JP2011121182A - Nano-imprint pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method which can obtain a pattern with a superior shape. <P>SOLUTION: The pattern forming method includes a process (1) for applying a composition containing a resin and a solvent on a substrate, a process (2) in which the solvent is removed from a layer applied on the substrate to form a composition layer, a process (3) in which while the composition layer is immersed in water, the pattern surface of a mold is pressed on the composition layer to transfer the pattern of the mold, a process (4) for drying the composition layer with the pattern of the mold transferred, and a process (5) for making the obtained composition layer leave the mold. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a nanoimprint pattern forming method useful for forming a fine pattern.

Molded products with fine patterns include optical elements (microlens arrays, optical waveguides, optical switching, Fresnel zone plates, binary optical elements, blazed optical elements, photonic crystals, etc.), antireflection filters, biochips, microreactor chips, recording It is useful as a medium, display material, catalyst carrier and the like. In recent years, with the demand for miniaturization of devices and the like, further miniaturization of the pattern has been required.
As a method for producing a resin molded body having such a fine structure on the surface, a nanoimprint method for forming a fine pattern by transferring a pattern of a mold having a fine pattern onto a resin as a transfer layer has attracted attention. As this nanoimprint method, a thermal nanoimprint method (Patent Document 1) has been proposed.
The thermal nanoimprint method is a method in which a layer containing a thermoplastic resin is heated, and a mold having a pattern is pressed against the softened thermoplastic resin layer to form a pattern on the thermoplastic resin layer, and then the mold is removed from the thermoplastic resin layer. This is a method of forming a thermoplastic resin layer having a pattern by separating.

JP-T-2004-504718

  However, this pattern manufacturing method may not always satisfy the shape of the pattern obtained.

The present invention includes the following inventions.
[1] (1) A step of applying a composition containing a resin and a solvent on a substrate, (2) A step of forming a composition layer by removing the solvent from the layer applied on the substrate, (3) A composition layer A step of pressure-bonding the pattern surface of the mold to the composition layer while immersing in water, (4) a step of drying the composition layer to which the pattern of the mold has been transferred, and (5) The pattern formation method including the process of releasing the obtained composition layer from a mold.
[2] The pattern forming method according to [1], wherein the water temperature is 20 ° C to 90 ° C.
[3] The pattern forming method according to [1] or [2], wherein the resin is a resin having a hydroxyl group.

［式（Ｉ）中、
Ｒ^１は、水素原子、ハロゲン原子又はハロゲン原子を有してもよいＣ_1-6アルキル基を表す。
Ｒ^２は、ハロゲン原子、水酸基、Ｃ_1-6アルキル基、Ｃ_1-6アルコキシ基、Ｃ_2-4アシル基、Ｃ_2-4アシルオキシ基、Ｃ_1-6アルコキシカルボニル基又はＣ_1-6ヒドロキシアルキル基を表す。
ｍは０〜４の整数を表す。ｍが２以上の整数である場合、複数のＲ^２は同一の種類の基であっても異なる種類の基であってもよい。］ [4] The pattern forming method according to any one of [1] to [3], wherein the resin is a resin having a structural unit represented by the formula (I).

[In the formula (I),
R ¹ represents a hydrogen atom, a halogen atom or a C _1-6 alkyl group which may have a halogen atom.
R ² represents a halogen atom, a hydroxyl group, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _2-4 acyl group, a C _2-4 acyloxy group, a C _1-6 alkoxycarbonyl group, or a C _1-6 hydroxy group. Represents an alkyl group.
m represents an integer of 0 to 4. When m is an integer of 2 or more, the plurality of R ² may be the same type of group or different types of groups. ]

［式（ＩＩ）中、
Ｒ^３は、水素原子、ハロゲン原子又はハロゲン原子を有していてもよいＣ_1-6アルキル基を表す。
Ｒ^４は、ハロゲン原子、水酸基、Ｃ_1-6アルキル基、Ｃ_1-6アルコキシ基、Ｃ_2-4アシル基、Ｃ_2-4アシルオキシ基、Ｃ_1-6アルコキシカルボニル基又はＣ_1-6ヒドロキシアルキル基を表す。
ｎは０〜４の整数を表す。ｎが２以上の整数である場合、複数のＲ^４は同一の種類の基であっても異なる種類の基であってもよい。
Ｒ^５及びＲ^６はそれぞれ独立に、水素原子又はＣ_1-12炭化水素基を表す。
Ａ^１は、単結合又は置換基を有していてもよいＣ_1-17飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は−Ｏ−で置き換わっていてもよい。
Ｒ^７は、Ｃ_1-12脂肪族炭化水素基、Ｃ_3-18飽和環状炭化水素基又はＣ_6-18芳香族炭化水素基を表し、該脂肪族炭化水素基、飽和環状炭化水素基及び芳香族炭化水素基に含まれる水素原子は、Ｃ_1-6アルコキシ基又はフェニルオキシ基で置換されていてもよい。］ [5] The pattern forming method according to any one of [1] to [4], wherein the resin is a resin further having a structural unit represented by the formula (II).

[In the formula (II),
R ³ represents a hydrogen atom, a halogen atom or a C _1-6 alkyl group which may have a halogen atom.
R ⁴ represents a halogen atom, a hydroxyl group, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _2-4 acyl group, a C _2-4 acyloxy group, a C _1-6 alkoxycarbonyl group, or a C _1-6 hydroxy group. Represents an alkyl group.
n represents an integer of 0 to 4. When n is an integer of 2 or more, the plurality of R ⁴ may be the same type of group or different types of groups.
R ⁵ and R ⁶ each independently represents a hydrogen atom or a C _1-12 hydrocarbon group.
A ¹ represents a C _1-17 saturated hydrocarbon group which may have a single bond or a substituent, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O—.
R ⁷ represents a C _1-12 aliphatic hydrocarbon group, a C _3-18 saturated cyclic hydrocarbon group or a C _6-18 aromatic hydrocarbon group, and the aliphatic hydrocarbon group, saturated cyclic hydrocarbon group and aromatic The hydrogen atom contained in the group hydrocarbon group may be substituted with a C _1-6 alkoxy group or a phenyloxy group. ]

  According to the present invention, a pattern having an excellent shape can be obtained.

In the pattern forming method of the present invention, first, a composition containing a resin (hereinafter sometimes referred to as “resin (A)”) and a solvent (hereinafter sometimes referred to as “solvent (E)”) is prepared.
<Resin (A)>
The resin (A) used in the present invention is suitably one having a hydroxyl group.
As the resin having a hydroxyl group, a resin having a structural unit derived from a monomer having a phenolic hydroxyl group or a monomer having a hydroxyadamantyl group is preferable. Among these, a resin having a structural unit derived from a monomer having a phenolic hydroxyl group is more preferable.

  Examples of the structural unit derived from a monomer having a phenolic hydroxyl group include a structural unit derived from p- or m-hydroxystyrene represented by the formula (I).

［式（Ｉ）中、
Ｒ^１は、水素原子、ハロゲン原子又はハロゲン原子を有してもよいＣ_1-6アルキル基を表す。
Ｒ^２は、ハロゲン原子、水酸基、Ｃ_1-6アルキル基、Ｃ_1-6アルコキシ基、Ｃ_2-4アシル基、Ｃ_2-4アシルオキシ基、Ｃ_1-6アルコキシカルボニル基又はＣ_1-6ヒドロキシアルキル基を表す。
ｍは０〜４の整数を表す。ｍが２以上の整数である場合、複数のＲ^２は同一の種類の基であっても異なる種類の基であってもよい。］

[In the formula (I),
R ¹ represents a hydrogen atom, a halogen atom or a C _1-6 alkyl group which may have a halogen atom.
R ² represents a halogen atom, a hydroxyl group, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _2-4 acyl group, a C _2-4 acyloxy group, a C _1-6 alkoxycarbonyl group, or a C _1-6 hydroxy group. Represents an alkyl group.
m represents an integer of 0 to 4. When m is an integer of 2 or more, the plurality of R ² may be the same type of group or different types of groups. ]

In the present specification, examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
Examples of the alkyl group which may have a halogen atom include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoro sec-butyl, perfluoro tert-butyl, perfluoropentyl, perfluorohexyl groups and the like. .
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, and dodecyl groups.
Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-hexoxy group and the like.
Examples of the acyl group include acetyl, propionyl, butyryl and the like.
Examples of the acyloxy group include acetyloxy, propionyloxy, butyryloxy and the like.
Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl, n-hexoxy group and the like. Is mentioned.
Examples of the hydroxyalkyl group include hydroxymethyl, dihydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, trihydroxyethyl, hydroxybutyl, dihydroxybutyl, trihydroxybutyl, hydroxypentyl group and the like. .
In the present specification, unless otherwise specified, specific substituents to be described later can be applied to any chemical structural formula having the same substituents while appropriately selecting the number of carbon atoms. Those which can take any of linear, branched or cyclic are included unless otherwise specified, and in the same group, linear, branched or cyclic partial structures are mixed. May be. Furthermore, each substituent can be a monovalent or divalent substituent depending on the binding site.

In the structural unit of the formula (I), the alkyl group is preferably a C _1-4 alkyl group, more preferably a methyl or ethyl group, and particularly preferably a methyl group.
As the alkoxy group, a C _1-4 alkoxy group is preferable, a methoxy or ethoxy group is more preferable, and a methoxy group is particularly preferable.

A polymer having a structural unit derived from a monomer having such a phenolic hydroxyl group can be obtained, for example, by radically polymerizing acetoxystyrene and then deacetylating with an acid.
Examples of the monomer having a phenolic hydroxyl group include the following vinylphenol monomers.

  Of the above monomers, 4-hydroxystyrene or 4-hydroxy-α-methylstyrene is particularly preferred.

The resin used in the present invention is 10 mol% or more, preferably 15 to 95 mol% of the resin having the structural unit (I) derived from the monomer having a phenolic hydroxyl group, based on the structural units of all resins. A resin mainly composed of a structural unit derived from a monomer having a phenolic hydroxyl group and containing 20 to 90 mol% is preferable.
It is preferable that the structural unit (I) derived from the monomer having a phenolic hydroxyl group is 50% by mass or more because, for example, the adhesion between the substrate and the composition can be improved.

  Examples of the structural unit derived from a monomer having a hydroxyadamantyl group include a structural unit represented by the formula (III).

［式（III）中、
Ｒ^８は、水素原子又はメチル基を表す。
Ｒ^９及びＲ^１０は、それぞれ独立に、水素原子、メチル基又はヒドロキシ基を表す。
Ｌは、−Ｏ−又は−Ｏ−（ＣＨ₂）_ｋ−ＣＯ−Ｏ−を表し、ｋは１〜７の整数を表す。 ｔは、０〜１０の整数を表す。]

[In the formula (III),
R ⁸ represents a hydrogen atom or a methyl group.
R ⁹ and R ¹⁰ each independently represents a hydrogen atom, a methyl group or a hydroxy group.
L represents —O— or —O— (CH ₂ ) _k —CO—O—, and k represents an integer of 1 to 7. t represents an integer of 0 to 10. ]

In the formula (III), L is preferably —O—, —O— (CH ₂ ) _f —CO—O— (f is an integer of 1 to 4), more preferably —O—. -.
R ⁸ is preferably a methyl group.
R ⁹ is preferably a hydrogen atom.
R ¹⁰ is preferably a hydrogen atom or a hydroxy group.
t is preferably an integer of 0 to 3, more preferably 0 or 1.

  Examples of the monomer having a hydroxyadamantyl group include the following.

これらの中でも、３−ヒドロキシ−１−アダマンチル（メタ）アクリレート、３，５−ジヒドロキシ−１−アダマンチル（メタ）アクリレート及び（メタ）アクリル酸１−（３，５−ジヒドロキシ−１−アダマンチルオキシカルボニル）メチルが好ましい。特に、３−ヒドロキシ−１−アダマンチル（メタ）アクリレート及び３，５−ジヒドロキシ−１−アダマンチル（メタ）アクリレートがより好ましく、３−ヒドロキシ−１−アダマンチルメタクリレート及び３，５−ジヒドロキシ−１−アダマンチルメタクリレートがさらに好ましい。

Among these, 3-hydroxy-1-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate and (meth) acrylic acid 1- (3,5-dihydroxy-1-adamantyloxycarbonyl) Methyl is preferred. In particular, 3-hydroxy-1-adamantyl (meth) acrylate and 3,5-dihydroxy-1-adamantyl (meth) acrylate are more preferable, and 3-hydroxy-1-adamantyl methacrylate and 3,5-dihydroxy-1-adamantyl methacrylate are more preferable. Is more preferable.

［式（ＩＩ）中、
Ｒ^３は、水素原子、ハロゲン原子又はハロゲン原子を有してもよいＣ_１−６のアルキル基を表す。
Ｒ^４は、ハロゲン原子、水酸基、Ｃ_1-6アルキル基、Ｃ_1-6アルコキシ基、Ｃ_2-4アシル基、Ｃ_2-4アシルオキシ基、Ｃ_1-6アルコキシカルボニル基又はＣ_1-6ヒドロキシアルキル基を表す。
ｎは０〜４の整数を表す。ｎが２以上の整数である場合、複数のＲ^４は同一の種類の基であっても異なる種類の基であってもよい。
Ｒ^５及びＲ^６はそれぞれ独立に、水素原子又はＣ_1-12炭化水素基を表す。
Ａ^１は、単結合又は置換基を有していてもよいＣ_1-17飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は−Ｏ−で置き換わっていてもよい。
Ｒ^７は、Ｃ_1-12脂肪族炭化水素基、Ｃ_3-18飽和環状炭化水素基又はＣ_6-18芳香族炭化水素基を表し、該脂肪族炭化水素基、飽和環状炭化水素基及び芳香族炭化水素基に含まれる水素原子は、Ｃ_1-6アルコキシ基又はフェニルオキシ基で置換されていてもよい。］ Furthermore, the resin (A) may contain a structural unit derived from a monomer in which the hydroxyl group of vinylphenol is protected with an acetal.
Examples of the structural unit derived from the monomer in which the hydroxyl group of vinylphenol is protected with an acetal include the structural unit represented by the formula (II).

[In the formula (II),
R ³ represents a hydrogen atom, a halogen atom or a C _1-6 alkyl group which may have a halogen atom.
R ⁴ represents a halogen atom, a hydroxyl group, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _2-4 acyl group, a C _2-4 acyloxy group, a C _1-6 alkoxycarbonyl group, or a C _1-6 hydroxy group. Represents an alkyl group.
n represents an integer of 0 to 4. When n is an integer of 2 or more, the plurality of R ⁴ may be the same type of group or different types of groups.
R ⁵ and R ⁶ each independently represents a hydrogen atom or a C _1-12 hydrocarbon group.
A ¹ represents a C _1-17 saturated hydrocarbon group which may have a single bond or a substituent, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O—.
R ⁷ represents a C _1-12 aliphatic hydrocarbon group, a C _3-18 saturated cyclic hydrocarbon group or a C _6-18 aromatic hydrocarbon group, and the aliphatic hydrocarbon group, saturated cyclic hydrocarbon group and aromatic The hydrogen atom contained in the group hydrocarbon group may be substituted with a C _1-6 alkoxy group or a phenyloxy group. ]

芳香族炭化水素基としては、例えば、フェニル基、ナフチル基、アントラニル基、ｐ−メチルフェニル基、ｐ−ｔｅｒｔ−ブチルフェニル基、ｐ−アダマンチルフェニル基等が挙げられる。 Hydrocarbon groups include straight or branched, cyclic hydrocarbons and combinations thereof. For example, the alkyl group mentioned above; the alicyclic hydrocarbon mentioned later; 2-alkyl-2-adamantyl group, 1- (1-adamantyl) -1-alkyl group, etc. are mentioned.
Examples of the saturated hydrocarbon group include divalent groups including an alkylene group and a cycloalkylene group.
Examples of the alkylene group include a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, and a dodecamethylene group. , Tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptacamethylene group, ethylene group, propylene group, isopropylene group, sec-butylene group and tert-butylene group.
Examples of the divalent group containing a cycloalkylene group include the divalent groups of the groups exemplified as the following saturated cyclic hydrocarbon groups.
Examples of the aliphatic hydrocarbon group include the same alkyl groups as described above.
Examples of the saturated cyclic hydrocarbon group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, 1-adamantyl group, 2-adamantyl group, Examples thereof include alicyclic hydrocarbon groups such as isobornyl group and groups shown below.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthranyl group, a p-methylphenyl group, a p-tert-butylphenyl group, and a p-adamantylphenyl group.

In formula (II), the alkyl group is preferably a _C1-4 alkyl group, more preferably a methyl or ethyl group, and particularly preferably a methyl group.
As the alkoxy group, a C _1-4 alkoxy group is preferable, a methoxy or ethoxy group is more preferable, and a methoxy group is particularly preferable.
Examples of the substituent for A ¹ include a halogen atom, a hydroxyl group, a C _1-6 alkyl group, a C _1-6 alkoxy group, and the like.

  Examples of the monomer in which the hydroxyl group of vinylphenol is protected with acetal include the following monomers.

In the resin used in the present invention, the structural unit (I) derived from the monomer having the phenolic hydroxyl group described above and the monomer obtained by protecting the hydroxyl group of vinylphenol described above with an acetal with respect to the structural units of all resins. The resin having 50% by mass or more, preferably 55 to 95% by mass, and more preferably 60 to 90% by mass of the resin having the structural unit (II) to be formed may be used.
When the monomer having a phenolic hydroxyl group and the structural units (I) and (II) derived from the monomer in which the hydroxyl group of such a monomer is protected are 50% by mass or more, the adhesion is increased as described above. Because it can.

<Solvent (E)>
In the composition of the present invention, it is necessary for forming a pattern for uniformly applying the composition layer. The solvent (E) varies depending on the viscosity of the composition, but generally 10% by mass or more (preferably 20% by mass or more, more preferably 30% by mass or more), 99% by mass or less (preferably in the composition). It is suitable that it is contained in 98% by mass or less.
The content of the solvent (E) can be measured by a known analysis means such as liquid chromatography or gas chromatography.

  Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and And esters such as ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; A solvent (E) may be used individually by 1 type, and may use 2 or more types together.

  The composition of the present invention may contain other components as required. Such components are not particularly limited, and additives known in the nanoimprint field, such as polymerizable compounds, mold release agents, silane coupling agents, polymerization inhibitors, antioxidants, ultraviolet absorbers, light Stabilizer, anti-aging agent, plasticizer, adhesion promoter, thermal polymerization initiator, colorant, inorganic particles, elastomer particles, photoacid breeder, photobase generator, basic compound, flow regulator, antifoaming agent, Examples thereof include a dispersant, a dissolution inhibitor, a surfactant, a stabilizer, and a dye.

<Pattern formation method>
The pattern forming method of the present invention comprises:
(1) The process of apply | coating the composition containing resin and a solvent on a board | substrate,
(2) a step of removing the solvent from the layer applied on the substrate to form a composition layer;
(3) a step of transferring the pattern of the mold by pressing the pattern surface of the mold onto the composition layer while immersing the composition layer in water;
(4) drying the composition layer to which the pattern of the mold has been transferred, and
(5) including a step of releasing the dried composition layer from the mold.

  The substrate to which the composition is applied is not particularly limited, for example, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, Polymer substrate such as paper, SOG, polyester film, polycarbonate film, polyimide film or transparent plastic substrate, TFT array substrate, PDP electrode plate, glass substrate, conductive substrate such as ITO or metal, insulating substrate, silicon, Examples include semiconductor fabrication substrates such as silicon nitride, polysilicon, silicon oxide, and amorphous silicon. The shape of the substrate is not particularly limited, and examples thereof include a plate shape and a roll shape.

Application of the composition onto the substrate is usually performed by, for example, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, slit scanning, etc. This can be done depending on the equipment used.
Application of the composition onto the substrate may be performed once (single layer) or multiple times.
Although the film thickness of a composition layer changes with uses to be used, 0.05 micrometer-30 micrometers are illustrated.

The solvent can be removed, for example, by evaporating the solvent using a heating device such as a hot plate or using a decompression device. Thereby, the composition layer from which the solvent has been removed can be formed. As for the temperature in this case, about 50-200 degreeC is illustrated, for example. The pressure is exemplified by about 1 to 1.0 × 10 ⁵ Pa.

The obtained composition layer is immersed in water. In this case, for example, it is suitable to immerse in water at 20 ° C. to 90 ° C., and simultaneously with the immersion, the pattern surface of the mold is pressure-bonded to the composition layer to transfer the pattern of the mold.
As the mold used at this time, a mold having a pattern to be transferred is used.
The mold has a pattern formed in advance according to the desired processing accuracy, for example, by photolithography, electron beam drawing, or the like. A mold that has been subjected to a release treatment in order to improve the peelability between the composition layer and the mold may be used.
The pressing of the mold is preferably performed at 10 atm or less. In addition, the pressure bonding time is, for example, about several seconds to several tens of minutes.

After transferring the pattern of the mold, the composition layer to which the pattern is transferred is dried. Drying is suitably performed at a temperature of about 50 to 200 ° C. and a pressure of about 1 to 1.0 × 10 ⁵ Pa, for example.
Thereafter, the pattern can be formed by releasing the dried composition layer from the mold.
The drying is suitably performed before the composition layer is released from the mold, but may be performed after the composition layer is released from the mold.

Hereinafter, the pattern forming method of the present invention will be described in detail with reference to examples.
In Examples and Comparative Examples, “%” and “part” representing content and use amount are based on mass unless otherwise specified.
The weight average molecular weight is a value obtained by gel permeation chromatography (HLC-8120GPC type, manufactured by Tosoh Corporation, three columns are “TSKgel Multipore HXL-M”, and the solvent is tetrahydrofuran) using polystyrene as a standard product. is there.
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

Examples and Comparative Examples Each component shown in Table 1 was mixed and dissolved in 40 parts of a solvent, and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a composition. Each composition was evaluated as follows.

[solvent]
Propylene glycol monomethyl ether acetate 25 parts Propylene glycol monomethyl ether 14 parts γ-butyrolactone 1 part

[Resin A1: Polyvinylphenol polymer]
A1: Mw = 20000 Mw / Mn = 1.20

[Resin A2: Polyvinylphenol-based polymer]
A2: Mw = 12000 Mw / Mn = 1.65

[Resin A3: Polyvinylphenol polymer]
A3: Mw = 12000 Mw / Mn = 1.78

[Resin A4: Polyvinylphenol-based polymer]
A4: Mw = 12000 Mw / Mn = 1.68

[Resin A5: Polyvinylphenol polymer]
A5: Mw = 15000 Mw / Mn = 1.18

[Resin A6: Hydroxyadamantyl polymer]
A6: Mw = 8000 Mw / Mn = 1.54

(Indenter pattern shape evaluation 1)
A 2-inch square glass substrate (# 1737; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On the glass substrate, the above composition was spin-coated so that the film thickness after drying was the film thickness shown in the film thickness column of Table 1.
After coating the composition, it was pre-baked on a direct hot plate at the temperature shown in Table 1 for 90 seconds to form a composition layer.
In the state where the surface of the obtained glass substrate was immersed in water, it was installed in a dynamic ultra-micro hardness tester (DUH-W201; manufactured by Shimadzu Corporation), and the temperature of water was kept at 70 ° C. The cone indenter was pressed against the composition layer with a force of 5 mN for 5 seconds to transfer the pattern.
Then, water was removed and the glass substrate was dried.
Subsequently, the indenter was detached from the composition layer.
The shape of the pressure-bonded part of the indenter in the composition layer was observed.
The case where the shape of the indenter was reflected up to the glass substrate portion was evaluated as “◯”, and the case where a residue was observed on the glass substrate or the case where the shape of the indenter was not reflected was evaluated as “x”.
The results are shown in Table 2.

(Pencil hardness 1 and 2)
A 2-inch square glass substrate (# 1737; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On the glass substrate, the above composition was spin-coated so that the film thickness after drying was the film thickness shown in the film thickness column of Table 1.
After application of the composition, it was pre-baked on a direct hot plate at the temperature shown in Table 1 for 90 seconds to form a composition layer.
With the water kept at the temperature shown in the water immersion temperature column of Table 1, the pencil hardness 1 of the composition layer on the obtained glass substrate was measured.
Then, after removing water and drying, pencil hardness 2 was measured.
These results are shown in Table 2.

(Mold pattern shape evaluation 2)
First, a mold used for this evaluation was formed.
Synthesis of ethyl etherified poly (p-vinylphenol) resin 400 g of poly (p-vinylphenol) [Linker M (manufactured by Maruzen Petrochemical); weight average molecular weight 4900] was dissolved in 2 liters of acetone. Thereafter, 250 g of potassium carbonate and 84 g of ethyl iodide were added, and the mixture was heated to reflux for 10 hours. The reaction mixture was filtered and the resulting filtrate was poured into 10 liters of water. The resulting precipitate was dissolved by adding 2 liters of ethyl acetate, and the resulting solution was washed with 1 liter of 5% oxalic acid water. The organic layer was washed with water until the washing solution became neutral, and the solvent was distilled off under reduced pressure. The concentrated residue was dissolved in 1 liter of acetone and poured into 10 liters of water. The precipitate was filtered and dried to obtain partially ethyl etherified poly (p-vinylphenol).
^The ethyl etherification rate determined by ¹ H-NMR was 16 mol%.
13.5 parts of partially ethyl etherified poly (p-vinylphenol) obtained by synthesis of ethyl etherified poly (p-vinylphenol) resin, 1.0 part of hexamethylol melamine hexamethyl ether and 3.0 parts of N-hydroxysuccinimidopropyl sulfonic acid ester was dissolved in 48 parts of diethylene glycol dimethyl ether. This solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.1 μm to prepare a resin composition.
This resin composition was applied to a glass wafer washed by a conventional method to a thickness of 2.0 μm using a spin coater.
Next, the glass wafer was pre-baked on a hot plate at 100 ° C. for 1 minute.
After pre-baking, the coating film was irradiated with a scanning electron beam at an acceleration voltage of 50 KeV.
After irradiation, the glass wafer was heated on a hot plate at 90 ° C. for 1 minute to form a latent image.
This was developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide for 1 minute to form line patterns of 0.50 μm and 1.00 μm on the glass wafer. The portions where the line patterns of 0.50 μm or 1.00 μm were obtained were cut to obtain molds to be used later.

A 2-inch square glass substrate (# 1737; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On the glass substrate, the composition was spin-coated so that the film thickness after drying was the film thickness shown in the film thickness column of Table 1.
After coating the composition, it was pre-baked on a direct hot plate at the temperature shown in Table 1 for 90 seconds to form a composition layer.
In the state immersed in the water of 70 degreeC to the obtained glass substrate, the mold created previously was crimped | bonded and the mold pattern was transcribe | transferred.
Subsequently, water was removed and the mold was dried while the mold was pressed.
Subsequently, by removing the mold from the composition layer, a 0.50 μm or 1.00 μm extraction pattern was formed.
A punched pattern of 0.50 μm or 1.00 μm was observed with a scanning electron microscope.
A case where a pattern in which the shape of the mold was satisfactorily reflected was formed was judged as ◯, a case where the mold shape was not reflected, and a case where the pattern was cracked was judged as x.
The results are shown in Table 3.

  According to the present invention, an optical element (microlens array, optical waveguide, optical switching, Fresnel zone plate, binary optical element, blaze optical element, photonics crystal, etc.), antireflection filter, biochip, microreactor chip, recording medium, The present invention can be widely applied to compacts intended for fine patterns with excellent shapes, such as display materials and catalyst carriers.

Claims (5)

(1) The process of apply | coating the composition containing resin and a solvent on a board | substrate,
(2) a step of removing the solvent from the layer applied on the substrate to form a composition layer;
(3) a step of transferring the pattern of the mold by pressing the pattern surface of the mold onto the composition layer while immersing the composition layer in water;
(4) drying the composition layer to which the pattern of the mold has been transferred, and
(5) A pattern forming method including a step of releasing the obtained composition layer from the mold.   The pattern forming method according to claim 1, wherein the temperature of the water is 20 ° C. to 90 ° C.   The pattern forming method according to claim 1, wherein the resin is a resin having a hydroxyl group. The pattern forming method according to claim 1, wherein the resin is a resin having a structural unit represented by the formula (I).

[In the formula (I),
R ¹ represents a hydrogen atom, a halogen atom or a C _1-6 alkyl group which may have a halogen atom.
R ² represents a halogen atom, a hydroxyl group, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _2-4 acyl group, a C _2-4 acyloxy group, a C _1-6 alkoxycarbonyl group, or a C _1-6 hydroxy group. Represents an alkyl group.
m represents an integer of 0 to 4. When m is an integer of 2 or more, the plurality of R ² may be the same type of group or different types of groups. ] The pattern forming method according to claim 1, wherein the resin is a resin further having a structural unit represented by the formula (II).

[In the formula (II),
R ³ represents a hydrogen atom, a halogen atom or a C _1-6 alkyl group which may have a halogen atom.
R ⁴ represents a halogen atom, a hydroxyl group, a C _1-6 alkyl group, a C _1-6 alkoxy group, a C _2-4 acyl group, a C _2-4 acyloxy group, a C _1-6 alkoxycarbonyl group, or a C _1-6 hydroxy group. Represents an alkyl group.
n represents an integer of 0 to 4. When n is an integer of 2 or more, the plurality of R ⁴ may be the same type of group or different types of groups.
R ⁵ and R ⁶ each independently represents a hydrogen atom or a C _1-12 hydrocarbon group.
A ¹ represents a C _1-17 saturated hydrocarbon group which may have a single bond or a substituent, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O—.
R ⁷ represents a C _1-12 aliphatic hydrocarbon group, a C _3-18 saturated cyclic hydrocarbon group or a C _6-18 aromatic hydrocarbon group, and the aliphatic hydrocarbon group, saturated cyclic hydrocarbon group and aromatic The hydrogen atom contained in the group hydrocarbon group may be substituted with a C _1-6 alkoxy group or a phenyloxy group. ]