JP2009283760A - Curing composition for transcription material and method for forming minute pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curing composition for transcription material which improves selectivity of a dry etching speed and is capable of forming a minute pattern to be used for a resist or the like by thermal or UV nano imprinting, and to provide a method for forming the same. <P>SOLUTION: There is provided a curing composition for transcription material which contains a curing silicon compound constituted of polysiloxane containing acryloyl group, wherein the end of molecule is -O-Si(OR)<SB>3</SB>(wherein R is an alkyl group with the number of carbons 1 to 4) or is -O-Si(OX)<SB>3</SB>(wherein X is a group containing an acryloyl group), and an existential ratio of X in all R is 0.1 or more. Further, there is provided a method for forming minute pattern using the same. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an energy beam curable or thermosetting curable composition for transfer material for forming a fine pattern by an imprint method and a fine pattern forming method using the same.

  Nanoimprint technology has attracted attention as a method for producing a fine pattern in a semiconductor manufacturing process, a magnetic recording medium manufacturing process such as patterned media, and the like, and an excellent transfer material for use therewith is demanded.

  A thermoplastic resin such as polymethylmethacrylate is used as a transfer material for nanoimprinting. In that case, the applied material is heated to a temperature above the glass transition point, embossed, cooled, and then removed from the mold. There was a problem that it took a very long time and the throughput was poor.

  On the other hand, there is disclosed a technique for obtaining a fine pattern by using silsesquioxane hydride, which is one of siloxane compounds, forming a coating film on a substrate and then embossing at room temperature. (Patent Document 1). In addition, a technique for obtaining a fine pattern by forming a coating film made of a composition comprising a catechol derivative and a resorcinol derivative on a substrate and then embossing at room temperature is disclosed (Patent Document 2). This method is called a room temperature imprint method, and although there is no heating and cooling cycle, the time required for embossing is long and the throughput is still not sufficient. In addition, since the stamper is pressed at a high pressure, there is a difficulty in the life of the stamper, which is not sufficient as a mass production technique.

  Therefore, a technique called UV nanoimprint using a photocurable resin that is cured by ultraviolet rays has been proposed. In this process, after the photocurable resin is applied, the resin is cured by irradiating with ultraviolet rays while embossing with a stamper. Thereafter, the fine pattern is formed by removing the stamper. This process has no cycle of heating and cooling, and curing with ultraviolet rays can be performed in a very short time, and the pressure of the embossing can be lowered.

  However, the resin usually used in UV nanoimprint is an acrylic organic resin. When using the formed fine pattern as a resist, the selectivity of the etching rate depending on the type of dry etching gas is important. When functioning as a resist, it is highly resistant to the gas used and needs to be easily removed when removed. Gases often used as an etching gas include a fluorine-based gas and oxygen. In general, in the case of an organic resin, there is no significant difference in the etching rate between a fluorine-based gas and an oxygen gas. Usually, a silicon compound is used in order to obtain selectivity in fluorine gas and oxygen gas. The hydrogenated silsesquioxane or the like is one example, and the etching rate with a fluorine gas is high, whereas the etching rate with oxygen gas is very slow. However, since it does not have photocurability, it cannot be used for the UV nanoimprint method.

For this reason, although a technique using a silicon compound having a curable functional group synthesized by a sol-gel method has been shown (Patent Document 3), it further satisfies the etching rate in a fluorine-based gas and the etching resistance in an oxygen gas, and is flexible. There is still a need for the development of silicon compounds that realize fine patterns with excellent properties.
JP2003-100609 JP-A-2005-277280 JP2007-72374A

  An object of the present invention is to provide a curable composition for a transfer material that has high selectivity for dry etching rate and can form a fine pattern used for a resist or the like by a thermal or UV nanoimprint method, and a method for forming the same. To do.

  As a result of intensive studies on the above-mentioned problems, the present inventors have not only had good imprintability by using the following curable silicon compound as a transfer material for imprinting, but also processed the underlayer after pattern formation. It has been found that the composition has excellent etching resistance, which is the performance as a resist, and exhibits excellent characteristics in the processing of semiconductors and magnetic recording media.

Specifically, it is described in [1] to [14] below.
[1] It has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and the terminal of the molecule is —O—Si (OR) ₃ (where R is the formula (1) ) Or —O—Si (OX) ₃ (wherein X is synonymous with X in formula (2)), and the ratio of X to all R is 0. A curable composition for transfer materials for forming a fine pattern, comprising a curable silicon compound that is 1 or more.

(In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)

(In the formula, X represents a structure represented by the following formula (3).)

(Wherein R ¹ represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue having 1 to 12 carbon atoms, R ² represents a hydrogen atom or a methyl group, Z represents an oxygen atom or —NR ³ indicates the above NR ³
R ³ therein represents a hydrogen atom or a methyl group. )
[2] The curable composition for transfer materials according to the above [1], wherein the curable silicon compound is produced by reacting the following (A) and (B) while distilling off the generated alcohol.
(A) Tetraalkoxysilane or its condensate (B) Compound having a structure represented by the following formula (4)

(Wherein R ¹ represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue having 1 to 12 carbon atoms, R ² represents a hydrogen atom or a methyl group, Z represents an oxygen atom or —NR ³ -. the indicating R ³ in the NR ³ is a hydrogen atom or a methyl group).
[3] The curable composition for transfer materials according to the above [2], wherein the component (A) is tetramethoxysilane or tetraethoxysilane, and water is further added during the reaction. [4] The radical curable composition according to any one of [1] to [3], further containing a radical curable compound other than the curable silicon compound according to [1].
[5] The curable composition for transfer materials according to any one of [1] to [4], wherein the fine pattern is a fine pattern of 10 μm or less.
[6] The curable composition for transfer materials according to any one of [1] to [5], further comprising a thermal radical initiator.
[7] The curable composition for transfer materials according to any one of [1] to [5], further comprising an active energy ray radical initiator.
[8] A step of applying the curable composition for transfer materials according to the item [6] to a substrate to form a coating film;
Pressing the mold against the curable composition for transfer material applied to the substrate;
Curing the transfer material curable composition by heating the transfer material curable composition in a pressed state; and
And a step of removing a mold from the cured curable composition for a transfer material.
[9] A step of applying the curable composition for transfer material according to [7] to a substrate to form a coating film;
Pressing the mold against the curable composition for transfer material applied to the substrate;
Curing the transfer material curable composition by irradiating the curable composition for transfer material with active energy rays in a state where the mold is pressed;
And a step of removing a mold from the cured curable composition for a transfer material.
[10] The fine pattern formation according to [9], wherein the mold is formed of a material that transmits active energy rays, and the active energy rays pass through the substrate and irradiate the coating film. Method.
[11] The fine pattern formation according to [9], wherein the substrate is formed of a material that transmits active energy rays, and the active energy rays pass through the substrate and irradiate the coating film. Method.
[12] A fine pattern is formed by the method according to any one of [8] to [11] using a substrate having a magnetic film on a substrate, and a part of the magnetic film is formed using the fine pattern as a resist. A method for producing a finely patterned magnetic recording medium, comprising removing or demagnetizing part of the magnetic film.
[13] A magnetic recording medium obtained by the production method according to [12].
[14] A magnetic recording / reproducing apparatus comprising the magnetic recording medium according to [13].

  According to the fine pattern forming method of the present invention, a fine pattern with high throughput and high selectivity for dry etching resistance can be formed. Moreover, the composition for forming a fine pattern of the present invention can be used for a method for forming such a fine pattern. Also, by using this forming method, a fine pattern in the semiconductor field, magnetic recording medium manufacturing process, or the like can be created.

Hereinafter, the curable composition for transfer materials and the method for forming a fine pattern of the present invention will be described in detail.
[Curable composition for transfer material]
The curable composition for transfer materials of the present invention has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and the terminal of the molecule is —O—Si (OR). ₃ (wherein R is synonymous with R in formula (1)) or —O—Si (OX) ₃ (where X is synonymous with X in formula (2)), It contains a curable silicon compound in which the ratio of X to R is 0.1 or more.

In the formula (1), R is an alkyl group having 1 to 4 carbon atoms. R in the formula (1) is preferably a methyl group or an ethyl group, particularly preferably a methyl group.

In the formula (2), X has a structure represented by the above formula (3). In Formula (3), R ¹ represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue having 1 to 12 carbon atoms, R ² is a hydrogen atom or a methyl group, and Z is an oxygen atom or —NR ³ —. R ³ in the NR ³ is a hydrogen atom or a methyl group. The curable silicon compound has a molecular end of —O—Si (OR) ₃ or —O—Si (OX) ₃ . R in —O—Si (OR) ₃ is the same as R in formula (1), and is preferably a methyl group or an ethyl group, and particularly preferably a methyl group. X in the —O—Si (OX) ₃ is the same as X in the formula (2).

In the formula (3), R ¹ is preferably a divalent aliphatic hydrocarbon residue having 1 to 4 carbon atoms, R ² is a hydrogen atom or a methyl group, Z is an oxygen atom or —NR ³ —. R ³ is a hydrogen atom or a methyl group. More preferably, R ¹ is an ethylene group, R ² is a hydrogen atom or a methyl group, Z is an oxygen atom or —NR ³ —, and R ³ is a hydrogen atom or a methyl group. More preferably, R ¹ is an ethylene group, R ² is a hydrogen atom or a methyl group, Z is —NR ³ —, and R ³ is a hydrogen atom or a methyl group. Particularly preferably, R ¹ is an ethylene group, R ² is a hydrogen atom, Z is —NR ³ —, and R ³ is a hydrogen atom.

  The curable composition for transfer material of the present invention contains the above curable silicon compound, so that the transfer performance at the time of imprinting is good, and fluorine gas is used for bottoming out and peeling after imprinting. It has been found that it can be easily removed by reactive ion etching, and shows resistance in etching processes such as oxygen etching and Ar milling during substrate-medium processing.

  In the curable silicon compound, the ratio of X to all R, that is, the ratio of the number of X to the number of R present in one molecule of the curable silicon compound is 0.1 or more, preferably 0.8. 1-2. If the ratio of X to all R is less than 0.1, the effect of improving the curability and the hardness of the cured product is low.

  The weight average molecular weight of the curable silicon compound is preferably 300 to 3,000, and particularly preferably 400 to 1500. In this molecular weight region, it exhibits a relatively low viscosity liquid and is easy to handle. In addition, a weight average molecular weight means the molecular weight of polystyrene conversion measured by gel permeation chromatography.

  The curable silicon compound may have a linear structure or a branched structure. Moreover, the curable composition for transfer materials of this invention can contain multiple types of said curable silicon compound.

The curable silicon compound of the present invention can be produced, for example, by reacting the following (A) and (B).
(A) Tetraalkoxysilane or its condensate (B) Compound having a structure represented by the following formula (4)

(Wherein R ¹ represents an aliphatic, alicyclic or aromatic hydrocarbon residue having 1 to 12 carbon atoms, R ² represents a hydrogen atom or a methyl group, Z represents an oxygen atom or —NR ³ —. shown. R ³ in the NR ³ is a hydrogen atom or a methyl group.)
Specific examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, and the like. From the viewpoint of reactivity, tetramethoxysilane and tetraethoxysilane. Are preferred, and tetramethoxysilane is particularly preferred.

Specific examples of the tetraalkoxysilane condensate include a tetramethoxysilane condensate and a tetraethoxysilane condensate.
In Formula (4), R ¹ is preferably a divalent aliphatic hydrocarbon residue having 1 to 4 carbon atoms, R ² is a hydrogen atom or a methyl group, and Z is an oxygen atom or —NR ³ —. R ³ is a hydrogen atom or a methyl group. More preferably, R ¹ is an ethylene group, R ² is a hydrogen atom or a methyl group, Z is an oxygen atom or —NR ³ —, and R ³ is a hydrogen atom or a methyl group. More preferably, R ¹ is an ethylene group, R ² is a hydrogen atom or a methyl group, Z is —NR ³ —, and R ³ is a hydrogen atom or a methyl group. Particularly preferably, R ¹ is an ethylene group, R ² is a hydrogen atom, Z is —NR ³ —, and R ³ is a hydrogen atom.

Specific examples of the compound having the structure of the formula (4) include hydroxyethyl acrylate, hydroxyethyl methacrylate, 1,4-butanediol monoacrylate, 1,4-cyclohexanedimethanol monoacrylate, N- (2-hydroxy Ethyl) acrylamide, N-methylolacrylamide, N-methyl-N- (2-hydroxyethyl) acrylamide) and the like.

This reaction is preferably carried out while distilling off the alcohol produced during the reaction.
When tetraalkoxysilane is used as the component (A), water is added during the reaction. In this case, it is preferable to carry out the reaction while distilling off the alcohol produced by the alcohol exchange reaction between tetraalkoxysilane and water.

  When only the tetraalkoxysilane condensate is used as the component (A), water may or may not be added during the reaction. If water is added, the reaction proceeds while further condensing the condensates with each other. If water is not added, hydrolysis condensation of the condensate does not occur, and only an alcohol exchange reaction with the condensate proceeds. . At this time, it is preferable to adjust the amount of water to be added so that the resulting curable silicon compound has the preferred weight average molecular weight shown above.

Moreover, it is preferable to supply the water used for the reaction with deionized water or distilled water with a small amount of ionic impurities. In the reaction, the amount of component (B) added is based on the amount of alkoxy groups in component (A). It is preferable that it is 10-150 mol with respect to 100 mol of effective alkoxy groups which deducted the amount of OH of the water to add, and it is still more preferable that it is 20-120 mol. When the amount of component (B) added is less than 10 moles, the crosslinkability of the curable silicon compound decreases, and when it exceeds 150 moles, the amount of unreacted component (B) component compounds increases and the reaction solution tends to become cloudy and remains. There exists a tendency for the physical property of hardened | cured material to fall for a monomer. Furthermore, as the addition amount of water when using tetraalkoxysilane as the component (A), the molar ratio of the component (A) to water is preferably 5: 1 to 5: 4, and 4: 1 to 4 : 3 is more preferable. If the amount of water added is less than this range, crystallization tends to occur, and solidification or turbidity over time tends to occur. On the other hand, if the amount of water added is greater than this range, the molecular weight increases, and there is a risk that workability will decrease and gelation may occur due to increased viscosity.

In addition, in the above reaction, when water is added to the reaction, water is not initially charged all at once, but the reaction of the components (A) and (B) is performed at the initial stage of the reaction, and the dealcoholization reaction rate is at least It is preferable to add water to the reaction solution when it reaches 10% or more from the viewpoint of preventing cloudiness and preventing gelation. In addition, the dealcoholization reaction rate here is a value calculated by the amount of distilled alcohol with respect to the theoretical production amount of alcohol generated by elimination of the alkoxy group derived from the component (A).

  The reaction temperature is preferably in the range of 60 to 200 ° C, more preferably in the range of 80 to 150 ° C. When the reaction temperature is lower than 60 ° C., the reaction rate is lowered, and when it exceeds 200 ° C., the product is liable to undergo thermal polymerization. As the reaction conditions, a method is preferred in which the first half of the reaction (up to an alcohol reaction rate of about 50%) is reacted at a relatively low temperature of 80 to 110 ° C., and the second half is promoted to increase the reaction temperature with time. When tetraalkoxysilane is used as the component (A), it is necessary to pay attention not to cause loss due to distillation of the raw material. In particular, when tetramethoxysilane is used, the distillation temperature is set to the boiling point of methanol (64-65). Note that there is no loss due to distillation of the raw material. The reaction time depends on the distillation rate of the alcohol. If the distillation can be carried out efficiently, the reaction time is completed in several hours. The preferred reaction time is 2 to 20 hours depending on the reaction temperature. When the reaction time is shorter than 2 hours, the reaction rate is low, and when it exceeds 20 hours, the product is liable to undergo thermal polymerization. Depending on the charging ratio of each component and the reaction conditions, the unreacted component (B) remains in the product in the order of several% to 10%. When it is necessary to remove this residual content, the reaction system may be decompressed under heating to remove the residual content.

  Moreover, an acidic catalyst and a basic catalyst can be used. The catalyst is preferably a trialkylamine such as triethylamine, tripropylamine, or tributylamine. Considering the possibility of poor stability due to a small amount of residual catalyst, triethylamine or tripropylamine having a low boiling point is particularly preferable.

Further, it is desirable to add a polymerization inhibitor for the purpose of preventing gelation during the reaction. Such inhibitors include hydroquinone, p-methoxyphenol, 2-t-butylhydroquinone, 2-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 4- t-butylcatechol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 4,4′-thio-bis (6-t-butyl-m-cresol), 2,6 -Di-t-butyl-4-ethylphenolstearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (
4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-) -T-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ',
5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) -s-triazine-2,4,6- (
1H, 3H, 5H) phenolic compounds such as trione, tocopherol, phenothiazine, styrylphenothiazine, dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thio Examples thereof include sulfur compounds such as dipropionate and copper dibutyldithiocarbamate, and phosphorus compounds such as triphenyl phosphite, diphenylisodecyl phosphite and phenyl diisodecyl phosphite. These can be used singly or in combination of two or more, and the addition amount is preferably 100 to 10,000 ppm, more preferably 500 to 2000 ppm with respect to the reaction solution. If it is less than 100 ppm, there is no effect, and if it exceeds 10000 ppm, the curability and coloring are adversely affected.

  Similarly, it is desirable to react in the presence of oxygen for the purpose of preventing polymerization. The oxygen concentration to be coexisted is desirably 10 mol% or less as the concentration in the gas phase in consideration of the explosion limit. Even if it exceeds 10 mol%, the polymerization inhibition is effective, but if there is an ignition source, it is easy to ignite and dangerous.

The reaction between the component (A) and the component (B) is preferably carried out until 10% or more of the alkoxy groups in the component (A) are transesterified.
In the above reaction, a solvent may not be used, but a solvent may be used. Solvents that can be used include aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloroethane and chlorobenzene, esters such as ethyl acetate, propyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, ethanol, 1-propanol And alcohols such as 2-propanol and 1-butanol.

Since the curable silicon compound has a (meth) acryloyl group or a (meth) acrylamide group as a functional group, the curable composition for transfer materials of the present invention is free from radical polymerization or polyaddition with polythiol. The combined radical addition polymerization can be performed. In the present specification, the (meth) acryloyl group means at least one selected from an acryloyl group and a methacryloyl group, and a (meth) acrylamide group has the same meaning.
<Other components of curable composition for transfer material>
The curing method of the curable composition for transfer materials according to the present invention includes a thermal curing method and an active energy ray curing method, and an optimum initiator is selected depending on the polymerization mode. It is desirable to add it to the composition.

In the case of thermal polymerization, it is desirable to add a thermal radical initiator. Examples of the thermal radical initiator include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetate peroxide, acetyl acetate peroxide, 1,1-bis (t-butylperoxy) butane, 1,1-bis ( t-butylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-hexylperoxy) -cyclohexane, 1,1-bis (t-hexylperoxy)-
3,3,5-trimethylcyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, t-butyl hydroperoxide, t-hexyl hydroperoxide, 1,1,3 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-methyl hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, α, α '-Bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,
5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,3,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, Succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2 -Ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-S-butyl peroxydicarbonate, di (3-methyl-3-methyl Toxibutyl) peroxydicarbonate, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, 1,1,3,3 -Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxypivalate, t-hexylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5 -Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl- -Methyl ethyl peroxy-2-ethyl hexanoate, t-butyl peroxy-3,5,5-trimethyl hexanoate, t-butyl peroxyisopropyl monocarbonate, t-hexyl peroxyisopropyl monocarbonate, t- Butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxyallyl monocarbonate, t-butyl peroxyisobutyrate, t-butyl peroxymalate, t-butyl peroxybenzoate, t-
Hexyl peroxybenzoate, t-butyl peroxy-m-toluyl benzoate, t-butyl peroxylaurate, t-butyl peroxyacetate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2, 5-bis (m-toluylperoxy) hexane, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-
Organic peroxides such as butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2,3-dimethyl-2,3-diphenylbutane, or 1- [(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′- Azobisisobutyronitrile, 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2-phenylazo-4-methoxy -2,4-dimethylvaleronitrile, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,
2-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [N- (4-Hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2′-azobis [N- ( 2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2
-Methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2'-
Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2 ′
-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2 ' -Azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-azobis [2- (4,5,6,7
-Tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (5-hydroxy-3,4,5,6
-Tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamide), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis {2-methyl-N- [1,1-
Bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2′-azobis (2-methylpropane), 2,2′-azobis (2,4,4-trimethylpentane), dimethyl 2,2′-azobis (2-methylpropionate), 4,
Examples include thermal radical polymerization initiators such as azo compounds such as 4'-azobis (4-cyanopentanoic acid) and 2,2'-azobis [2- (hydroxymethyl) propionitrile].

  In the case of active energy ray curing, the acrylic group may be cured without a polymerization initiator as in the case of using an electron beam. Depending on the type, it is desirable to add an active energy ray radical initiator as necessary. Examples of the types of active energy rays include vacuum ultraviolet rays, ultraviolet rays, visible rays, near infrared rays, infrared rays, far infrared rays, microwaves, electron beams, β rays, and γ rays.

Examples of the ultraviolet curable initiator used in the present invention include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-cyclohexylacetophenone 2- Hydroxy-2-phenyl-1-phenylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzene Acetophenone photoradical polymerization initiators such as dil-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl methyl ketal, etc. Benzoin photoradical polymerization initiator, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-
Methyl diphenyl sulfide, 3,3′-dimethyl-4-methoxybenzophenone, 4
, 4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, benzophenone photoradical polymerization initiators, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 2,4-dichlorothioxanthone, etc. Thioxanthone photoradical polymerization initiator, α-acyloxime ester, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquino 4 ', 4''-diethylisophthalophenone, etc.
Imidazole photoradical polymerization initiators such as ketone photoradical polymerization initiators and 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-imidazole And acylphosphine oxide photoradical polymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, carbazole photoradical polymerization initiators, triphenylphosphonium hexafluoroantimonate, triphenylphosphonium hexafluorophosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron-hexaph And photoradical polymerization initiators such as onium salts of Lewis acids such as urophosphate.

These polymerization initiators can be used alone or in combination of two or more.
The curable composition for transfer materials of the present invention can further contain a radical curable compound other than the curable silicon compound. For example, in addition to homopolymerization of the curable silicon compound, it is possible to adjust the curing speed, viscosity, etc. by coexisting a compound having a functional group that can be copolymerized with a (meth) acryloyl group or a (meth) acrylamide group. It is. Examples of such a compound include a compound having a (meth) acryloyl group, a styryl group, a vinyl group, an allyl group, a maleyl group, a fumarate group, etc. Among them, a compound having a (meth) acryloyl group is particularly preferable. A monomer or oligomer having a plurality of meth) acrylic acid esters is preferably used.

Specifically, monofunctional or polyfunctional (meth) acrylates can be used as (meth) acrylic acid esters and derivatives thereof, although there are restrictions on the amount used, methyl (meth) acrylate, ) Ethyl acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-sec-butyl, ( Hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate , (Meth) acrylic acid benzyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropy , (Meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-2-hydroxybutyl, (meth) acrylic acid-2-hydroxyphenylethyl, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol penta (Meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-acryloylmorpholine and the like.

  Also, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic type Epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, silicone modified epoxy A so-called epoxy acrylate obtained by adding (meth) acrylic acid to an epoxy resin such as a resin or an ε-caprolactone-modified epoxy resin can also be used.

  Polyisocyanate compounds, such as 2,4- or 2,6-tolylene diisocyanate, m- or p-xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate or modified products or polymers thereof, Hexamethylene diisocyanate, isophorone diisocyanate, 1,4-tetramethylene diisocyanate, naphthalene diisocyanate and the like, and active hydrogen-containing (meth) acrylate monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate , Tripropylene glycol (meth) acrylate, 1,4-butylene glycol mono (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, Roll mono (meth) acrylate, glycerol di (meth) acrylate, glycerol methacrylate acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate such as a urethane acrylate obtained by reacting such can also be used.

  Examples of styrene and derivatives thereof include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, and 3,4-dimethyl. Styrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-chlorostyrene , M-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene , P-hydroxystyrene, 2-vinylbiphenyl, 3-vinyl Biphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p- Isopropenyltoluene, 2,4-dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene , Α-chlorostyrene, divinylbenzene, divinylbiphenyl, diisopropylbenzene, and the like.

Examples of (meth) acrylonitrile and derivatives thereof include acrylonitrile and methacrylonitrile.
Examples of vinyl esters of organic carboxylic acids and their derivatives include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, Examples include vinyl cyclohexanecarboxylate, vinyl pivalate, vinyl octylate, vinyl benzoate, and divinyl adipate.

  Allyl esters of organic carboxylic acids and derivatives thereof include oligos such as allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, diallyl phthalate, diallyl 1,4-cyclohexanedicarboxylate, oligopropylene terephthalate, etc. An allyl ester resin obtained by reacting esters with allyl alcohol.

  Dialkyl esters of fumaric acid and derivatives thereof include dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate And dibenzyl fumarate.

  Dialkyl esters of maleic acid and derivatives thereof include dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate And dibenzyl maleate.

  Dialkyl esters of itaconic acid and derivatives thereof include dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2-ethylhexyl itaconate And dibenzyl itaconate.

Examples of N-vinylamide derivatives of organic carboxylic acids include N-methyl-N-vinylacetamide.
Examples of maleimide and derivatives thereof include N-phenylmaleimide and N-cyclohexylmaleimide.

As polythiol compounds used in combination with (meth) acrylic acid groups, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), Ethylene glycol bis (3-mercaptopropionate), trimethylolpropane-tris- (β-thiopropionate), tris-2-hydroxyethyl-isocyanurate tris-β-mercaptopropionate, pentaerythritol tetrakis (β -Thiopropionate), 1,8-dimercapto-3,6-dioxaoctane, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) Le) and benzene.

In the curable composition for transfer materials of the present invention, (I) the preferred ratio of the curable silicon compound and the radical curable compound other than (II) (I) is (I) ) 30-95 parts by mass, (II) 70-5 parts by mass, more preferably (I) 50-95 parts by mass, (II) 50-5 parts by mass, particularly preferred mixing ratio is (I) 70- 95 parts by mass, (II) 30 to 5 parts by mass. (II) The curability | hardenability and adhesiveness of a composition can be improved by mix | blending radical curable compounds other than (I) in said ratio.

When the curable composition for transfer materials of the present invention further contains (III) an active energy ray radical initiator or a thermal radical initiator, the preferred ratio of the three components is the total amount of (I) and (II). It is (III) 0.2-10 mass parts with respect to 100 mass parts, More preferable mixing ratio is (III) 0.5-7 mass parts, Especially preferable mixing ratio is (III) 1-5 mass Part. When the proportion of (III) is less than 0.2 parts by mass, the curability is low, and when it exceeds 10 parts by mass, the physical properties of the coating film are deteriorated.
In addition to the polymerization initiator, additives such as a viscosity modifier, a dispersant, and a surface modifier can be added. In that case, it is preferable that the total be 30% by mass or less of the curable composition. When there is too much quantity of an additive, there exists a possibility that the etching performance of the fine pattern obtained using the curable composition of this invention may be inferior.

When forming a fine pattern using the curable composition of this invention, a solvent etc. can be added as needed. Diluent solvents include ketone solvents such as methyl isobutyl ketone, aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, 2-propanol, butanol and hexanol, Examples thereof include alcohol solvents such as propylene glycol mono-n-propyl ether and ethylene glycol monoethyl ether, ether solvents such as ethylene glycol diethyl ether and diethylene glycol diethyl ether.
[Method for forming fine pattern]
Next, a method for forming a fine pattern using the curable composition for transfer materials of the present invention will be described. In particular, according to this forming method, a fine pattern of 10 μm or less can be formed. Here, the fine pattern of 10 μm or less is a pattern in which the line width dimension of the unevenness etched into the mold is 10 μm or less, that is, the total of one concave line width and one convex line width is 10 μm or less. Means a pattern.

  An example of the method for forming a fine pattern of the present invention includes a step of applying the curable composition for transfer material of the present invention to a substrate to form a coating film, and a mold for the curable composition for transfer material applied to the substrate. A step of pressing, a step of curing the curable composition for transfer material by heating the curable composition for transfer material in a state of pressing the mold, and removing the mold from the cured curable composition for transfer material Process.

Other examples of the fine pattern forming method of the present invention include a step of applying the curable composition for transfer material of the present invention to a substrate to form a coating film, and a curable composition for transfer material applied to the substrate. A step of pressing a mold against an object, a step of curing the curable composition for transfer material by irradiating the curable composition for transfer material with active energy rays in a state of pressing the mold, and a cured transfer material Removing the mold from the curable composition.
[1, Application process]
The method for applying the curable composition to the substrate is not particularly limited, and for example, a method such as spin coating or dip coating can be used, but the film thickness of the coating film made of the curable composition for transfer material on the substrate can be used. It is preferable to use a method in which the is uniform. FIG. 1A shows a state in which the curable composition of the present invention is applied on a substrate, and a coating film 14 is provided on the substrate 16.

The “substrate” refers to a substrate in which a layer on which a pattern such as a magnetic film and / or a protective film is to be formed is provided on a substrate such as a glass plate.
[2. Transfer process and curing process]
For fine patterns, press a mold that already has a fine pattern on the coating film (transfer)
Can be formed. After pressing the mold against the coating film, curing with active energy rays or heat curing is performed to cure the curable composition. Moreover, both methods can be combined and an active energy ray can also be irradiated under a heating. FIGS. 1B and 1C show a process of pressing a mold against the curable composition of the present invention applied on a substrate and curing the composition by irradiation with active energy rays and / or heat. . 1B shows a state in which the mold 16 is pressed against the coating film 14 provided on the substrate 16, and FIG. 1C shows a state in which the mold 12 is pressed against the coating film 14. The coating film 14 is irradiated with active energy rays or heat is applied.

  There are no particular restrictions on the material of the mold, but when the curable composition is cured with an active energy ray such as ultraviolet rays, the active energy ray is transmitted when a resin, glass or quartz die that transmits the active energy ray is used. Even when a substrate that is not used is used, the active energy ray is irradiated to the coating film through the mold from the side of the mold opposite to the surface that is in contact with the coating film. By this, a curable composition can be hardened and a fine pattern can be formed, which is preferable. That is, in FIG. 1C, an active energy ray is emitted on the upper side of the mold 12, passes through the mold 12, and is applied to the coating film 14 on which the fine pattern is formed. When the substrate is a transparent substrate or the like that transmits active energy rays, the active energy rays usually pass through the substrate from the side of the substrate opposite to the surface in contact with the coating film, and Curing is performed by irradiating the coating film. That is, in FIG. 1C, active energy rays are emitted below the substrate 16, pass through the substrate 16, and irradiate the coating film 14 on which the fine pattern is formed.

The active energy ray used in the present invention is not particularly limited as long as it acts on the (meth) acryloyl group or (meth) acrylamide group of the curable silicon compound to cure the composition. Examples thereof include radiation such as ultraviolet rays and X-rays, and electron beams. In these, an ultraviolet-ray and an electron beam can be used conveniently.

Moreover, there is no particular limitation on the atmosphere when pressing the mold, or subsequent heating or energy ray irradiation, but it is preferably a vacuum in order to prevent bubbles from remaining in the cured curable composition. In addition, when the curable functional group is a carbon-carbon double bond such as a (meth) acryl group, an allyl group, or a vinyl group, the inhibition of polymerization by oxygen can be prevented. Or it is preferable to perform energy beam irradiation in a vacuum.
[3. Mold release process]
After hardening the coating film which consists of a curable composition of this invention, a type | mold is removed from a coating film. FIG. 1D shows a state in which the mold 12 is removed from the coating film 14 which has been cured and formed with a fine pattern. After removing the mold, heating can be performed to improve the heat resistance and physical strength of the fine pattern. At this time, there is no particular limitation on the heating method, but the temperature is gradually raised while maintaining the temperature below the glass transition point of the coating film so that the formed pattern does not collapse, and the upper limit of heating is the thermal decomposition of the coating film. In order to prevent it, it is preferable to set it as 250 degreeC.

  In this way, a fine pattern of 10 μm or less is formed. This fine pattern is obtained by curing the curable composition for transfer material of the present invention, and has high selectivity in etching rate between fluorine-based gas and oxygen gas. Therefore, the fine pattern formed by the fine pattern forming method of 10 μm or less of the present invention has high resistance to the gas used for etching, so the degree of etching can be easily controlled, and the gas used for removal Is easily removed because of its low resistance. Therefore, since the fine pattern becomes an excellent resist, it can be applied to a wide range of applications including semiconductors and magnetic recording media.

As described above, the curable composition for transfer materials of the present invention can be applied to a wide range of applications including magnetic recording media. More specifically, as a use of the magnetic recording medium, the above-mentioned fine pattern can be applied to a method for removing a part of the magnetic film of the magnetic recording medium or making it nonmagnetic. The method will be described below.

(1. Bottoming out)
By etching the curable composition by reactive ion etching (RIE, also called ion milling), the concave and convex portions are etched to expose the surface of the magnetic film. FIG. 4 shows an outline of this process. In FIG. 4, a cured film having a fine pattern formed of the curable composition of the present invention is provided on the magnetic film of a substrate having a magnetic film provided on a substrate. Reactive ion etching is performed from above (the upper diagram in FIG. 4). As a result, the concave portion of the cured film on which the fine pattern is formed is cut, and a portion where the cured film does not exist on the magnetic film is formed corresponding to the fine pattern (the lower diagram in FIG. 4).

(2. Partial removal or demagnetization of the magnetic layer)
The magnetic part exposed by ion milling is etched or the magnetic part exposed by the reactive gas is made nonmagnetic. At this time, the curable composition must be resistant to ion milling and reactive gases. FIG. 5 shows an outline of this process. The figure on the left of FIG. 5 shows a step of ion milling (ion etching). When the cured film on which the fine pattern is formed and the bottom is removed is ion-milled from above (the figure on the upper left of FIG. 5), curing is performed. The portion of the magnetic film where no film is present is etched (the lower left figure in FIG. 5). The right figure of FIG. 5 shows the process of the demagnetization process by reactive gas, and when the cured film in which the fine pattern was formed and the bottom was made was processed with the reactive gas from the upper direction (FIG. 5, upper right) ), The portion of the magnetic film where the cured film does not exist is rendered non-magnetic (the lower right figure in FIG. 5). In addition, as a method for demagnetizing the magnetic part, for example, as described in JP 2007-273067 A, the magnetic part is formed by silicon, boron, fluorine, phosphorus, tungsten, carbon, ion beam method, etc. There is a method in which atoms such as indium, germanium, bismuth, krypton, and argon are implanted to make the magnetic part amorphous.

Thereafter, the magnetic recording medium is obtained by removing the film made of the curable composition.
By incorporating the magnetic recording medium manufactured by the above method into the magnetic recording / reproducing apparatus, it is possible to manufacture a magnetic recording / reproducing apparatus having a greatly increased recording density while ensuring recording / reproducing characteristics equivalent to or higher than those of the conventional one.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

A 500 mL three-necked glass flask was equipped with a stirrer, a thermometer and a distillation apparatus, and 195.6 g (1.70 mol) of N- (2-hydroxyethyl) acrylamide (manufactured by Kojin Co., Ltd.), methyl silicate 51 ( Tetramethoxysilane oligomer (manufactured by Colcoat Co., Ltd.)
Average tetramer oligomer} 200 g (0.425 mol) and 0.791 g of p-methoxyphenol were charged. The flask was heated and stirred in an oil bath at 120 ° C., and reacted for 2 hours while distilling methanol. Continue the reaction by reducing the pressure, and gradually increase the degree of vacuum to 3
After 1 hour, the reaction pressure was set to 0.14 kPa by a vacuum pump, and the reaction was carried out for 1 hour.

  The reaction solution is slightly turbid but in a liquid state, the viscosity obtained from an E-type viscometer is 520 mPa · s at 25 ° C., the number average molecular weight obtained from gel permeation chromatography is 500 in terms of polystyrene, and the weight average molecular weight Was 700 in terms of polystyrene. From the NMR measurement, the ratio of X to all R was 0.4.

With respect to 100 parts by mass of this reaction solution, 900 parts by mass of propylene glycol monomethyl acetate, photo radical polymerization initiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173 Ciba Specialty Chemicals Co., Ltd.) 3 parts by mass) were added and dissolved, and then filtered through a 0.2 μm filter, and 0.5 ml of the obtained curable composition was dropped onto a glass substrate set in a spin coater. A thin film was formed on the glass substrate by rotating the glass substrate at 500 rpm for 5 seconds, then at 3000 rpm for 2 seconds, and further at 5000 rpm for 20 seconds (the film thickness was approximately 0.2 μm). The glass substrate coated with the resin was irradiated with ultraviolet rays (illuminance 35 mW / cm 2 at a wavelength of 365 nm) under a nitrogen stream.
) For 60 seconds. The reactive ion etching rate by CF ₄ gas and oxygen of the obtained resin thin film was measured.
(Etching rate measurement method)
A small piece of glass was affixed on the cured thin film, and an etching process was performed with a reactive ion etching apparatus under the following conditions. The glass piece was removed, and the thin film portion protected by the glass piece and the etched thin film portion step were measured.

Etching rate (nm / sec) = step difference (nm) ÷ processing time (sec)
Conditions for reactive ion etching (fluorine gas)
Etching gas: Carbon tetrafluoride Pressure: 0.5Pa
Gas flow rate: 40sccm
Plasma voltage: 200W
Bias voltage: 20W
Processing time: 20 sec
(oxygen)
Etching gas: Oxygen Pressure: 0.5Pa
Gas flow rate: 40sccm
Plasma voltage: 200W
Bias voltage: 20W
Processing time: 600 sec
[Comparative Example 1]

  A 500 mL three-necked glass flask was equipped with a stirrer and a thermometer, and charged with 2.4 g of 10% tetramethylammonium hydroxide, 6.3 g of water, and 61.3 g of 2-propanol. 33.6 g (0.14 mol) of 3-acryloxypropyltrimethoxysilane was added dropwise over 60 minutes while stirring the flask at room temperature. Stirring was continued for 18 hours at room temperature. 1.6 g of 10% nitric acid aqueous solution was added little by little to neutralize. 300 g of propylene glycol monomethyl ether acetate was added, and methanol and solvent 2-propanol produced by the reaction using an evaporator and excess water were removed. The solution was transferred to a separatory funnel, 100 g of water was added to wash the organic layer, and salts generated during neutralization were removed. Thereafter, water was removed again with an evaporator. The number average molecular weight determined from gel permeation chromatography was 1800 in terms of polystyrene, and the weight average molecular weight was 2400 in terms of polystyrene.

3 parts by mass of a photo-radical polymerization initiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173 manufactured by Ciba Specialty Chemicals Co., Ltd.) is added to 1000 parts by mass of this solution. , And then filtered through a 0.2 μm filter,
A curable composition was obtained. A thin film was prepared in the same manner as in Example 1 (the film thickness was approximately 0.2 μm) and irradiated with ultraviolet rays (illuminance 35 mW / cm 2 at a wavelength of 365 nm) for 60 seconds. The reactive ion etching rate by CF ₄ gas and oxygen of the obtained resin thin film was measured.

  Table 1 shows the reactive ion etching rates in the gases of Example 1 and Comparative Example 1.

It can be seen that the resin of Example 1 has a low oxygen etching rate and high oxygen etching resistance. It can also be seen that Example 1 is faster in etching rate with respect to CF _{4 and} has a very high selectivity and can be suitably used as a resist.

950 parts by mass of propylene glycol monomethyl acetate with respect to 50 parts by mass of the reaction solution of Example 1 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173 Ciba Specialty Chemicals Co., Ltd.) The product was added and dissolved in 3 parts by mass, filtered through a 0.2 μm filter, and 0.5 ml of the resulting curable composition was dropped onto a glass substrate set in a spin coater. A thin film was formed on the glass substrate by rotating the glass substrate at 500 rpm for 5 seconds, then rotating at 3000 rpm for 2 seconds, and further rotating at 5000 rpm for 20 seconds.

  Next, the patterned surface of the quartz glass mold shown in FIG. 2 is placed on the surface of the prepared glass disk with the curable composition film, and the UV nanoimprint press apparatus ST50 (Toshiba Machine). The product was set and pressed, and irradiated with ultraviolet light having an intensity of 6.5 mW / cm 2 for 60 seconds at a wavelength of 365 nm. When the disk on which the mold was placed was taken out of the press device, the mold was removed, and the film on the glass disk was observed. As a result, no defective coating such as missing patterns or uneven coating was observed.

  The result of the cross-sectional SEM measurement of the transferred substrate is shown in FIG.

FIG. 1 is a diagram showing the steps of a method for forming a fine pattern of 10 μm or less using the curable composition for transfer materials of the present invention. FIG. 2 is a diagram showing a quartz glass disk in which the uneven shape of Example 2 is patterned along the radial direction. The width (L) of the concave portion is 80 nm in the radial direction of FIG. 1, and the width (S) of the convex portion is 120 nm in the radial direction of the drawing. FIG. 3 shows a field emission electron microscope image of a cross section of the glass substrate of Example 2 in which the pattern shape was transferred to the thin film. FIG. 4 shows a bottoming process in the processing of the magnetic film of the magnetic recording medium. FIG. 5 shows an outline of a process for removing a part of the magnetic film of the magnetic recording medium or making it non-magnetic.

Explanation of symbols

12 type 14 coating film 16 made of curable composition for transfer material of the present invention 16 substrate

Claims (14)

It has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and the terminal of the molecule is —O—Si (OR) ₃ (where R is R in the formula (1)). Or -O-Si (OX) ₃ (wherein X is synonymous with X in formula (2)), and the ratio of X to all R is 0.1 or more. A curable composition for transfer materials for forming a fine pattern, comprising a curable silicon compound.
(In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)
(In the formula, X represents a structure represented by the following formula (3).)
(Wherein R ¹ represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue having 1 to 12 carbon atoms, R ² represents a hydrogen atom or a methyl group, Z represents an oxygen atom or —NR ³ indicates the above NR ³
R ^{3 in it} represents hydrogen or a methyl group. ) The curable composition for transfer materials according to claim 1, wherein the curable silicon compound is produced by reacting the following (A) and (B) while distilling off the alcohol to be produced.
(A) Tetraalkoxysilane or its condensate (B) Compound having a structure represented by the following formula (4)
(Wherein R ¹ represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue having 1 to 12 carbon atoms, R ² represents hydrogen or a methyl group, and Z represents an oxygen atom or —NR ^3. -. it shows the R ³ in the NR ³ is a hydrogen or a methyl group).   The curable composition for transfer materials according to claim 2, wherein the component (A) is tetramethoxysilane or tetraethoxysilane, and water is further added during the reaction. Furthermore, the radical curable composition of any one of Claims 1-3 containing radical curable compounds other than the curable silicon compound of Claim 1.   The curable composition for transfer materials according to claim 1, wherein the fine pattern is a fine pattern of 10 μm or less.   Furthermore, the curable composition for transfer materials of any one of Claims 1-5 containing a thermal radical initiator.   Furthermore, the curable composition for transfer materials of any one of Claims 1-5 containing an active energy ray radical initiator. Applying the curable composition for transfer material according to claim 6 to a substrate to form a coating film;
Pressing the mold against the curable composition for transfer material applied to the substrate;
Curing the transfer material curable composition by heating the transfer material curable composition in a pressed state; and
And a step of removing a mold from the cured curable composition for a transfer material. Applying the curable composition for transfer material according to claim 7 to a substrate to form a coating film;
Pressing the mold against the curable composition for transfer material applied to the substrate;
Curing the transfer material curable composition by irradiating the curable composition for transfer material with active energy rays in a state where the mold is pressed;
And a step of removing a mold from the cured curable composition for a transfer material.   The method for forming a fine pattern according to claim 9, wherein the mold is formed of a material that transmits active energy rays, and the active energy rays pass through the substrate and irradiate the coating film.   The fine pattern forming method according to claim 9, wherein the substrate is formed of a material that transmits active energy rays, and the active energy rays pass through the substrate and are applied to the coating film.   Whether a fine pattern is formed by the method according to any one of claims 8 to 11 using a substrate having a magnetic film on a substrate, and a part of the magnetic film is removed using the fine pattern as a resist. Or a method for producing a finely patterned magnetic recording medium, wherein a part of the magnetic film is made non-magnetic.   A magnetic recording medium obtained by the manufacturing method according to claim 12.   A magnetic recording / reproducing apparatus comprising the magnetic recording medium according to claim 13.