group or a halogen atom. In the formula: SiX'4, X' is a hydrolyzable group such as an alkoxyl group or a halogen atom. Since the alkyl groups, such as methyl groups, are suitably left in the coating film, the coating film is richly elastic and highly strong, and is difficult to generate cracks.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an article having fine irregularities on its surface, particularly to a micro-optical element and an information recording medium substrate, a method for producing the same, and a preparation composition therefor.

[0002]

2. Description of the Related Art Optical components such as a diffractive optical element, a Fresnel lens, and a flat microlens (a lens array in which a large number of microlenses are arranged in parallel on a flat plate), a CD-ROM, and other information recording media have microscopic surfaces on their surfaces. It has an uneven structure. The minute irregularities on the surface converge or diffuse light in an optical component, function as a diffraction grating or a microlens, and function as pits or tracking guides in an information recording medium.

In order to form these irregularities on the surface,
The following methods (1) to (4) are known. (1) A method has been known in which an ultraviolet curable resin is uniformly spread on a substrate, and the resin is irradiated with ultraviolet light while being pressed by a mold having irregularities (JP-A-63-49702).

(2) Japanese Patent Application Laid-Open No. 62-102445 discloses a method of applying a solution containing silicon alkoxide on a glass substrate, and heating while pressing a mold having irregularities to form irregularities. A production method by a sol-gel method is described.

(3) JP-A-6-242303 describes a method of forming a plurality of layers on a substrate when a film having a thickness of several μm or more is formed by using a sol-gel method. . In this case, the components of each layer are developed with a solution or a sol, pressurized and heated while pressing with a mold, and then
The solution or sol was further poured on the completely solidified layer to form the upper layer.

(4) J. Am. Ceram. Soc., Vol. 81, No. 11, page
2849-2852, (1998) discloses a method for producing an optical disc having a fine groove structure by applying a solution containing methyltriethoxysilane and tetraethoxysilane on a substrate.

[0007]

However, the above-mentioned prior art has the following problems. First, in the above method (1), the UV-curable resin has low heat resistance.
Decomposition and yellowing occur when the temperature exceeds 50 ° C. Therefore, a substrate having an uneven portion made of an ultraviolet curable resin cannot be heated by soldering or the like, and it is difficult to mount the substrate on an apparatus or the like.

On the other hand, the uneven portion of the silicon alkoxide formed by the sol-gel method of the above (2) has high heat resistance and can be soldered. However, this sol-gel method has a problem that a thick film cannot be formed. When a layer of silicon alkoxide of several μm is actually formed by the sol-gel method, minute cracks (hereinafter, referred to as cracks) are generated on the surface. This is because when the silicon alkoxide solution gels and solidifies, the degree of progress of the polycondensation reaction between the surface and the inside of this layer is different, so that a large stress is generated on the surface. Further, the layer may be separated from the substrate due to the stress.

In the method (3), a method of forming an organopolysiloxane layer sequentially to form a multi-layer is used, and the method comprises several tens of μm.
An organopolysiloxane layer having an uneven shape with a thickness of m can be formed. However, since the manufacturing process becomes longer, it causes a rise in cost, and after the lower layer is completely cured,
Since the next layer was injected, unnecessary air was likely to enter between the mold and the solution or sol, and the dimensional accuracy of the irregularities was not high.

In the method (4), an optical disk having a maximum sol-gel film thickness of less than 300 nm can be manufactured. However, when the film thickness is 500 nm or more
In the case of forming a diffractive optical element extending over several μm, for example, when forming a diffractive optical element, there is a problem that when the formed film is heated to a temperature required for soldering, for example, 350 ° C., and then cooled, a crack occurs in the film. .

The present invention has been made by paying attention to such a problem existing in the prior art. The purpose is to have high heat resistance, from 500 nm (0.5 μm)
It is an object of the present invention to provide a method for manufacturing an article having a fine uneven surface with high dimensional accuracy, in which no crack is generated on the surface of a single-layer film having a thickness of several μm and the surface is not separated from the substrate. Another object of the present invention is to provide an article having irregularities produced by the method of the present invention. Still other objects and advantages of the present invention will become apparent from the following description.

[0012]

According to the present invention, the above objects and advantages of the present invention are as follows: first, a silane compound (A) represented by the following chemical formula (1) and a silane compound (A) represented by the following chemical formula (2): A solution for film formation obtained by subjecting a stock solution containing the silane compound (B) to be subjected to hydrolysis and dehydration condensation reaction to a catalyst is placed in close contact with a substrate and a mold, and arranged in a film form. A method for manufacturing an article having an uneven surface, in which an uneven film having a surface having a shape obtained by inverting the surface shape of the mold by heating is coated on a substrate surface, the film forming liquid includes:
The silane compounds (A) and (B) in the form of unhydrolyzed product are respectively added to the silane compounds (A) and (B) in the undiluted solution in an amount of 0.
5 to 40% by weight and 0.5 to 60% by weight, and that the condensate formed as a result of the dehydration condensation reaction in the film-forming liquid has a molecular weight of 300 to 1900. This is achieved by a method for manufacturing an article having a characteristic uneven surface.

Embedded image RSiX ₃ (1) where R is a non-hydrolyzable organic group and X is a hydrolyzable group.

Embedded image SiX ′ ₄ (2) where X ′ is a hydrolyzable group.

In the present invention, R is a non-hydrolyzable group in the silane compound (A) represented by the above chemical formula (1) contained in the raw solution before being subjected to hydrolysis and dehydration condensation to form a film-forming liquid. For example, alkyl group, phenyl group, vinyl group, N
-(2-aminoethyl) 3-aminopropyl group, 3-aminopropyl group, 3-glycidoxypropyl group, 2- (3,4
-Epoxycyclohexyl) ethyl group, 3-chloropropylmethyl group, 3-chloropropyl group, 3-methacryloxypropyl group, 3-mercaptopropyl group, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyl And the like. X is a hydrolyzable group such as an alkoxyl group or a halogen atom. The alkyl group for R may be linear or branched, and is preferably an alkyl group having 1 to 3 carbon atoms. Further, the alkoxyl group of X may be linear or branched.
It is preferably an alkoxyl group having 1 to 4 carbon atoms, and particularly preferably an alkoxyl group having 1 to 2 carbon atoms. X
Examples of the above halogen atom include fluorine, chlorine and bromine, and among them, chlorine is particularly preferably used. However, when the article having the uneven surface according to the present invention is used in close proximity to various memories and other electronic circuits, the presence of chlorine in the article of the present invention may shorten the life of these electronic circuits. Therefore, it is preferable to use an alkoxyl group as X.

In the silane compound (B) represented by the chemical formula (2) contained in the stock solution, X 'is a hydrolyzable group, for example, an alkoxyl group or a halogen atom. The four X's do not need to be the same group, but may be different groups independently. The alkoxyl group of X ′ may be linear or branched, and is preferably an alkoxyl group having 1 to 4 carbon atoms, and particularly preferably an alkoxyl group having 1 to 2 carbon atoms. Examples of the halogen atom for X ′ include fluorine, chlorine, and bromine, and among them, chlorine is particularly preferably used. However, when the article having the uneven surface according to the present invention is used in close proximity to various memories and other electronic circuits, the presence of chlorine in the article of the present invention may shorten the life of these electronic circuits. Therefore, it is preferable to use an alkoxyl group as X ′.

As the silane compound (A) represented by the chemical formula (1), for example, methyltriethoxysilane,
Ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, Octyltrimethoxysilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, butyltrichlorosilane, hexyltrichlorosilane, octyltrichlorosilane, methyltribromosilane, ethyltribromosilane, propyltribromosilane, butyltribromosilane, hexyl Tribromosilane, octyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane,
N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- [2- (vinyl Benzylamino) ethyl] -3-aminopropyltrimethoxysilane and the like. Among them, carbon number 1
Silane compound (A) having an alkyl group of 3 and an alkoxyalkyl group having 1 to 2 carbon atoms, ie, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyl Triethoxysilane,
It is particularly preferably used because alcohol generated by the hydrolysis reaction is easily volatilized.

Examples of the silane compound (B) represented by the chemical formula (2) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrachlorosilane, trichloromethoxysilane, trichloroethoxysilane, dichlorodimethoxysilane. Examples thereof include silane, dichlorodiethoxysilane, and monochlorotrimethoxysilane. Among these,
Those having a relatively small molecular weight, for example, a tetraalkoxysilane having an alkoxyl group having 1 to 2 carbon atoms, that is, tetramethoxysilane and tetraethoxysilane, the alcohol generated by the hydrolysis reaction is easily volatilized and a dense film is formed. It is preferably used because it is easy.

The stock solution is prepared by mixing the silane compound (A) represented by the above formula (1) and the silane compound (B) represented by the above formula (2) with (B) per mole of the component (A). )) Component is preferably contained in a ratio of 0.05 to 1 mol.

In the stock solution, a part or all of the component (B) is replaced with (C) the following chemical formula (3):

Embedded image Here, X ″ is an alkoxyl group or a halogen atom that undergoes hydrolysis, and n is an integer of 1 to 10, and more preferably an integer of 1 to 5; 1 / (n + 1) moles per mole of the components include those substituted.

Examples of the silane compound (C) represented by the above formula (3) include a partial hydrolysis condensate of the silane compound (B) represented by the above formula (2). For example, hexaethoxydisiloxane (n = 1), octaethoxytrisiloxane (n = 2), decaethoxytetrasiloxane (n = 3), ethoxypolysiloxane (n
≧ 4) can be used. “Ethyl silicate 40” comprising a mixture of a monomer (n = 0) and a condensate (n ≧ 1)
(Trade name, manufactured by Colcoat Co., Ltd.) Cihla
r, Colloids and Surfaces A: Physicoche
m. Eng. Aspects 70 (1993), pp. 253 to 268, and by weight fraction, monomer: 12.8% by weight, dimer: 10.2% by weight, trimer: 12 0.0% by weight, tetramer: 7.0% by weight, multimer (n ≧ 4): 56.2% by weight, and ethanol: 1.8% by weight].

In the present invention, the component (A) and the component (B)
The above-mentioned stock solution containing the components and the catalyst is hydrolyzed and dehydrated and condensed to prepare a film-forming solution, which is coated on a substrate, and the non-hydrolyzed component (A) is finally obtained in the obtained film. Organic groups, such as alkyl groups, remain in moderate amounts. Since the alkyl group functions to reduce the brittleness of the film and impart elasticity to the film, it is possible to suppress the thermal stress generated inside the film, so that cracks in the film and peeling of the film from the article base material can be suppressed. Is prevented.

Hereinafter, for convenience of explanation, the case where the component (A) is an alkyl trialkoxysilane and the component (B) is a tetraalkoxysilane will be described.

In the film according to the present invention, the trialkoxysilane and the tetraalkoxysilane are mixed, so that a trifunctional silane having an alkyl group and a tetrafunctional silane having no alkyl group are three-dimensionally bonded. It is presumed that the groups cause the three-dimensional skeleton to have room, and this film structure gives elasticity to the film, reduces brittleness of the film, and enables formation of a thick film.

When the film according to the present invention contains an alkylsilyl group, the oxide skeleton structure in the film is used as a bulk to suppress the brittleness of the film and give the film elasticity. Let it be.

Next, the hydrolysis and dehydration condensation of the components (A) and (B) of the present invention will be described. When the degree of the hydrolysis reaction of the components (A) and (B) of the present invention is low, a large amount of alkoxyl groups remains in the film-forming solution after the dehydration-condensation reaction. When the film is placed in close contact with the base material and the mold and shrinks when heating to obtain a gelled film, resulting in poor dimensional accuracy, or when subsequently heated to 300 ° C. or more and cooled. To
It is not preferable because the film is peeled off or cracks are easily formed. In addition, when a large amount of alkoxyl groups remain in the film-forming solution during application to a glass substrate, the affinity of the film-forming solution for the substrate surface is deteriorated, and the film-forming solution is repelled from the substrate surface. Disadvantages such as the occurrence of Conversely, if the rate of hydrolysis is too high, the subsequent dehydration condensation reaction proceeds more than necessary, so that the molecular weight of the condensate composed of only each of the components (A) and (B) in the film-forming liquid Is too large to cause a phase separation of the component (A) and / or the component (B) in the film, so that the film is liable to be peeled off during the molding step, or when heated and cooled at 300 ° C. or more. In this case, portions having different degrees of shrinkage are formed inside the film, and cracks are easily formed in the film. Conversely, the component (A) and the component (B)
If the degree of the hydrolysis reaction of the components is too high and the residual amount of the alkoxyl group in the film-forming liquid is too low, the elasticity of the obtained film becomes insufficient and cracks occur in the film. The film forming solution obtained by the hydrolysis and dehydration condensation of the components (A) and (B) in the stock solution contains (A)
A condensate of the component, a condensate of the component (B), a cocondensate of the component (A) and the component (B), a hydrolyzate of the component (A),
It contains the hydrolyzate of the component (B) and the components (A) and (B) in the state of an unhydrolyzed product, respectively. The film forming solution contains the unhydrolyzed silane compound (A) therein in an amount of 0.5 to 40% by weight based on the content of the silane compound (A) in the stock solution. More preferably, it is contained in an amount of 2 to 30% by weight, and the silane compound (B) in the form of an unhydrolyzed product is added in an amount of 0.1 to 0.1% based on the content of the silane compound (B) in the stock solution. It is contained in an amount of 5 to 60% by weight, more preferably 3 to 55% by weight. The remaining amount of the unhydrolyzed product in the film-forming solution can be measured by gas chromatography, and the film is obtained from the amounts of the silane compounds (A) and (B) blended in the original solution and the above-mentioned remaining value. The ratio of the unhydrolyzed product in the forming solution (the unhydrolyzed rate) can be calculated.

Next, the degree of the dehydration condensation reaction of the components (A) and (B) of the present invention will be described. When the molecular weight of the condensate formed in the film-forming liquid by the hydrolysis and dehydration condensation reaction of the raw material components of the present invention is too large, the viscosity of the solution is significantly increased, and the film thickness tends to be uneven during coating, and In addition, since a difference occurs in the degree of shrinkage at the time of subsequent cooling, cracks tend to occur on the formed film surface. Further, the homogeneity of the mixed state of the component (A) and the component (B) deteriorates. Also, if the dehydration condensation reaction proceeds too much,
The number of OH groups in the hydrolyzate of the component (A) and the component (B), which has a high affinity for the surface of the glass substrate, is reduced, which causes defects such as film peeling. Therefore, the condensate in the film forming liquid preferably has a molecular weight (weight average) of 300 to 1900.

Regarding the ratio of the component (A) and the component (B) in the raw solution (and the film-forming liquid), if the component (B) is too small relative to the component (A), the film and the substrate may not be mixed. Adhesion deteriorates, and the film is easily peeled off at the time of final heating (at the time of firing) or after a durability test. On the other hand, if the component (B) is too large relative to the component (A), the flexibility of the film is impaired, and the film having a thickness of 0.5 μm or more cracks during the final heating or cooling after the final heating. ) Is more likely to occur. Therefore, as described above, the stock solution contains the component (B) per 1 mol of the component (A), preferably 0.05 to 1%.
It is contained in a molar ratio, more preferably in a ratio of 0.05 to 0.5 mol, and still more preferably in a ratio of 0.05 to 0.1 mol. When part or all of the component (B) is replaced by the component (C) (degree of polymerization M = n + 1), for example, in the case of total replacement, the stock solution is prepared by adding (C) to 1 mol of the component (A). ) Component, preferably (0.05 / M to 1 /
M) in a molar ratio, more preferably (0.05 / M to
(0.5 / M) mole, more preferably (0.0 / M) mole.
(5 / M to 0.1 / M).

As a raw solution as a raw material of the sol-gel material in the present invention, an alcohol is added as a solvent to a mixture of the components (A) and (B). As the alcohol to be added, a lower alcohol having 1 to 4 carbon atoms, particularly, methanol or ethanol having a small boiling point is suitably used.
The reason is that the alcohol can be quickly removed from the solution by a heat treatment at a relatively low temperature after the hydrolysis and during the molding step. The amount of the alcohol to be added is represented by a molar ratio and is 0.3% based on the total of the components (A) and (B).
It is preferably 5 to 1.5 times, more preferably 0.5 to 1.5 times.

A catalyst for hydrolyzing the components (A) and (B) is added to the stock solution. As the catalyst, an acid catalyst is preferably used, and as the acid catalyst, it is preferable to use at least one acid among formic acid, acetic acid, tetrafluoroacetic acid, propionic acid, oxalic acid, hydrochloric acid, nitric acid, and sulfuric acid in the form of an aqueous solution. The amount of the acid catalyst to be added varies depending on the type of the acid and the strength as the protonic acid (weak acid, strong acid). The molecular weight becomes too large, and the precipitate or the coating solution tends to gel, which is not preferable. The silane compounds (A) and (B) in which the film-forming liquid is in the form of an unhydrolyzed product as it is are added to the content of the silane compounds (A) and (B) in the stock solution. On the other hand, 0.5 ~
Among these acid catalysts, organic acids, which are weak acids, are preferably used in order to contain them in amounts of 40% by weight and 0.5 to 60% by weight, respectively. Among organic acids, formic acid is particularly preferably used because of its low molecular weight and easy evaporation. The amount of the acid catalyst to be added is, for example, in the case where formic acid is used as the acid catalyst, expressed in a molar ratio, when the total of the component (A) and the component (B) and / or the component (C) is 1 mol. , Preferably 0.5 mmol to 5 mmol,
More preferably, it is 0.7 mmol to 2 mmol. Further, it is preferable to add water at a stoichiometric ratio necessary for hydrolysis. If the amount of water added is less than the stoichiometric ratio, the unreacted silane compounds (A) and (B) tend to volatilize during heat treatment for gelation. Usually, the amount of water to be added is 1.1 to 30 times the required stoichiometric ratio, including the water of the catalyst aqueous solution, and is represented by a molar ratio, and the components (A) and (B) and / or ( C) 2-2 based on the total of components
It is preferably 0 times, more preferably 3 to 10 times. In addition, when the article having the uneven surface of the present invention is used in proximity to various memories and other electronic circuits, the chlorine contained in the article of the present invention may shorten the life of these electronic circuits. Therefore, it is preferable to use an acid catalyst containing no chlorine.

In the present invention, the film-forming liquid, which is a raw material of the sol-gel material, is a stock solution comprising the components (A) and (B), an alcohol solvent, water and a catalyst, for example, at room temperature,
It is prepared by hydrolyzing both alkoxysilanes while holding with stirring for 20 to 120 minutes. Thereafter, the room temperature (20 ° C.) to 60 ° C., more preferably 30 to 50 ° C.
Then, it is preferable to carry out the polycondensation reaction by dehydration by holding for 1 to 20 hours. Accordingly, shrinkage after film formation can be suppressed as much as possible to prevent cracking of the film, and a cured film can be formed without generating bubbles in the film at the time of final heating. If the polycondensation reaction due to the dehydration proceeds too much, the viscosity of the solution becomes too high, and it is difficult to coat the surface of the mold or the substrate. Conversely, if the method of conducting the polycondensation reaction by dehydration is insufficient, repelling of the coating solution on the substrate during coating or generation of bubbles in the film at the time of final heating cannot be prevented. It is preferable to select the temperature and the holding time so that the viscosity of the solution is 10 cP or less, thereby controlling the method of conducting the polycondensation reaction by dehydration.

In the present invention, a surfactant, a leveling agent,
The flow control agent is used in an amount of preferably 5% or less, more preferably 0.001% by weight, based on the total amount of the coating solution.
~ 0.5%, more preferably 0.001-0.1%,
It may be added. The above addition can improve the defect of the film at the time of coating.

As the surfactant, leveling agent and flow control agent, compounds such as silicone compounds and fluorinated silicone compounds are preferably used.

The sol-gel material obtained as described above is closely adhered between the article base material and the mold, and is arranged in a film form. The surface is heated to reverse the surface shape of the mold. An article having an uneven surface coated with a gel film having the following is produced. As a process of forming the fine uneven film, the following method can be typically given.

The gel film is formed by applying a film-forming solution to a substrate surface by a coating method such as spin coating, dip coating, screen printing, gravure coating, flexographic printing, or meniscus coating. When the liquid film has plasticity, the mold is pressed against the film on the surface of the article substrate, heated as it is, and after transfer molding, the mold is released, and This is a method of performing heating. That is, the surface of the article substrate to be coated is kept horizontal, a liquid sol-gel material having a viscosity of 10 cP or less is poured onto the substrate, and the sol-gel material is spin-coated on the substrate so as to have a predetermined thickness. And spread it into a film by dip coating or the like (step 1). In that state,
The mixture is kept at 60 to 80 ° C. for 10 to 120 minutes to advance the polycondensation reaction by dehydration (step 2). Then, a mold having minute irregularities is pressed onto the sol-gel material in the form of a film to obtain a pressure of 0.5 to 120 kg / cm ² and a temperature of 60 ° C. to 80 ° C.
For 60 seconds to 60 minutes to substantially complete the polycondensation reaction due to dehydration of the sol-gel material and to gel (step 3). Then, by peeling the mold, a polysiloxane film, which is a gelled film having an uneven shape obtained by inverting the uneven shape of the mold on the surface, is formed in a state of being bonded to the surface of the base material (Step 4). . Then, for example, 180 ~
By final heating at 350 ° C. for 10 to 150 minutes,
The remaining silanol groups of the polysiloxane film are polycondensed, and the water generated by the polycondensation is vaporized, so that the film slightly shrinks in volume in the thickness direction to form a dense film (step 5). In this way, an article having a concave-convex surface coated with a film having a surface having a shape inverted from the surface shape of the mold is obtained. At least one of Steps 2 to 4 may be performed under reduced pressure.

For the above mold, for example, the surface of a glass substrate having a flat surface is precisely etched to form a concave shape having a desired shape, for example. Using this as a seed type,
A convex metal matrix can be produced by electroless and electrolytic plating methods. Also, using the concave mold as a mother mold, a convex metal seed mold is produced by the plating method, and the seed mold is further plated by the plating method.
A concave metal matrix can be manufactured. These convex or concave molds can be used as molds. In the above plating method, metals such as nickel and chromium are preferably used.

The cross section of the polysiloxane film of the present invention has one or more chevron shapes, sawtooth shapes, circular arcs, elliptical arcs, or the like. Various functions can be imparted to the base material by changing the shape of the projection. For example, a function as a grating, a function as a flat microlens array, or a function as a prism array can be imparted by changing the fine unevenness.

The thickness of the polysiloxane film (after the final heating) is 0.5 μm to 0.5 μm, which is represented by the average height of the convex portions and concave portions of the film.
5.0 mm. When the film thickness is 0.5 μm or more, the minimum value d _min (the distance between the bottom of the concave portion of the uneven film and the substrate) and the maximum value d _max (the distance between the top of the convex portion of the uneven film and the substrate). Is 0.25 or more, that is, d _min / d _max ≧ 0.
A value of 25 is desirable for preventing separation between the substrate and the film and for preventing cracking of the film. If the ratio of the minimum value to the maximum value of the film thickness (minimum value / maximum value) is less than 0.25, the substrate and the film may peel off at the interface where the film thickness is minimum in the film forming process, or This is because the film is likely to crack.
Further, d _max and d _min preferably satisfy all of the following formulas (1) to (3), and furthermore, the following formulas (4) to (4).
It is more preferable to satisfy all of (6).

[0037]

0.5 μm ≦ (d _max −d _min ) ≦ 1.5 μm (1)

_Dmax ≦ 5 μm (2)

[Expression 12] d _min ≧ 0.5 μm (3)

(13) 0.6 μm ≦ (d _max −d _min ) ≦ 1.1 μm (4)

_Dmax ≦ 4 μm (5)

D _min ≧ 0.5 μm (6)

The above-mentioned stock solution contains methyltrialkoxysilane as the component (A) and the component (B) in a proportion of 0.05 to 0.5 mol per 1 mol of the component (A). Is used, the concavo-convex film of the obtained article having a concavo-convex surface is formed by adding a methylsilyl group (D) represented by the following chemical formula (4) and a siloxy group (E) represented by the following chemical formula (5) to (E) ) The component (D) is contained in a proportion of 2 to 20 mol per 1 mol of the component.

_{Embedded image} CH ₃ SiO _3/2 (4)

_{Embedded image} SiO _4/2 (5)

Thus, according to the present invention, 350
Excellent heat resistance to withstand ℃, with a film thickness of 0.5 μm to 5 μm
Thus, 1.440 to 1.46, which is close to the refractive index of general glass.
A monolayer film of organopolysiloxane having a refractive index of 0 and having fine irregularities is formed on the article substrate. The organopolysiloxane constituting this film contains 11 to 21% by weight of an alkyl group such as a methyl group.
This film has strong adhesion to the substrate, has high film strength, and does not easily crack. In addition, no foaming during molding is observed inside the film, and excellent transferability with extremely high dimensional accuracy of the fine irregularities on the film surface can be realized. Specifically, for example, when a large number of protrusions having a height of 2 μm are formed, the variation in the height of the film surface protrusions is 0.2 μm or less. In addition, the deviation of the distance between the protrusions on the film surface from the mold is measured accuracy (0.2 μm).
It is as follows. Since the article having the uneven surface according to the present invention has excellent heat resistance, for example, the diffraction grating manufactured by the present invention can be used as a mold for a resin diffraction grating.

The article substrate used in the present invention may have any shape such as a flat plate, a curved plate, and a bar.
It is desirable that the amount of warpage of the substrate surface at 200 ° C. and 20 ° C. (the length of thermal deformation in the direction perpendicular to the surface per unit length in the surface direction of the substrate) is within ± 5 μm per cm. . If the amount of warpage exceeds this range, the substrate and the film may peel or crack at the interface during the film forming process. Therefore, it is preferable to select the material, dimensions and shape of the substrate.

The substrate preferably has a coefficient of linear expansion of 1.5 × 10 ⁻⁵ / ° C. or less. When the coefficient of linear expansion of the substrate exceeds 1.5 × 10 ⁻⁵ / ° C., in the case of a plastics substrate having a high coefficient of thermal expansion such as polypropylene (9 to 15 × 10 ⁻⁵ / ° C.), an organo In the process of forming the polysiloxane film, the substrate and the film peel off at the interface,
This is because cracks occur in the film. Ordinary inorganic glass:
It has a coefficient of linear expansion of 5 × 10 ⁻⁵ / ° C. or less. Preferably, at least the surface of the substrate is an oxide. If the surface of the substrate in contact with the organopolysiloxane film is not an oxide, the adhesive strength tends to decrease during the film forming process, and in some cases, the substrate and the film may peel at the interface. Preferred examples of the material of the substrate include oxide glass such as silicate glass, borate glass, and phosphate glass, quartz, ceramics, metals, epoxy resins, and glass fiber reinforced polystyrene. The organopolysiloxane film does not bond with the metal as it is, but if the surface of the metal is treated with an oxidizing agent in advance, it can be suitably used as a substrate.

When an object transparent to light of a desired wavelength, for example, light in the visible, ultraviolet, or infrared region is used as the substrate in the present invention, the article having the uneven surface of the present invention is It can exhibit the function as a transmission optical element such as a diffraction grating (relief type diffraction grating and blazed diffraction grating), a lens, a prism, and the like. When a transparent or opaque material is used as the base material, reflection diffraction is performed by forming a metal (aluminum, silver, etc.) or a dielectric film (magnesium fluoride, titanium oxide, etc.) on the film. Reflective optical elements such as gratings and Fresnel reflectors,
It is suitable for use as a CD-ROM or other information recording medium.

When the article having an uneven surface according to the present invention is a diffraction grating, this diffraction grating can be used as an integrated optical device in combination with other optical elements. For example, it can be used as a wavelength separation optical element in a wavelength monitor module for optical communication, especially for high-density multiplexing / demultiplexing. Dense wavelength division multiplexing (DWDM) technology is a technology for simultaneously transmitting a plurality of signals on a single optical path, and does not greatly increase the cost in an optical fiber communication system.
This is a very important technology because it can increase the communication capacity. That is, the system capacity can be increased by increasing the number of communication channels that can be carried by the optical fiber.
As signals used in optical communication, light having wavelengths of 1.55 μm and 1.3 μm is used. A diffraction grating that diffracts light of these wavelengths with high efficiency and has excellent wavelength resolution is preferably used. The diffractive optical element manufactured by using the method of the present invention has excellent heat resistance and environmental resistance, and is therefore preferably used as a micro optical element requiring high precision. When the diffraction grating of the present invention is used as a wavelength monitor module for high-density multiplexing / multiplexing / demultiplexing, it is used in combination with an optical fiber, a collimator lens, a photosensitive semiconductor element, and the like. Further, by inserting a polarization filter and a polarization converter between the collimator lens and the diffraction grating, an integrated optical element having improved polarization characteristics can be manufactured. Also, an array-shaped microlens may be arranged between the collimator lens and the array-shaped photosensitive semiconductor element so as to be in contact with the array-shaped photosensitive semiconductor element. This array of micro lenses is NSG
America, Inc. Is marketed as “PML” (trade name). By using such a lens,
Adjacent crosstalk between the arrayed photosensitive semiconductor elements can be reduced.

[0044]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. The production method of the present invention is generally performed according to the following procedures (1), (2), (3) and (4). (1) Preparation of an organopolysiloxane coating solution,
(2) application of a coating solution to a substrate and heat treatment; (3) bonding, heat treatment and release; (4) final heating (firing).

[Coating solution for film formation (solutions A1, A2, A
3, Preparation of A4, A5 and A6)] 0.09 mol (16.0 g) of methyltriethoxysilane and 0.01 mol (2.08 g) of tetraethoxysilane were placed in a beaker and stirred. 0.1 mol of ethanol is added to this solution and stirred, and 0.1 mol% of formic acid is added to 0.4 mol (7.3 g) of water.
Aqueous solution dissolved so that
The mixture was stirred for 0.5 hour (solution A1). This solution was heated in an oven at 40 ° C. for 1 hour (solution A2). This one
It was left at room temperature overnight (solution A3). This was left still at room temperature for 6 days (solution A4).

0.08 mol (14.3 g) of methyltriethoxysilane and 0.02 mol (4.16 g) of tetraethoxysilane were placed in a beaker and stirred. 0.1 mol of ethanol was added to this solution and stirred, and an aqueous solution in which formic acid was dissolved to a concentration of 0.1% by weight in 0.4 mol (7.3 g) of water was further added thereto. After stirring, the solution was heated in an oven at 40 ° C. for 1 hour (solution A5). This was left overnight at room temperature (solution A
6).

[Coating solution for film formation (solutions B1, B2, B
3, and Preparation of B4)] 0.09 mol (16.0 g) of methyltriethoxysilane and 0.01 mol (2.08 g) of tetraethoxysilane were placed in a beaker and stirred. 0.1 mol of ethanol was added to this solution, and the mixture was stirred. An aqueous solution obtained by dissolving 0.1 mol% of hydrochloric acid in 0.4 mol (7.3 g) of water was further added thereto, and the mixture was stirred for 0.5 hour. (Solution B1). This was left still at room temperature for 6 days (solution B2).

0.09 mole of methyltriethoxysilane and 0.01 mole of tetraethoxysilane were placed in a beaker and stirred. 0.4 mol of ethanol was added to this solution and stirred, and 0.4 mol (7.3 g) of water was added with 0.1 mol of hydrochloric acid.
The aqueous solution dissolved so as to have a weight% was further added thereto, followed by stirring for 0.5 hour (solution B3). This is another 6
The mixture was allowed to stand at room temperature for a day (solution B4).

[Coating solution for film formation (solutions C1, C2, C
3, and Preparation of C4)] 0.09 mol of methyltriethoxysilane and 0.01 mol of "ethyl silicate 40" [condensate is converted to tetraethoxysilane] (1.53 g, converted to tetraethoxysilane) in a beaker And stirred. 0.1 mol of ethanol is added to this solution, and the mixture is stirred. An aqueous solution in which formic acid is dissolved in 0.4 mol (7.3 g) of water to a concentration of 0.1% by weight is further added thereto, and the mixture is stirred for 0.5 hour. (Solution C1). Put this solution in an oven for 40
Heated at C for 1 hour (solution C2). This was left overnight at room temperature (solution C3). This was left still at room temperature for 2 days (solution C4).

[Coating solution for film formation (solutions D1, D2, D
3, and preparation of D4)] tetraethoxysilane 0.0
1 mol (2.08 g) was placed in a beaker, 0.1 mol of ethanol was added to this solution, and the mixture was stirred.
An aqueous solution obtained by dissolving 0.1% by weight of formic acid in g) was further added thereto, followed by stirring at 60 ° C. for 0.5 hour.
To this solution was added 0.09 mol of methyltriethoxysilane (1
6.0 g) and heated in an oven at 40 ° C. for 1 hour (solution D1). This was allowed to stand at room temperature overnight (solution D).
2). This was allowed to stand at room temperature for another 2 days (solution D
3). This was left still at room temperature for 3 days (solution D
4).

[Preparation of Coating Solution (Solution E1) for Forming Film] 0.09 mol (16.0 g) of methyltriethoxysilane was placed in a beaker and stirred. To this solution was added 0.1 mol of ethanol, and the mixture was stirred. An aqueous solution of 0.1 mol% of formic acid dissolved in 0.4 mol (7.3 g) of water was further added thereto. Stir for 5 hours. To this solution was added 0.01 mol (2.08 g) of tetraethoxysilane,
Heated in an oven at 40 ° C. for 1 hour (solution E1).

[Preparation of Coating Solution (Solution F1) for Film Formation] Phenyltriethoxysilane 0.05 mol (12.02)
g) and 0.05 mol of tetraethoxysilane (10.4
g) was placed in a beaker and stirred. 0.1 mol of ethanol is added to this solution, and the mixture is stirred. An aqueous solution in which formic acid is dissolved in 0.4 mol (7.3 g) of water to a concentration of 0.1% by weight is further added thereto, and the mixture is stirred for 0.5 hour. did. This solution was heated in an oven at 40 ° C. for 1 hour (solution F1).

The above solutions A1-A6, B1-B4, C1-
The amount of the unhydrolyzed product in C4, D1 to D4, E1, and F1 was measured, and the silane compound (A) in the raw material of the solution was measured.
(Methyltriethoxysilane, phenyltriethoxysilane) and (B) (tetraethoxysilane, “ethyl silicate 40”), the above silane compound remaining without being hydrolyzed in the solution with respect to each mole number The proportions of (A) and (B) were calculated and defined as the unhydrolysate amount (%). The silane compounds (A) and (B) remaining without being hydrolyzed refer to those in which a plurality of hydrolyzable groups in the silane compound are not hydrolyzed at all, and The silane compounds that are hydrolyzed at all times are excluded. The measurement of the unhydrolyzed amount was performed by gas chromatography. The molecular weight (weight average) of the condensate of the coating liquid for film formation is calculated by preparing a calibration curve with polystyrene having a known molecular weight using gel filtration chromatography and calculating the weight average molecular weight in terms of polystyrene. went.

[Coating of Solution to Substrate, Pressing and Heat Treatment] The coating solution for forming a film is applied on a quartz glass substrate by a spin coating method, and dried on a hot plate at 60 ° C. for 20 minutes. Press the mold against the membrane, 2kg /
30 ° C at 60 ° C while pressing with a pressing pressure of ² cm2.
Heat treatment was performed under reduced pressure for minutes. Thereafter, the mold was released.
As a result, a fine uneven plate to which the shape of the mold was transferred was obtained.

[Final Heating] The fine uneven plate obtained by releasing the mold was heated at 350 ° C. for 15 minutes to obtain an article having an uneven surface. The performance and characteristics of the obtained article having an uneven surface were evaluated by the following methods.

[Measurement of Variation in Convex Height] The variation in convex height of the outermost layer was measured by a laser microscope.

[Measurement of Heat Resistance and Optical Properties] With respect to the articles having the uneven surface produced in Examples and Comparative Examples, 350
After performing a heat resistance test at 2 ° C. for 2 hours, the temperature was returned to room temperature, and the occurrence of cracks (cracks) was observed to evaluate the heat resistance. Moreover, the diffraction pattern of the diffraction grating was measured and evaluated using a He-Ne laser before and after the heat resistance test.

Example 1 A glass substrate having a thickness of 3.0
2.5 mm square quartz glass substrate (linear expansion coefficient:
1.0 × 10 ⁻⁵ / ° C.). A blazed resin diffraction grating (pitch: 1.1 μm, groove depth: 0.8 μm, sawtooth, Cr / Au coating film on the surface, average thickness: about 50 μm) was prepared as a mold. FIG. 1 shows the cross-sectional shape of the groove. Table 1 shows the proportions of the silane compounds (A) and (B) remaining without being hydrolyzed in the coating solution A2 for film formation and the molecular weight of the condensate in the coating solution A2. 0.5 ml on the above substrate
Was applied dropwise, and spin coating was performed at a rotation speed of 500 rpm. This is dried on a hot plate heated to 60 ° C. for 15 minutes, and the above-mentioned mold is pressed onto the sol-gel material to apply a pressure of 50 kg / cm ² .
It was kept under reduced pressure at a temperature of 60 ° C. for 90 minutes. Then, the pressure was returned to normal pressure, and the mold was peeled off. Then, this was finally heated at 350 ° C. for 20 minutes to obtain a blazed diffraction grating in which an organopolysiloxane uneven film having a surface shape obtained by transferring the surface shape of a molding die was coated on a quartz glass substrate. . The organopolysiloxane uneven film is formed by adding the methylsilyl group (D) represented by the chemical formula (4) and the siloxy group (E) represented by the chemical formula (5) to 1 mol of the component (E). The component (D) was contained at a ratio of 9 mol.

[0059]

[Table 1] ────────────────────────────── Example coating liquid catalyst Unhydrolyzed product amount (%) Molecular weight ─── ─────────────────────────── Silane compound (A) (B) ─────────────── ─────────────── Example 1 A2 formic acid 20 50 700 Example 2 A3 formic acid 2 10 1000 Example 3 C1 formic acid 15 55 1300 Example 4 C2 formic acid 10 40 1450 Example 5 C3 formic acid 522 1500 Example 6 C4 formic acid 15 1600 Example 7 D1 formic acid 238 1000 Example 8 D2 formic acid 566 1200 Example 9 D3 formic acid 25 1400 Example 10 D4 formic acid 1 3 1400 Example 1 20 50 700 Example 12 A6 Formic acid 2 10 1 00 Example 13 F1 Formic acid 3 10 1500 1500 Comparative example 1 A1 Formic acid less than 65 85 300 Comparative example 2 A4 Formic acid 0.0 0.0 2000 Comparative example 3 B1 hydrochloric acid 0.0 0.0 2100 Comparative example 4 B2 hydrochloric acid 0.0 0.0 2300 Comparative example 5 B3 hydrochloric acid 0.0 0.0 2600 Comparative example 6 B4 hydrochloric acid 0.0 0.0 3000 Comparative example 7 E1 formic acid 0.0 95 1000 ───── ─────────────────────────

The organopolysiloxane film produced as described above is transparent, and the thickness of the convex portion (d _max )
It was 3.0 μm. The film thickness of the concave part (d _min )
2.2 μm. d _max and d _{min are, 0.6μm ≦ (d max -d min} = 0.8μm) ≦ 1.1μm (d max = 3.0μm) ≦ 4.0μm (d min = 2.2μm) ≧ 0.5μm Which satisfies the ranges of the above-described equations (4), (5) and (6).

As shown in Table 2, the coating solution dropped onto the substrate during spin coating of the film forming coating solution A2 did not repel. Further, when the mold was peeled off, as shown in Table 2, no film peeling occurred. As a result of evaluating the heat resistance (heating and quenching test at 350 ° C.) of the diffraction grating, as shown in Table 2, no crack was generated in the film, and the appearance, the height of the convex portion of the film, Its standard deviation,
No change was observed in the diffraction pattern compared to the value before the heat test.

[0062]

[Table 2] Example Coating liquid number Spin coating Press molding 350 ℃ heating quenching test １ Example 1 A2 No liquid repelling No film peeling No crack 2 A3 No liquid repelling No film peeling No crack 3 C1 No liquid repelling No film peeling No crack 4 C2 No liquid repelling No film peeling No crack 5 C3 No liquid repelling No film peeling No cracking 6 C4 No liquid repelling No film peeling No cracking 7 D1 No liquid repelling No film peeling No cracking 8 D2 No liquid repelling No film peeling No cracking 9 D3 No liquid repelling No film peeling No cracking 10 D4 No liquid repelling No film peeling No rack 11 A5 No liquid repelling No film peeling No crack 12 A6 No liquid repelling No film peeling No crack 13 F1 No liquid repelling No film peeling No crack Comparative example 1 A1 No liquid repelling No film peeling No cracking 2 A4 No liquid repelling There is peeling and cannot be evaluated. 3 B1 No liquid repelling. There is no film peeling and cannot be evaluated. 4 B2 No liquid repelling. There is no film peeling and cannot be evaluated. 5 B3 No liquid repelling. There is no film peeling and cannot be evaluated. 6 B4 No liquid repelling. Liquid repelled, film peeled, not evaluated ────────────────────────────────────

[Examples 2 to 13] Instead of the film forming coating solution A2 used in Example 1, the film forming coating solutions A3, A5,
A6 was performed in the same manner as in Example 1 except that A6, C1 to C4, D1 to D4, and F1 were used. Table 1 shows the proportions of the silane compounds (A) and (B) remaining without being hydrolyzed in each coating solution for forming a film, and the molecular weight of the condensate in the coating solution. In addition, as shown in Table 2, the liquid repelling during spin coating, the film peeling during press molding, and the heat resistance of the diffraction grating were the same as in Example 1, with no liquid repelling, no film peeling, and no heat resistance. In addition, the appearance, the height of the projections of the film, its standard deviation, and the diffraction pattern did not change compared to the values before the heat test.

Embodiment 14 A resin blazed diffraction grating having a groove cross-sectional shape shown in FIG. 2 (pitch: 1.1 μm, groove depth: 0.8 μm, sawtooth-shaped groove has a continuous curved surface, The bottom of the recess has a flat portion of about 0.3 μm.
It has a Cr / Au coating film on the surface. An average thickness of about 50 μm) is prepared. A resin blazed diffraction grating shown in FIG. 2 was used in place of the resin blazed diffraction grating used as the mold in Example 1, and a coating solution A5 was used instead of the film forming coating solution A2 used in Example 1. Other than the above, application of the solution to the substrate in the same manner as in Example 1,
Pressing, heat treatment, and final heating were performed to obtain an article having an uneven surface. Since the cross-sectional shape of the used mold had more curved surfaces and a flat portion at the bottom of the concave portion than the mold of Example 1, the mold releasing operation of the mold was easy. When the heat resistance and the optical characteristics of the obtained article having an uneven surface were measured in the same manner as in Example 1,
As in Example 1, no cracks were generated in the film, and the appearance and the height of the convex portion of the film, its standard deviation, and the diffraction pattern were not changed as compared with the values before the heat test. I couldn't.

[Comparative Examples 1 to 7] Instead of the coating solution A2 for film formation used in Example 1, the coating solutions A1, A4 and B for film formation.
Except for using E1 to B4 and E1, a fine uneven plate was formed by the method described in Example 1 using the same substrate and mold as in Example 1. Table 1 shows the proportions of the silane compounds (A) and (B) remaining without being hydrolyzed in each coating solution for film formation, and the molecular weight of the condensate in the coating solution.
Shown in Table 2 shows the presence or absence of liquid repelling during spin coating, the presence or absence of film peeling during press molding, and the heat resistance of the diffraction grating.

As shown in Table 2, in Comparative Examples 1 and 7, liquid repelling occurred during spin coating, and in Comparative Examples 2 to 6, film peeling occurred during press molding. Comparative Example 1,
In No. 6, cracks occurred in the film during cooling in the heat resistance test, and a part of the film was peeled off, so that it was not possible to evaluate the unevenness dimensions. As a result of evaluating the heat resistance of this substrate, cracks in the film were further increased and the film was further partially peeled. Therefore, the height of the convex portion of the film after the heat resistance test and the standard deviation thereof were not measurable, and the diffraction pattern showed a large change compared to before the heat resistance test. Further, in Comparative Examples 2 to 5 and 7, the film strongly adhered to the mold, and the release operation was troublesome. In addition, most of the film after release has adhered to the mold, and almost no film remains on the glass substrate.
No further evaluation was possible.

Example 15 A wavelength monitor module for a wavelength division multiplex communication system was manufactured using the diffraction grating obtained in Example 1 in which an aluminum film having a thickness of 5 nm was formed on the surface by sputtering. Each optical element was arranged in the order of an optical fiber array, a collimator lens, and the diffraction grating of the present invention. The collimator lens was arranged so that the fiber array was located at the focal plane. The optical signal multiplexed into 16 channels coming out of the optical fiber array is
The light was converted into a parallel light by the collimator lens and was irradiated on the diffraction grating surface. This irradiation light was demultiplexed and reflected at diffraction angles corresponding to each wavelength of 16 channels on the surface of a diffraction grating set at an angle such that light having a wavelength of 1.55 μm was selectively blazed. The reflected diffracted light passed through the collimator lens and was focused on the photosensitive semiconductor elements arranged in 16 channels for each channel. The insertion loss of the incident light was 5 dB, and the adjacent channel crosstalk was 15 dB, which sufficiently functioned as an optical integrated device of a wavelength monitor module for a wavelength division multiplex communication system. Also, insertion loss value,
The crosstalk value did not change significantly in the temperature range of 0 to 85 ° C.

[0068]

According to the present invention, there are few disadvantages such as repelling during coating, cracks are less likely to be formed when forming a gel film, and an alkyl group such as a methyl group is appropriately left in the film to form a film. It is possible to provide an optical element or the like having an uneven surface with high elasticity (less brittleness), high strength of the film, and less occurrence of cracks in the film.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a groove shape of a molding die used in an embodiment of the present invention.

FIG. 2 is a sectional view showing a groove shape of a molding die used in another embodiment of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) B29L 11:00

Claims (17)

[Claims] A raw solution containing a silane compound (A) represented by the following chemical formula (1), a silane compound (B) represented by the following chemical formula (2), and a catalyst is subjected to a hydrolysis and dehydration condensation reaction. The film-forming liquid formed is placed in the form of a film by closely adhering it between the base material and the molding die, and then the surface of the molding die is inverted by heating to form a concavo-convex film. In the method for producing an article having an uneven surface coated on the surface, the film-forming liquid contains the silane compounds (A) and (B) in the form of unhydrolyzed products, respectively.
With respect to the content of the silane compounds (A) and (B) in the stock solution, respectively, from 0.5 to 40% by weight.
And 0.5 to 60% by weight, and the condensate formed as a result of the dehydration condensation reaction in the film forming liquid has a weight average molecular weight of 300 to 1900. A method for producing an article having an uneven surface. Embedded image RSiX ₃ (1) wherein R is a non-hydrolyzable organic group and X is a hydrolyzable group. Embedded image SiX ′ ₄ (2) where X ′ is a hydrolyzable group. 2. The method according to claim 1, wherein the catalyst is an organic acid. 3. The method for producing an article having an uneven surface according to claim 2, wherein the organic acid is formic acid. 4. The raw solution contains the components (A) and (B) in a proportion of 0.05 to 1 mol of the component (B) per 1 mol of the component (A). 4. The method for producing an article having an uneven surface according to claim 3. 5. The raw solution contains the component (A), the component (B), alcohol, water and a catalyst, and the film-forming solution is hydrolyzed while stirring the raw solution; The method for producing an article having an uneven surface according to any one of claims 1 to 4, wherein the article is prepared by heating to cause a dehydration condensation reaction to proceed. 6. The undiluted solution may contain a part or all of the component (B) and (C) the following chemical formula (3): Here, X ″ is an alkoxyl group or a halogen atom that undergoes hydrolysis, and n is an integer of 1 to 10. By the silane compound represented by the formula, 1 / (n + 1 The method for producing an article having an uneven surface according to any one of claims 1 to 5, wherein the article is substituted at a molar ratio. 7. The method for producing an article having an uneven surface according to claim 6, wherein the component (C) is a silane compound in which X ″ in the chemical formula (3) is an alkoxyl group. 8. The method according to claim 1, wherein both X in the formula (1) of the component (A) and X ′ in the formula (2) of the component (B) are alkoxyl groups. A method for producing an article having an uneven surface. 9. The method for manufacturing an article having an uneven surface according to claim 1, wherein the component (A) is methyltriethoxysilane, and the component (B) is tetraethoxysilane. . 10. An article manufactured by the method for manufacturing an article having an uneven surface according to any one of claims 1 to 9. 11. The method according to claim 1, wherein the uneven film has the following formula (1):
A film having a maximum film thickness d _max (distance between the top of the convex portion of the concave-convex film and the substrate) and a minimum film thickness d _min (distance between the bottom of the concave portion of the concave-convex film and the substrate) satisfying all of (3). An article according to item 10. 0.5 μm ≦ (d _max −d _min ) ≦ 1.5 μm (1) d _max ≦ 5 μm (2) d _min ≧ 0.5 μm (3) 12. The method according to claim 1, wherein the uneven film has the following formula (4):
The film having a maximum film thickness d _max (distance between the top of the convex portion of the uneven film and the substrate) and a minimum film thickness d _min (distance between the bottom of the concave portion of the uneven film and the substrate) satisfying all of (6). An article according to item 10. 0.6 μm ≦ (d _max −d _min ) ≦ 1.1 μm (4) d _max ≦ 4 μm (5) d _min ≧ 0.5 μm (6) 13. The uneven film comprises a methylsilyl group (D) represented by the following chemical formula (4) and a siloxy group (E) represented by the following chemical formula (5), relative to 1 mol of the component (E). The article according to any one of claims 10 to 12, wherein component (D) is contained at a ratio of 2 to 20 mol. _{Embedded image} CH ₃ SiO _3/2 (4) SiO _4/2 (5) 14. The article according to claim 10, wherein the article is a relief type diffraction grating. 15. The article according to claim 10, wherein the article is a blazed diffraction grating. 16. A wavelength monitor for a wavelength division multiplex communication system using the relief type diffraction grating according to claim 14 or the blazed diffraction grating according to claim 15. 17. A maximum film thickness d _max (distance between a top of a convex portion of a concavo-convex film and a substrate) and a minimum film thickness d satisfying all of the following formulas (1) to (3) on a surface of a glass substrate. _min
(Distance between the bottom of the concave portion of the concave-convex film and the substrate) and an organopolysiloxane concave-convex film containing no chlorine are formed,
The concave-convex film is formed by adding a methylsilyl group (D) represented by the following chemical formula (4) and a siloxy group (E) represented by the following chemical formula (5) to 1 mol of the component (E). Having a concave-convex surface containing 2 to 20 moles of the following. 0.5 μm ≦ (d _max −d _min ) ≦ 1.5 μm (1) d _max ≦ 5 μm (2) d _min ≧ 0.5 μm (3) CH ₃ SiO _3/2 (4) _{embedded image} SiO _4/2 (5)