JP2010031254A - Hydrosilylated reaction product and method for producing the same, transfer material curable composition containing the same, and production method of transfer layer using the same or transfer material curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrosilylated reaction product which is applicable to a nanoimprint method for forming a minute pattern with high throughput and having high etching rate selectivity between fluorine gas and oxygen gas, or a transfer material curable composition containing the same, and to provide a hydrosilylated reaction product which can suppress transfer of minute unevenness and minute irregularities except a pattern of an injection-molded resin stamper and a film stamper used for nanoimprinting or a transfer material curable composition containing the same. <P>SOLUTION: The hydrosilylated reaction product is obtained by mutually reacting a specific cage silsesquioxane compound (A) having an Si-H bond-containing group, a compound (B) having a curable functional group and a carbon-carbon unsaturated bond-containing group except the curable functional group, and a specific cage silsesquioxane compound (C) having a carbon-carbon unsaturated bond-containing group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hydrosilylation reaction product and a production method thereof, a curable composition for a transfer material containing the hydrosilylation reaction product, and a transfer layer using the hydrosilylation reaction product or the curable composition for a transfer material. It relates to a manufacturing method.

  Nanoimprint technology is attracting attention as a method for forming fine patterns in semiconductor manufacturing processes, magnetic recording medium manufacturing processes such as patterned media, and the like, and an excellent transfer material for use in nanoimprinting technology is required.

  A thermoplastic resin such as polymethyl methacrylate may be used as the nanoimprint transfer material. When a thermoplastic resin is used as a transfer material, a pattern forming method is generally employed in which the applied transfer material is heated to a glass transition point or higher, pressed, cooled, and then removed from the mold. However, such a pattern formation method is very time consuming and has a problem of poor throughput.

  On the other hand, in Patent Document 1, a solution containing silsesquioxane hydride, which is one of siloxane compounds, and a solvent is coated on a substrate, and then the coated surface is embossed at room temperature. A method of forming a fine pattern by removing a solvent and hydrolytically curing is disclosed. Patent Document 2 discloses a method for forming a fine pattern by forming a coating film of a composition containing a compound comprising a catechol derivative and a compound comprising a resorcinol derivative on a substrate and then embossing at room temperature. Is disclosed.

  These methods are called room temperature imprinting methods, and the steps of heating and cooling can be omitted. However, the time required for embossing is long and sufficient throughput is not obtained. Further, since the stamper (mold) has a short life because it is pressed at a high pressure, further improvement is necessary in the case of mass production.

  Therefore, a technique called a UV nanoimprint method using a photocurable resin that is cured by ultraviolet rays has been proposed. The UV nanoimprint method is a method of forming a fine pattern by applying a photocurable resin, irradiating ultraviolet rays while embossing with a stamper, curing the resin, and then removing the stamper. In the UV nanoimprint method, there are no heating and cooling steps, curing with ultraviolet rays is possible in a very short time, and embossing can be performed at a low pressure. Therefore, there is a high possibility that the above various problems can be solved.

  However, in the UV nanoimprint method, a resin that is usually used is an acrylic organic resin, which has a problem in that the selectivity of the etching rate is low. When the formed fine pattern is used as a resist, the selectivity of the etching rate depending on the type of dry etching gas is important. Here, the selectivity of the etching rate means that the etching rate varies depending on the type of etching gas. And it is said that the selectivity of an etching rate is high that an etching rate differs greatly.

In order for the fine pattern to function as a resist, the etching rate needs to have high selectivity depending on the type of etching gas. As the etching gas, fluorine-based gas and oxygen gas are often used. In general, in the case of an acrylic organic resin, there is no significant difference in the etching rate between the fluorine-based gas and the oxygen gas, and the selectivity of the etching rate is low.

  A silicon compound is usually used as a material having a high etching rate selectivity between a fluorine-based gas and an oxygen gas. The hydrogenated silsesquioxane or the like is one example, and the etching rate in a fluorine-based gas is large, whereas the etching rate in oxygen gas is very slow. However, hydrogenated silsesquioxane has a problem that it cannot be used in the UV nanoimprint method because it does not have photocurability.

  As a method for solving such a problem, Patent Document 3 proposes a pattern forming method using a silicon compound having a functional group synthesized by a sol-gel method. However, in this method, if the molecular weight of the silicon compound is increased during the sol-gel process, the molecular weight cannot be increased because gelation forms a compound that is insoluble and infusible in the solvent. There is a problem that it is difficult to balance the strength and flexibility.

Japanese Patent Laid-Open No. 2003-100609 JP 2005-277280 A JP 2007-72374 A

  The present invention provides a hydrosilylation reaction product capable of forming a fine pattern with high throughput and high etching rate selectivity between a fluorine-based gas and an oxygen gas, a method for producing the same, and the hydrosilylation reaction product. It is an object of the present invention to provide a curable composition for a transfer material, and a method for producing a transfer layer using the hydrosilylation reaction product or the curable composition for a transfer material. Further, a hydrosilylation reaction product capable of suppressing the transfer of minute unevenness and fine irregularities other than patterns of injection molded resin stamper and film stamper used for UV nanoimprint, a method for producing the same, and a transfer containing the hydrosilylation reaction product It is an object of the present invention to provide a curable composition for materials, and a method for producing a transfer layer using the hydrosilylation reaction product or the curable composition for transfer materials. Furthermore, it aims at providing the curable composition for transfer materials containing the hydrosilylation reaction material which can be applied to UV nanoimprint method, and can be applied also to a thermal nanoimprint method depending on the case.

  As a result of intensive studies to solve the above problems, the present inventors are able to solve the above problems by using a specific hydrosilylation reaction product or a curable composition for transfer materials containing the hydrosilylation reaction product. I found.

  That is, the present invention relates to the following [1] to [20], for example.

[1]
A cage silsesquioxane compound (A) having a Si-H bond-containing group represented by the following formula (1);
A compound (B) having a curable functional group and a carbon-carbon unsaturated bond-containing group other than the curable functional group;
A hydrosilylation reaction product obtained by reacting a caged silsesquioxane compound (C) having a carbon-carbon unsaturated bond-containing group represented by the following formula (2):

(In formula (1), R ² and R ³ each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and Y represents independently Represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and at least one of the eight Ys is a hydrogen atom.)

(In formula (2), each R ¹ independently represents —OSiR ² R ³ Z, —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , and at least one of the eight R ¹ is , —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , wherein Z is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. R ² and R ³ each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.)
[2]
The hydrosilylation reaction product according to [1], wherein the ratio of the cage silsesquioxane skeleton shown in (x) below is in the range of 15 to 45% by mass.

[3]
The hydrosilylation reaction product according to [1] or [2], wherein the curable functional group of the compound (B) is an active energy ray-curable functional group.

[4]
The hydrosilylation reaction product according to [3], wherein the active energy ray-curable functional group is a (meth) acryloyloxy group or an epoxy group.

[5]
The hydrosilylation reaction product according to [1] or [2], wherein the compound (B) is at least one selected from the group consisting of the following compound (a), compound (b) and compound (c);

(In the above compounds (a) to (c), R ⁴ — is a group represented by any of the following formulas (i) to (iv), and R ⁵ is a hydrogen atom or a methyl group.)

(In the formula (i), R ⁶ is a hydrogen atom or a methyl group. In the formula (ii), R ⁷ is a hydrogen atom or a methyl group. In the formula (iii), R ⁸ is a hydrogen atom or a methyl group. A methyl group, R ⁹
Is an alkylene group having 2 to 8 carbon atoms).

[6]
[1] A curable composition for transfer materials, comprising the hydrosilylation reaction product according to any one of [5] and a polymerization initiator or a curing agent.

[7]
The curability for transfer material according to [6], wherein the curable functional group of the hydrosilylation reaction product according to any one of [1] to [5] is an epoxy group, and the curing agent is an acid anhydride. Composition.

[8]
The curability for transfer material according to [6], further comprising a polythiol compound, wherein the curable functional group of the hydrosilylation reaction product according to any one of [1] to [5] is a (meth) acryloyloxy group. Composition.

[9]
The curable composition for transfer materials according to [6], further comprising a compound having a vinyl ether group, wherein the curable functional group of the hydrosilylation reaction product according to any one of [1] to [5] is an epoxy group. object.

[10]
A method for producing a hydrosilylation reaction product according to [1],
A cage silsesquioxane compound (A) having a Si-H bond-containing group represented by the following formula (1);
A compound (B) having a curable functional group and a carbon-carbon unsaturated bond-containing group other than the curable functional group;
Hydrosilylation characterized by including the process of mixing with the cage silsesquioxane compound (C) which has a carbon-carbon unsaturated bond containing group represented by the following formula | equation (2), and carrying out a hydrosilylation reaction, A method for producing a reactant.

(In formula (1), R ² and R ³ each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and Y represents independently Represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and at least one of the eight Ys is a hydrogen atom.)

(In the formula (2), each R ¹ independently represents —OSiR ² R ³ Z, —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , and at least one of the eight R ¹ Are —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , and Z is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon having 6 to 14 carbon atoms. R ² and R ³ each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.)
[11]
When the average number of moles of Si-H bonds of the compound (A) is A, and the average number of moles of carbon-carbon unsaturated bonds of the compound (B) and the compound (C) is B and C in this order ,
The method for producing a hydrosilylation reaction product according to [10], wherein A / (B + C) is in the range of 1/1 to 1/10 and B / C is in the range of 1 to 79.

[12]
A method for producing a transfer layer having a concavo-convex pattern,
The hydrosilylation reaction product according to any one of [1] to [5] or the curable composition for transfer material according to any one of claims 6 to 9 is applied on a substrate to be curable for transfer material. Forming a composition layer;
A step of pressing a mold having a concavo-convex pattern onto the surface of the curable composition layer for transfer material;
And a step of curing the curable composition layer for a transfer material in a state where the mold is pressed to form a transfer layer.

[13]
The method for producing a transfer layer according to [12], wherein the step of curing the curable composition layer for transfer material is performed by heating and / or irradiating active energy rays to the curable composition layer for transfer material. .

[14]
The method for producing a transfer layer according to [13], wherein the active energy ray irradiation is performed from the mold side toward the curable composition layer for transfer material.

[15]
The method for producing a transfer layer according to [13], wherein the substrate is a transparent substrate, and the active energy ray irradiation is performed from the transparent substrate side toward the curable composition layer for transfer material. .

[16]
The method for producing a transfer layer according to any one of [12] to [15], wherein the substrate is a substrate having a magnetic film on a substrate.

[17]
Forming a transfer layer having a concavo-convex pattern on a substrate having a magnetic film on a substrate by the transfer layer manufacturing method according to [16];
Etching the concave and convex recesses formed in the transfer layer to expose a part of the surface of the magnetic film;
A step of removing the exposed portion of the magnetic film or demagnetizing the exposed portion of the magnetic film in this order using the transfer layer as a mask.

[18]
The imprint method according to [17], wherein in the uneven pattern, the sum of the line width of one concave portion and the line width of one convex portion is 10 μm or less.

[19]
A magnetic recording medium obtained by the imprint method according to [18].

[20]
A magnetic recording / reproducing apparatus comprising the magnetic recording medium according to [19].

If the hydrosilylation reaction product or the curable composition for transfer material of the present invention is used, a fine pattern with high selectivity of the etching rate of fluorine-based gas and oxygen gas can be formed with high throughput. In addition, it is possible to suppress the transfer of minute unevenness and fine irregularities other than the pattern of the injection molded resin stamper and film stamper used for UV nanoimprint.

  The transfer layer manufacturing method of the present invention using the hydrosilylation reaction product or the transfer material curable composition has good transfer performance during imprinting. When removing the bottom for exposing the magnetic layer after imprinting or removing the cured film formed from the reactant or the composition, reactive ion etching using a fluorine-based gas can be performed easily. The cured film can be removed. On the other hand, in etching such as oxygen etching and Ar milling when processing the medium, it shows good resistance as a resist.

  Further, by using the transfer layer manufacturing method of the present invention, a fine pattern in a semiconductor or magnetic recording medium manufacturing process or the like can be satisfactorily formed.

FIG. 1 is a diagram showing the steps of a method for producing a transfer layer having a fine pattern of 10 μm or less using the curable composition for transfer material of the present invention. FIG. 2A is a diagram showing a quartz glass disk in which the uneven shape of Example 2 is patterned along the radial direction. FIG. 2B is an enlarged view (a cross-sectional view (bottom) and a plan view (top)) of an encircled portion of the disk. The width (L) of the concave portion is 80 nm in the radial direction, and the width (S) of the convex portion is 120 nm in the radial direction. FIG. 3 shows a field emission electron microscope image of a cross section of a glass substrate having a pattern shape transferred to a thin film in Example 2. 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 nonmagnetic. FIG. 6 shows a surface image obtained by measuring the glass substrate having the pattern shape transferred to the thin film with an optical surface analyzer (OSA) in Example 2. FIG. 7 shows a surface image obtained by measuring the glass substrate of Reference Example 1 on which the pattern shape is transferred to the thin film using an optical surface analyzer (OSA). FIG. 8 shows a field emission electron microscope image of a cross section of a glass substrate having a pattern transferred to a thin film in Example 4. FIG. 9 shows a surface image obtained by measuring an optical surface analyzer (OSA) on the glass substrate having the pattern shape transferred to the thin film in Example 4. FIG. 10 shows a surface image obtained by measuring the glass substrate of Reference Example 2 having a pattern shape transferred to a thin film with an optical surface analyzer (OSA).

  Hereinafter, the hydrosilylation reaction product of the present invention, a method for producing the same, a curable composition for a transfer material containing the hydrosilylation reaction product, and a transfer layer using the hydrosilylation reaction product or the curable composition for a transfer material The manufacturing method will be described in detail.

[Hydrosilylation reaction product]
The hydrosilylation reaction product of the present invention is a cage silsesquioxane compound (A) having a Si—H bond-containing group represented by the following formula (1) (hereinafter also simply referred to as “compound (A)”). A compound (B) having a curable functional group and a carbon-carbon unsaturated bond-containing group other than the curable functional group (hereinafter also simply referred to as “compound (B)”), and the following formula (2): It is characterized by being obtained by reacting a caged silsesquioxane compound (C) having a carbon-carbon unsaturated bond-containing group (hereinafter also simply referred to as “compound (C)”).

(In formula (1), R ² and R ³ each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and Y represents independently Represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and at least one of the eight Ys is a hydrogen atom.)

(In formula (2), each R ¹ independently represents —OSiR ² R ³ Z, —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , and at least one of the eight R ¹ is , —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , wherein Z is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. R ² and R ³ each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.)
In the above formula (1), at least one of the eight Ys is a hydrogen atom, so the compound (A) contains at least one Si—H bond.

  Examples of the compound (A) include a cage silsesquioxane compound having a Si—H bond-containing group represented by the following formula (1) ′.

(In Formula (1) ′, R ² and R ³ each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.)
The hydrosilylation reaction product can be produced by subjecting the compounds (A) to (C) to a hydrosilylation reaction. Specifically, it can be produced by hydrosilylating the Si—H bond of the compound (A) and the carbon-carbon unsaturated bond of the compounds (B) and (C).

  For example, when the compound (A) is a caged silsesquioxane compound having a Si—H bond-containing group represented by the above formula (1) ′, eight Si—H groups of the compound (A) M react with the carbon-carbon unsaturated bond-containing group of the compound (B), and n react with the carbon-carbon unsaturated bond-containing group of the compound (C). Here, m and n are integers of 1 to 7, and m + n ≦ 8. By the hydrosilylation reaction, a mixture containing a plurality of hydrosilylation reactants usually having different m and n is obtained. The hydrosilylation reactant of the present invention usually means such a mixture.

  In the hydrosilylation reaction product, the ratio of the cage silsesquioxane skeleton portion shown in the following (x) is preferably in the range of 15 to 45% by mass, and in the range of 20 to 35% by mass. It is more preferable that it is in the range of 22 to 30% by mass.

  The conditions for the hydrosilylation reaction will be described in detail in the paragraph of the method for producing a hydrosilylation reaction product.

<Compound (A)>
Examples of the compound (A) include compounds having at least one Si—H bond-containing group in the same molecule represented by the following formula (1).

In the above formula (1), R ² and R ³ each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and Y represents each independently Represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and at least one of eight Ys is a hydrogen atom.

In the above formula (1), R ² and R ³ are preferably each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, such as a methyl group or an ethyl group Or it is more preferable that it is a phenyl group, and it is further more preferable that it is a methyl group.

  In the above formula (1), each Y is preferably independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. It is more preferably a group, and even more preferably hydrogen.

  Specific examples of the compound (A) include octakis (dimethylsilyloxy) silsesquioxane, octakis (methylphenylsilyloxy) silsesquioxane, octakis (dimethylphenylsilyloxy) silsesquioxane, uni (trimethylsilyloxy) Heptakis (dimethylsilyloxy) silsesquioxane, bis (trimethylsilyloxy) hexakis (dimethylsilyloxy) silsesquioxane, tris (trimethylsilyloxy) pentakis (dimethylsilyloxy) silsesquioxane, tetrakis (trimethylsilyloxy) tetrakis ( Dimethylsilyloxy) silsesquioxane, pentakis (trimethylsilyloxy) tris (dimethylsilyloxy) silsesquioxane, hexakis (trimethylsilylo) Shi) bis (dimethylsilyl oxy) silsesquioxane, heptakis (trimethylsilyloxy) Uni (butyldimethylsilyloxy) silsesquioxane and the like. Preferred is octakis (dimethylsilyloxy) silsesquioxane.

Among these compounds, for example, octakis (substituted silyloxy) silsesquioxane is a tetramethylammonium salt of Si ₈ O ₂₀ ⁸⁻ using the method disclosed in J. Organomat. Chem., 441, 373 (1992). It can be synthesized by reacting a salt with a chlorinated alkyl-substituted silicon compound such as dimethylchlorosilane, methylphenylchlorosilane, diphenylchlorosilane, or trimethylchlorosilane.

  The said compound (A) may be used individually by 1 type, and may be used in mixture of 2 or more types.

<Compound (B)>
The compound (B) has a curable functional group and a carbon-carbon unsaturated bond-containing group other than the curable functional group. The carbon-carbon unsaturated bond-containing group included in the compound (B) is a portion that performs a hydrosilylation reaction with the Si—H group included in the compound (A). Examples of the carbon-carbon unsaturated bond-containing group that the compound (B) has include a vinyl group, an allyl group, an isopropenyl group, and a propargyl group.

  Moreover, the curable functional group which a compound (B) has is a curable functional group which reacts with an active energy ray or a heat | fever. The curable functional group is much more reactive than the above-described carbon-carbon unsaturated bond-containing group and reacts preferentially.

  The curable functional group possessed by the compound (B) is preferably a curable functional group that reacts with active energy rays (hereinafter also referred to as “active energy ray-curable functional group”). Among them, a (meth) acryloyloxy group or an epoxy group that reacts with active energy rays is preferable. Here, the epoxy group in the present specification means a group having a triangular structure in which two directly bonded carbon atoms are bridged by an oxygen atom, in addition to a direct or other atom ( This means a group having a structure in which two carbon atoms bonded mainly via carbon atoms are bridged by an oxygen atom, and includes a glycidyl group, an oxetanyl group, a cyclohexene oxide group, and the like.

  As a compound having both of these functional groups in the molecule, that is, a compound having a curable functional group and a carbon-carbon unsaturated bond-containing group other than the curable functional group (compound (B)), 1,2- Compounds having an epoxy group and an allyl group such as epoxy-4-vinylcyclohexane and allyl 3,4-epoxycyclohexanecarboxylate, (meth) acrylic acid diethylene glycol monoallyl ether, (meth) acrylic acid dipropylene glycol monoallyl ether, etc. Examples include compounds such as a compound containing a (meth) acryloyloxy group and an allyl group.

  Other specific examples of compound (B) include at least one selected from the group consisting of compound (a), compound (b) and compound (c) shown below.

In the above compounds (a) to (c), R ⁴ — is any structure represented by the following formulas (i) to (iv), and R ⁵ is a hydrogen atom or a methyl group.

In the formula (i), R ⁶ is a hydrogen atom or a methyl group. In the formula (ii), R ⁷ is a hydrogen atom or a methyl group. In the formula (iii), R ⁸ is a hydrogen atom or a methyl group. R ⁹
Is an alkylene group having 2 to 8 carbon atoms.

  The compound (B) is preferably allyl methacrylate.

  The said compound (B) may be used individually by 1 type, and may be used in mixture of 2 or more types.

<Compound (C)>
The compound (C) is a cage silsesquioxane compound having a carbon-carbon unsaturated bond-containing group, and is represented by the following formula (2).

In formula (2), each R ¹ independently represents —OSiR ² R ³ Z, —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , and at least one of the eight R ¹ is —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , and Z independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. R ² and R ³ each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.

In the above formula (2), since at least one of eight R ¹ is —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , the compound (C) contains at least one carbon-carbon. Contains unsaturated bonds.

In the above formula (2), each R ¹ is preferably independently —OSi (CH ₃ ) ₃ , —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ . R ² and R ³ are each independently preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and may be a methyl group, an ethyl group or a phenyl group. Is more preferable, and a methyl group is more preferable.

  Specific examples of the compound (C) include octavinylsilsesquioxane, octakis (dimethylvinylsilyloxy) silsesquioxane, octakis (methylphenylvinylsilyloxy) silsesquioxane, uni (trimethylsilyloxy) heptakis (dimethyl). Vinylsilyloxy) silsesquioxane, bis (trimethylsilyloxy) hexakis (dimethylvinylsilyloxy) silsesquioxane, tris (trimethylsilyloxy) pentakis (dimethylvinylsilyloxy) silsesquioxane, tetrakis (trimethylsilyloxy) tetrakis ( Dimethylvinylsilyloxy) silsesquioxane, pentakis (trimethylsilyloxy) tris (dimethylvinylsilyloxy) silsesquioxane, hexakis (trime Rushiriruokishi) bis (dimethyl vinyl silyl-oxy) silsesquioxane, heptakis (trimethylsilyloxy) Uni (dimethylvinylsilyl oxy) silsesquioxane, and the like. Octavinylsilsesquioxane is preferred.

  The said compound (C) may be used individually by 1 type, and may be used in mixture of 2 or more types.

<Method for producing hydrosilylation reaction product>
The method for producing a hydrosilylation reaction product of the present invention is a method for producing the hydrosilylation reaction product described above, and is a cage silsesquioxane compound having a Si—H bond-containing group represented by the following formula (1): (A), a compound (B) having a curable functional group and a carbon-carbon unsaturated bond-containing group other than the curable functional group, and a carbon-carbon unsaturated bond-containing compound represented by the following formula (2) It is characterized by including a step of mixing a caged silsesquioxane compound (C) having a group and subjecting it to a hydrosilylation reaction.

(In formula (1), R ² and R ³ each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and Y represents independently Represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and at least one of the eight Ys is a hydrogen atom.)

(In formula (2), each R ¹ independently represents —OSiR ² R ³ Z, —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , and at least one of the eight R ¹ is , —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , wherein Z is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. R ² and R ³ each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.)
The hydrosilylation reaction product obtained by this step is a silsesquioxane skeleton-containing compound having a curable functional group.

  A general hydrosilylation reaction is shown below.

  In the above reaction formula, R represents a residue bonded to a carbon-carbon unsaturated bond of a compound having a carbon-carbon unsaturated bond.

  As described above, the silsesquioxane skeleton-containing compound having a curable functional group in the present invention can be produced by reacting the compounds (A) to (C). A compound having only a carbon-carbon double bond capable of reacting with the Si—H bond can be partially used in place of the compound (B) as long as the subsequent curing reaction is not affected. Examples of such compounds include allyl alcohol, 1-pentene, 1-hexene, 1-octene, styrene, vinyltoluene and the like.

  Moreover, the compound which has Si-H bond containing groups other than a compound (A) can be used together in the range which does not impair the selectivity of the etching rate of the hardened | cured material of a hydrosilylation reaction product. Examples of such a compound include a compound in which two or more hydrogen atoms are bonded to a silicon atom, such as a monoalkylsilane such as phenylsilane, diphenylsilane, and dialkylsilane such as methylphenylsilane, or the following general formula: And those synthesized using a polyhydrogensiloxane compound represented by the group as a raw material.

In the above formula, each of R ¹¹ independently represents an alkyl group having 1 to 5 carbon atoms, and each of R ^{12 to} R ¹⁵ independently represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, HSiO _3/2 ) _n represents cage-like and ladder-like silsesquioxane, and m _{1 to} m ₃ and n _{1 to} n ₅ are each independently an integer from ₁ to 500.

  In the hydrosilylation reaction, the average number of moles of carbon-carbon unsaturated bonds of the compound (B) and the compound (C) is defined as A, where the average number of moles of Si—H bonds of the compound (A) is A. Is B and C in order, A / (B + C) is preferably in the range of 1/1 to 1/10, and more preferably in the range of 1/8 to 1/9. B / C is preferably in the range of 1 to 79. As a reaction method, a method in which a catalyst is slowly dropped into a reaction flask in which the compounds (A) to (C) are mixed is preferably reacted. Note that the hydrosilylation reaction product may be used in a pattern transfer step to be described later in a state where the partially unreacted compound (B) is left in the hydrosilylation reaction product.

  When performing the hydrosilylation reaction, it is preferable to use a catalyst. Examples of such a catalyst include a platinum catalyst, a rhodium catalyst, a palladium catalyst, and a ruthenium catalyst, and a platinum catalyst is more preferable. Platinum catalysts include chloroplatinic acid, a reaction product of chloroplatinic acid and an alcohol, a reaction product of chloroplatinic acid and an olefin compound, a reaction product of chloroplatinic acid and a vinyl group-containing siloxane, a platinum olefin complex, and a platinum vinyl group. Examples thereof include siloxane complexes and platinum carbonyl complexes, which are preferably used by dissolving or dispersing them in a solvent such as alcohol. Specifically, it is preferable to use a 2% divinyltetramethyldisiloxane platinum complex xylene solution (manufactured by GELEST INC.) Or the like.

  The amount of the catalyst used is not particularly limited as long as it is effective for the reaction. Specifically, the raw material for the hydrosilylation reaction, that is, the compound (A) (including a compound having a Si—H bond-containing group other than the compound (A) in some cases), (B) (in some cases, those (Including compounds having only carbon-carbon double bonds capable of reacting with Si—H bonds other than compound (B)) and the total amount of compound (C) as a metal element such as platinum, based on mass 0.01 to 10000 ppm, preferably 0.1 to 1000 ppm.

  The reaction temperature of the hydrosilylation reaction is usually 0 to 250 ° C. In the sense of preventing a polymerization reaction of a functional group that becomes a curable functional group of the silsesquioxane skeleton-containing compound, 0 to 100 ° C. is preferable. The reaction time of the hydrosilylation reaction is usually 0.1 to 5 hours, preferably 0.1 to 3 hours. In some cases, the reaction rate may be slow depending on the raw material system. In such a case, it is desirable to heat to 40 ° C. or higher. However, in the case of heating, the polymerization inhibitor is reacted according to the curable functional group. It is desirable to add it to the system. In addition, since the reaction may become unstable due to moisture, the reaction can be performed under an atmosphere of argon or nitrogen as necessary.

  Since the hydrosilylation reaction generates intense heat, a reaction solvent can be used as necessary. For example, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane and octane, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, etc. An ester solvent, an ether solvent such as diisopropyl ether or 1,4-dioxane, an alcohol solvent such as isopropanol propylene glycol mono-n-propyl ether or ethylene glycol monoethyl ether, or a mixed solvent thereof can be used. A cyano group-containing compound such as acetonitrile can also be used as a reaction solvent. Among these, an aromatic hydrocarbon solvent or an aliphatic hydrocarbon solvent is more preferable.

<Curable composition for transfer material>
The curable composition for transfer materials of the present invention (hereinafter, also simply referred to as “curable composition”) includes the hydrosilylation reaction product, that is, a silsesquioxane skeleton-containing compound having a curable functional group, and polymerization initiation. Or a curing agent. The curable composition for transfer materials of the present invention may further contain a polythiol compound, a compound having a functional group that reacts with the curable functional group, and the like.

  The curable functional group in the silsesquioxane skeleton-containing compound is derived from the curable functional group of the compound (B), and examples thereof include a (meth) acryloyloxy group or an epoxy group as described above.

  When the curable functional group of the silsesquioxane skeleton-containing compound is a (meth) acryloyloxy group, the silsesquioxane skeleton-containing compound alone or a functional group that reacts with the (meth) acryloyloxy group Radical polymerization in the presence of a compound or radical polymerization using polyaddition with polythiol in the presence of a polythiol compound can be performed. By performing radical polymerization in the presence of a compound having a functional group that reacts with a (meth) acryloyloxy group, it is possible to adjust the curing speed, viscosity, etc. of the curable composition for transfer materials of the present invention. .

  Examples of the compound having a functional group that reacts with the (meth) acryloyloxy group include a compound having a (meth) acryloyloxy group, a styryl group, a vinyl group, an allyl group, a maleyl group, a fumarate group, and the like. Among these, a compound having a (meth) acryloyloxy group is particularly preferable. For example, a monomer or oligomer having one or more (meth) acrylic acid ester structures is preferable.

  Monofunctional or polyfunctional (meth) acrylate can be used as the monomer or oligomer having one or more structures of the (meth) acrylic acid ester, such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) Acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-sec-butyl, (meth) acrylic acid hexyl, ( Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl (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 ( And (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-acryloylmorpholine, and the like.

Further, as a compound having a functional group that reacts with (meth) acryloyloxy group, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type Epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic 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 (Meth) acrylic acid was added to epoxy resins such as resins, rubber-modified epoxy resins, dicyclopentadiene phenolic epoxy resins, silicone-modified epoxy resins, and ε-caprolactone-modified epoxy resins. So-called epoxy acrylate can also be used.

  Furthermore, the following compounds can be given as other examples of compounds having a functional group that reacts with a (meth) acryloyloxy group.

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, etc .;
As active hydrogen-containing (meth) acrylate monomers, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tripropylene glycol (meth) acrylate, 1,4-butylene glycol mono (meth) acrylate 2-hydroxy-3-chloropropyl (meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, glycerol methacrylate acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate and the like A reacted urethane acrylate or the like can also be used.

  Styrene and its derivatives can also be used as compounds having a functional group that reacts with a (meth) acryloyloxy group. Specifically, styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6 -Dimethylstyrene, 3,4-dimethylstyrene, 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-vinyl vinyl Enyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-iso Propenyltoluene, 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.

  (Meth) acrylonitrile and its derivatives can also be used as compounds having a functional group that reacts with a (meth) acryloyloxy group. Examples thereof include acrylonitrile and methacrylonitrile.

  Vinyl esters of organic carboxylic acids and derivatives thereof can also be used as compounds having a functional group that reacts with a (meth) acryloyloxy group. For example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, divinyl adipate and the like can be mentioned.

  Allyl esters of organic carboxylic acids and derivatives thereof can also be used as compounds having a functional group that reacts with a (meth) acryloyloxy group. Examples include allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, and diallyl phthalate.

  Dialkyl esters of fumaric acid and derivatives thereof can also be used as compounds having a functional group that reacts with a (meth) acryloyloxy group. Examples include dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, dibenzyl fumarate, and the like.

  A dialkyl ester of maleic acid and a derivative thereof can also be used as a compound having a functional group that reacts with a (meth) acryloyloxy group. Examples include dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, dibenzyl maleate and the like.

  Dialkyl esters of itaconic acid and derivatives thereof can also be used as compounds having a functional group that reacts with a (meth) acryloyloxy group. Examples 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.

  An N-vinylamide derivative of an organic carboxylic acid can also be used as a compound having a functional group that reacts with a (meth) acryloyloxy group. For example, N-methyl-N-vinylacetamide and the like can be mentioned.

  Maleimide and derivatives thereof can also be used as compounds having a functional group that reacts with a (meth) acryloyloxy group. Examples thereof include N-phenylmaleimide and N-cyclohexylmaleimide.

  When the curable functional group of the silsesquioxane skeleton-containing compound is a (meth) acryloyloxy group, radical polymerization in the presence of a compound having a functional group that reacts with the (meth) acryloyloxy group, Can be used in combination with polyaddition.

  Examples of the polythiol compound include 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopro Pionate), 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 (me Kaputomechiru) benzene, 1,3,5-tris (mercaptomethyl) benzene.

  On the other hand, when the curable functional group is an epoxy group, cationic polymerization may be performed in the presence of the silsesquioxane skeleton-containing compound alone or a compound having a functional group that reacts with an epoxy group such as a vinyl ether group. Polymerization such as polyaddition using an acid anhydride as a curing agent can be performed. When the curable functional group is an epoxy group, by performing cationic polymerization in the presence of a compound having a functional group that reacts with the epoxy group, the curing rate, viscosity, etc. of the curable composition for transfer materials of the present invention Can be adjusted.

As such a compound having a functional group that reacts with an epoxy group, a compound having a vinyl ether group can be used. Examples of the compound having a vinyl ether group include triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, trimethylolpropane trivinyl ether, cyclohexane-1,4-dimethylol divinyl ether, 1,4-butanediol divinyl ether, polyester diester. Examples thereof include vinyl ether and polyurethane polyvinyl ether.

  In addition, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, phenol novolak type as compounds having functional groups that react with epoxy groups Epoxy resin, cresol novolac type epoxy resin, alicyclic 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 And epoxy compounds having two or more epoxy groups in one molecule, such as dicyclopentadiene phenolic epoxy resin, silicone-modified epoxy resin, and ε-caprolactone-modified epoxy resin.

  Specifically, the following can also be mentioned.

Bisphenol A type epoxy resins such as trade name Epicoat 828, 1002, 1004 manufactured by Japan Epoxy Resin Co., Ltd .;
Bisphenol F type epoxy resins such as trade name Epicoat 806, 807, 4005P manufactured by Japan Epoxy Resin Co., Ltd., trade name YDF-170 manufactured by Toto Kasei Co., Ltd .;
Phenol novolac type epoxy resins such as trade name Epicoat 152 and 154 manufactured by Japan Epoxy Resin Co., Ltd. and trade name EPPN-201 manufactured by Nippon Kayaku Co., Ltd .;
O-cresol novolac type epoxy resins such as Nippon Kayaku Co., Ltd. trade names EOCN-125S, 103S, 104S;
Biphenyl type epoxy resins such as trade name Epicoat YX-4000, YL-6640 manufactured by Japan Epoxy Resin Co., Ltd .;
Product name Epicoat 1031S manufactured by Japan Epoxy Resin Co., Ltd. Product name Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd. Product names Denacol EX-611, EX-614, EX-614B manufactured by Nagase Kasei Co., Ltd. Polyfunctional epoxy resins such as EX-622, EX-512, EX-521, EX-421, E-411, EX-321;
Product name Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd. Product name YH-434 manufactured by Toto Kasei Co., Ltd. Product names TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd., Nippon Kayaku Co., Ltd. Amine type epoxy resins such as trade name GAN manufactured by Sumitomo Chemical Co., Ltd. and trade name ELM-120 manufactured by Sumitomo Chemical Co., Ltd .;
Heterocycle-containing epoxy resins such as trade name Araldite PT810 manufactured by Ciba Specialty Chemicals;
Alicyclic epoxy resins such as EHPE3150, EHPE3150CE, Celoxide 2000, Celoxide 2021, Celoxide 2081 and Epoxide PB3600 Epoxide GT401 manufactured by Daicel Chemical Industries, Ltd .;
Epoxidized polybutadiene such as Epolide PB3600 manufactured by Daicel Chemical Industries. These can be used individually by 1 type or in combination of 2 or more types.

A compound having an oxetanyl group can also be used as the compound having a functional group that reacts with an epoxy group. Examples of the compound having an oxetanyl group include 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3- Ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, 2-ethyl-2-hydroxymethyloxetane Etc.

  When the curable functional group is an epoxy group, particularly a glycidyl group, the curable composition can be cured by polyaddition using an acid anhydride as a curing agent. Examples of acid anhydrides include aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Examples include cyclic fatty acid anhydrides such as acids.

  The usage-amount of these acid anhydrides is 0.7-1.2 equivalent with respect to an epoxy group, Preferably it is 0.8-1.1 equivalent. Further, imidazoles, tertiary amines, and organic phosphine compounds can be used as curing accelerators.

  There are two methods for curing the hydrosilylation reaction product or curable composition of the present invention: active energy ray curing and thermal curing. When the radical polymerization or cationic polymerization described above is performed by these methods, an optimal polymerization initiator is used depending on the polymerization mode.

  When the curable functional group is a (meth) acryloyloxy group, or when the curable functional group is a (meth) acryloyloxy group and the curable composition contains the polythiol compound, radical polymerization starts. It is preferable to use an agent.

In the case of thermal polymerization, as a thermal radical initiator, 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, 1,1-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 hydroper Oxide, 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 Kisaido, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide,

m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxy Dicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-S-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate , Α, α′-bis (neodecanoylperoxy) diisopropylbenzene, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxy Neodecanoate, 1-siku Rohexyl-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-ethylhexa Noylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyisopropyl monocarbonate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl Monocarbonate, t-butylperoxyallyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxymalate, t-butylperoxybenzoate, t-hexylperoxybenzoate, t-butylperoxy-m -Toluylbenzoate, 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-butyltrimethylsilyl peroxide,

3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2,3
Organic peroxides such as 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-methoxyvalero) Nitrile), 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-imidazoline-2
-Yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazoline-
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-diazepine-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,
Azo compounds such as 2′-azobis (2-methylpropionate), 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis [2- (hydroxymethyl) propionitrile], etc. Is mentioned.

As the polymerization initiator when the curable functional group is an epoxy group, melamine, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptacilimidazole, 2-ethyl-4-ethylimidazole, 2- Phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl- 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazole Liuto Melitite, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-S-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]- Ethyl-S-triazine, 2,4-diamino-6- [
2'-ethyl-4'-imidazolyl- (1 ')]-ethyl-S-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-S-triazine isocyanuric acid Adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3 -Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 4,4'-methylenebis (2-ethyl-5-methylimidazole), 1-dodecyl-2-methyl-3-benzylimidazolium chloride, Imidazoles, 1,8-diazabicyclo (5.4.0) undecene-7, and phenol salts thereof, oct Organic salts such as sodium salt, p-toluenesulfonate, formate, orthophthalate, or phenol novolac resin salt, 1,5-diazabicyclo (4.3.0) nonene-5, and its phenol novolac resin salt Bases and salts thereof, anionic initiators such as ureas such as quaternary phosphonium bromide, aromatic dimethylurea and aliphatic dimethylurea, silanol-based cation catalysts such as triphenylsilanol, aluminum tris (acetylacetone), etc. Examples of the aluminum chelate catalyst can be mentioned.

  The active energy ray is not particularly limited as long as it acts on the curable functional group of the silsesquioxane skeleton-containing compound to cure the silsesquioxane skeleton-containing compound or the curable 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. For example, when an electron beam is used as an active energy ray and the curable functional group is a (meth) acryloyloxy group, the silsesquioxane skeleton-containing compound can be cured without a polymerization initiator. When the silsesquioxane skeleton-containing compound is cured, it is desirable to add a polymerization initiator according to the combination of the active energy ray and the curable functional group.

When the curable functional group is a (meth) acryloyloxy group, or when the curable functional group is a (meth) acryloyloxy group and a polythiol compound is contained in the curable composition, as a radical polymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-cyclohexylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 2-hydroxy-2-phenyl-1-phenylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-isopropyl Phenyl) -2-hydroxy-2-methylpropane-1-o 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1, acetophenone photoradical polymerization initiators, benzoin photoradical polymerization initiators such as benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzylmethyl ketal, benzophenone, benzoylbenzoic acid, benzoylbenzoic acid Acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide,
3,3′-dimethyl-4-methoxybenzophenone, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, etc. Benzophenone photoradical polymerization initiators, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 1-chloro Thiopanthone photoradical polymerization initiators such as -4-propoxythioxanthone and 2,4-dichlorothioxanthone, α-acyloxime ester, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphor Ketone-based photoradical polymerization initiators such as quinone, dibenzosuberone, 2-ethylanthraquinone, 4 ′, 4 ″ -diethylisophthalophenone, and 2,2′-bis (2-chlorophenyl) -4,4 ′ , 5,5'-tetraphenyl-1,2'-imidazole, imidazole-based photoradical polymerization initiator, acylphosphine oxide-based photoradical polymerization initiator, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Carbazole photo radical polymerization initiator, triphenylphosphonium hexafluoroantimonate, triphenylphosphonium hexafluorophosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4-chlorophenyldiphenylsulfonium hexafluoro Phosphate, (2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene] - Iron - such as hexafluorophosphate, photoradical polymerization initiator such as an onium salt of a Lewis acid.

  When the curable functional group is an epoxy group, or when the curable functional group is an epoxy group and a compound having a vinyl ether group is contained in the curable composition, triphenylsulfonium hexafluoroantimonate, diphenyl Examples include photocationic polymerization initiators such as sulfonium salt systems such as [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, or iodonium salt systems, diazonium salt systems, and allene-ion complex systems.

  These polymerization initiators can be used singly or in combination of two or more, and preferably used in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the hydrosilylation reaction product.

  In the curable composition of the present invention, additives such as a viscosity modifier, a dispersant, and a surface modifier can be added in addition to the hydrosilylation reaction product, the polymerization initiator, and the curing agent. In that case, it is preferable that the total be 30 parts by mass or less with respect to 100 parts by mass of the hydrosilylation reaction product. When there is too much quantity of an additive, there exists a possibility that the etching performance of the fine pattern obtained using the hydrosilylation reaction material or curable composition of this invention may be inferior.

  In addition, a solvent or the like can be added to the hydrosilylation reaction product or curable composition of the present invention as necessary for improving coating properties. As the diluting solvent, the solvent used in the hydrosilylation reaction can be used as it is, or the reaction solvent can be distilled off under reduced pressure and then diluted with a different solvent.

  Such 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 Examples include alcohol solvents such as hexanol propylene glycol mono-n-propyl ether and ethylene glycol monoethyl ether.

[Method for producing transfer layer]
The method for producing a transfer layer according to the present invention is a method for producing a transfer layer having a concavo-convex pattern, wherein the above-described hydrosilylation reaction product or curable composition is applied onto a substrate and cured for the hydrosilylation reaction product or transfer material. Forming a layer having a concavo-convex pattern on the surface of the curable composition layer for transfer material, and a step for forming a layer of the transfer composition (hereinafter also referred to as “curable composition layer for transfer material”). It includes a pressing step (transfer step) and a step of curing the curable composition layer for transfer material in a state where the mold is pressed to form a transfer layer (curing step).

  Hereinafter, each step will be described.

<Application process>
There is no particular limitation on the method for applying the hydrosilylation reaction product or the curable composition for transfer material on the substrate, and for example, a method such as spin coating or dip coating can be used. It is preferable to use a method in which the thickness of the curable composition layer for transfer material on the substrate is uniform. FIG. 1 (a) shows a state where a hydrosilylation reaction product or a curable composition for transfer material is applied on a substrate. The “substrate” is a substrate provided with a magnetic film on a substrate such as a glass plate. On the substrate, not only a magnetic film but also a layer on which a pattern is to be formed is provided via a resist.

<Transfer process and curing process>
The concavo-convex pattern can be formed by pressing (transferring) a mold having the concavo-convex pattern onto the surface of the curable composition layer for transfer material. The curable composition layer for transfer material is cured with the mold pressed against the surface of the curable composition layer for transfer material. Examples of the curing method include a method in which the curable composition layer for transfer material is heated or irradiated with active energy rays. Moreover, both the hardening methods by heating and active energy ray irradiation can be combined, and active energy rays can be irradiated under heating. FIGS. 1B and 1C show a curable composition for transfer material by pressing a mold against the surface of the curable composition layer for transfer material applied on a substrate and irradiating with active energy rays and / or heat. An example of the process of hardening a physical layer is shown.

  Although there is no restriction | limiting in particular about the raw material of the said type | mold, It is preferable to use the type | mold made from resin, glass, or quartz which an active energy ray permeate | transmits. When such a mold is used, even when a substrate that does not transmit active energy rays such as ultraviolet rays is used, the irradiation of the active energy rays is performed from the mold side toward the curable composition layer for transfer material. Thus, the hydrosilylation reaction product or the curable composition can be cured. In the case where the substrate is a transparent substrate or the like that transmits active energy rays, the active energy ray irradiation is performed from the transparent substrate side toward the curable composition layer for a transfer material, whereby a hydrosilylation reaction product is obtained. Alternatively, the curable composition can be cured.

  Further, there is no particular limitation on the atmosphere when pressing the mold, or subsequent heating or irradiation with active energy rays, but it is preferably a vacuum in order to prevent bubbles from remaining in the cured transfer layer. When the curable functional group is a carbon-carbon double bond such as a (meth) acryloyloxy group, an allyl group, or a vinyl group, the mold is pressed and then heated or activated to prevent polymerization inhibition by oxygen. It is preferable to perform energy beam irradiation in a vacuum.

<Mold release process>
After the curable composition layer for transfer material is cured to form a transfer layer, the mold is removed from the transfer layer. After removing the mold, heating can be performed to improve the heat resistance and physical strength of the pattern. At this time, the heating method is not particularly limited, but the temperature is gradually raised while maintaining the temperature below the glass transition point of the transfer layer so that the formed pattern does not collapse. The upper limit of heating is preferably 250 ° C. in order to prevent thermal decomposition of the transfer layer.

  The transfer layer having the concavo-convex pattern formed by the above process is a transfer layer having the concavo-convex pattern obtained by curing the above-described hydrosilylation reaction product or curable composition for transfer material. High etch rate selectivity. Therefore, the transfer layer having the concavo-convex pattern has high resistance to the oxygen gas used for etching, so the degree of etching can be easily controlled, and the transfer layer having resistance to the fluorine-based gas used for removal. Since it is low, it is easily removed. Therefore, the transfer layer having the concavo-convex pattern becomes an excellent resist and can be applied to a wide range of applications including semiconductors and magnetic recording media.

[Imprint method]
The imprinting method of the present invention comprises a step of forming a transfer layer having a concavo-convex pattern on a substrate having a magnetic film on a substrate by the above-described transfer layer manufacturing method, and the concavo-convex formed on the transfer layer. Etching a recess to expose the surface of the magnetic film, and using the transfer layer as a mask, removing a part of the magnetic film or demagnetizing a part of the magnetic film. It is a feature.

  In the concavo-convex pattern, it is preferable that the line width dimension (pitch) of the concavo-convex inscribed in the mold is 10 μm or less, that is, the total of the line width of one concave portion and the line width of one convex portion is 10 μm or less.

  The step of forming the transfer layer having the concavo-convex pattern is as described above. The subsequent steps will be described below.

<Bottom>
The concave and convex portions of the transfer layer are etched by reactive ion etching (also called RIE or ion milling) to expose a part of the magnetic film surface. FIG. 4 shows an outline of this process.

<Exposed part removal processing or demagnetization of magnetic film>
The magnetic film portion exposed by reactive ion etching is removed by ion milling using argon or the like, or made nonmagnetic by ion beam irradiation. At this time, the transfer layer must be resistant to ion milling and ion beams. FIG. 5 shows an outline of this process. In addition, as a method for demagnetizing the exposed magnetic film portion, for example, as described in JP 2007-273067 A, a magnetic film portion is formed by silicon, boron, fluorine, phosphorus, There is a method in which atoms such as tungsten, carbon, indium, germanium, bismuth, krypton, and argon are implanted to make the magnetic film portion amorphous.

  The imprint method of the present invention can be applied to a magnetic recording medium. More specifically, the present invention can be applied to a method of removing an exposed portion of a magnetic film of a magnetic recording medium or a method of demagnetizing (ion beam method). After the exposed portion removal processing or demagnetization of the magnetic film described above, the magnetic recording medium is obtained by removing the transfer layer.

  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.

[Example 1]
To a three-necked flask equipped with a thermometer and a condenser tube, 3.0 g (2.94 mmol) of octakis (dimethylsilyloxy) silsesquioxane (manufactured by Toagosei Co., Ltd .: Q-2), 2.86 g of allyl methacrylate (22 0.7 mmol), 0.5597 g (0.88 mmol) of octavinylsilsesquioxane (manufactured by Aldrich: PSS-Octaviny Substituted), and 40 ml of toluene were added, and the mixture was stirred at room temperature under a stream of Ar. 0.0223 g of a 2% divinyltetramethyldisiloxane platinum complex xylene solution (manufactured by GELEST INC.) (The weight of platinum metal was 1000 ppm of the raw material charged) was added little by little. After stirring at room temperature for 2 hours, unreacted allyl methacrylate and the solvent were distilled off under reduced pressure to obtain the desired product. From the difference between the total mass of the raw materials and the mass of the target product obtained, it was found that 30% of allyl methacrylate was unreacted. The ratio of the cage silsesquioxane skeleton portion in the obtained target product was 28.7% by mass.

  The obtained target product was dissolved in propylene glycol monomethyl ether acetate so as to have a target product concentration of 10% by mass.

The resulting solution was subjected to photo radical polymerization initiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173 Ciba Specialty Chemicals (
3 parts by mass with respect to 100 parts by mass of the target product, dissolved, and then filtered through a 0.2 μm filter, and 0.5 ml of the resulting curable composition set in a spin coater It was dripped on the substrate. The glass substrate was rotated at 500 rpm for 5 seconds, then rotated at 3000 rpm for 2 seconds, and further rotated at 5000 rpm for 20 seconds to form a thin film on the glass substrate. Under a nitrogen stream, the glass substrate coated with the curable composition was irradiated with ultraviolet rays. Reactive ion etching rate of CF ₄ gas and oxygen gas of the obtained cured thin film
It measured by the method shown below. The measurement results are shown in Table 1.

(Etching rate measurement method)
A small piece of glass was pasted 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, the step between the thin film portion protected by the glass piece and the etched thin film portion was measured, and the etching rate was calculated by the following equation.

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: 30 sec
(Oxygen gas)
Etching gas: Oxygen Pressure: 0.5Pa
Gas flow rate: 40sccm
Plasma voltage: 200W
Bias voltage: 20W
Processing time: 600 sec.

[Example 2]
To a three-necked flask equipped with a thermometer and a condenser tube, 3.0 g (2.94 mmol) of octakis (dimethylsilyloxy) silsesquioxane (manufactured by Toagosei Co., Ltd .: Q-2), 2.86 g of allyl methacrylate (22 0.7 mmol), 0.5597 g (0.88 mmol) of octavinylsilsesquioxane (manufactured by Aldrich: PSS-Octaviny Substituted), and 40 ml of toluene were added, and the mixture was stirred at room temperature under a stream of Ar. 0.0223 g of a 2% divinyltetramethyldisiloxane platinum complex xylene solution (manufactured by GELEST INC.) (The weight of platinum metal was 1000 ppm of the raw material charged) was added little by little. After stirring at room temperature for 2 hours, unreacted allyl methacrylate and the solvent were distilled off under reduced pressure to obtain the desired product. From the difference between the total mass of the raw materials and the mass of the target product obtained, it was found that 30% of allyl methacrylate was unreacted. The ratio of the cage silsesquioxane skeleton portion in the obtained target product was 28.7% by mass.

  The obtained target product was dissolved in propylene glycol monomethyl ether acetate so as to have a target product concentration of 5%.

The resulting solution was subjected to photo radical polymerization initiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173 Ciba Specialty Chemicals (
3 parts by mass with respect to 100 parts by mass of the target product was dissolved and then filtered through a 0.2 μm filter, and 0.5 ml of the resulting curable composition was set in a spin coater. It was dripped on the glass substrate. The glass substrate was rotated at 500 rpm for 5 seconds, then rotated at 3000 rpm for 2 seconds, and further rotated at 5000 rpm for 20 seconds to form a thin film on the glass substrate.

  Next, on the surface of the glass substrate (in the shape of a disk) on which the curable composition film was formed, the concavo-convex shape was patterned along the radial direction as shown in FIG. A mold (quartz glass disc) was placed with the patterned side down. The substrate on which the mold was placed was set in a UV nanoimprint press apparatus ST200 (manufactured by Toshiba Machine Co., Ltd.) and pressed. Next, the substrate on which the mold was placed was irradiated with ultraviolet light having a wavelength of 365 nm and an intensity of 6.5 mW. When the substrate on which the mold was placed was taken out of the press device, the mold was removed, and the coating on the glass substrate was observed, no defects in the coating such as missing patterns or uneven coating were observed. FIG. 3 shows a cross-sectional SEM measurement result of the substrate onto which the pattern was transferred. Further, the appearance of the surface of the coating on the glass substrate was observed with an optical surface analyzer (OSA). The results are shown in FIG.

[Reference Example 1]
In a three-necked flask equipped with a thermometer and a condenser tube, 1.0 g (0.98 mmol) of octakis (dimethylsilyloxy) silsesquioxane (manufactured by Toagosei Co., Ltd .: Q-2), 1.98 g of allyl methacrylate (15 0.7 mmol) and 30 ml of toluene were added, and the mixture was stirred at room temperature under an Ar stream. 0.093 g of a 2% divinyltetramethyldisiloxane platinum complex xylene solution (manufactured by GELEST INC.) (The weight of platinum metal was 1000 ppm of the raw material charged) was added little by little. After stirring at room temperature for 2 hours, unreacted allyl methacrylate and the solvent were distilled off under reduced pressure to obtain a product. The ratio of the cage silsesquioxane skeleton portion in the obtained product was 20.6% by mass.

  The obtained product was dissolved in propylene glycol monomethyl ether acetate to a product concentration of 10% by mass.

The resulting solution was subjected to photo radical polymerization initiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173 Ciba Specialty Chemicals (
3 parts by mass was added to 100 parts by mass of the product and dissolved, and then filtered through a 0.2 μm filter, and 0.5 ml of the resulting curable composition was set in a spin coater. It was dripped on the glass substrate. The glass substrate was rotated at 500 rpm for 5 seconds, then rotated at 3000 rpm for 2 seconds, and further rotated at 5000 rpm for 20 seconds to form a thin film on the glass substrate. Under a nitrogen stream, the glass substrate coated with the curable composition was irradiated with ultraviolet rays. The reactive ion etching rate by CF ₄ gas and oxygen gas of the obtained cured thin film was measured in the same manner as in Example 1. The measurement results are shown in Table 1. Further, in the same manner as in Example 2, the state of the surface of the coating film on the glass substrate was observed with an optical surface analyzer (OSA). The results are shown in FIG.

[Comparison between Examples 1 and 2 and Reference Example 1]
Both the curable compositions in Example 1 and Reference Example 1 were found to have a low etching rate with oxygen gas and high oxygen etching resistance. Further, the curable composition in Example 1 and Reference Example 1 together, CF ₄ fast etching rate by gas, easily was able to be peeled by etching with CF ₄ gas. In particular, with respect to oxygen etching resistance, which is important in processing, it was found that the curable composition in Example 1 was significantly more resistant to oxygen etching than the curable composition in Reference Example 1. . As mentioned above, it turned out that the curable composition in Example 1 can be used very suitably as a resist material.

  Further, when the appearance of the surface of the coating on the glass substrate was observed with an optical surface analyzer (OSA), the curable composition in Reference Example 1 showed fine unevenness of the injection molded resin stamper and film stamper used for UV nanoimprinting. Small irregularities other than the pattern were transferred, and it was not smooth (see FIG. 7). On the other hand, in the curable composition in Example 2, no fine unevenness of the injection-molded resin stamper and film stamper, and fine irregularities other than the pattern were observed (see FIG. 6). That is, it was suggested that by using the curable composition in Example 2, it is possible to suppress the transfer of fine unevenness and fine irregularities other than the pattern of the injection molded resin stamper and film stamper used for UV nanoimprint. .

[Example 3]
To a three-necked flask equipped with a thermometer and a condenser tube, 1.0 g (0.98 mmol) of octakis (dimethylsilyloxy) silsesquioxane (manufactured by Toagosei Co., Ltd .: Q-2), 0.86 g of allyl glycidyl ether (7 .56 mmol), octavinylsilsesquioxane (manufactured by Aldrich: 0.19 g (0.29 mmol) of PSS-Octaviny Substituted), and 10 ml of toluene were added and stirred at room temperature under an Ar stream. 0.011 g (platinum metal weight: 2.2 × 10 ⁻⁴ g) of 2% divinyltetramethyldisiloxane platinum complex xylene solution (manufactured by GELEST INC.) Was added little by little. After stirring at room temperature for 2 hours, unreacted allyl glycidyl ether and the solvent were distilled off under reduced pressure to obtain the desired product. From the difference between the total mass of the raw materials and the mass of the obtained target product, it was found that 30% of allyl glycidyl ether was unreacted. The ratio of the cage silsesquioxane skeleton part in the obtained target product was 26.0% by mass.

  The obtained target product was dissolved in propylene glycol monomethyl ether acetate so as to have a target product concentration of 10% by mass.

3 parts by mass of the photocationic polymerization initiator diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (CPI-101A manufactured by San Aapro Co., Ltd.) is added to 100 parts by mass of the target product and dissolved. Then, the mixture was 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. The glass substrate was rotated at 500 rpm for 5 seconds, then rotated at 3000 rpm for 2 seconds, and further rotated at 5000 rpm for 20 seconds to form a thin film on the glass substrate. Under a nitrogen stream, the glass substrate coated with the curable composition was irradiated with ultraviolet rays. The reactive ion etching rate by CF ₄ gas and oxygen gas of the obtained cured thin film was measured by the method shown below. The measurement results are shown in Table 1.

(Etching rate measurement method)
A small piece of glass was pasted 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, the step between the thin film portion protected by the glass piece and the etched thin film portion was measured, and the etching rate was calculated by the following equation.

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: 30 sec
(Oxygen gas)
Etching gas: Oxygen Pressure: 0.5Pa
Gas flow rate: 40sccm
Plasma voltage: 200W
Bias voltage: 20W
Processing time: 600 sec.

[Example 4]
To a three-necked flask equipped with a thermometer and a condenser tube, 1.0 g (0.98 mmol) of octakis (dimethylsilyloxy) silsesquioxane (manufactured by Toagosei Co., Ltd .: Q-2), 0.86 g of allyl glycidyl ether (7 .56 mmol), octavinylsilsesquioxane (manufactured by Aldrich: 0.19 g (0.29 mmol) of PSS-Octaviny Substituted), and 10 ml of toluene were added and stirred at room temperature under an Ar stream. 0.011 g (platinum metal weight: 2.2 × 10 ⁻⁴ g) of 2% divinyltetramethyldisiloxane platinum complex xylene solution (manufactured by GELEST INC.) Was added little by little. After stirring at room temperature for 2 hours, unreacted allyl glycidyl ether and the solvent were distilled off under reduced pressure to obtain the desired product. From the difference between the total mass of the raw materials and the mass of the obtained target product, it was found that 30% of allyl glycidyl ether was unreacted. The ratio of the cage silsesquioxane skeleton part in the obtained target product was 26.0% by mass.

  The obtained target product was dissolved in propylene glycol monomethyl ether acetate so as to have a target product concentration of 5%.

Photocationic polymerization initiator diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (CPI-101A, San Aapro Co., Ltd.) was added to the resulting solution.
3 parts by mass with respect to 100 parts by mass of the target product, dissolved, filtered through a 0.2 μm filter, and 0.5 ml of the resulting curable composition was dropped on a glass substrate set in a spin coater did. The glass substrate was rotated at 500 rpm for 5 seconds, then rotated at 3000 rpm for 2 seconds, and further rotated at 5000 rpm for 20 seconds to form a thin film on the glass substrate.

  Next, on the surface of the glass substrate (in the shape of a disk) on which the curable composition film was formed, the concavo-convex shape was patterned along the radial direction as shown in FIG. A mold (quartz glass disc) was placed with the patterned side down. The substrate on which the mold was placed was set in a UV nanoimprint press apparatus ST200 (manufactured by Toshiba Machine Co., Ltd.) and pressed. Next, the substrate on which the mold was placed was irradiated with ultraviolet light having a wavelength of 365 nm and an intensity of 6.5 mW. When the substrate on which the mold was placed was taken out of the press device, the mold was removed, and the coating on the glass substrate was observed, no defects in the coating such as missing patterns or uneven coating were observed. FIG. 8 shows a cross-sectional SEM measurement result of the substrate onto which the pattern was transferred. Further, the appearance of the surface of the coating on the glass substrate was observed with an optical surface analyzer (OSA). The results are shown in FIG.

[Reference Example 2]
In a three-necked flask equipped with a thermometer and a condenser tube, 1.0 g (0.98 mmol) of octakis (dimethylsilyloxy) silsesquioxane (manufactured by Toagosei Co., Ltd .: Q-2), 1.79 g of allyl glycidyl ether (15 0.7 mmol) and 10 ml of toluene were added, and the mixture was stirred at room temperature under an Ar stream. 0.011 g (weight of platinum metal: 2.2 × 10 ⁻⁴ ) of 2% divinyltetramethyldisiloxane platinum complex xylene solution (manufactured by GELEST INC.) Was added little by little. After stirring at room temperature for 2 hours, unreacted allyl glycidyl ether and the solvent were distilled off under reduced pressure to obtain a product. The ratio of the cage silsesquioxane skeleton portion in the obtained product was 21.6% by mass.

  The obtained product was dissolved in propylene glycol monomethyl ether acetate to a product concentration of 10% by mass.

3 parts by mass of a photocationic polymerization initiator diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (CPI-101A manufactured by San Aapro Co., Ltd.) is added to 100 parts by mass of the resulting solution and dissolved. Then, the mixture was 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. The glass substrate was rotated at 500 rpm for 5 seconds, then rotated at 3000 rpm for 2 seconds, and further rotated at 5000 rpm for 20 seconds to form a thin film on the glass substrate. Under a nitrogen stream, the glass substrate coated with the curable composition was irradiated with ultraviolet rays. The reactive ion etching rate by CF ₄ gas and oxygen gas of the obtained cured thin film was measured in the same manner as in Example 3. The measurement results are shown in Table 1.

  Further, the surface state of the coating film on the glass substrate was observed with an optical surface analyzer (OSA) in the same manner as in Example 4. The results are shown in FIG.

[Comparison between Examples 3 to 4 and Reference Example 2]
Both the curable compositions in Example 3 and Reference Example 2 were found to have a low etching rate with oxygen gas and high oxygen etching resistance. Further, the curable composition in Example 3 and Reference Example 2 are both, CF ₄ fast etching rate by gas, easily was able to be peeled by etching with CF ₄ gas. In particular, with respect to oxygen etching resistance, which is important in processing, it was found that the curable composition in Example 3 was significantly more resistant to oxygen etching than the curable composition in Reference Example 2. . As mentioned above, it turned out that the curable composition in Example 3 can be used very suitably as a resist material.

  Further, when the appearance of the surface of the coating on the glass substrate was observed with an optical surface analyzer (OSA), the curable composition in Reference Example 2 was found to have fine unevenness in the injection molded resin stamper and film stamper used for UV nanoimprinting. Fine irregularities other than the pattern were transferred, and the surface was not smooth (see FIG. 10). On the other hand, in the curable composition in Example 4, no fine unevenness of the injection-molded resin stamper and film stamper and fine irregularities other than the pattern were observed (see FIG. 9). In other words, it was suggested that by using the curable composition in Example 4, it is possible to suppress the transfer of fine irregularities other than the pattern and fine irregularities of the injection molded resin stamper and film stamper used for UV nanoimprint. .

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

Claims (16)

A cage silsesquioxane compound (A) having a Si-H bond-containing group represented by the following formula (1);
A compound (B) having a curable functional group and a carbon-carbon unsaturated bond-containing group other than the curable functional group;
A hydrosilylation reaction product obtained by reacting a caged silsesquioxane compound (C) having a carbon-carbon unsaturated bond-containing group represented by the following formula (2):
(In formula (1), R ² and R ³ each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and Y represents independently Represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and at least one of the eight Ys is a hydrogen atom.)
(In formula (2), each R ¹ independently represents —OSiR ² R ³ Z, —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , and at least one of the eight R ¹ is , —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , wherein Z is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. R ² and R ³ each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.) 2. The hydrosilylation reaction product according to claim 1, wherein the ratio of the cage silsesquioxane skeleton shown in the following (x) is in the range of 15 to 45 mass%.
The hydrosilylation reaction product according to claim 1 or 2, wherein the curable functional group of the compound (B) is an active energy ray-curable functional group.   The hydrosilylation reaction product according to claim 3, wherein the active energy ray-curable functional group is a (meth) acryloyloxy group or an epoxy group. The hydrosilylation reaction product according to claim 1 or 2, wherein the compound (B) is at least one selected from the group consisting of the following compound (a), compound (b) and compound (c);
(In the above compounds (a) to (c), R ⁴ — is a group represented by any of the following formulas (i) to (iv), and R ⁵ is a hydrogen atom or a methyl group.)
(In the formula (i), R ⁶ is a hydrogen atom or a methyl group. In the formula (ii), R ⁷ is a hydrogen atom or a methyl group. In the formula (iii), R ⁸ is a hydrogen atom or a methyl group. A methyl group, R ⁹
Is an alkylene group having 2 to 8 carbon atoms).   A curable composition for transfer materials, comprising the hydrosilylation reaction product according to claim 1 and a polymerization initiator or a curing agent.   The curable composition for transfer materials according to claim 6, wherein the curable functional group of the hydrosilylation reaction product according to claim 1 is an epoxy group, and the curing agent is an acid anhydride. .   The curable composition for transfer materials according to claim 6, further comprising a polythiol compound, wherein the curable functional group of the hydrosilylation reaction product according to any one of claims 1 to 5 is a (meth) acryloyloxy group. .   The curable composition for transfer materials according to claim 6, further comprising a compound having a vinyl ether group, wherein the curable functional group of the hydrosilylation reaction product according to claim 1 is an epoxy group. A method for producing a hydrosilylation reaction product according to claim 1,
A cage silsesquioxane compound (A) having a Si-H bond-containing group represented by the following formula (1);
A compound (B) having a curable functional group and a carbon-carbon unsaturated bond-containing group other than the curable functional group;
Hydrosilylation characterized by including the process of mixing with the cage silsesquioxane compound (C) which has a carbon-carbon unsaturated bond containing group represented by the following formula | equation (2), and carrying out a hydrosilylation reaction, A method for producing a reactant.
(In formula (1), R ² and R ³ each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and Y represents independently Represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and at least one of the eight Ys is a hydrogen atom.)
(In formula (2), each R ¹ independently represents —OSiR ² R ³ Z, —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , and at least one of the eight R ¹ is , —OSiR ² R ³ CH═CH ₂ or —CH═CH ₂ , wherein Z is independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. R ² and R ³ each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.) When the average number of moles of Si-H bonds of the compound (A) is A, and the average number of moles of carbon-carbon unsaturated bonds of the compound (B) and the compound (C) is B and C in this order ,
The method for producing a hydrosilylation reaction product according to claim 10, wherein A / (B + C) is in the range of 1/1 to 1/10 and B / C is in the range of 1 to 79. A method for producing a transfer layer having a concavo-convex pattern,
The curable composition for transfer materials by applying the hydrosilylation reaction product according to any one of claims 1 to 5 or the curable composition for transfer materials according to any one of claims 6 to 9 onto a substrate. Forming a layer;
A step of pressing a mold having a concavo-convex pattern onto the surface of the curable composition layer for transfer material;
And a step of curing the curable composition layer for a transfer material in a state where the mold is pressed to form a transfer layer. 13. The method for producing a transfer layer according to claim 12, wherein the step of curing the curable composition layer for transfer material is performed by heating and / or irradiation with active energy rays to the curable composition layer for transfer material. . Forming a transfer layer having a concavo-convex pattern on a substrate provided with a magnetic film on a substrate by the transfer layer manufacturing method according to claim 12 or 13,
Etching the concave and convex recesses formed in the transfer layer to expose a part of the surface of the magnetic film;
A step of removing the exposed portion of the magnetic film or demagnetizing the exposed portion of the magnetic film in this order using the transfer layer as a mask.   A magnetic recording medium obtained by the imprint method according to claim 14.   A magnetic recording / reproducing apparatus comprising the magnetic recording medium according to claim 15.