JP2006114882A - Pattern, forming method and article with pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern, forming method capable of continuously and accurately transcribing mold patterns on a substrate, and to provide an article with patterns transcribed accurately. <P>SOLUTION: The problem is solved by the pattern forming method that comprises a process for applying a hardening material containing a polymeric compound (A) with 40 to 70 mass% fluorine content and polymerization initiator (B) to a substrate 12, process to push a mold 14 with a concavo-convex pattern 13 formed pressing against the hardening material on the substrate 12, process for hardening the hardening material, and process for separating the mold 14 from a hardened object 16 of the hardening material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for forming a fine pattern and an article having a fine pattern.

  A technique for transferring a fine pattern of a mold to a transfer layer provided on a substrate, a so-called nanoimprint technique, is known as a technique for achieving both formation of a fine pattern of 50 μm or less and mass productivity in the manufacture of a semiconductor device. (See Patent Documents 1 to 5). As a technique for transferring a fine pattern with high dimensional accuracy, a nanoimprint technique at room temperature using an ultraviolet curable resin for a transfer layer is known (see Patent Documents 6 and 7).

  However, in the case of the nanoimprint technology using an ultraviolet curable resin for the transfer layer, the ultraviolet curable resin is in close contact with the mold, so that it is necessary to apply a fluorine or silicon release agent to the mold surface. It was. Further, it is difficult to accurately transfer the mold pattern due to the film thickness of the release agent itself, uneven application of the release agent, and the like. In addition, since a part of the mold release agent is peeled off from the mold and the mold release agent has a lifetime, it is difficult to transfer the pattern continuously and accurately during mass production.

US Pat. No. 5,772,905 JP 2000-323461 A JP 2003-155365 A US Pat. No. 6,482,742 US Pat. No. 6,719,915 US Pat. No. 6,696,220 JP 2004-71934 A

  An object of the present invention is to provide a pattern forming method capable of continuously and precisely transferring a mold pattern onto a substrate, and an article on which the mold pattern is accurately transferred.

  The pattern forming method of the present invention includes a step of applying a curable material containing a polymerizable compound (A) having a fluorine content of 40 to 70% by mass and a polymerization initiator (B) on a substrate, and a surface. Pressing the mold on which the pattern is formed against the curable material on the substrate so that the pattern is in contact with the curable material; curing the curable material while pressing the mold against the curable material; and curing. And a step of separating the mold from the cured product of the functional material.

  Moreover, the method for forming a pattern of the present invention includes a step of bringing a substrate and a mold having a pattern formed on the surface closer or in contact so that the pattern is on the substrate side, and a fluorine content of 40 to 70% by mass. A step of filling a curable material containing the polymerizable compound (A) and the polymerization initiator (B) between the substrate and the mold, and curing the curable material in a state in which the substrate and the mold are close to or in contact with each other. And a step of separating the mold from the cured product of the curable material.

In the pattern forming method of the present invention, a pattern was formed on the surface of a curable material containing a polymerizable compound (A) having a fluorine content of 40 to 70% by mass and a polymerization initiator (B). A step of applying on the pattern of the mold, a step of pressing the substrate against the curable material on the mold, a step of curing the curable material with the substrate pressed against the curable material, and a mold from a cured product of the curable material And a step of separating.
The polymerization initiator (B) is preferably a photopolymerization initiator.
The minimum dimension of the pattern is preferably 50 μm or less.

  The article of the present invention has a pattern formed by the pattern forming method of the present invention.

  According to the pattern forming method of the present invention, the pattern of the mold can be continuously and precisely transferred onto the substrate. Moreover, according to the pattern formation method of the present invention, an article having the pattern of the present invention, in which the mold pattern is precisely transferred, can be produced with high productivity.

  In the present invention, the monomer represented by the formula (1) is represented as monomer 1. Monomers represented by other formulas are represented similarly.

  For example, as shown in FIG. 1, the pattern forming method of the present invention includes a step of applying a curable material 11 on a substrate 12 (hereinafter referred to as an application step), and a surface as shown in FIG. A step of pressing the mold 14 on which the concavo-convex pattern 13 is formed against the curable material 11 on the substrate 12 so that the concavo-convex pattern 13 is in contact with the curable material 11 (hereinafter referred to as a mold pressing step); As shown in FIG. 3, a concavo-convex pattern 15 corresponding to the concavo-convex pattern 13 of the mold 14 is transferred as a step of curing the curable material 11 in a state where the curable material 11 is pressed against the curable material 11 (hereinafter referred to as a curing step). And a step of separating the mold 14 from the cured product 16 of the cured curable material (hereinafter referred to as a mold release step).

<Application process>
Examples of the method for applying the curable material 11 onto the substrate 12 include a potting method, a spin coating method, a roll coating method, a casting method, a dip coating method, a die coating method, a Langmuir projet method, and a vacuum deposition method.

  When the substrate 12 is larger than the mold 14, the curable material 11 may be applied to the entire surface of the substrate 12, or the curable material 11 is provided so that the curable material 11 exists only in a range where the mold 14 is embossed. It may be applied to a part of the substrate 12.

(substrate)
Examples of the substrate 12 include a substrate made of an inorganic material such as a silicon wafer, glass, quartz glass, and metal, and a substrate made of an organic material such as a fluorine resin, a silicone resin, an acrylic resin, and a polycarbonate resin. In order to improve the adhesion to the curable material 11, the substrate 12 may be subjected to a surface treatment such as a rough surface treatment, a silane coupling treatment, or a silazane treatment.

(Curable material)
The curable material 11 contains a polymerizable compound (A) having a fluorine content of 40 to 70% by mass and a polymerization initiator (B). If necessary, other polymerizable compounds (C), A photosensitizer (D) and a solvent (E) may further be contained.

  The polymerizable compound in the present invention is a compound having a polymerizable group such as a polymerizable unsaturated bond-containing group (hereinafter simply referred to as a polymerizable unsaturated group) or an epoxy group. As the polymerizable compound, a compound having a polymerizable unsaturated group is preferable. As the polymerizable unsaturated group, a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group is preferable. From the viewpoint of polymerizability, an acryloyl group or a methacryloyl group is particularly preferable. Moreover, the polymerizable unsaturated group may have a fluorine atom.

(Polymerizable compound (A))
The polymerizable compound (A) is a polymerizable compound having a fluorine content of 40 to 70% by mass. The fluorine content of the polymerizable compound (A) is preferably 45 to 65% by mass. By setting the fluorine content of the polymerizable compound (A) to 40% by mass or more, the curable material 11 (cured product 16) after curing does not adhere to the mold 14 and the releasability is improved. By setting the fluorine content of the polymerizable compound (A) to 70% by mass or less, compatibility with the polymerization initiator (B) is improved, and curing proceeds uniformly. The fluorine content in the present invention is a mass ratio of fluorine atoms to all atoms constituting the polymerizable compound (A).

  The polymerizable compound (A) in the present invention contains the following monomer 1, the following monomer 2, the following monomer 3, the following monomer 4, the following monomer 5, the following monomer 6, the following monomer 7, and a polymerizable unsaturated group. One or more selected from the group consisting of fluoroprepolymers are preferred.

However, the symbol in a formula shows the following meaning.
In monomer 1, R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a polyfluoroalkyl group having 1 to 3 carbon atoms, and Q ¹¹ Represents a single bond, a polyfluoroalkylene group having 1 to 20 carbon atoms, or a polyfluoroalkylene group containing an etheric oxygen atom having 1 to 20 carbon atoms, and X ¹¹ represents a bromine atom, an iodine atom, —CH ₂ OH. , —COOH, —COOCH ₃ , —COOM ¹ , —SO ₂ F, —SO ₃ H, —SO ₃ M ² , —CN, —CH ₂ OPO ₂ H, or —CH ₂ PO ₃ H ₂ (where M ¹ and M ² each independently represents an alkali metal), and z represents 0 or 1.

In monomer 2, R ²¹ , R ²² , and R ²³ each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a polyfluoroalkyl group having 1 to 3 carbon atoms, and Q ²¹ Represents a polyfluoroalkylene group which may contain a hydroxyl group having 1 to 20 carbon atoms, or a polyfluoroalkylene group containing an etheric oxygen atom which may contain a hydroxyl group having 1 to 20 carbon atoms, X ²¹ is a hydrogen atom, a fluorine _{atom, -CH 2 OH, -COOH, -COOCH} 3, -COOM 1, -SO 2 F, -SO 3 H, -SO 3 M 2, -CN, -CH 2 OPO 2 H Or —CH ₂ PO ₃ H ₂ (wherein M ¹ and M ² each independently represents an alkali metal).

In monomers 3 and 4, R ³¹ , R ³² , R ³³ , and R ³⁴ each independently represent a fluorine atom, a C 1-3 perfluoroalkyl group, or a C 1-3 perfluoroalkoxy group, R ⁴¹ and R ⁴² each independently represents a fluorine atom or a C 1-7 perfluoroalkyl group.

In monomer 5, R ⁵¹ and R ⁵² each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a polyfluoroalkyl group having 1 to 3 carbon atoms, and Q ⁵¹ represents polyfluoro An alkylene group and a polyfluoroalkylene group containing a hydroxyl group are represented.

In monomer 6, R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , and R ⁶⁶ each independently represent a hydrogen atom, a fluorine atom, a methyl group, or a polyfluoroalkyl group having 1 to 3 carbon atoms. , At least one is a fluorine atom. Q ⁶¹ and Q ⁶² each independently represent a single bond, an oxygen atom, a methylene group, a difluoromethylene group, an oxydifluoromethylene group, a fluorine atom, a C 1-3 perfluoroalkyl group or a C 1-3 perfluoro. Represents a methylene group substituted with an alkoxy group, R ⁶⁷ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a porfluoroalkyl group having 1 to 3 carbon atoms, and R ⁶⁸ represents a hydrogen atom. , A fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a polyfluoroalkyl group having 1 to 3 carbon atoms, a hydroxyl group, a sulfonyl group, a thiol group, a carboxyl group, and a functional group selected from an amino group. 6 polyfluoroalkyl groups are represented.

In monomer 7, Q ⁷¹ represents a fluorine-containing alkylene group which may have a ring structure.

The monomer 1, for _{example, CF 2 = CFOCF 2 CF 2} SO 2 F, CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF 2 SO 2 F, CF 2 = CFCOOH, CF 2 = CFO (CF 2) 3 _{COOCH 3, CF 2 = CFO (} CF 2) 3 CH 2 OH, CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF 2 CH 2 I , and the like.

As the monomer 2, for example, CH ₂ = CHCOO (CH ₂ ) ₂ (CF ₂ ) ₁₀ F, CH ₂ = CHCOO (CH ₂ ) ₂ (CF ₂ ) ₈ F, CH ₂ = CHCOO (CH ₂ ) ₂ (CF _{2) 6 F, CH 2 =} C (CH 3) COO (CH 2) 2 (CF 2) 10 F, CH 2 = C (CH 3) COO (CH 2) 2 (CF 2) 8 F, CH 2 = _{C (CH 3) COO (CH} 2) 2 (CF 2) 6 F, CH 2 = CHCOOCH 2 (CF 2) 6 F, CH 2 = C (CH 3) COOCH 2 (CF 2) 6 F, CH 2 = _{CHCOOCH 2 (CF 2) 7 F} , CH 2 = C (CH 3) COOCH 2 (CF 2) 7 F, CH 2 = CHCOOCH 2 CF 2 CF 2 H, CH 2 = CHCOOCH 2 (CF 2 CF 2) 2 H _{, CH 2 = CHCOOCH 2 (CF} 2 CF 2) 4 H, CH 2 = C (CH 3) COO _{H 2 (CF 2 CF 2)} H, CH 2 = C (CH 3) COOCH 2 (CF 2 CF 2) 2 H, CH 2 = C (CH 3) COOCH 2 (CF 2 CF 2) 4 H, CH 2 _{= CHCOOCH 2 CF 2 OCF 2 CF} 2 OCF 3, CH 2 = CHCOOCH 2 CF 2 O (CF 2 CF 2 O) 3 CF 3, CH 2 = C (CH 3) COOCH 2 CF 2 OCF 2 CF 2 OCF 3, _{CH 2 = C (CH 3)} COOCH 2 CF 2 O (CF 2 CF 2 O) 3 CF 3, CH 2 = CHCOOCH 2 CF (CF 3) OCF 2 CF (CF 3) O (CF 2) 3 F, CH _{2 = CHCOOCH 2 CF (CF 3} ) O (CF 2 CF (CF 3) O) 2 (CF 2) 3 F, CH 2 = C (CH 3) COOCH 2 CF (CF 3) OCF 2 CF (CF 3) O (CF ₂ ) ₃ F, CH ₂ ═C (CH ₃ ) COOCH ₂ CF (CF _{3) O (CF 2 CF (} CF 3) O) 2 (CF 2) 3 F, CH 2 = CFCOOCH 2 CH (OH) CH 2 (CF 2) 6 CF (CF 3) 2, CH 2 = CFCOOCH 2 CH _{(CH 2 OH) CH 2 (} CF 2) 6 CF (CF 3) 2, CH 2 = CFCOOCH 2 CH (OH) CH 2 (CF 2) 10 F, CH 2 = CFCOOCH 2 CH (CH 2 OH) CH 2 (CF ₂ ) ₁₀ F and the like.

  Examples of the monomers 3 and 4 include those represented by the following formula.

  Examples of the monomer 5 include those represented by the following formula.

  (However, k1 and k2 each independently represents an integer of 3 to 10.)

As the monomer 6, for _{example, CF 2 = CFCF 2 CF =} CF 2, CF 2 = CFOCF 2 CF = CF 2, CF 2 = CFOCF 2 CF 2 CF = CF 2, CF 2 = CFOCF (CF 3) CF 2 CF _{= CF 2, CF 2 = CFOCF} 2 CF (CF 3) CF = CF 2, CF 2 = CFOCF 2 OCF = CF 2, CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF = CF 2, CF 2 = CFCF ₂ C (OH) (CF ₃ ) CH ₂ CH═CH ₂ , CF ₂ = CFCF ₂ C (OH) (CF ₃ ) CH═CH ₂ , CF ₂ = CFCF ₂ C (CF ₃ ) (OCH ₂ OCH ₃ ) _{CH 2 CH = CH 2, CF} 2 = CFCH 2 C (C (CF 3) 2 OH) (CF 3) CH 2 CH = CH 2 and the like.

  Other preferable polymerizable compounds (A) include a polymerizable compound (A) composed of 2 to 20 repeating units obtained by polymerization of one or more monomers selected from the group consisting of monomers 1 to 7, and the following monomer 8 And fluoronorbornene.

  As the fluoro prepolymer having a polymerizable unsaturated group (hereinafter, also simply referred to as a fluoro prepolymer), a fluoro prepolymer having a (meth) acryloyl group or a fluoro prepolymer having a vinyl group is preferable. However, the (meth) acryloyl group means an acryloyl group or a methacryloyl group.

  The number average molecular weight of the fluoroprepolymer is preferably 500 to 50,000 from the viewpoint of curability.

  The fluoroprepolymer having a (meth) acryloyl group includes a fluoroprepolymer obtained by reacting a fluoropolymer obtained by copolymerization of a fluoromonomer and a monomer containing a hydroxyl group with a haloformate; an isocyanate group ( Examples thereof include a fluoroprepolymer obtained by reacting a monomer containing a (meth) acryloyl group.

  The fluoromonomer in the fluoroprepolymer is preferably at least one selected from the group consisting of the monomers 1 to 9 and other fluoromonomers. Examples of other fluoromonomer include polyfluoroolefin, chlorofluoroolefin, polyfluoro (alkenyl ether), polyfluorovinyl ester and the like.

Examples of the polyfluoroolefin include CF ₂ = CF ₂ , CF ₂ = CHF, CF ₂ = CH ₂ , CHF = CH ₂ , CF ₂ = CFCF ₃ , CH ₂ = CFCF ₃ , CH ₂ = CX ¹ R ^F1 ( R ^F1 represents a polyfluoroalkyl group having 1 to 8 carbon atoms, and X ¹ represents a hydrogen atom or a fluorine atom.) (CH ₂ ═CFCF ₂ CF ₃ , CH ₂ ═CF (CF ₂ ) ₄ H, CH ₂ = CHCF ₂ CF ₃ , CH ₂ = CH (CF ₂ ) ₄ F, etc.).

Examples of the chlorofluoroolefin include CF ₂ ═CFCl.

As polyfluoro (alkenyl ether), for example, CF ₂ ═CFOR ^F2 (R ^F2 represents a polyfluoroalkyl group which may contain an etheric oxygen atom having 1 to 8 carbon atoms.
), CF ₂ = CFO (CF ₂ ) ₃ F, CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₃ F, CF ₂ = CFOCH ₂ CF ₃ , CF ₂ = CFCF ₂ OR ^F3 (R ^F3 is Represents a polyfluoroalkyl group which may contain an etheric oxygen atom having 1 to 8 carbon atoms.) (CF ₂ = CFCF ₂ O (CF ₂ ) ₃ F etc.).

Examples of the polyfluorovinyl ester include CH ₂ ═CHOC (O) CF ₃ .

  Further, olefins such as ethylene and propylene, vinyl ethers, vinyl esters, allyl ethers, allyl esters, acrylic acids, methacrylic acids, and the like may be appropriately used as monomers.

  As the monomer containing a hydroxyl group in the fluoroprepolymer, a monomer containing a hydroxyl group described in the monomers 1 to 9 and a monomer containing another hydroxyl group (such as hydroxyl butyl vinyl ether) are preferable.

  As the haloformate in the fluoroprepolymer, polymerizable chloroformate (such as 2-chloroformylethyl methacrylate) is preferable.

(Polymerization initiator (B))
Examples of the polymerization initiator (B) include a photopolymerization initiator and a thermal polymerization initiator. In the present invention, since the dimensional accuracy of the obtained pattern is good, curing by a photopolymerization method is preferable. Therefore, a photopolymerization initiator is preferable as the polymerization initiator (B).

  The photopolymerization initiator causes a radical reaction or an ionic reaction by light, and a photopolymerization initiator that causes a radical reaction is preferable. Examples of the photopolymerization initiator include the following photopolymerization initiators.

  Acetophenone-based photopolymerization initiators: acetophenone, p-tert-butyltrichloroacetophenone, chloroacetophenone, 2,2-diethoxyacetophenone, hydroxyacetophenone, 2,2-dimethoxy-2′-phenylacetophenone, 2-aminoacetophenone, dialkyl Aminoacetophenone and the like.

  Benzoin-based photopolymerization initiators: benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-2-methyl Propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal and the like.

  Benzophenone photopolymerization initiators: benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxypropylbenzophenone, acrylic benzophenone, 4,4'-bis (dimethylamino) ) Benzophenone and the like.

  Thioxanthone photopolymerization initiators: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, diethylthioxanthone, dimethylthioxanthone, and the like.

  Photopolymerization initiators containing fluorine atoms: perfluoro (tert-butyl peroxide), perfluorobenzoyl peroxide and the like.

  Other photopolymerization initiators: α-acyloxime ester, benzyl- (o-ethoxycarbonyl) -α-monooxime, acylphosphine oxide, glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram Sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate and the like.

  When the polymerizable compound (A) in the present invention is a polymerizable compound having an epoxy group, a photoacid generator is used as the photopolymerization initiator. However, the photoacid generator is a compound that generates an acid by light. As the photoacid generator, an acid generator compound used in a normal chemically amplified resist composition can be employed. Specific examples of the photoacid generator include onium salts, diazoketone compounds, sulfone compounds, sulfonic acid compounds and the like.

  Specific examples of the onium salts include iodonium salts (diphenyliodonium triflate, bis (4-tert-butylphenyl) iodonium triflate, etc.), sulfonium salts (triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, 1 -(Naphthylacetomethyl) thioranium triflate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium triflate, dicyclohexyl (2-oxocyclohexyl) sulfonium triflate, etc.), phosphonium salts, diazonium salts, pyridinium salts and the like.

  The polymerization initiator (B) is preferably used in an amount of 0.05 parts by mass or more, based on a total of 100 parts by mass of the polymerizable compound (A) and the other polymerizable compound (C), and is 0.1 to 10 masses. It is particularly preferable to use parts. By setting it to 0.05 parts by mass or more, the curing proceeds sufficiently, and the polymerizable compound does not remain in the cured product, and by setting it to 10 parts by mass or less, the molecular weight of the cured product becomes sufficiently high, The mechanical properties of the resulting precision pattern are not impaired.

(Other polymerizable compound (C))
The other polymerizable compound (C) is a polymerizable compound containing no fluorine atom that can be copolymerized with the polymerizable compound (A), or a polymerizable compound having a fluorine content of less than 40% by mass.

Examples of the former polymerizable compound include the following compounds.
Hydrocarbon olefins: ethylene, propylene, butene, norbornene, etc.
Hydrocarbon diene: norbornadiene, butadiene and the like.
Hydrocarbon alkenyl ethers: cyclohexyl methyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, alkyl vinyl ethers such as ethyl vinyl ether, glycidyl vinyl ether, and the like.
Hydrocarbon vinyl ester: vinyl acetate, vinyl pivalate, etc.

  (Meth) acrylic acid derivatives: (meth) acrylic acid, aromatic (meth) acrylate [phenoxyethyl acrylate, benzyl acrylate, etc. ], Hydrocarbon-based (meth) acrylate [stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, allyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol di Acrylate, trimethylolpropane triacrylate, pentaaerythritol triacrylate, dipentaerythritol hexaacrylate and the like. ], Hydrocarbon-based (meth) acrylates containing etheric oxygen atoms [ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfryl acrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyoxyethylene glycol diacrylate , Tripropylene glycol diacrylate and the like. ], A hydrocarbon-based (meth) acrylate [2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N-vinyl pyrrolidone, dimethylaminoethyl methacrylate, etc. ], Silicone-based acrylates, and the like.

Other compounds: maleic anhydride, vinylene carbonate, etc.
However, (meth) acrylic acid means acrylic acid or methacrylic acid, and (meth) acrylate means acrylate or methacrylate.

  Examples of the latter polymerizable compound include the monomers 1 to 9 and the fluoroprepolymer having a fluorine content of less than 40% by mass.

  The ratio (mass ratio) between the other polymerizable compound (C) and the polymerizable compound (A) is preferably 0: 100 to 99.5: 0.5, and more preferably 0: 100 to 50:50. The ratio of the other polymerizable compound (C) and the polymerizable compound (A) is such that the average fluorine content of all the polymerizable compounds is 40 to 70% by mass, and the polymerizable compound (A ) And the other polymerizable compound (C) are preferably in such a ratio that the contact angle to water of a cured product is 75 degrees or more.

(Photosensitizer (D))
As the photosensitizer (D), n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzisoisouronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate , Amine compounds such as triethylenetetramine and 4,4′-bis (dialkylamino) benzophenone.

  The photosensitizer (D) is preferably 0 to 4 moles, more preferably 0 to 2 moles, relative to the polymerization initiator (B). By making the photosensitizer (D) 4 moles or less with respect to the polymerization initiator (B), the molecular weight of the cured product becomes sufficiently high, and the mechanical properties of the resulting precision pattern are not impaired. .

(Solvent (E))
A solvent (E) may be added to the curable material 11 as necessary. In the case of adding the solvent (E), it is necessary to evaporate the solvent (E) by heating after applying the curable material to the substrate before the next embossing step. As the solvent (E), a solvent having a boiling point of 100 ° C. to 200 ° C. that uniformly dissolves the curable material is preferable. Further, the heating temperature for evaporating the solvent (E) is preferably 50 ° C. to 200 ° C. depending on the solvent used.

  Examples of the solvent (E) include organic solvents containing no fluorine atom such as xylene and butyl acetate; perfluoro (2-butyltetrahydrofuran), methylperfluoroisopropylether, methyl (perfluorohexylmethyl) ether, methylperfluorooctylether, and the like. Examples include fluorine-containing organic solvents.

<Embossing process>
In the mold pressing step, the mold 14 having the uneven pattern 13 formed on the surface is pressed against the curable material 11 on the substrate 12.

  From the viewpoint of the viscosity of the curable material 11, the press pressure (gauge pressure) when pressing the mold 14 against the curable material 11 on the substrate 12 may be 10 MPa or less.

(mold)
Examples of the material of the mold 14 include materials that transmit light, that is, quartz glass, ultraviolet transmitting glass, sapphire, diamond, polydimethylsiloxane, and other silicon materials, fluororesin, and other light transmitting resin materials. Further, if the substrate 12 is a material that transmits light, the mold 14 may not transmit light. Examples of the material of the mold 14 that does not transmit light include a silicon wafer, a SiC substrate, and a mica substrate. Further, when the curable material 11 is cured by heating, the substrate 12 and the mold 14 do not need to transmit light.

  The shape of the uneven pattern 13 formed on the surface of the mold 14 is appropriately determined according to the article to be obtained.

  In the present invention, even if the minimum dimension of the concavo-convex pattern 13 is 50 μm or less, smaller is 500 nm or less, and even smaller is 50 nm or less, the fine pattern can be accurately transferred to the curable material 11. The minimum dimension of the concavo-convex pattern in the present invention is the minimum value of the height of the convex portion, the minimum value of the concave portion, the minimum value of the width of the convex portion or the concave portion, and the minimum value of the length of the convex portion or the concave portion. Of these, the smallest dimension is meant. In addition, the minimum of the minimum value is not specifically limited, 1 nm or more is preferable.

<Curing process>
The curing method is not particularly limited as long as it is a method for curing the curable material 11. According to the kind of the polymerization initiator (B) of the curable material 11, a method of curing the curable material 11 by heat and / or light irradiation is preferable. From the viewpoint of curing proceeding at a low temperature (0 to 60 ° C.) and a high reaction yield, a method of curing the curable material 11 by light irradiation using the photopolymerization initiator as the polymerization initiator (B) is particularly preferable. When curing is performed at a low temperature, there is an effect that volume change of the cured product due to temperature and coloring associated with curing are suppressed.

  As shown in FIG. 4, when the mold 14 is made of a material that transmits light, the light is irradiated from the mold 14 side. When the substrate 12 is made of a material that transmits light, the light is irradiated from the substrate 12 side. The method of irradiating light is mentioned.

  The light used for the light irradiation may be light that reacts with the photopolymerization initiator. From the viewpoint that the photopolymerization initiator easily reacts and the curable material can be cured at a lower temperature, light having a wavelength of 400 nm or less (active energy rays such as ultraviolet rays, X-rays, and γ rays) is preferable. From the viewpoint of operability, light having a wavelength of 200 to 400 nm is particularly preferable.

  Moreover, you may accelerate hardening of the curable material 11 by heating the whole at the time of light irradiation. The temperature range for heating is preferably 300 ° C. or lower, more preferably 0 to 60 ° C., and particularly preferably 25 to 50 ° C. In this temperature range, the accuracy of the pattern shape formed on the cured product is kept high. Further, the curable material 11 may be cured only by heating without performing light irradiation.

<Release process>
After the curing process, the mold 14 is cooled to around 25 ° C. or, when heated in the curing process, to about 25 ° C., and the mold 14 is separated from the cured product 16 of the curable material, thereby corresponding to the uneven pattern 13 of the mold 14. Thus, an article in which a precise uneven pattern 15 made of the cured curable material 11 is formed on the surface of the substrate 12 is obtained.

<Other forming methods>
The pattern forming method of the present invention is not particularly limited as long as the curable material is sandwiched between the pattern surface of the mold and the substrate, and the mold 14 and the curable material 11 are brought into contact with each other. Any method may be used as long as the uneven pattern 13 can be transferred to the curable material 11.

  As another forming method, for example, the step of bringing the substrate 12 and the mold 14 having the concave and convex pattern 13 formed on the surface so as to approach or contact so that the concave and convex pattern 13 is on the substrate 12 side, and the curable material 11 The step of filling the substrate 12 and the mold 14 by capillary action, suction, or the like, and the substrate 12 and the mold 14 approaching or contacting each other to irradiate the curable material 11 with light so that the curable material 11 is irradiated. The method of having the process to harden | cure and the process of isolate | separating the mold 14 from the hardened | cured material 16 of a curable material is mentioned.

  As another forming method, a step of applying the curable material 11 onto the concavo-convex pattern 13 of the mold 14 having the concavo-convex pattern 13 formed on the surface thereof by pouring or the like, and a curable material on the mold 14 with the substrate 12 are applied. 11, a step of irradiating the curable material 11 with light while the substrate 12 is pressed against the curable material 11, and curing the curable material 11; and a mold 14 is separated from the cured product 16 of the curable material. The method which has a process to do.

  According to the pattern forming method of the present invention, since the curable material 11 contains the polymerizable compound (A) having a fluorine content of 40 to 70% by mass, separation of the curable material 11 itself after curing is performed. The moldability is good, and it is not necessary to apply a release agent to the mold 14. Therefore, the uneven pattern 13 of the mold 14 can be accurately transferred to the curable material 11. Moreover, since it is not necessary to apply a mold release agent to the mold 14, the concave / convex pattern 13 can be transferred continuously, and an article having a pattern can be manufactured with high productivity. Furthermore, since the labor of applying a release agent to the mold 14 can be saved, the productivity of an article having a pattern is further improved. Furthermore, there is no pattern contamination by the release agent.

<Article with pattern>
The article having the pattern of the present invention is an article in which the cured product 16 on which the uneven pattern 15 is formed by the pattern forming method of the present invention is formed on the substrate 12. The cured product 16 can be excellent in physical properties such as heat resistance, chemical resistance, releasability, and optical properties (transparency and low refractive index).

  An article having the pattern of the present invention includes an optical element such as a microlens array, an optical waveguide, optical switching, a Fresnel zone plate, a binary optical element, a blazed optical element, and a photonic crystal; AR (Anti Reflection) coating member, biochip, μ -It is useful as a chip for TAS (Micro-Total Analysis Systems), a microreactor chip, a recording medium, a display material, a catalyst carrier, a filter, a sensor member, and the like.

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

(Synthesis example)
Synthesis of fluoro prepolymer 1:
58 g of isophorone diisocyanate, 39 g of 2-hydroxyethyl acrylate, 0.02 g of p-methoxyphenol and 0.005 g of dibutyltin dilaurate were placed in a 500 ml glass reaction vessel. Next, while the inside of the reaction vessel was well mixed, the reaction temperature was kept at 70 ° C. or lower to react to obtain a monomer containing an isocyanate group. Subsequently, 161 g of a fluoropolymer containing a hydroxyl group (manufactured by Asahi Glass Co., Ltd., trade name: Lumiflon LF-910LM) was added to the reaction vessel, and the reaction temperature was maintained at 80 to 90 ° C. while stirring well to dibutyltin dilaurate. Of 0.02 g was added. As a result of analyzing an infrared absorption spectrum of fluoroprepolymer 1 (fluorine content 41% by mass) (hereinafter referred to as polymerizable compound (A1)) obtained by purifying the contents of the reaction vessel, the disappearance of isocyanate groups, Formation of an acryloyl group was confirmed.

Example 1
In a clean room where ultraviolet rays are cut, in a 1.6 ml vial container, 0.1 g of the polymerizable compound (A1), 0.06 g of polyethylene glycol diacrylate, 0.03 g of trimethylolpropane triacrylate, and xylene 0.3 g was added. Next, 0.01 g of a photopolymerization initiator (trade name “Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed to obtain a photocurable material.

  The photocurable material is spin-coated on a silicon wafer, heated at 110 ° C. for 1 minute, and dried. A quartz mold in which a groove having a width of 400 nm, a depth of 100 nm, and a length of 5 mm shown in FIG. 5 is pressed against a photocurable material on a silicon wafer and pressed at 25 ° C. with a pressure of 2 MPa (gauge pressure). From the cured photocurable material, the photocurable material was irradiated with light from a high pressure mercury lamp (having main wavelengths of 255 nm, 315 nm, and 365 nm at 1.5 kHz to 2.0 kHz) for 30 seconds through the quartz mold. Separate the quartz mold slowly. On the silicon wafer, a convex pattern made of a cured photocurable material corresponding to the groove of the quartz mold is formed. The dimensions of the convex pattern (width (nm), height (nm)) and mold releasability are evaluated. The evaluation results are shown in Table 1. With regard to releasability, × when the mold cannot be separated from the photocurable material, Δ when the mold can be separated from the photocurable material by an operation such as ultrasonic wave, and Δ from the photocurable material without any special operation. The case where it can be separated is evaluated as ○.

(Example 2)
In a clean room where ultraviolet rays are cut, in a 1.6 ml vial container, 0.1 g of polymerizable compound (A1), 0.06 g of polyethylene glycol diacrylate, 0.03 g of trimethylolpropane triacrylate, n-butylamine Of 0.005 g and 0.3 g of xylene were added. Next, 0.01 g of a photopolymerization initiator (trade name “Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed to obtain a photocurable material. A convex pattern made of a cured photocurable material is formed on a silicon wafer in the same manner as in Example 1 except that the photocurable material is used. The dimensions of the convex pattern (width (nm), height (nm)) and mold releasability are evaluated. The evaluation results are shown in Table 1.

(Example 3)
In a clean room where ultraviolet rays are cut, a 6 ml vial container contains fluorine-containing diacrylate [CH ₂ ═CHCOO—CH ₂ —X—CH ₂ —COOCH═CH ₂ ; X is a perfluoro (1,4-cyclohexylene) group. To express. ] 0.3 g of CH ₂ ═CHCOOCH ₂ (CF ₂ ) ₆ F (fluorine content 55% by mass) and 0.15 g of trimethylolpropane triacrylate added. Next, a solution obtained by dissolving 0.05 g of a photopolymerization initiator (trade name “Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd.) in 0.2 g of butyl acetate was added and mixed, and a photocurable material was obtained. Obtained. A convex pattern made of a cured photocurable material is formed on a silicon wafer in the same manner as in Example 1 except that the photocurable material is used. The dimensions of the convex pattern (width (nm), height (nm)) and mold releasability are evaluated. The evaluation results are shown in Table 1.

Example 4
UV at cut within clean room, to a vial of 6 ml 1,1,2,3,3-pentafluoro-4-trifluoromethyl-4-methoxymethyloxy-1,6-heptadiene [CF ₂ = CFCF ₂ 0.95 g of a polymerizable compound (A3) (fluorine content 48% by mass) composed of C (CF ₃ ) (OCH ₂ OCH ₃ ) CH ₂ CH═CH ₂ ] was added. Next, 0.05 g of a photopolymerization initiator (trade name “Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed to obtain a photocurable material. A convex pattern made of a cured photocurable material is formed on a silicon wafer in the same manner as in Example 1 except that the photocurable material is used. The dimensions of the convex pattern (width (nm), height (nm)) and mold releasability are evaluated. The evaluation results are shown in Table 1.

(Comparative Example 1)
In a clean room where ultraviolet rays were cut, 0.07 g of hexanediol diacrylate and 0.03 g of pentaerythritol triacrylate were added to a 1.6 ml vial container. Next, 0.005 g of a photopolymerization initiator (1,1-dimethoxy-1-phenylacetophenone) was added and mixed to obtain a photocurable material. The photocurable material is cured in the same manner as in Example 1 except that the photocurable material is used. Attempts to separate the quartz mold from the cured photocurable material, but cannot separate.

(Comparative Example 2)
In a clean room where ultraviolet rays were cut, 0.07 g of hexanediol diacrylate and 0.03 g of pentaerythritol triacrylate were added to a 1.6 ml vial container. Next, 0.005 g of a photopolymerization initiator (1,1-dimethoxy-1-phenylacetophenone) was added and mixed to obtain a photocurable material. The photocurable material is dropped onto a silicon wafer. The surface of the same quartz mold as in Example 1 was previously treated with a fluorine-based silane coupling agent as a release agent, and the quartz mold was pressed against a photocurable material on a silicon wafer, and at 25 ° C., 2 MPa Press with pressure (gauge pressure). After irradiating the photocurable material with ultraviolet rays for 30 seconds through the quartz mold, the quartz mold is slowly separated from the cured photocurable material. On the silicon wafer, a convex pattern made of a cured photocurable material corresponding to the groove of the quartz mold is formed. The dimensions of the convex pattern (width (nm), height (nm)) and mold releasability are evaluated. The evaluation results are shown in Table 1.

(Comparative Example 3)
In a clean room where ultraviolet light was cut, 0.95 g of perfluorovinyl ether [CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ ] (fluorine content 71% by mass) was added to a 6 ml vial container. Next, 0.05 g of a photopolymerization initiator (trade name “Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed to obtain a photocurable material. However, Irgacure is hardly soluble and cannot be tested.

(Comparative Example 4)
In a clean room where ultraviolet light is cut, 0.95 g of methyl α-trifluoromethacrylate (fluorine content: 37% by mass) and 0.005 g of 1,1-dimethoxy-1-phenylacetophenone in a 1.6 ml vial container. Were mixed to obtain a photocurable material. The photocurable material is cured in the same manner as in Example 1 except that the photocurable material is used. Attempts to separate the quartz mold from the cured photocurable material, but cannot separate.

  In Examples 1 to 3 using a photocurable material containing a monomer having a fluorine content of 40 to 70% by mass, a convex pattern corresponding to the groove pattern of the quartz mold can be accurately transferred onto the silicon wafer.

  In Comparative Example 1 using a photocurable material that does not contain the polymerizable compound (A), since the release agent was not applied to the quartz mold, the quartz mold cannot be separated from the cured photocurable material.

  In Comparative Example 2 in which a photocurable material containing no polymerizable compound (A) was used and a release agent was applied to the quartz mold, the quartz mold could be separated from the cured photocurable material, but the convex pattern Cannot be accurately transferred onto a silicon wafer.

  The pattern forming method of the present invention includes optical elements (microlens array, optical waveguide, optical switching, Fresnel zone plate, binary optical element, blazed optical element, photonic crystal, etc.), AR coating member, biochip, and μ-TAS. It can be used in a manufacturing method of a chip, a microreactor chip, a recording medium, a display material, a catalyst carrier, a filter, a sensor member, and the like;

It is a schematic sectional drawing which shows a mode that the curable material was apply | coated on the board | substrate. It is a schematic sectional drawing which shows a mode that the mold was pressed on the curable material on a board | substrate. It is a schematic sectional drawing which shows a mode that the mold was isolate | separated from the hardened | cured curable material. It is a schematic sectional drawing which shows a mode that light is irradiated to a curable material in the state which pressed the mold against the curable material. It is a perspective view which shows the quartz mold used in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Curable material 12 Substrate 13 Uneven pattern 14 Mold 16 Cured material of curable material

Claims (6)

  A step of applying a curable material containing a polymerizable compound (A) having a fluorine content of 40 to 70% by mass and a polymerization initiator (B) on a substrate, and a mold having a pattern formed on the surface, Presses the curable material on the substrate so that it contacts the curable material, cures the curable material while pressing the mold against the curable material, and separates the mold from the cured curable material. And a pattern forming method.   A step of bringing a substrate and a mold having a pattern formed thereon into contact or contact so that the pattern is on the substrate side; a polymerizable compound (A) having a fluorine content of 40 to 70% by mass; and a polymerization initiator From the step of filling the curable material containing (B) between the substrate and the mold, the step of curing the curable material in a state where the substrate and the mold are close to or in contact with, and a cured product of the curable material. And a step of separating the mold.   A step of applying a curable material containing a polymerizable compound (A) having a fluorine content of 40 to 70% by mass and a polymerization initiator (B) onto a pattern of a mold having a pattern formed on the surface; A step of pressing the curable material on the mold, a step of curing the curable material with the substrate pressed against the curable material, and a step of separating the mold from a cured product of the curable material. Pattern forming method.   The pattern formation method according to any one of claims 1 to 3, wherein the polymerization initiator (B) is a photopolymerization initiator.   The pattern forming method according to claim 1, wherein a minimum dimension of the pattern is 50 μm or less. An article having a pattern formed by the pattern forming method according to any one of claims 1 to 5.

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