KR20170021746A - Curable composition, method for forming pattern and method for producing device - Google Patents

Abstract

A curable composition which is excellent in ink jet discharge property and can form a pattern having excellent strength and etching resistance, a pattern forming method, and a manufacturing method of a device. The curable composition comprises a (meth) acrylate monomer A1 and a bifunctional or more (meth) acrylate monomer A2 having at least one structure selected from an aliphatic condensed ring structure, an aliphatic crosslinked ring structure and an aliphatic crosslinked condensed ring structure, , A trifunctional or more (meth) acrylate monomer A3 and a photopolymerization initiator, wherein the total mass of A1, A2 and A3 is 70 mass% or more of the total mass of the curable composition, A1 Is contained in an amount of from 5 to 65 parts by mass based on 100 parts by mass of A2, and the viscosity of the curable composition at 23 캜 is 25 mPa · s or less.

Description

Technical Field [0001] The present invention relates to a curable composition, a pattern forming method, and a device manufacturing method,

The present invention relates to a curable composition, a pattern forming method and a device manufacturing method.

The imprint method develops an embossing technique known in the manufacture of an optical disc, and is a technique for precisely transferring a fine pattern of a mold (generally called a stamper or a template) having a concavo-convex pattern formed thereon. When a mold is once fabricated, the microstructure such as a nanostructure can be simply and repeatedly molded, which is economical, and application in various fields is expected in recent years.

As the imprint method, for example, an optical imprint method using a photo-curable composition has been proposed. The optical imprint method is a method of transferring a fine pattern to a light cured product by curing the photo-curable composition by irradiating light through a light-transmissive mold or a light-transmissible substrate and then peeling the mold. This method can be imprinted at room temperature, and therefore, application to the formation of a high-density semiconductor integrated circuit, a transistor of a liquid crystal display, a protective film, and the like is attempted.

Patent Document 1 describes that imprinting is carried out by using a curable composition comprising a (meth) acrylate monomer and / or an oligomer containing a cyclic structure and a photopolymerization initiator.

Patent Document 2 discloses imprinting using a curable composition comprising a copolymer of a specific vinyl compound, a compound having at least one acryloyloxy group or methacryloyloxy group, and a photopolymerization initiator.

Japanese Patent Application Laid-Open No. 2007-186570 Japanese Patent Application Laid-Open No. 2010-206189

As a method of applying the curable composition for imprint on a substrate or a mold, there is an inkjet method. The inkjet method has an advantage of being able to reduce the thickness irregularity of the remaining film and to improve the pattern transfer property in the etching process because the coating amount of the curable composition can be adjusted in accordance with the density of the pattern. Further, as compared with the spin coating method, the utilization efficiency of the material is high, and there is also an advantage of reducing the production cost and reducing the environmental load.

There is also a method in which a substrate is etched using a pattern formed by the imprint method as a mask. When a pattern formed by the imprint method is applied to such a use, there is a demand for a composition capable of forming a pattern having good etching resistance and excellent strength.

Thus, in recent years, it has been desired to develop a composition capable of forming a pattern having good ink-jet discharge property and excellent in etching resistance and strength, in the curable composition for imprint.

The inventors of the present invention have studied the curable compositions described in Patent Documents 1 and 2, and found that it is difficult to link the inkjet ejectability of the curable composition with the etching resistance and strength of the pattern.

Accordingly, an object of the present invention is to provide a curable composition, a pattern forming method, and a device manufacturing method which can form a pattern having good ink-jet dischargeability and excellent etching resistance and strength.

Based on such a situation, the inventors of the present invention have conducted intensive studies and have found that (A) a monofunctional (meth) acrylate monomer A1 and at least one structure selected from an aliphatic condensed ring structure, an aliphatic crosslinked ring structure and an aliphatic crosslinked condensed ring structure (Meth) acrylate monomer A2 having a bifunctionality or more and a trifunctional or more (meth) acrylate monomer A3 at a specific ratio described below, and having a viscosity at 25 DEG C of 25 mPa.s or less at 23 DEG C The present invention has been accomplished on the basis of the finding that the above object can be achieved by using the above- The present invention provides the following.

(1) a monofunctional (meth) acrylate monomer A1,

(Meth) acrylate monomer A2 having at least one structure selected from an aliphatic condensed ring structure, an aliphatic crosslinked ring structure and an aliphatic crosslinked condensed ring structure,

(Meth) acrylate monomer A2, a trifunctional or more (meth) acrylate monomer A3 and a polyfunctional (meth)

Photopolymerization initiator

Wherein the curable composition is a curable composition,

(Meth) acrylate monomer A1, the (meth) acrylate monomer A2, and the (meth) acrylate monomer A3 is at least 70 mass% of the total mass of the curable composition,

(Meth) acrylate monomer A2 is contained in an amount of 40 to 130 parts by mass relative to 100 parts by mass of the (meth) acrylate monomer A2,

(Meth) acrylate monomer A3 is contained in an amount of 5 to 65 parts by mass relative to 100 parts by mass of the (meth) acrylate monomer A2,

Wherein the curable composition has a viscosity at 23 캜 of 25 mPa s or less.

<2> The curable composition according to <1>, which contains 40 to 100 parts by mass of (meth) acrylate monomer A1 relative to 100 parts by mass of the (meth) acrylate monomer A2.

<3> The curable composition according to <1> or <2>, which contains 5 to 30 parts by mass of (meth) acrylate monomer A3 relative to 100 parts by mass of the (meth) acrylate monomer A2.

<4> The curable composition according to any one of <1> to <3>, wherein the (meth) acrylate monomer A2 contains 30 to 60 mass% of the total mass of the curable composition.

<5> The curable composition according to any one of <1> to <4>, wherein the (meth) acrylate monomer A1 comprises a monofunctional (meth) acrylate monomer having a cyclic structure.

<6> The (meth) acrylate monomer A1 is a monomer having a cyclic structure in which a monofunctional (meth) acrylate monomer is contained in an amount of 50 to 100 mass% based on the total mass of the (meth) acrylate monomer A1 The curable composition according to any one of < 5 > to < 5 >.

<7> The curable composition according to any one of <1> to <6>, wherein the (meth) acrylate monomer A2 has at least one structure selected from an aliphatic crosslinked ring structure and an aliphatic crosslinked condensed ring structure.

<8> The curable composition according to any one of <1> to <7>, wherein the (meth) acrylate monomer A2 has an aliphatic crosslinked condensed ring structure.

<9> The curable composition according to any one of <1> to <8>, wherein the (meth) acrylate monomer A2 has an aliphatic crosslinked condensed ring structure including a bicyclo ring or a tricyclo ring.

<10> The positive resist composition according to any one of <1> to <10>, wherein the (meth) acrylate monomer A2 is at least one selected from tricyclodecane dimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate and dicyclopentenyl (meth) The curable composition according to any one of &lt; 1 &gt; to &lt; 9 &gt;.

<11> The curable composition according to any one of <1> to <10>, wherein the (meth) acrylate monomer A3 is a chain aliphatic (meth) acrylate monomer.

<12> The curable composition according to any one of <1> to <11>, further comprising a release agent.

<13> The curable composition according to <12>, wherein the mold release agent is a silicone oil.

<14> The curable composition according to any one of <1> to <13>, which is for an ink jet.

<15> The curable composition according to any one of <1> to <14>, which is for imprinting.

<16> A process for producing a curable composition, comprising the steps of: applying the curable composition according to any one of <1> to <15> on a mold having a substrate or pattern; holding the curable composition between the mold and the substrate; A step of curing the curable composition by irradiating light in a state sandwiched between the mold and the substrate, and a step of peeling the mold.

<17> A pattern forming method according to <16>, wherein the curable composition is applied onto a substrate or a mold having a pattern by an inkjet method.

<18> A method of manufacturing a device, comprising: forming a pattern on a substrate by a pattern forming method according to <16> or <17>; and etching the substrate using the formed pattern as a mask.

According to the present invention, it becomes possible to provide a curable composition, a pattern forming method, and a manufacturing method of a device which can form a pattern having good ink jet dischargeability and excellent etching resistance and strength.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

In the present specification, &quot; &quot; is used to mean that the numerical values described before and after the lower limit and the upper limit are included.

In the present specification, the term "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acryl" refers to acrylic and methacryl, "(meth) acryloyl" And methacryloyl.

In the present specification, the term &quot; imprint &quot; refers to pattern transfer of a size of 1 nm to 10 mm, and more preferably, pattern transfer of a size of 10 nm to 100 m (nanoimprint).

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes a group having a substituent and a group having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, the term &quot; light &quot; includes not only electromagnetic waves but also radiation having wavelengths in the ultraviolet, extinction, non-atomic, visible, and infrared regions. Radiation includes, for example, microwave, electron beam, extreme ultraviolet (EUV), and X-ray. Further, a laser beam such as a 248 nm excimer laser, a 193 nm excimer laser, or a 172 nm excimer laser can also be used. These lights may be monochromatic light (single wavelength light) through an optical filter, or may be lights of different wavelengths (composite light).

In this specification, the solid content refers to the total mass of components excluding the solvent in the composition of the composition.

&Lt; Curable composition >

The curable composition of the present invention comprises

Monofunctional (meth) acrylate monomers A1,

(Meth) acrylate monomer A2 having at least one structure selected from an aliphatic condensed ring structure, an aliphatic crosslinked ring structure and an aliphatic crosslinked condensed ring structure,

(Meth) acrylate monomer A2, a trifunctional or more (meth) acrylate monomer A3 and a polyfunctional (meth)

Photopolymerization initiator

Wherein the curable composition is a curable composition,

(Meth) acrylate monomer A1, the (meth) acrylate monomer A2, and the (meth) acrylate monomer A3 is at least 70 mass% of the total mass of the curable composition,

(Meth) acrylate monomer A2 is contained in an amount of 40 to 130 parts by mass relative to 100 parts by mass of the (meth) acrylate monomer A2,

(Meth) acrylate monomer A3 is contained in an amount of 5 to 65 parts by mass relative to 100 parts by mass of the (meth) acrylate monomer A2,

The viscosity of the curable composition at 23 캜 is 25 mPa s or less.

With the above configuration, it becomes possible to provide a curable composition which is capable of forming a pattern having good ink-jet dischargeability and excellent etching resistance and strength. This effect is presumed to be due to the following.

Since the curable composition of the present invention contains the monofunctional (meth) acrylate monomer A1, the viscosity of the composition can be lowered and the inkjet dischargeability can be improved. Further, since the curable composition of the present invention contains the above (meth) acrylate monomer A2, the carbon density of the cured film can be increased and the etching resistance can be improved. Further, since the curable composition of the present invention contains the above (meth) acrylate monomer A3, the cross-linking density of the cured film can be increased, and a pattern having excellent strength can be formed, and pattern collapse and the like can be suppressed. The (meth) acrylate monomer A1, the (meth) acrylate monomer A2, and the (meth) acrylate monomer A3 are contained in the predetermined ratio, and the By setting the viscosity to 25 mPa s or less, a curable composition capable of forming a pattern having excellent ink-jet dischargeability and excellent in etching resistance and strength could be obtained.

In the curable composition of the present invention, the total mass of the (meth) acrylate monomer A1, the (meth) acrylate monomer A2 described later, and the (meth) acrylate monomer A3 described later is preferably 70 By mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. The upper limit can be, for example, 99 mass% or less. When the total mass of each of the (meth) acrylate monomers is within the above range, a curable composition capable of forming a pattern having excellent ink-jet dischargeability and excellent etching resistance and strength can be obtained.

Each component of the curable composition of the present invention will be described below.

<< (Meth) acrylate monomer A1 >>

The curable composition of the present invention contains a monofunctional (meth) acrylate monomer A1.

Any of (meth) acrylate monomers A1 may be used as long as it is a compound (monomer) having a (meth) acryloyl group in one molecule. The (meth) acrylate monomer A1 may be a chain aliphatic (meth) acrylate monomer or a (meth) acrylate monomer having a cyclic structure. Alternatively, it may be a (meth) acrylate monomer having a silicon atom and / or a fluorine atom. Examples of the cyclic structure include an aliphatic ring and an aromatic ring. The aliphatic ring and aromatic ring may be monocyclic or condensed rings. The aliphatic ring may have a crosslinked structure.

In the present invention, the term &quot; chain aliphatic (meth) acrylate monomer &quot; means a linear or branched aliphatic (meth) acrylate monomer containing no cyclic structure such as an aliphatic or aromatic ring.

Specific examples of the (meth) acrylate monomer A1 include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, N-vinylpyrrolidinone, 2-acryloyloxyethyl phthalate, 2- Acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl acrylate, (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (Meth) acrylate, benzyl (meth) acrylate, 1- or 2-naphthyl (meth) acrylate, butoxyethyl (meth) acrylate, cetyl Quot; EO &quot;) cresol (meth) acrylate, (Meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dipropylene glycol (meth) acrylate, Acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, , Methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (Meth) acrylate, octyl (meth) acrylate, para-cumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin ECH ") modified phenoxy acrylate, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxy tetraethylene glycol Acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tribroole (meth) acrylate, polyethylene glycol (Meth) acrylate, EO-modified tribromophenyl (meth) acrylate, and tridodecyl (meth) acrylate.

As the monofunctional (meth) acrylate monomer having a fluorine atom, a compound having a fluorine-containing group selected from a fluoroalkyl group and a fluoroalkyl ether group is preferable.

The fluoroalkyl group is preferably a fluoroalkyl group having 2 to 20 carbon atoms, more preferably a fluoroalkyl group having 4 to 8 carbon atoms. Preferred examples of the fluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a hexafluoroisopropyl group, a nonafluorobutyl group, a tridecafluorohexyl group, and a heptadecafluorooctyl group have.

As the fluoroalkyl ether group, a group having a trifluoromethyl group, a group having a perfluoroethyleneoxy group, a group containing a perfluoropropyleneoxy group and the like are preferable. In _{addition, - (CF (CF 3)} CF 2 O) - are preferred airway fluoro having a trifluoromethyl group, such as having a trifluoromethyl group at the terminal of the alkyl ether group with an alkyl ether unit and / or fluoro.

Specific examples of the monofunctional (meth) acrylate monomer having a fluorine atom include trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) (Meth) acrylate, perfluorooctyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, perfluorooctyl ) Acrylate, and the like.

Examples of monofunctional (meth) acrylate monomers having a silicon atom include compounds having an alkylsilyl group, an alkoxysilyl group, a chain siloxane structure, a cyclic siloxane structure, and a cage siloxane structure. For example, by blending a monofunctional (meth) acrylate having an alkoxysilyl group (preferably a trialkoxysilyl group), it is easy to form a pattern having excellent adhesion to a substrate.

Specific examples of monofunctional (meth) acrylate monomers having a silicon atom include 2- (trimethylsilyl) ethyl (meth) acrylate, 3- [tris (trimethylsilyloxy) (Meth) acryloyloxymethyltris (trimethylsiloxy) silane, 3- (meth) acryloyloxypropylbis (trimethylsiloxy) methylsilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- Acryloyloxypropyltriethoxysilane, and the like.

Examples of commercially available monofunctional (meth) acrylates having an alkoxysilyl group include KBM-5103 (3-acryloyloxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.), KBM-502 (Shin- 3-methacryloxypropylmethyldimethoxysilane), KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropyltrimethoxysilane), KBE-502 (Shinetsu Kagaku Kogyo Co., 3-methacryloxypropylmethyldiethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.), KBE-503 (3-methacryloxypropyltriethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

In the present invention, the (meth) acrylate monomer A1 preferably contains a monofunctional (meth) acrylate monomer having a cyclic structure. According to this aspect, it is easy to form a pattern having excellent etching resistance. The content of the monofunctional (meth) acrylate monomer having a cyclic structure is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, based on the total mass of the (meth) acrylate monomer A1. The upper limit may be, for example, 99 mass% or less, or 95 mass% or less.

In the present invention, the (meth) acrylate monomer A1 is preferably a monofunctional (meth) acrylate monomer other than a monofunctional (meth) acrylate monomer having a fluorine atom and / or a silicon atom (Meth) acrylate monomer having a cyclic structure is contained in an amount of preferably 50 to 100 mass%, more preferably 60 to 100 mass%, and most preferably 70 By mass to 100% by mass, and particularly preferably 80% by mass to 100% by mass. The (meth) acrylate monomer A1-1 may be composed only of a (meth) acrylate monomer having a substantially cyclic structure. In addition, the (meth) acrylate monomer A1-1 is composed of only a (meth) acrylate monomer having a substantially cyclic structure. For example, the content of the (meth) acrylate monomer having a cyclic structure is ) Acrylate monomer A1-1 is preferably 99% by mass or more, and more preferably 99.9% by mass or more. According to this aspect, it is easy to form a pattern having excellent etching resistance.

In the present invention, the content of the monofunctional (meth) acrylate monomer having a fluorine atom and / or a silicon atom in the (meth) acrylate monomer A1 is preferably in the range of, Is preferably 50 mass% or less, and more preferably 40 mass% or less. The lower limit may be, for example, 1% by mass or more, or 5% by mass or more. Further, it may be a composition substantially not containing a monofunctional (meth) acrylate monomer having a fluorine atom and / or a silicon atom. The expression "substantially free of a monofunctional (meth) acrylate monomer having a fluorine atom and / or a silicon atom means that the content of a monofunctional (meth) acrylate monomer having a fluorine atom and / or a silicon atom Is preferably 0.1 mass% or less, more preferably 0.01 mass% or less, based on the total mass of the (meth) acrylate monomer A1.

In the present invention, the (meth) acrylate monomer A1 preferably has a viscosity at 23 캜 of 10 mPa s or less. The lower limit is preferably 1 mPa · s or more, more preferably 1.5 mPa · s or more. The upper limit is preferably 8 mPa · s or less, more preferably 5 mPa · s or less. The value of the viscosity in the present invention is a value measured by the method described in the following Examples.

The curable composition of the present invention preferably contains the (meth) acrylate monomer A1 in an amount of 10 to 50 mass% in the curable composition of the present invention. The lower limit is more preferably not less than 20% by mass, and more preferably not less than 25% by mass. The upper limit is more preferably 40 mass% or less. When the content of the (meth) acrylate monomer A1 is 10 mass% or more, inkjet dischargeability can be improved. When the content of the (meth) acrylate monomer A1 is 50 mass% or less, a pattern having excellent etching resistance and strength is easily formed.

The curable composition of the present invention preferably contains (meth) acrylate monomer A1 in an amount of 40 to 130 parts by mass, and 40 to 100 parts by mass with respect to 100 parts by mass of (meth) acrylate monomer A2 described later . The lower limit is preferably 50 parts by mass or more, more preferably 55 parts by mass or more. The upper limit is preferably 95 parts by mass or less, more preferably 90 parts by mass or less.

The curable composition of the present invention is a curable composition comprising a (meth) acrylate monomer A1 in a total mass of (meth) acrylate monomer A1, (meth) acrylate monomer A2, and (meth) By mass. The lower limit is more preferably not less than 20% by mass, and more preferably not less than 25% by mass. The upper limit is more preferably 40 mass% or less.

The (meth) acrylate monomer A1 may be used alone, or two or more thereof may be used in combination. When two or more kinds are used, the total amount is preferably in the above range.

<< (Meth) acrylate monomer A2 >>

The curable composition of the present invention contains a bifunctional or more (meth) acrylate monomer A2 having at least one structure selected from an aliphatic condensed ring structure, an aliphatic crosslinked ring structure and an aliphatic crosslinked condensed ring structure.

In the present invention, an aliphatic fused ring structure means a structure in which two or more aliphatic rings share a side-by-side relationship when expressed in a chemical structural formula. The aliphatic crosslinked ring structure means a structure in which two or more atoms not adjacent to each other are connected to each other in one aliphatic ring. The aliphatic crosslinked condensed ring structure means a structure in which two or more aliphatic rings share one to one side and two or more atoms of the same aliphatic ring which are not adjacent to each other are connected to each other or a structure in which other aliphatic rings are adjacent to each other Or more than two atoms connected together.

The aliphatic condensed ring structure, the aliphatic crosslinked ring structure and the aliphatic crosslinked condensed ring structure are preferably a 5-membered ring or a 6-membered ring.

The condensed number of the aliphatic condensed ring structure and the aliphatic crosslinked condensed ring structure is preferably from 2 to 10, more preferably from 2 to 6, still more preferably from 2 to 4, and particularly preferably from 2 to 3.

The (meth) acrylate monomer A2 preferably has at least one structure selected from an aliphatic crosslinked ring structure and an aliphatic crosslinked condensed ring structure, more preferably an aliphatic crosslinked condensed ring structure. According to this aspect, it is easy to form a pattern having excellent etching resistance and strength.

Specific examples of the aliphatic condensed ring structure include the following structures.

Specific examples of the aliphatic crosslinked ring structure and the aliphatic crosslinked condensed ring structure include the following structures.

In the present invention, the (meth) acrylate monomer A2 is preferably 2 to 10 functional groups, more preferably 2 to 6 functional groups, more preferably bifunctional or trifunctional functional groups, and particularly preferably 2 functional groups. According to this aspect, it is easy to obtain an effect that the increase in the viscosity of the curable composition can be reduced. In particular, if the bifunctional is used, the increase in the viscosity of the curable composition can be further reduced.

The (meth) acrylate monomer A2 preferably has a viscosity at 23 캜 of 200 mPa s or less. The lower limit is preferably 2 mPa · s or more, more preferably 5 mPa · s or more. The upper limit is preferably 150 mPa s or less, more preferably 100 mPa s or less. The value of the viscosity in the present invention is a value measured by the method described in the following Examples.

Specific examples of the (meth) acrylate monomer A2 include tricyclodecane dimethanol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, dicyclopentanyl di (meth) acrylate, decahydrodiacrylate, iso (Meth) acrylate, tricyclodecanetri (meth) acrylate, and the like.

Among them, (meth) acrylate having an alicyclic condensed ring structure including a bicyclo ring or tricyclo ring is preferable, and tricyclodecane dimethanol di (meth) acrylate, dicyclopentenyl (meth) acrylate And dicyclopentanyl di (meth) acrylate are more preferable. According to this aspect, it is easy to form a pattern having excellent etching resistance and strength.

The curable composition of the present invention preferably contains the (meth) acrylate monomer A2 in an amount of 10 to 80 mass% in the curable composition of the present invention. The lower limit is more preferably 20 mass% or more, more preferably 30 mass% or more, and particularly preferably 40 mass% or more. The upper limit is more preferably 75 mass% or less, and further preferably 70 mass% or less. When the content of the (meth) acrylate monomer A2 is within the above range, it is easy to form a pattern having excellent ink-jet dischargeability and excellent etching resistance and strength.

The curable composition of the present invention is a curable composition wherein the (meth) acrylate monomer A2 is contained in the total mass of the (meth) acrylate monomer A1, the (meth) acrylate monomer A2 and the (meth) By mass. The lower limit is more preferably 20 mass% or more, more preferably 30 mass% or more, and particularly preferably 40 mass% or more. The upper limit is more preferably 75 mass% or less, and further preferably 70 mass% or less.

The (meth) acrylate monomer A2 may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range.

<< (Meth) acrylate monomer A3 >>

The curable composition of the present invention is a polyfunctional (meth) acrylate monomer other than the above-mentioned (meth) acrylate monomer A2 and contains a trifunctional or more (meth) acrylate monomer A3.

The (meth) acrylate monomer A3 is preferably a compound having three or more (meth) acryloyl groups and not having an aliphatic condensed ring structure, an aliphatic crosslinked ring structure and an aliphatic crosslinked condensed ring structure . The (meth) acrylate monomer A3 may be a chain aliphatic (meth) acrylate monomer. Further, a (meth) acrylate monomer having a monocyclic aliphatic cyclic structure (except for an aliphatic cyclic cyclic structure) may be used. Further, it may be a (meth) acrylate monomer having an aromatic ring structure. Alternatively, it may be a (meth) acrylate monomer having a silicon atom and / or a fluorine atom.

In the present invention, the (meth) acrylate monomer A3 is preferably a chain aliphatic (meth) acrylate monomer. According to this aspect, an effect of minimizing an increase in viscosity of the curable composition is apt to be obtained.

In the present invention, the (meth) acrylate monomer A3 is preferably 3 to 10-functional, more preferably 3 to 6-functional. According to this aspect, it is easy to suppress an increase in the viscosity of the curable composition.

Specific examples of the (meth) acrylate monomer A3 include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, propylene oxide (hereinafter referred to as PO) modified glycerol tri (meth) (Meth) acrylate, EO modified triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate, caprolactone modified (methacrylic acid) Dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, alkyl-modified dipenta (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra Methacrylate, and the like. Examples of commercially available products include Miramer M300 (manufactured by Miwon, trimethylolpropane triacrylate), A-TMMT (pentaerythritol triacrylate manufactured by Shin Nakamura Chemical Co., Ltd.), KAYARAD DPHA (manufactured by Nihon Kayaku Co., Pentaerythritol pentaacrylate), and the like.

In the present invention, the (meth) acrylate monomer A3 preferably has a viscosity of 300 mPa s or less at 23 캜. The lower limit is preferably 5 mPa · s or more, more preferably 10 mPa · s or more. The upper limit is preferably 250 mPa s or less, more preferably 200 mPa s or less. The value of the viscosity in the present invention is a value measured by the method described in the following Examples.

The curable composition of the present invention preferably contains (meth) acrylate monomer A3 in an amount of 1 to 30 mass% in the curable composition of the present invention. The lower limit is more preferably 2% by mass or more. The upper limit is more preferably 20 mass% or less, and further preferably 15 mass% or less. When the content of the (meth) acrylate monomer A3 is within the above range, a pattern having good ink-jet dischargeability and excellent strength with suppressed pattern collapse is likely to be obtained.

The curable composition of the present invention preferably contains (meth) acrylate monomer A3 in an amount of 5 to 65 parts by mass, and preferably 5 to 30 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer A2.

The curable composition of the present invention comprises (meth) acrylate monomer A3 in an amount of from 1 to 30 mass%, based on the total mass of (meth) acrylate monomer A1, (meth) acrylate monomer A2 and (meth) . The lower limit is more preferably 2% by mass or more, and still more preferably 2.5% by mass or more. The upper limit is more preferably 20% by mass or less, and still more preferably 15% by mass or less.

The (meth) acrylate monomer A3 may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range.

<< (Meth) acrylate monomer A4 >>

The curable composition of the present invention may contain the above (meth) acrylate monomer A1, (meth) acrylate monomer A2, and (meth) acrylate monomer A4 other than the (meth) acrylate monomer A3.

As the (meth) acrylate monomer A4, bifunctional (meth) acrylate monomers which do not have an aliphatic condensed ring structure, an aliphatic crosslinked ring structure and an aliphatic crosslinked condensed ring structure are exemplified.

For example, a bifunctional (meth) acrylate monomer having a monocyclic aliphatic cyclic structure (except an aliphatic cyclic cyclic structure), a bifunctional (meth) acrylate monomer having an aromatic cyclic structure, a bifunctional And bifunctional (meth) acrylate monomers.

Specific examples include (meth) acrylates such as ortho, meta, para-phenylene di (meth) acrylate, ortho-, meta-, para-xylylene di (meth) acrylate, bisphenol A di (meth) acrylate, EO modified bisphenol A di (Meth) acrylate, cyclohexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethylene modified (meth) acrylate, PO modified bisphenol A di (meth) acrylate, EO modified bisphenol F di Butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, (Meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,9-nonanediol di (Meth) acrylate, 1,10-decanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethyl (Meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, polytetramethylene glycol di (meth) acrylate, EO-modified neopentyl glycol di (meth) acrylate, PO-modified neopentyl glycol di (meth) acrylate, 2,2- (Meth) acryloyloxy) propionic acid, 2,2-dimethyl-3 - ((meth) acryloyloxy) propyl, 2-hydroxy- (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, There may be mentioned tris (2- (meth) acryloyloxyethyl) isocyanurate.

When the curable composition of the present invention contains the (meth) acrylate monomer A4, the content of the (meth) acrylate monomer A4 is preferably from 1 to 10 mass%, more preferably from 1 to 5 mass% % By mass is more preferable. The (meth) acrylate monomer A4 may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range.

Further, the curable composition of the present invention may have a composition substantially not containing the (meth) acrylate monomer A4. Means that the content of the (meth) acrylate monomer A4 is preferably 0.5% by mass or less, more preferably 0.1% by mass or less with respect to the mass of the curable composition.

<< Polymerizable compound other than (meth) acrylate monomer >>

The curable composition of the present invention may contain a polymerizable compound other than the (meth) acrylate monomer (hereinafter, referred to as another polymerizable compound). Examples of other polymerizable compounds include epoxy compounds, oxetane compounds, vinyl ether compounds, styrene derivatives, propenyl ether, butenyl ether, and the like. Examples of commercially available epoxy compounds include EX-321L (manufactured by Nagase ChemteX Corporation). Specific examples thereof include those described in paragraphs 0020 to 0098 of Japanese Patent Application Laid-Open No. 2011-231308, the contents of which are incorporated herein by reference. In the present invention, the other polymerizable compound is a compound other than the silane coupling agent described later. That is, the other polymerizable compound in the present invention is a compound having no alkoxysilane structure.

When the curable composition of the present invention contains other polymerizable compounds, the content of other polymerizable compounds is preferably from 1 to 10 mass%, more preferably from 1 to 5 mass%, based on the curable composition of the present invention desirable.

In addition, the curable composition of the present invention may be a composition that does not substantially contain other polymerizable compounds. Means that the content of the other polymerizable compound is substantially 0.5% by mass or less, more preferably 0.1% by mass or less, relative to the mass of the curable composition.

The curable composition of the present invention is characterized in that the total mass of (meth) acrylate monomer A1, (meth) acrylate monomer A2, and (meth) acrylate monomer A3 is 70% by mass or more of the total mass of the curable composition, , More preferably from 70 to 99.9 mass%, further preferably from 80 to 99.9 mass%, still more preferably from 90 to 99 mass%.

<< Photopolymerization initiator >>

The curable composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator may be any compound as long as it generates an active species capable of polymerizing a polymerizable compound such as a (meth) acrylate monomer by irradiation with light. As the photopolymerization initiator, a radical polymerization initiator and a cation polymerization initiator are preferable, and a radical polymerization initiator is more preferable.

As the photopolymerization initiator, oxime compounds, acetophenone compounds, acylphosphine oxide compounds and the like are preferable from the viewpoints of curing sensitivity and absorption characteristics. Among them, an oxime compound is preferable. As specific examples of the oxime compounds, compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-80068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166 can be used.

In the present invention, an oxime compound having a fluorine atom may be used as a photopolymerization initiator. Specific examples of the fluorine atom-containing oxime compound include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, compounds described in JP-A-2013-164471 (C-3), and the like. The contents of which are incorporated herein by reference.

Examples of commercially available photopolymerization initiators include Irgacure (registered trademark) 1173, Irgacure 184, Irgacure 2959, Irgacure 127, Irgacure 907, Irgacure 369, Irgacure 379, Lucilin TMO, Irgacure 819, Irgacure OXE- -02, Irgacure OXE-03, Irgacure 651, and Irgacure 754 (manufactured by BASF). As the photopolymerization initiator, the compound described in paragraph No. 0091 of Japanese Patent Application Laid-Open No. 2008-105414 may be used.

The photopolymerization initiator may be used singly or in combination of two or more.

The content of the photopolymerization initiator is preferably from 0.1 to 15 mass%, more preferably from 0.5 to 10 mass%, and still more preferably from 1 to 5 mass%, based on the curable composition. The curable composition may contain only one type of photopolymerization initiator or two or more types of photopolymerization initiators. When two or more kinds are included, the total amount is preferably in the above range.

When the content of the photopolymerization initiator is 0.1% by mass or more, the sensitivity (fast curability), resolution, line edge roughness, and film strength tend to be improved, which is preferable. When the content of the photopolymerization initiator is 15 mass% or less, light transmittance, coloring property, handling property and the like tend to be improved, which is preferable.

<< Release Agent >>

The curable composition of the present invention may contain a release agent. By including the releasing agent, the surface area of the curable composition is improved, and the degree of pattern (accuracy) tends to be improved. Further, the mold releasability is improved, and occurrence of pattern defects can be suppressed.

The content of the releasing agent is preferably 0.001 to 5% by mass, more preferably 0.002 to 4% by mass, and still more preferably 0.005 to 3% by mass in the curable composition. When two or more kinds of release agents are used, the total amount is preferably in the above range. When the content of the releasing agent is within the above range, the above-mentioned effect is easily obtained.

Examples of the release agent include a silicone-based release agent, a fluorine-based release agent, a silicone-fluorine-based release agent, and a hydrocarbon-based release agent. Here, the silicon-fluorine-based releasing agent means a releasing agent having a fluorine atom and a silicon atom.

As the silicone-based releasing agent, it is preferable to use a compound having an HLB (Hydrophile-Lipophile Balance) of 6 to 11. Herein, HLB is a numerical value of a hydrophilic / hydrophobic balance of a compound. From the viewpoint of compatibility, the above range is determined. Specifically, there is a mega catalog or the like.

As the silicone-based releasing agent, an unmodified or modified siloxane compound is preferable. Among them, a silicone oil is preferable, and a modified silicone oil obtained by modifying the side chain and / or terminal of the polysiloxane is particularly preferable. Examples of the silicone oil include polyether-modified silicone oil, methylstyryl-modified silicone oil, alkyl-modified silicone oil, higher fatty ester-modified silicone oil, hydrophilic special modified silicone oil, higher alkoxy- have.

As the fluorine-containing releasing agent, a compound having a fluoroalkyl group is preferable. The number of carbon atoms of the fluoroalkyl group is preferably from 1 to 20, more preferably from 1 to 10. The fluoroalkyl group may be linear, branched or cyclic. The fluoroalkyl group may have an ether bond in the molecular chain. A plurality of fluoroalkyl groups may be contained in the same molecule.

Examples of the hydrocarbon-based releasing agent include a non-polymerizable compound having a polyoxyalkylene structure. Here, the non-polymer compound means a compound having no polymerizable group.

In the non-polymerizable compound having a polyoxyalkylene structure, the polyoxyalkylene structure is more preferably a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, or a mixed structure thereof, and the polyoxyethylene structure Or a polyoxypropylene structure is more preferable, and a polyoxypropylene structure is particularly preferable. In addition, it is also preferable to use a structure in which a polyhydric alcohol such as glycerin or pentaerythritol is used as a core and branched structure.

The polyoxyalkylene structure preferably has 3 to 30 polyoxyalkylene constituent units, more preferably 5 to 20, more preferably 7 to 15, and more preferably 9 to 13 Is particularly preferable.

The hydroxyl group at the terminal of the polyoxyalkylene structure may be unsubstituted or substituted with at least one organic group or all of them may be substituted with an organic group.

The organic group is preferably an organic group having 1 to 20 carbon atoms. The organic group is preferably bonded to the polyoxyalkylene structure through an ether bond, an ester bond, or a divalent linking group. Specific examples of the organic group include hydrocarbon groups such as methyl group, ethyl group, butyl group, octyl group, benzyl group and phenyl group.

The number average molecular weight of the non-polymerizable compound is preferably 300 to 3,000, more preferably 400 to 2,000, and still more preferably 500 to 1,500.

Specific examples of the non-polymerizable compound include polyoxyethylene (also referred to as polyethylene glycol), polyoxypropylene (also referred to as polypropylene glycol), polyoxybutylene, polyoxyethylene polyoxypropylene (block and random), polyoxyethylene (Hereinafter abbreviated as PEG) glyceryl ether, polyoxypropylene (abbreviated as PPG) glyceryl ether, PEG.PPG glyceryl ether, PEG bisphenol A ether, PEG trimethylol propane ether, PEG pentaerythritol ether, PEG PEG trimethylol propane ether, PEG methyl ether, PEG butyl ether, PEG2-ethylhexyl ether, PEG lauryl ether, PEG oleyl ether, PPG methyl ether, PPG butyl ether, PPG lauryl ether, PPG ole PEG phenyl ether, PEG octyl phenyl ether, PEG nonyl phenyl ether, PEG naphthyl ether, PEG styrenated phenyl ether, PPG phenyl ether, PPG octyl phenyl ether , PPG nonylphenyl ether, PEG dimethyl ether, PEG dibenzyl ether, PPG dimethyl ether, PPG dibenzyl ether, PEG.PPG dimethyl ether, PEG glyceryl ether trimethyl ether, PPG glyceryl ether trimethyl ether, PEG monoacetate, PEG mono PEG monooleate, PPG monoacetate, PPG monooleate, PPG monooleate, PEG diacetate, PEG dilaurate, PEG diolate, PPG diacetate, PPG dilaurate, PPG diolate, Ethylene oxide adducts such as PEG glycerin fatty acid esters, PEG sorbitan fatty acid esters, PEG sorbitol fatty acid esters and 2,4,7,9-tetramethyl-5-decyne-4,7-diol (for example, , E1010 and E1020 (manufactured by Nisshin Chemical Industries, Ltd.), and Saponol 420, 440, 465, 485, 2502 and 2505 (manufactured by Air Products and Chemicals)).

With regard to the above non-polymerizable compound, the description of paragraphs 0105 to 0106 of Japanese Patent Application Laid-Open No. 2013-036027 may be taken into consideration, and the contents thereof are incorporated herein.

S-242, S-243 (manufactured by AGC Seiyaku Chemical Co., Ltd.), F-4431 (manufactured by Sumitomo 3M Ltd.) EF-PN31M-04, EF-PN31M-05, EF-PN31M-06, MF-100 (manufactured by Mitsubishi Materials Denshigasai), Polyfox PF-636, PF-6320, PF DSD-401, DS-403, DS-406, DS-451, DSN (trade name) manufactured by Nippon Zeon Co.), PF-6520 and PF-6520 (manufactured by OMNOVA), futanut 250, 251, 222F and 212M DFX- F-555, F-559, F-562, F-565, F-554, F- F-567, F-569, R-40 (manufactured by DIC Corporation), Capstone FS-3100 and Zonyl FSO-100 (manufactured by DuPont).

SH-3749, SH-3771, SH-8400, and TH-8700 (manufactured by Dow Corning Toray Industries, Inc.), polyether-modified KF-642, KF-6020, XF-355A, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-352A, KF- 22-6191, X-22-4515, KF-6011, KF-6012 and KF-6015 (polyether-modified polysiloxane oil made by Shin-Etsu Chemical Co., Ltd.).

X-70-091, X-70-092, X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.), Mega Park R-08, XRB- 4 (manufactured by DIC Corporation).

<< Wetting improver >>

The curable composition of the present invention may contain a wettability improver. By including the wettability improving agent, the fluidity of the curable composition of the present invention in the cavity of the mold concave portion at the time of pattern formation is improved, and good pattern transferability is easily obtained.

As the wettability improver, an aliphatic amide compound and the like can be mentioned. As the aliphatic amide compound, a compound represented by the following formula (1) is preferable.

^{R 101 -C (= O) NH} 2 ... Equation (1)

In the formula, R ¹⁰¹ represents an alkyl group having 5 to 30 carbon atoms or an alkenyl group having 5 to 30 carbon atoms.

The alkyl group and alkenyl group represented by R &lt; ¹⁰¹ &gt; preferably have 5 to 30 carbon atoms. The lower limit is preferably 7 or more, more preferably 10 or more. The upper limit is preferably 26 or less, more preferably 24 or less.

Specific examples of the fatty acid amide compound represented by the formula (1) include oleic acid amide, erucic acid amide, behenic acid amide, lauric acid amide, stearic acid amide, octanamide and hexanamide. Commercially available products include diamide (registered trademark) O-200 (oleic acid amide manufactured by Nippon Kayaku Co., Ltd.) and the like.

The content of the wettability improver is, for example, preferably 0.001 to 5 mass%, more preferably 0.002 to 4 mass%, and still more preferably 0.005 to 3 mass% in the curable composition. When two or more kinds of wettability improving agents are used, the total amount is preferably in the above range. When the content of the wettability improver is within the above range, the above-mentioned effect is easily obtained.

<< Silane coupling agent >>

The curable composition of the present invention may contain a silane coupling agent. The kind of the silane coupling agent used in the present invention is not particularly defined, but a compound having at least one member selected from the group consisting of an epoxy group, an ethylenic unsaturated group, an alkyl group substituted with a chloro group, and a mercapto group and a compound having an alkoxysilane structure desirable. By blending a silane coupling agent into the curable composition, it is easy to form a pattern having excellent adhesion to a substrate.

In the present invention, among the silane coupling agents having a (meth) acryloyl group, those corresponding to the aforementioned (meth) acrylate monomer A1, (meth) acrylate monomer A2 or (meth) acrylate monomer A3, (Meth) acrylate monomer A1, (meth) acrylate monomer A2 or (meth) acrylate monomer A3.

Specific examples of the silane coupling agent include vinyl trichlorosilane, vinyltris (? -Methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane,? - (3,4-epoxycyclohexyl ) -Ethyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Chloropropylmethyldimethoxysilane,? - Chloropropylmethyldiethoxysilane, and the like.

The molecular weight of the silane coupling agent is preferably 150 to 400.

The content of the silane coupling agent is preferably, for example, 1 to 20% by mass in the curable composition. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more. The upper limit is preferably 15 mass% or less.

<< Other Ingredients >>

The curable composition of the present invention may contain, in addition to the above-described components, a photosensitizer, an antioxidant, an ultraviolet absorber, a polymerization inhibitor, a light stabilizer, an antioxidant, a plasticizer, a thermal polymerization initiator, Particles, elastomer particles, basic compounds, photoacid generators, photo acid generators, chain transfer agents, antistatic agents, flow control agents, antifoaming agents, dispersants and the like. As specific examples of such components, reference may be made to paragraphs 0031 to 0052 of Japanese Patent Application Laid-Open No. 3133517, the contents of which are incorporated herein by reference.

<< Water >>

The content of water in the curable composition of the present invention is preferably 2.0 mass% or less, more preferably 1.5 mass% or less, and further preferably 1.0 mass% or less. When the content of water is 2.0 mass% or less, the curable composition has excellent storage stability.

<< Solvent >>

 The curable composition of the present invention may contain a solvent. The content of the solvent in the curable composition of the present invention is preferably 5 mass% or less, more preferably 3 mass% or less, and particularly preferably substantially free of solvent. Here, the term substantially solvent-free means that it is preferably 1% by mass or less, more preferably 0.5% by mass or less, and more preferably, not more than 0.5% by mass with respect to the mass of the curable composition of the present invention. When the curable composition of the present invention is coated on a substrate by an ink-jet method, it is preferable that the content of the solvent is small because the viscosity change of the curable composition due to volatilization of the solvent can be suppressed.

Thus, the curable composition of the present invention does not necessarily contain a solvent, but may be optionally added when the viscosity of the curable composition is finely adjusted. The solvent which can be preferably used in the curable composition of the present invention is a solvent which is generally used in the curable composition for imprinting or the photoresist and which dissolves and uniformly disperses each component used in the present invention, Is not particularly limited as long as it does not react with the component. Examples of the solvent usable in the present invention include those described in paragraph No. 0088 of Japanese Patent Application Laid-Open No. 2008-105414, the contents of which are incorporated herein.

&Lt; Preparation method and use of curable composition >

The curable composition of the present invention can be prepared by mixing the respective components described above. The mixing of each component is usually carried out in the range of 0 ° C to 100 ° C. Further, it is preferable to mix the respective components and then filter them with a filter, for example. The filtration may be performed in multiple steps or repeated a plurality of times. Further, the filtrate may be re-filtered.

The filter is not particularly limited as long as it is conventionally used for filtration and the like. For example, a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon-6 or nylon-6,6, a polyolefin resin such as polyethylene or polypropylene (PP) And a polyolefin resin). Of these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore diameter of the filter is preferably about 0.003 to 5.0 mu m, for example. Within this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the composition while suppressing filtration clogging.

When using a filter, other filters may be combined. At that time, the filtration in the first filter may be performed once, or may be performed two or more times. When two or more filtrations are performed in combination with other filters, it is preferable that the filter used in the second filtration after the first filtration is equal to or smaller than the pore size of the filter used in the first filtration. When filtration is performed twice or more, a first filter having different pore diameters may be combined within the above-described range. Here, the pore size can refer to the nominal value of the filter maker. As a commercially available filter, for example, commercially available products such as Nippon Polybutylene terephthalate, Advan Tech Yoga Bushi Co., Ltd., Nippon Ince Grease Co., Ltd. (formerly Nippon Microlis Co., Ltd.) Can be selected from among various filters provided by the user.

The curable composition of the present invention preferably has a viscosity of 25 mPa · s or less at 23 ° C. The lower limit is, for example, preferably 5 mPa · s or more, more preferably 8 mPa · s or more, and even more preferably 10 mPa · s or more. The upper limit is more preferably 23 mPa s or less, for example, and further preferably 21 mPa s or less. By setting this range, ink jet dischargeability can be improved. Further, the filling property of the mold to the concavo-convex pattern can be improved, and the pattern forming property is also excellent. The value of the viscosity in the present invention is a value measured by the method described in the following Examples.

The curable composition of the present invention is favorable as a curable composition for ink jet because of its excellent ink jet dischargeability.

In addition, the curable composition of the present invention is suitable as a curable composition for imprinting because it can form a fine pattern with excellent strength without pattern collapse and the like by the imprint method. In particular, it is a curable composition for optical imprint.

Further, the curable composition of the present invention is suitable as a curable composition for forming an etching mask because it can form a pattern having excellent etching resistance and strength.

&Lt; Pattern formation method >

Next, the pattern forming method of the present invention will be described. In the pattern forming method of the present invention, it is preferable to form the pattern by the optical imprint method using the curable composition of the present invention.

Hereinafter, a pattern forming method using the curable composition of the present invention will be described in detail. In the pattern forming method of the present invention, first, the curable composition of the present invention is applied onto a mold having a substrate or pattern. Next, the curable composition is sandwiched between the mold and the substrate. Next, the curable composition is cured by light irradiation (exposure) in a state sandwiched between the mold and the substrate. Finally, the mold is peeled from the surface of the cured product.

As a method of applying the curable composition of the present invention on a substrate or a mold having a pattern, there can be used generally known coating methods such as a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, A coating film or a droplet can be arranged on a substrate by using a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method, or an inkjet method. Particularly, since the curable composition of the present invention is excellent in inkjet dischargeability, it is suitable for an inkjet method.

The coating film thickness of the curable composition varies depending on the application, but is preferably 0.05 to 30 占 퐉. The curable composition may be applied by multiple application.

When the curable composition is applied onto the mold, the curable composition is applied to the side of the mold where the pattern is formed.

The substrate can be selected according to various applications, and examples of the substrate include a polymer substrate such as quartz, glass, an optical film, a ceramic material, a polyester film, a polycarbonate film and a polyimide film, a transistor (TFT) (PDP), an electrically conductive substrate such as indium tin oxide (ITO) or metal, an insulating substrate such as glass or plastic, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, silicon carbide, SOG ), SOC (Spin On Carbon), and color filters. The shape of the substrate may be a plate shape or a roll shape. Further, depending on the combination with the mold, a light-transmitting or non-light-transmitting base material can be selected.

In order to improve adhesion with the curable composition, a base material on which a lower layer film is formed by applying a composition for forming a lower layer film on the surface of the base material may be used. As the resin composition for forming a lower layer film, for example, a resin composition containing a polymerizable compound and a solvent is used. As the resin composition for forming a lower layer film, for example, those described in paragraphs 0016 to 0088 of Japanese Patent Application Laid-Open No. 2014-24322 and paragraphs 0016 to 0044 of Japanese Patent Application Laid-Open No. 2013-93552 can be used. The contents are incorporated herein. As a method of applying the resin composition for forming a lower layer film, a coating method is preferable. As the coating method, for example, the above-mentioned methods can be mentioned.

The mold has a pattern. The pattern possessed by the mold can be formed according to a desired degree of processing, for example, by photolithography, a transfer method using another mold, an electronic line drawing method, or the like.

The material of the mold is not particularly limited, but any material having a predetermined strength and durability may be used. And may be a light-transmitting material or a non-light-transmitting material. And may be appropriately selected depending on the combination with the substrate. As the material of the light-transmitting mold, for example, light transparent resin such as glass, quartz, acrylic resin, polycarbonate resin, transparent metal vapor deposition film, metal film and the like are exemplified. The material of the non-light-permeable mold is exemplified by a ceramic material, a vapor deposition film, a magnetic film, a reflective film, a metal substrate, SiC, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon and silicon carbide. In addition, the shape of the mold is not particularly limited, and either a plate-like mold or a roll-shaped mold may be used. The roll-on mold is applied especially when the continuous productivity of the warrior is required.

The mold may be subjected to mold release treatment to improve the releasability between the curable composition and the surface of the mold. Examples of such molds include those obtained by treatment with a silane coupling agent such as a silicone type or fluorine type; for example, off-tool DSX manufactured by Daikin Industries Co., Ltd., Novec EGC-1720 manufactured by Sumitomo 3M Co., A commercially available release system can be used as a convenience.

The pattern formed on the surface of the mold can be transferred onto the surface of the curable composition by fitting the substrate or the curable composition applied on the mold with the mold and the substrate.

When the curable composition is sandwiched between the mold and the substrate, it is preferable to perform the mold pressing force at 1 MPa or less. By setting the mold pressing force to 1 MPa or less, it is difficult for the mold or the substrate to be deformed, and the degree of the pattern tends to be improved. It is also preferable that the device is shrunk because the pressure is low.

Further, when the curable composition is sandwiched between the mold and the substrate, a helium gas may be introduced between the mold and the substrate. By using such a method, the permeation of the mold of the gas can be promoted, and the disappearance of the residual bubbles can be promoted. In addition, inhibition of radical polymerization in exposure can be suppressed by reducing dissolved oxygen in the curable composition. Further, instead of helium, a condensable gas may be introduced between the mold and the substrate. By employing such a method, it is possible to further accelerate the disappearance of the residual bubbles by utilizing the fact that the introduced condensable gas condenses and the volume is reduced. The condensable gas means a gas which condenses in accordance with a temperature or a pressure. For example, trichlorofluoromethane, 1,1,1,3,3-pentafluoropropane, etc. can be used. As regards the condensable gas, for example, reference may be made to the description of paragraph 0003 of Japanese Patent Application Laid-Open No. 2004-103817, and of paragraph 0003 of Japanese Patent Application Publication No. 2013-254783, the contents of which are incorporated herein .

Next, the curable composition is cured by light irradiation (exposure) with the mold and the substrate sandwiched therebetween.

The light used for curing the curable composition is not particularly limited, and examples thereof include light or radiation having a wavelength in a region of high energy ionizing radiation, extraordinary, non-atomic, visible, infrared, and the like. Examples of the high energy ionizing radiation source include electron beams accelerated by accelerators such as a cocroof type accelerator, a Vandegraph type accelerator, a linear accelerator, a betatron, and a cyclotron. Also, radiation such as γ rays, X rays, α rays, neutron rays, and proton rays emitted from radioactive isotopes or reactors may be used. Examples of the ultraviolet source include ultraviolet fluorescent lamps, low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, xenon lamps, carbon arc lamps, and the like.

The light irradiation is preferably performed in a range of 1 to 200 mW / cm 2. By setting the exposure illuminance to 1 mW / cm &lt; 2 &gt; or more, the exposure time can be shortened and productivity is improved. By setting the exposure illuminance to 200 mW / cm 2 or less, the deterioration of the properties of the cured film due to the occurrence of side reactions tends to be suppressed, which is preferable. The exposure dose in light irradiation is preferably in the range of 5 to 1000 mJ / cm 2.

In light irradiation, it is preferable to control the oxygen concentration in the atmosphere to 10 ㎪ or less by flowing an inert gas such as nitrogen, helium, argon, or carbon dioxide in order to suppress the inhibition of radical polymerization by oxygen. More preferably, the oxygen concentration in the atmosphere is 3 kPa or less, more preferably 1 kPa or less.

At the time of light irradiation, the substrate temperature is usually room temperature, but light irradiation may be performed while heating to increase the reactivity. As a preliminary stage of light irradiation, light irradiation may be conducted in a vacuum state since it is effective in preventing air bubble mixing, suppressing decrease in reactivity due to oxygen incorporation, and improving adhesion between the mold and the curable composition. The preferable degree of vacuum at the time of light irradiation is in the range of 10 ^-1 Pa to atmospheric pressure.

The pattern forming method of the present invention may include a step of curing the curable composition by light irradiation and then curing the composition by adding heat to the cured pattern as required.

When the curable composition is thermally cured after light irradiation, the heating temperature is preferably 150 to 280 占 폚, more preferably 200 to 250 占 폚. The heating time is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.

After the curable composition is cured as described above, the mold is peeled off to produce a cured product having a pattern in which the pattern of the mold is transferred.

Specific examples of the pattern forming method include those described in paragraphs 0125 to 0136 of Japanese Patent Application Laid-Open No. Hei. 2012-169462, the contents of which are incorporated herein.

The pattern formation method of the present invention can be applied to the pattern inversion method. Specifically, a pattern is formed on the substrate to be processed provided with a carbon film (SOC) by the pattern forming method of the present invention. Next, after covering the pattern with the Si-containing film (SOG), the upper part of the Si-containing film is etched to expose the pattern, and the exposed pattern is removed with oxygen plasma or the like to form an inverted pattern of the Si-containing film. The reversal pattern of the Si-containing film is transferred to the carbon film by etching the carbon film underneath using the reversed pattern as an etching mask. Finally, the substrate is etched using the carbon film on which the reversed pattern is transferred as an etching mask. As an example of such a method, Japanese Unexamined Patent Application Publication No. 5-267253, Japanese Unexamined Patent Application Publication No. 2002-110510, Japanese Unexamined Patent Publication No. 2006-521702, paragraphs 0016 to 0030, Japanese Unexamined Patent Application Publication No. 2010-541193 , The contents of which are incorporated herein by reference.

<Pattern>

As described above, the pattern formed by the pattern forming method of the present invention can be used as a permanent film used for a liquid crystal display (LCD) or the like, or as an etching resist for semiconductor processing.

For example, a recording medium such as a semiconductor integrated circuit, a micro electro mechanical system (MEMS), an optical disk, a magnetic disk, a light receiving element such as a solid-state image pickup element, an optical device such as a light emitting element such as an LED or an organic EL, Optical elements such as a hologram, an optical waveguide, an optical filter and a microlens array, a member for a flat panel display such as a thin film transistor, an organic transistor, a color filter, an antireflection film, a polarizing element, , Immunoassay chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, and guide patterns for directed self-assembly (DSA) using self-organization of block copolymers Can be used.

The pattern formed by the pattern forming method of the present invention is particularly useful as an etching resist because of its excellent strength and etching resistance. When the curable composition of the present invention is used as an etching resist, a pattern is formed on the substrate by the pattern forming method of the present invention. Thereafter, a desired pattern can be formed on the substrate by etching with hydrogen fluoride in the case of wet etching or etching gas such as CF _{4 in} the case of dry etching. The curable composition of the present invention has good etching resistance against dry etching using fluorocarbon or the like.

&Lt; Device Manufacturing Method >

The method for manufacturing a device of the present invention includes the above-described pattern forming method.

That is, after a pattern is formed by the above-described method, a device used for manufacturing various devices can be applied.

The pattern may be included in the device as a permanent film. The substrate may be subjected to an etching treatment using the pattern as an etching mask. For example, a method of forming a pattern on a substrate by the above-described method of forming a pattern of the present invention, and etching the substrate using the formed pattern as a mask. More specifically, dry etching is performed using the formed pattern as an etching mask to selectively remove the upper layer portion of the substrate. By repeating such processing for a substrate, a device can also be manufactured. Examples of the device include a semiconductor device such as an LSI (large-scale integrated circuit) and various displays such as a liquid crystal display.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts used, the ratios, the treatment contents, the treatment procedures and the like shown in the following examples can be changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

(Method of measuring viscosity)

The number of revolutions was set to 50 rpm by using an E-type rotational viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34 '× R24), and the temperature of the sample cup was adjusted to 23 ± 0.1 ° C. The viscosity was measured.

<Preparation of Curable Composition>

The raw materials were mixed at the mass ratios shown in Table 1 below and then filtered through a 0.1 占 퐉 PTFE filter to prepare a curable composition.

[Table 1]

The raw materials shown in the table are as follows.

A-11: Benzyl acrylate (Viscot # 160, manufactured by Osaka Yuki Kagaku Co., Ltd.)

A-12: Cyclohexyl acrylate (Viscot # 155, manufactured by Osaka Yuki Kagaku Co., Ltd.)

A-13: Isobornyl acrylate (IB-XA, manufactured by Osaka Yuki Kagaku Co., Ltd.)

A-14: 2-ethylhexyl acrylate (HA, manufactured by Mitsubishi Kagaku Co., Ltd.)

A-15: KBM-5103 (3-acryloyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

A-21: tricyclodecane dimethanol diacrylate (Miramer M262, bifunctional (meth) acrylate monomer having an aliphatic crosslinked condensed ring structure, manufactured by Miwon)

A-22: dicyclopentenyl diacrylate (bifunctional (meth) acrylate monomer having an aliphatic crosslinked condensed ring structure)

A-23: dicyclopentanyl diacrylate (bifunctional (meth) acrylate monomer having an aliphatic crosslinked condensed ring structure)

A-24: Decahydronaphthalene diacrylate

A-25: Isobornyl diacrylate (bifunctional (meth) acrylate monomer having an aliphatic crosslinked ring structure)

A-27: tricyclodecane triacrylate (trifunctional (meth) acrylate monomer having an aliphatic crosslinking condensed ring structure)

a-21: neopentyl glycol diacrylate (KAYARAD NGPDA, a bifunctional (meth) acrylate monomer having an aliphatic condensed ring structure, an aliphatic crosslinked ring structure and an aliphatic crosslinked condensed ring structure, manufactured by Nippon Kayaku Co., Ltd.)

a-22: ECH-modified hexahydrophthalic acid diacrylate (denacol DA-722, manufactured by Nagase ChemteX, aliphatic condensed ring structure, aliphatic crosslinked ring structure and bifunctional (meth) acrylate monomer having no aliphatic crosslinked condensed ring structure )

a-23: naphthalene diacrylate (bifunctional (meth) acrylate monomer having an aliphatic condensed ring structure, an aliphatic crosslinked ring structure and an aliphatic crosslinked condensed ring structure)

A-31: trimethylolpropane triacrylate (Miramer M300, manufactured by Miwon)

A-32: Pentaerythritol triacrylate (A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.)

A-33: dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by Nihon Kayaku Co., Ltd.)

P-1: Lucilin TPO-L (manufactured by BASF)

P-2: Irgacure OXE-01 (manufactured by BASF)

P-3: Irgacure OXE-02 (manufactured by BASF)

P-4: Irgacure OXE-03 (manufactured by BASF)

C-1: KF-6012 (manufactured by Shin-Etsu Chemical Co., Ltd., releasing agent, polyether-modified silicone oil)

C-2: KF-6011 (manufactured by Shin-Etsu Chemical Co., Ltd., releasing agent, polyether-modified silicone oil)

C-3: KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd., releasing agent, polyether-modified silicone oil)

O-1: oleic acid amide (diamide O-200, manufactured by Nippon Kayaku Co., Ltd.)

O-2: EX-321L (epoxy compound, manufactured by Nagase Chemtex Co., Ltd.)

&Lt; Evaluation of inkjet dischargeability &

Each of the curable compositions was evaluated for discharging property by using an ink jet discharging device (DMP2800, manufactured by Fuji Film Dimatix Co., Ltd.). As the ink jet head, 16 nozzles (the number of nozzles) were used, and the presence or absence of nozzle clogging after ejection a predetermined number of times was checked.

5: No nozzle clogging after ejection of 10,000 times

4: After ejection of 10 million times, one nozzle clogging

3: After ejection of 100,000 times, two nozzle clogging

2: After ejection of 100,000 times, nozzle clogging 3 to 5 places

1: After ejection of 100,000 times, nozzle clogging at 6 points or more

&Lt; Evaluation of imprinting property (transferability) >

Each of the curable compositions was applied to the glass substrate by ink-jet so as to have a film thickness of 200 nm. The coated substrate Co., Oak assay Saku high pressure mercury lamp (lamp power 2000㎽ / ㎠) vacuum level in the setting for nanoimprint apparatus as a light source, a mold pressing force 0.8kN, and exposure is 10Torr (about 1.33 × 10 ⁴ ㎩) of syoje , A polydimethylsiloxane having a 100 nm line / space pattern and a groove depth of 100 nm (&quot; SILPOT 184 &quot; manufactured by Dow Corning Toray Co., Ltd.) was cured at 80 캜 for 60 minutes under the conditions of , And further exposed from the surface of the mold under the condition of 240 mJ / cm &lt; 2 &gt;. After exposure, the mold was peeled off to obtain a resist pattern. The pattern shape after transfer was observed with a scanning electron microscope (100,000 times) and an optical microscope (1,000 times), and the pattern shape was evaluated according to the following criteria.

5: Transfer rate of mold shape 95% or more

4: Transfer rate of mold shape 90% or more and less than 95%

3: Transfer rate of mold shape 80% or more and less than 90%

2: Transfer rate of mold shape 70% or more and less than 80%

1: Transfer rate of mold shape is less than 70%

&Lt; Evaluation of dry etching titration &

(Evaluation of etching resistance (etching rate)

Similarly to the evaluation of the imprinting property, after the application and exposure, the mold was peeled off to obtain a resist pattern. The obtained pattern was subjected to dry etching using a dry etching apparatus &quot; CDE-80N (manufactured by Shibaura Mechatronics Co., Ltd.) &quot;, and as an etching gas, CF ₄ 50 ml / min, O ₂ 10 ml / min, Second, the film thickness before and after the treatment was measured, and the film reduction amount with respect to the time of dry etching was calculated. And evaluated according to the following criteria.

5: Etching rate less than 3 nm / sec

4: Etching rate is 3 nm / sec or more and less than 4 nm / sec

3: Etching rate of 4 nm / sec or more and less than 5 nm / sec

2: Etching rate of 5 nm / sec or more and less than 6 nm / sec

1: Etching rate of 6 nm / sec or more

(Evaluation of Strength (Pattern Collapse)

The pattern shape after the dry etching treatment was observed with a scanning electron microscope (100,000 times) and an optical microscope (1,000 times), and the presence or absence of pattern collapse was evaluated according to the following criteria.

5: No pattern collapse

4: Pattern collapse occurs less than 0.5% of total area

3: Pattern collapse occurs more than 0.5% and less than 1% of the whole area

2: Pattern collapse occurs more than 1% and less than 3% of the whole area

1: Pattern collapse occurs more than 3% of the whole area

[Table 2]

As shown in the above results, the examples were good in ink jet dischargeability. In addition, the etching rate was good and the etching resistance was excellent. Further, it is possible to form a pattern having excellent strength, and it is possible to suppress occurrence of pattern collapse.

On the other hand, in the comparative example, at least one of the inkjet dischargeability, the etching rate, and the pattern collapse was inferior to those in Examples.

Claims (18)

Monofunctional (meth) acrylate monomers A1,
(Meth) acrylate monomer A2 having at least one structure selected from an aliphatic condensed ring structure, an aliphatic crosslinked ring structure and an aliphatic crosslinked condensed ring structure,
As the polyfunctional (meth) acrylate monomer other than the (meth) acrylate monomer A2, a trifunctional or more (meth) acrylate monomer A3,
Photopolymerization initiator
Wherein the curable composition is a curable composition,
Wherein the total mass of the (meth) acrylate monomer A1, the (meth) acrylate monomer A2 and the (meth) acrylate monomer A3 is 70% by mass or more of the total mass of the curable composition,
(Meth) acrylate monomer A1 is contained in an amount of 40 to 130 parts by mass with respect to 100 parts by mass of the (meth) acrylate monomer A2,
(Meth) acrylate monomer A3 in an amount of 5 to 65 parts by mass based on 100 parts by mass of the (meth) acrylate monomer A2,
Wherein the curable composition has a viscosity at 23 캜 of 25 mPa s or less. The method according to claim 1,
Wherein the (meth) acrylate monomer A1 is contained in an amount of 40 to 100 parts by mass based on 100 parts by mass of the (meth) acrylate monomer A2. 3. The method according to claim 1 or 2,
Wherein the (meth) acrylate monomer A3 is contained in an amount of 5 to 30 parts by mass based on 100 parts by mass of the (meth) acrylate monomer A2. 3. The method according to claim 1 or 2,
Wherein the (meth) acrylate monomer (A2) contains 30 to 60 mass% of the total mass of the curable composition. 3. The method according to claim 1 or 2,
The (meth) acrylate monomer A1 comprises a monofunctional (meth) acrylate monomer having a cyclic structure. 3. The method according to claim 1 or 2,
The (meth) acrylate monomer A1 contains a monofunctional (meth) acrylate monomer having a cyclic structure in an amount of 50 to 100 mass% with respect to the total mass of the (meth) acrylate monomer A1. 3. The method according to claim 1 or 2,
Wherein the (meth) acrylate monomer (A2) has at least one structure selected from an aliphatic crosslinked ring structure and an aliphatic crosslinked condensed ring structure. 3. The method according to claim 1 or 2,
The (meth) acrylate monomer A2 has an aliphatic crosslinked condensed ring structure. 3. The method according to claim 1 or 2,
Wherein the (meth) acrylate monomer A2 has an aliphatic crosslinked fused ring structure including a bicyclo ring or a tricyclo ring. 3. The method according to claim 1 or 2,
Wherein the (meth) acrylate monomer A2 is at least one selected from tricyclodecane dimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate and dicyclopentenyl (meth) acrylate. . 3. The method according to claim 1 or 2,
Wherein the (meth) acrylate monomer A3 is a chain aliphatic (meth) acrylate monomer. 3. The method according to claim 1 or 2,
In addition, a curable composition comprising a release agent. 13. The method of claim 12,
Wherein the mold release agent is a silicone oil. 3. The method according to claim 1 or 2,
Ink jet, curable composition. 3. The method according to claim 1 or 2,
Curable composition for impregnation. A process for producing a curable composition, comprising the steps of: applying the curable composition of claim 1 onto a mold having a substrate or pattern;
A step of sandwiching the curable composition between the mold and the substrate,
Curing the curable composition by irradiating light with the curable composition sandwiched between the mold and the substrate;
And a step of peeling the mold. 17. The method of claim 16,
Wherein the curable composition is applied onto the substrate or a mold having the pattern by an inkjet method. A method for forming a pattern according to claim 16 or 17, comprising the steps of: forming a pattern on a substrate;
And etching the base material by using the formed pattern as a mask.