WO2019208613A1 - Curable composition and pattern manufacturing method - Google Patents

Abstract

The curable composition according to the present invention contains at least one type of polymerizable compound represented by formula (1) or formula (2), and a polymerization initiator. The curable composition has relatively fast photocuring speed, and can be suitably used in pattern formation using ink printing technology. (In the formulas, R¹ is a hydrogen atom or a methyl group, R² is a divalent or trivalent straight-chain, branched, or cyclic aliphatic hydrocarbon group, or a divalent or trivalent aromatic group, R³ is a divalent or trivalent aromatic group, and m and n are the integer 1 or 2.)

Description

CURABLE COMPOSITION AND METHOD FOR PRODUCING PATTERN

The present invention relates to a polymerizable compound used for imprint applications and the like, and a curable composition containing the polymerizable compound and a polymerization initiator. Moreover, it is related with the imprint which forms a pattern using the said curable composition.

Imprinting is one of the fine processing methods required for manufacturing semiconductor integrated circuits. Imprint is a state in which a mold having a fine concavo-convex pattern is pressed against a curable composition applied to a substrate, the curable composition is cured by light, heat, etc. This is a method for producing “a member in which a cured film having a fine concavo-convex pattern shape is arranged on a substrate” (hereinafter sometimes referred to as a member with a pattern). In imprinting, the formation of a nano-sized uneven pattern (1 nm or more and 100 nm or less) is particularly called nanoimprinting.

For example, Patent Document 1 discloses a (meth) acrylic acid ester monomer, vinyl ether compound, styrene derivative, propenyl having one or more (meth) acryloyl groups as a component (polymerizable compound) of a curable composition used for nanoimprinting. It is disclosed that ether or butenyl ether can be used.

Patent Document 2 describes that a specific divalent (meth) acrylic acid ester monomer having two benzene skeletons can be preferably used as a curable composition component of nanoimprint.

Patent Document 3 includes an amine compound (hydrogen donor) having a (poly) oxyalkylene group having a fluoroalkyl group in a nanoimprint curable composition containing various (meth) acrylic acid esters as monomer components. It is disclosed that when added as an agent, the curing sensitivity (curing speed) is remarkably improved when the curable composition is photocured.

In this specification, (meth) acryl means acryl and methacryl, (meth) acrylate means acrylate and methacrylate, and (meth) acryloyl means acryloyl and methacryloyl.

Imprint is composed of a plurality of processes, and among them, the time required for the “curing process” for curing the curable composition with light, heat, etc. greatly affects the overall imprint production efficiency. In Patent Document 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine is used to improve photocurability. The addition of chain transfer agents such as -2,4,6 (1H, 3H, 5H) -trione is disclosed. In Patent Document 3, as described above, a specific amine compound is allowed to coexist as an additive, and the photocuring rate has been successfully improved.

JP 2010-114209 A JP 2007-084625 A JP 2014-237632 A

In the present invention, it is an object to obtain a polymerizable compound having a high curing rate and a curable composition containing the polymerizable compound.

The influence of the molecular structure of the polymerizable compound (monomer) in the curable composition on the curing rate of the curable composition is not clear. For example, as shown in Comparative Examples 1 to 3 in this specification, phenyl acrylate, 4-hydroxyphenyl acrylate, or styrene, which is a typical styrene monomer, is often used as an acrylic monomer. , The cure rate ranged from 5.6% to 88.5%. In Comparative Examples 1 to 3, the curing rate of the curable composition largely depended on the basic skeleton of the monomer (whether it is an acrylic monomer or a styrene monomer).

As a result of intensive studies, the present inventors have surprisingly found that “—C (CF ₃ ) ₂ OH group” (hereinafter referred to as the “-C (CF ₃ ) ₂ OH group”) is maintained in the side chain while maintaining the basic skeleton (main chain structure) of these polymerizable compounds. It was found that the curing rate can be improved by using a novel curable composition containing a polymerizable compound into which a hexafluoroisopropanol group or a HFIP group is introduced).

As a result of further intensive studies by the inventors, it has been found that the above problem can be solved by providing the polymerizable compound represented by the formula (1) or the formula (2) to the curable composition for imprinting. It was.

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a divalent or trivalent linear, branched or cyclic aliphatic hydrocarbon group, or a divalent or trivalent aromatic group. R ³ is a divalent or trivalent aromatic group, and m and n are integers of 1 to 2.)

That is, the polymerizable monomer represented by the above formulas (1) and (2) has “—C (CF ₃ ) _{2 at} the end of the side chain of the polymerization site (C = C double bond site). This is common in that “OH group” (HFIP group) is introduced. When the polymerizable compound represented by the formula (1) and the formula (2) is used in the curable composition (Example of the present specification), the polymerizable compound having no HFIP group corresponding thereto is curable. When compared with the case of using the composition (Comparative Example of the present specification), the curing rate of the former was significantly higher than that of the latter. That is, the “HFIP group at the side chain end” has an effect of significantly increasing the curing rate as a polymerizable compound.

The present inventors have also found a manufacturing method (pattern forming method) of “a member in which a cured film having a pattern shape is arranged on a substrate” using the curable composition thus found, and completed the invention. I came to let you.

That is, the present invention includes the following inventions.

[Invention 1]
The curable composition containing at least 1 sort (s) of the polymeric compound represented by following formula (1) or Formula (2), and a polymerization initiator.

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a divalent or trivalent linear, branched or cyclic aliphatic hydrocarbon group, or a divalent or trivalent aromatic group. R ³ is a divalent or trivalent aromatic group, and m and n are integers of 1 to 2.)

[Invention 2]
Curability of Invention 1, wherein the polymerizable compound is any polymerizable compound represented by the following formula (1a), formula (1b), formula (1c), formula (1d), or formula (2a): Composition.

[Invention 3]
The curable composition of Invention 1 or Invention 2, wherein the polymerization initiator is a photopolymerization initiator.

[Invention 4]
The curable composition according to any one of Inventions 1 to 3, wherein the composition is an optical nanoimprinting composition.

[Invention 5]
The manufacturing method of the member which arranged the cured film which has a pattern shape on a board | substrate including the following each process.
Arranging step: A step of arranging the curable compositions of inventions 1 to 4 on a substrate.
Mold contact step: a step of bringing a mold having a pattern shape into contact with the curable composition disposed on the substrate.
Curing step: a step of curing the curable composition in contact with the mold with light or heat to form a cured film.
Mold release step: a step of separating the mold from the cured film to obtain the patterned member.

[Invention 6]
The manufacturing method of the member with a pattern of the invention 5 with which the said type | mold contact process is performed in the gas atmosphere containing a condensable gas.

[Invention 7]
The condensable gas in the contacting step is 1,1,1,3,3-pentafluoropropane (HFC-245fa), trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)) Cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1 , 3,3,3-tetrafluoropropene (HFO-1234ze (Z)).

According to the present invention, a polymerizable compound having a high curing rate can be obtained, and by using it, a curable composition having a high curing rate that is particularly useful in imprinting can be provided. Moreover, there exists an effect that the pattern formation method in the imprint using the said curable composition of this invention is provided.

It is a cross-sectional schematic diagram which shows the example of embodiment in the manufacturing method (pattern formation method) of the member with a film | membrane pattern of this invention.

The present invention will be described in detail. The present invention is not limited to the embodiments described below. Based on the ordinary knowledge of those skilled in the art, the present invention includes those in which the embodiments described below are appropriately modified and improved without departing from the spirit of the present invention.

In this specification, description will be given in the following order.
1. 1. A curable composition containing a polymerizable compound having an HFIP group as a constituent component About pattern formation method

1. About the curable composition containing the polymeric compound which has HFIP group as a structural component The curable composition of this invention is the following.
At least one polymerizable compound having an HFIP group represented by formula (1) or formula (2);
And a polymerization initiator.

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a divalent or trivalent linear, branched or cyclic aliphatic hydrocarbon group, or a divalent or trivalent aromatic group. R ³ is a divalent or trivalent aromatic group, and m and n are integers of 1 to 2.)

As shown in Formula (1) and Formula (2), the polymerizable compound used in the curable composition of the present invention has an HFIP group at the side chain end. As described above, it was found that the “HFIP group at the end of the side chain” of this polymerizable compound has an effect of significantly increasing the curing rate of the curable composition.
The cause of this is not necessarily clear, but in view of the fact that there is no significant difference in the cure rate between benzyl acrylate (Comparative Example 1 in this specification) and 4-hydroxybenzyl acrylate (Comparative Example 2), “Existence” alone cannot explain the increase in cure rate. Also, in the case of “a monomer having two CF ₃ groups but not having OH” (Reference Example 1), the curing rate is not so high, so only “existence of CF ₃ group” The increase in cure rate cannot always be explained. From these facts, it is speculated that the effect of improving the curing rate is attributed to the “unique skeleton having both the CF ₃ group and the OH group” of the polymerizable monomer of the present invention.

The curing rate (polymerization rate) may be increased by adding various additives to the curable composition as disclosed in Patent Documents 1 and 3 above. Also, the curing rate may be adjustable depending on the basic skeleton of the polymerizable monomer (for example, an acrylic monomer generally has a higher curing rate than a styrene monomer). However, it may be necessary to reduce the amount of additive used, and there may be a demand for using a certain amount of a basic skeleton having a relatively slow polymerization as a polymerizable monomer. In that respect, it is significant that the curing rate can be significantly increased only by introducing the HFIP group into the side chain.

It is a novel finding that the curing rate is increased by introducing HFIP groups into the side chain of the polymerizable compound contained in the curable composition. If the curable composition of the present invention is used, it is not necessary to add an additive separately to complicate the composition profile in the system, and it is possible to contribute to productivity improvement such as imprint.

In addition, the synthesis method of the compound represented by Formula (1) and Formula (2) is disclosed in JP 2011-164345 A, JP 2004-83900 A, JP 2005-239710 A, Chem. Mater. 2003.15.1512- 1517.

The curable composition of the present invention further includes, as an optional component,
A polymerizable compound other than the polymerizable compound represented by the above formula (1) or formula (2) (sometimes referred to as “other polymerizable compound” in this specification);
A sensitizer,
A surfactant,
A solvent,
Any one or more selected from the group consisting of various additives may be included.

Hereinafter, each component will be described. For convenience of explanation, “polymerizable compound represented by formula (1) or formula (2)” and “other polymerizable compounds” are collectively described as “polymerizable compound”. Other optional components will be described as “other additive components”.

1-1. Polymerizable Compound The polymerizable compound is a generic term for “polymerizable compound represented by formula (1) or formula (2)” and “other polymerizable compounds” as described above. The polymerizable compound is the main component of the curable composition for imprints. The content of the polymerizable compound in the curable composition is usually 50% by mass or more, and typically 80% by mass or more. When a curable composition contains a solvent, it is not prevented that there is little content of a polymeric compound from this.

In Formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is a divalent or trivalent aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is linear, branched or It is cyclic or a divalent or trivalent aromatic group, and m is an integer of 1 to 2.

Examples of the divalent aliphatic hydrocarbon group that can be used for R ² include linear or branched alkylene groups such as methylene, ethylene, isopropylene, and t-butylene, cyclobutene, cyclopropylene, cyclopentylene, and cyclohexylene. And cyclic structures such as norbornylene and adamantylene.

Examples of the trivalent aliphatic hydrocarbon group that can be used for R ² include alkanetriyl groups such as methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, and pentanetriyl group, cyclobutanetriyl group, cyclohexane Examples of the cyclic structure include cycloalkanetriyl groups such as propanetriyl group, cyclopentanetriyl group, and cyclohexanetriyl group, norbornanetriyl group, adamantanetriyl group, and norbornenetriyl group.

Examples of the divalent aromatic group that can be used for R ² include a phenylene group, a benzylylene group, a naphthylene group, and an anthrylene group.

Examples of the trivalent aromatic group that can be used for R ² include a benzenetriyl group, a naphthalenetriyl group, and an anthracentriyl group.

In the formula (2), R ¹ is a hydrogen atom or a methyl group, R ³ is a divalent or trivalent aromatic group, and n is an integer of 1 to 2.

Examples of the divalent aromatic group that can be used for R ³ include a phenylene group, a benzylylene group, a naphthylene group, and an anthrylene group.

Examples of the trivalent aromatic group that can be used for R ³ include a benzenetriyl group, a naphthalenetriyl group, and an anthracentriyl group.

R ² in formula (1) or R ³ in formula (2) is preferably an aromatic ring or alicyclic skeleton, more preferably a phenylene group, a benzylylene group, or a benzenetriyl group. This is because having an aromatic ring or an alicyclic skeleton improves the dry etching resistance, wet process resistance, mechanical strength, and the like of a cured film having a pattern shape obtained by curing the curable composition.

As a polymeric compound represented by Formula (1), the following structure can be illustrated as a preferable thing.

As a polymeric compound represented by Formula (2), the following structure can be illustrated as a preferable thing.

Among these, the polymerizable compound represented by the following formula (1a), formula (1b), formula (1c), formula (1d), and formula (2a) has a corresponding structure of “polymerization without HFIP group”. The increase in the curing rate (polymerization rate) when compared with the “polymeric compound” is remarkable, and is a particularly preferable polymerizable compound.

In addition, as shown in Examples 6 to 8 of the present specification, resins obtained by polymerizing (curing) these polymerizable compounds are excellent in releasability from the mold.

Further, as described above, if the “magnification rate” is particularly emphasized, the polymerizable compound of the formula (1), that is, the (meth) acrylic polymerizable compound is more polymerizable. It is advantageous over a compound, that is, a styrene-based polymerizable compound. In addition, among the polymerizable compounds of the formula (1), the “acrylic type (R ¹ is a hydrogen atom)” has a higher curing rate than the “methacrylic type (R ¹ is methyl)”. . That is, among the polymerizable compounds of the formulas (1a) to (1d) and the formula (2a), the formula (1a) belonging to the polymerizable compound of the formula (1) and corresponding to the “acrylic monomer”, The polymerizable compounds of formula (1b) and formula (1c) are particularly preferred (see Examples 1 to 3 herein).

However, what type of polymerizable compound is used should be determined in consideration of not only the curing rate but also the balance with other physical properties. In that respect, even if the styrene monomer of the formula (2a), which has a relatively low polymerization rate, is introduced, the curing rate is significantly improved by introducing the HFIP group compared to styrene having no HFIP group. What is noted is the notable point of the present invention.

As the polymerizable compound, the polymerizable compound represented by the formula (1) or the formula (2) may be used alone. However, “other polymerizable compounds” can be used in combination with the polymerizable compound represented by the formula (1) or the formula (2), so that the filling speed of the curable composition and the mechanical properties of the cured film can be increased. It may be possible to adjust the strength. The “other polymerizable compounds” are not particularly limited as long as they are radically polymerizable compounds, but are preferably compounds having one or more acryloyl groups or methacryloyl groups, that is, (meth) acrylic compounds. "Polymerizable compound of formula (1) or formula (2)" and "other polymerizable compound" relative to the total mass of "polymerizable compound of formula (1) or formula (2)" and "other polymerizable compound" The proportion of the “(meth) acrylic compound” in the mass is preferably 90% by mass or more.

There is no particular lower limit of the proportion of the polymerizable compound of formula (1) or formula (2) to the total mass of the polymerizable compound, but the proportion of the polymerizable compound of formula (1) or formula (2) is usually 10 It is at least 30% by mass, preferably at least 30% by mass. When emphasizing the excellent curability and releasability of the polymerizable compound of formula (1) or formula (2), the ratio is set to 60% by mass or more (including 100% by mass). This is particularly preferred. On the other hand, even if the content of the polymerizable compound represented by the formula (1) or the formula (2) is less than these, even if the content is relatively small due to the polymerizable compound, the curability The curability and releasability of the composition is improved by the contribution. Therefore, even when a smaller amount of the polymerizable compound represented by the formula (1) or the formula (2) is included, it is not excluded from the scope of the present invention.

Among the “other polymerizable compounds”, monofunctional (meth) acrylic compounds having one acryloyl group or methacryloyl group include phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, and phenoxyethoxyethyl. (Meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 3- (2-phenylphenyl) -2-hydroxy Propyl (meth) acrylate, EO-modified p-cumylphenol (meth) acrylate, 2-bromophenoxyethyl (meth) acrylate, 2,4-dibromophenoxyethyl (meth) acrylate, 2,4,6-tribromophene Xylethyl (meth) acrylate, EO-modified phenoxy (meth) acrylate, PO-modified phenoxy (meth) acrylate, polyoxyethylene nonylphenyl ether (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl -2-Adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropiyl (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, polyethylene Glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, diacetone (meth) Acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acryl Amide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, Alternatively, N, N-dimethylaminopropyl (meth) acrylamide can be exemplified, but is not limited thereto.

Commercial products corresponding to these monofunctional (meth) acrylic compounds include trade names, Aronix M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (above, Toagosei Co., Ltd.) Manufactured), MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, Viscoat # 150, # 155, # 158, # 190, # 192, # 193, # 220, # 2000, # 2100, # 2150 (above Osaka Organic Chemical Co., Ltd.), light acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO -A, P-200A, NP 4EA, NP-8EA, epoxy ester M-600A (above, manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD TC110S, R-564, R-128H (above, manufactured by Nippon Kayaku Co., Ltd.), NK ester AMP-10G, AMP- 20G (above, Shin-Nakamura Chemical Co., Ltd.), FA-511A, 512A, 513A (above, Hitachi Chemical Co., Ltd.), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), VP (manufactured by BASF Japan Ltd.), ACMO, DMAA, DMAPAA (above, manufactured by Kojin Co., Ltd.) and the like are exemplified, but not limited thereto.

Among the “other polymerizable compounds”, polyfunctional (meth) acrylic compounds having two or more acryloyl groups or methacryloyl groups include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and EO modification. Trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (acryloyl) Oxy) isocyanurate, bis (hydroxymethyl) tricyclodecane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified 2,2-bis (4-((meta ) Acryloxy) phenyl) propane, PO-modified 2,2-bis (4-((meth) acryloxy) phenyl) propane, or EO, PO-modified 2,2-bis (4-((meth) acryloxy) phenyl) propane Can be exemplified But it is not limited thereto.

In the present specification, EO represents ethylene oxide, and the EO-modified compound means that it has at least one ethyleneoxy group. PO represents propylene oxide, and the PO-modified compound means having at least one propyleneoxy group.

Commercially available products corresponding to polyfunctional (meth) acrylic compounds include trade names, Iupimer UV SA1002, SA2007 (above, manufactured by Mitsubishi Chemical Corporation), Biscoat # 195, # 230, # 215, # 260, # 335HP, # 295, # 300, # 360, # 700, GPT, 3PA (above, manufactured by Osaka Organic Chemical Co., Ltd.), Light Acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP- 4PA, TMP-A, PE-3A, PE-4A, DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (Nippon Kayaku Co., Ltd.), Aronix M208, M210 M215, M220, M240, M305, M309, M310, M315, M325, M400 (above, manufactured by Toagosei Co., Ltd.) or Lipoxy VR-77, VR-60, VR-90 (above, manufactured by Showa Denko KK) However, it is not limited to these.

Examples of vinyl compounds having one or more vinyl groups include styrene, 4-hydroxystyrene, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, Di- or trivinyl ether compounds such as dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, ethyl vinyl ether, n- Butyl vinyl ether, iso Til vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether And the like.

The above radical polymerizable compounds may be used alone or in combination of two or more.

1-2. Polymerization initiator The polymerization initiator includes a photopolymerization initiator and a thermal polymerization initiator.

[Photopolymerization initiator]
The photopolymerization initiator is a substance that generates reactive species that cause a polymerization reaction of the polymerizable compound by light stimulation. Specific examples include a photo radical generator that generates radicals by light stimulation.

Examples of the photo radical generator include 2,4,5-triarylimidazole dimer which may have a substituent, benzophenone derivative, aromatic ketone derivative, quinones, benzoin ether derivative, benzoin derivative, benzyl derivative, acridine Derivatives, N-phenylglycine derivatives, acetophenone derivatives, thioxanthone derivatives, other photoradical generators, and commercial products thereof can be mentioned. Each is illustrated below. The following photo radical generators may be used alone or in combination of two or more.
<2,4,5-triarylimidazole dimer optionally having substituent>
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4 , 5-diphenylimidazole dimer, or 2- (o- or p-methoxyphenyl) -4,5-diphenylimidazole dimer <benzophenone derivative>
Benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 4- chlorobenzophenone 4,4′-dimethoxybenzophenone or 4,4′-diaminobenzophenone <Aromatic ketone derivative>
2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one <Quinones>
2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, or 2,3-dimethylanthraquinone <Benzoin ether derivative>
Benzoin methyl ether, benzoin ethyl ether, or benzoin phenyl ether <benzoin derivative>
Benzoin, methylbenzoin, ethylbenzoin, or propylbenzoin <Benzyl derivatives>
Benzyldimethyl ketal <acridine derivative>
9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane <N-phenylglycine derivative>
N-phenylglycine <acetophenone derivative>
Acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, or 2,2-dimethoxy-2-phenylacetophenone <thioxanthone derivative>
Thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, or 2-chlorothioxanthone <Other photoradical generator>
Xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, or bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide <commercially available product>
Product name, Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173 (above, manufactured by Ciba Japan Co., Ltd.), Lucirin TPO , LR8883, LR8970 (above, manufactured by BASF Japan Ltd.), Ubekrill P36 (UCB Japan Ltd.), and the like, but are not limited thereto.

[Thermal polymerization initiator]
The thermal polymerization initiator is a substance that generates reactive species that cause a polymerization reaction of the polymerizable compound by thermal stimulation. Specific examples include thermal radical generators that generate radicals upon thermal stimulation.

Examples of the thermal radical generator include azo compounds and organic peroxides.
<Azo compound>
Azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyronitrile), 2,2′-azobis-2-methylbutyronitrile, Examples include 1,1′-azobis (1-cyclohexanecarbonitrile), 2,2′-azobis (methylisobutyrate), or 2,2′-azobis (2-amidinopropane) dihydrochloride.
<Organic peroxide>
Examples include dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, or paramentane hydroperoxide can do.

In the curable composition of the present invention, one polymerization initiator may be used alone, or two or more polymerization initiators may be used in combination. Here, in the case where the step of curing the curable composition is based on light, a photopolymerization initiator is used as the initiator, and in the case where it is based on heat, a thermal polymerization initiator is used as the initiator. Among these initiators, it is preferable to use a photopolymerization initiator when manufacturing a film to be a microstructure such as a semiconductor integrated circuit. This is because when a photopolymerization initiator is used, a heat process such as heating or cooling is not required in the process for producing a cured film, and productivity is excellent.

In the present invention, the content of the polymerization initiator contained in the curable composition is not particularly limited, but is preferably 0.01% by mass or more and 15% with respect to the mass (total mass) of the curable composition. It is below mass%. More preferably, they are 0.1 mass% or more and 7 mass% or less, Especially preferably, they are 1 mass% or more and 5 mass% or less. Within this range, both the curing rate of the curable composition and the strength (resin strength) of the film (cured film) are excellent.

1-3. Other Additive Components The curable composition of the present invention may contain additional additive components in addition to the above-described components as long as the effects of the present invention are not impaired, according to various purposes. Examples of such additive components include mold release agents, surfactants, sensitizers, hydrogen donors, antioxidants, solvents, and polymer components. In the present invention, the curable composition preferably contains a sensitizer. This will be described below.

[Sensitizer]
By including a sensitizer, there is a tendency that the polymerization reaction is accelerated and the reaction conversion rate is improved. Examples of the sensitizer include a hydrogen donor and a sensitizing dye.

When the curable composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 10% by mass or less with respect to the mass of the polymerizable compound. More preferably, it is 0.1 mass% or more and 5 mass% or less. Here, when the content of the sensitizer is 0.1% by mass or more, the polymerization promoting effect can be effectively expressed. Moreover, when content of a sensitizer is 10 mass% or less, there exists a tendency for solubility and storage stability to be excellent.

[Hydrogen donor]
A hydrogen donor is a compound in which hydrogen is donated to an initiation radical generated from a polymerization initiator or a radical at a polymerization growth terminal, and the hydrogen donor itself generates a radical. If the polymerization initiator is a photoradical generator, the polymerization rate may be improved.

Examples of the hydrogen donor include amine compounds and mercapto compounds. Examples of these compounds that act as hydrogen donors are shown below, but are not limited thereto.
<Amine compound>
N-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzylisothiouronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate, triethylenetetramine, 4,4'-bis (Dialkylamino) benzophenone, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethanolamine, or N-phenylglycine Specific examples of 4,4′-bis (dialkylamino) benzophenone include 4,4′-bis (diethylamino) benzophenone.
<Mercapto compound>
Examples thereof include 2-mercapto-N-phenylbenzimidazole and mercaptopropionic acid ester.

[Sensitizing dye]
A sensitizing dye is a compound that is excited by absorbing light of a specific wavelength and acts on a photopolymerization initiator. The action here refers to energy transfer or electron transfer from the sensitizing dye in the excited state to the photopolymerization initiator. If it is added when the photopolymerization initiator is a photoradical generator, the polymerization rate may be improved.

Sensitizing dyes include anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carabazole derivatives, benzophenone derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thiopyrylium salt dyes, merocyanine Examples of dyes include quinoline dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, and pyrylium salt dyes. However, it is not limited to these.

Sensitizers may be used alone or in combination of two or more.

[Polymer component]
The curable composition of the present invention may contain a polymer component. Examples of the polymer component herein include the above 1-1. (Meth) acrylic polymer (for example, polymethyl methacrylate) and vinyl polymer (for example, polystyrene) containing the repeating unit derived from the polymerizable compound described in the paragraph of (5) as a structural unit are included. The polymer component may be a copolymer.

[solvent]
The curable composition of the present invention may contain a solvent. The content of the solvent is preferably 3% by mass or less, more preferably 1% by mass or less, and particularly preferably not contained with respect to the mass of the entire composition. Solvents that can be preferably used in the composition of the present invention include those commonly used in curable compositions for nanoimprints and photoresists, and those that dissolve and uniformly disperse the compounds used in the present invention. There is no particular limitation as long as it does not react with these components.

Examples of the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, or esters. Each is illustrated below.
<Alcohols>
Methanol or ethanol <Ethers>
Tetrahydrofuran <Glycol ethers>
Ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, or ethylene glycol monoethyl ether <Ethylene glycol alkyl ether acetates>
Methyl cellosolve acetate or ethyl cellosolve acetate <Diethylene glycols>
Diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, or diethylene glycol monobutyl ether <Propylene glycol alkyl ether acetates>
Propylene glycol methyl ether acetate or propylene glycol ethyl ether acetate <Aromatic hydrocarbons>
Toluene or xylene <Ketone>
Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, or 2-heptanone <Esters>
Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, or ethyl lactate

It should be noted that the solvent is such that the curable composition containing the polymerizable compound of the present invention is in a liquid state or fluid even at a temperature (preferably 20 to 50 ° C.) of the “mold contact step” described later. It is not necessary to use it when showing the property. On the other hand, when the curable composition is solid at the temperature at which the “mold contact process” is performed and the fluidity is insufficient, the efficiency of the mold contact process can be easily improved by adding a solvent to increase the fluidity. ,preferable.

1-4. Preparation of curable composition [Temperature when compounding curable composition]
When preparing a curable composition by mixing and dissolving a polymerizable compound and a polymerization initiator, it is carried out under a predetermined temperature condition. From workability etc., Preferably, they are 0 degreeC or more and 100 degrees C or less, More preferably, they are 10 degreeC or more and 50 degrees C or less.

[Viscosity of curable composition]
The viscosity of the curable composition of the present invention is not critical to the practice of the present invention, but the viscosity at 23 ° C. of the mixture of components excluding the solvent is preferably 1 cP or more and 100 cP or less, more Preferably, it is 5 cP or more and 50 cP or less, More preferably, it is 6 cP or more and 20 cP or less. These may vary depending on the blend ratio of the polymerizable compound of the present invention and other polymerizable compounds, but can be adjusted by changing the blend ratio according to techniques of those skilled in the art.

[Surface tension of curable composition]
The surface tension of the curable composition of the present invention is preferably 5 mN / m or more and 70 mN / m or less, more preferably 7 mN / m or more and 35 mN / m at 23 ° C. for the mixture of components excluding the solvent. m or less, more preferably 10 mN / m or more and 32 mN / m or less. Here, when the surface tension is lower than 5 mN / m, when the curable composition is brought into contact with the mold, it may take a long time for the composition to fill the recesses in the fine pattern on the mold. On the other hand, when the surface tension is higher than 70 mN / m, the surface smoothness may be lowered. These are also physical properties that can be changed depending on the blend ratio of the polymerizable monomer of the present invention and the other monomer, and can be adjusted by changing the blend ratio by a person skilled in the art.

[Impurities such as particles mixed in the curable composition]
The curable composition of the present invention removes impurities such as particles as much as possible in order to prevent inadvertent irregularities in the photocured product due to particles mixed in the curable composition and pattern defects. Is desirable. Specifically, after mixing each component contained in the curable composition, it is preferable to filter with a filter having a pore diameter of 0.001 μm to 5.0 μm, for example. When performing filtration using a filter, it is more preferable to carry out in multiple stages or repeat many times. Moreover, you may filter the filtered liquid again.

As a filter used for filtration, a filter made of polyethylene resin, polypropylene resin, fluorine resin, nylon resin, or the like can be used, but is not particularly limited.

In addition, when using the curable composition of this invention for manufacture of a semiconductor integrated circuit, in order not to inhibit operation | movement of a product, the impurity (metal impurity) containing a metal atom mixes in a curable composition. It is preferable to avoid this as much as possible. Therefore, the concentration of metal impurities contained in the curable composition of the present invention is preferably 10 ppm or less, and more preferably 100 ppb or less.

2. About Pattern Forming Method Still another aspect of the present invention is a method for producing a “patterned member in which a cured film having a pattern shape is arranged on a substrate” (D) by imprinting using the above-described curable composition (hereinafter referred to as “patterned member”) , Simply referred to as the pattern forming method of the present invention), and includes the following steps.
Arrangement step: A step of arranging the above-mentioned curable composition on a substrate to obtain “a member in which the curable composition is arranged on the substrate” (A).
Mold contact step: A mold having a pattern shape is brought into contact with the curable composition in (A), and “a substrate / pattern composition having a curable composition / mold joined in this order” (B ).
Curing step: The curable composition in (B) is cured by light or heat to form a cured film, and “a member in which a substrate / patterned cured film / mold is joined in this order” (C) Obtaining step.
Mold release step: a step of separating the mold from (C) to obtain the patterned member (D).

In the pattern forming method of the present invention, the imprint includes a light imprint that is cured by light and a heat imprint that is cured by heat.

In this specification, the imprint is a method for producing “a member in which a cured film having a concavo-convex pattern shape of preferably 1 nm or more and 100 μm or less is arranged on a substrate”. Among them, nanoimprint is a method for producing “a member provided with a cured film having a concavo-convex pattern shape of 1 nm or more and 100 nm or less”. The pattern formation method of this invention can be used suitably for nanoimprint.
The “pattern forming method” is referred to here as “a member in which a cured film having a pattern shape is arranged on a substrate” described in [Invention 4] in imprinting (D). And includes the four steps of “arrangement step”, “die contact step”, “curing step”, and “mold release step” as essential. In the following description, for convenience, the “placement step”, “die contact step”, “curing step”, and “mold release step” are also referred to as steps [1] to [4], respectively.

FIG. 1 is a schematic cross-sectional view showing an example of an embodiment in the film production method of the present invention. The pattern forming method shown in FIG. 1 includes the following steps.
[1] Step of arranging a curable composition on a substrate (arrangement step, FIG. 1 (a))
[2] Step of contacting the mold with the curable composition (mold contact step, FIGS. 1 (b-1) and (b-2))
[3] Step of producing a cured film by curing the curable composition with light or heat (curing step, FIG. 1 (c))
[4] A step of separating the mold from the cured film (mold release step, FIG. 1 (d)).
Through the steps shown in [1] to [4] above, the cured product 5 and the electronic component (electronic device) or optical component having the cured product 5 can be obtained from the curable composition 1. Hereinafter, each step [1] to [4] will be described.

2-1. Step [1] (arrangement step; FIG. 1A)
First, the curable composition 1 is placed (applied) on the substrate 2 to form a coating film (FIG. 1A). The curable composition here is the curable composition of the present invention.

As the substrate to be processed corresponding to the substrate 2, a silicon wafer is usually used, but is not limited thereto. In addition to silicon wafers, aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, silicon nitride, and other known semiconductor device substrates can be selected and used. be able to. The substrate to be used (substrate to be processed) is a substrate that has improved adhesion to the curable composition by surface treatment such as silane coupling treatment, silazane treatment, or organic thin film formation. It may be used as

Examples of the method for disposing the curable composition 1 on the substrate 2 include, for example, an inkjet method, a dip coating method, an air knife coating method, a curtain coating method, a wire barcode method, a gravure coating method, an extrusion coating method, A spin coat method, a slit scan method, or the like can be used. The film thickness of the shape transfer layer (coating film) is, for example, from 0.01 μm to 100 μm, although it varies depending on the application used.

2-2. Step [2] (die contact step; FIG. 1 (b1), (b2))
Next, a step of bringing the mold 3 into contact with the coating film made of the curable composition 1 formed in the previous step (placement step) (a mold contact step, FIGS. 1B1 and 1B2) is performed. Since the mold 3 can be regarded as a seal, this process is also called a stamping process. In this step, when the mold 3 is brought into contact with the curable composition 1 (shaped transfer layer) (FIG. 1 (b1)), a coating film (part) 4 is formed on the uneven portion of the fine pattern formed on the mold 3. Is filled (FIG. 1 (b2)).

The mold 3 used in the mold contact process is made of a light transmissive material when the next process (curing process) is a photocuring process using light. Specific examples of the constituent material of the mold 3 include optically transparent resins such as glass, quartz, PMMA, and polycarbonate resins, transparent metal vapor-deposited films, flexible films such as polydimethylsiloxane, photocured films, and metal films. Can do. However, when a transparent resin is used as the constituent material of the mold 3, it is necessary to select a resin that does not dissolve in the curable composition 1. Quartz is particularly preferred because of its low thermal expansion coefficient. On the other hand, when the curing step is a thermosetting step, there is no limitation on the transparency of the material, and the above-described materials can be used as the constituent material of the mold 3.

The mold 3 may be subjected to a surface treatment before this step (die contact step) in order to improve the peelability between the cured film 5 and the surface of the mold 3. Examples of the surface treatment method include a method in which a release agent is applied to the surface of the mold 3 to form a release agent layer. Here, as a mold release agent applied on the surface of the mold 3, a silicon mold release agent, a fluorine mold release agent, a polyethylene mold release agent, a polypropylene mold release agent, a paraffin mold release agent, a montan mold release agent Agents, carnauba release agents and the like. For example, a commercially available coating mold release agent such as a trade name, Optool DSX, manufactured by Daikin Industries, Ltd. can be suitably used. In addition, a mold release agent may be used individually by 1 type, and may be used in combination of 2 or more types. Among these, a fluorine-type mold release agent is particularly preferable.

In the mold contact step, as shown in FIG. 1 (b1), when the mold 3 is brought into contact with the curable composition 1, the pressure applied to the curable composition 1 is not particularly limited, but is usually 0.1 MPa or more. , 100 MPa or less. Among them, it is preferably 0.1 MPa or more and 50 MPa or less, more preferably 0.1 MPa or more and 30 MPa or less, and further preferably 0.1 MPa or more and 20 MPa or less.

In addition, the time for bringing the mold 3 into contact with the curable composition 1 in this step is not particularly limited, but is usually 0.1 seconds or longer and 600 seconds or shorter, and is 0.1 seconds or longer and 300 seconds or shorter. Preferably, it is 0.1 seconds or more and 180 seconds or less, and particularly preferably 0.1 seconds or more and 120 seconds or less.

The environment in which this step is performed includes an air atmosphere, a reduced pressure atmosphere, and an inert gas atmosphere. Here, when performing this process, there is no restriction | limiting in particular about the pressure of atmosphere, For example, it can set suitably in the range of 1.0133 * 10 < ^-5 > MPa or more and 1.0133MPa or less.

[Inert gas]
When this step is performed in an inert gas atmosphere, examples of the inert gas used include nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbons, and a mixed gas thereof. When used for nanoimprinting, helium is preferred.

When helium is used as the inert gas, when the uneven portion of the fine pattern formed on the mold 3 in this step is filled with the inert gas in the atmosphere together with a part of the coating film 4, The inert gas can escape through the mold. For this reason, it is excellent in the filling property of the curable composition 1 to the uneven part of the mold 3.

[Condensable gas]
Moreover, you may perform this process in the gas atmosphere containing a condensable gas. In the present invention, the condensable gas refers to a gas that satisfies the following requirements (i) and (ii).
(I) A gas that exists as a gas in the atmosphere before the curable composition 1 (shaped transfer layer) and the mold 3 are in contact with each other in this step (FIG. 1 (b1)).
(Ii) The curable composition 1 and the mold 3 are in contact with each other in the atmosphere together with the coating film (part) 4 in the recesses of the fine pattern formed on the mold 3 and the gap between the mold and the substrate. Gas that is condensed and liquefied by the capillary pressure generated by the pressure at the time of filling.

Here, when the mold contact process is performed in a condensable gas atmosphere, the gas filled in the concave portions of the fine pattern of the mold 3 is liquefied, so that bubbles are less likely to be generated. The condensable gas (at least a part thereof) may be dissolved in the curable composition.

The boiling point of the condensable gas is not particularly limited as long as it is equal to or lower than the environmental temperature of this step, but a gas having a low boiling point in the range of 5 ° C. or higher and 50 ° C. or lower from the environmental temperature is preferable. If it exists in this range, the filling property of the curable composition 1 to the fine pattern uneven | corrugated | grooved part of the mold 3 will be further excellent.

In this step, the vapor pressure of the gas containing the condensable gas is not particularly limited as long as it is equal to or lower than the mold pressure at the time of imprinting in this step, but is preferably 0.1 MPa or more and 0.4 MPa or less. If it exists in this range, the filling property of the curable composition 1 to the fine pattern uneven | corrugated | grooved part of the mold 3 will be further excellent. Here, when the vapor pressure at the ambient temperature is larger than 0.4 MPa, there is a tendency that the effect of eliminating the bubbles cannot be sufficiently obtained. On the other hand, if the vapor pressure at ambient temperature is less than 0.1 MPa, pressure reduction is required, and the apparatus tends to be complicated.

The environmental temperature during this step is not particularly limited, but is preferably 20 ° C or higher and 50 ° C or lower.

Examples of condensable gases include chlorofluorocarbons (CFC), fluorocarbons (FC), hydrochlorofluoroolefins (HCFO), hydrofluoroolefins (HFO), hydrofluoroethers (HFE), and other fluorocarbons. To do.
<Chlorofluorocarbon (CFC)>
Chlorofluoromethane <Hydrochlorofluoroolefin (HCFO)>
Trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)), cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)), trans- 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (E)), cis-1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (Z)), 1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za), 1,1,2-trichloro-3,3,3-trifluoropropene (HCFO-1213xa), trans-1-chloro- 1,3,3,3-tetrafluoropropene (HCFO-1224zb (E)), cis-1-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224zb (Z))
<Hydrofluoroolefin (HFO)>
Trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz (E)), cis-1,1,1,4,4,4-hexafluoro-2-butene ( HFO-1336mzz (Z)), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)) )
<Hydrofluorocarbon (HFC)>
1,1,1,3,3-pentafluoropropane (CHF ₂ CH ₂ CF ₃ , HFC-245fa, PFP)
<Hydrofluoroether (HFE)>
Pentafluoroethyl methyl ether (CF ₃ CF ₂ OCH ₃ , HFE-245mc), 1,1,1,3,3,3-hexafluoro-2-methoxypropane (HFE-356 mmz)

Among these condensable gases, the enumeration is listed below from the viewpoint that the filling property of the curable composition 1 to the uneven portion of the fine pattern of the mold 3 is excellent when the environmental temperature of the mold contact process is 20 ° C. to 25 ° C. Are preferred.
・ 1,1,1,3,3-pentafluoropropane (vapor pressure at 23 ° C: 0.14 MPa, boiling point: 15 ° C)
・ Trichlorofluoromethane (vapor pressure 0.1056 MPa at 23 ° C., boiling point 24 ° C.)
・ Trans-1-chloro-3,3,3-trifluoropropene (boiling point 18 ° C)
・ Cis-1-chloro-3,3,3-trifluoropropene (boiling point 39 ° C.)
・ Trans-1,3,3,3-tetrafluoropropene (boiling point -19 ℃)
・ Pentafluoroethyl methyl ether Among these, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, cis-1 -Chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene are particularly preferred.

Condensable gas may be used alone or in combination of two or more. These condensable gases may be used by mixing with non-condensable gases such as air, nitrogen, carbon dioxide, helium, and argon. The non-condensable gas mixed with the condensable gas is preferably helium from the viewpoint of filling properties. When helium is used, even if it is used as a mixed gas formed by mixing a condensable gas and a non-condensable gas (helium), the filling property is excellent because helium penetrates the mold.

Of these atmospheres, the curing process does not depend on the photocuring process or the thermal curing process, and the influence on the curing reaction by oxygen or moisture can be prevented, so that the reduced pressure atmosphere, inert gas atmosphere or condensable gas can be used. An atmosphere is preferred.

2-3. Step [3] (Curing step; FIG. 1 (c))
Next, the coating film is cured. Specifically, the coating film 4 is irradiated with light through the mold 3 (FIG. 1C), or the coating film 4 is heated. In the curing step, the cured film 5 is formed by curing the coating film 4 with light or heat.

[Photocuring]
When the coating film 4 is cured by light, the light applied to the curable composition 1 constituting the coating film 4 is selected according to the sensitivity wavelength of the curable composition 1, and specifically, 150 nm to It is preferable to select and use ultraviolet light having a wavelength of about 400 nm, X-rays, electron beams or the like as appropriate. Here, many commercially available photopolymerization initiators are sensitive to ultraviolet light. For this reason, the light (irradiation light 6) applied to the curable composition 1 is particularly preferably ultraviolet light. Examples of light sources that emit ultraviolet light include high pressure mercury lamps, ultra high pressure mercury lamps, low pressure mercury lamps, deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F _2. Although an excimer laser etc. are mentioned, an ultrahigh pressure mercury lamp is especially preferable. The number of light sources used may be one or plural. Moreover, when performing light irradiation, you may carry out to the whole surface of the curable composition 1, and may carry out only to a one part area | region. Moreover, when using together a photoinitiator and a thermal-polymerization initiator, in addition to light irradiation, you may further heat-harden. The order of photocuring and thermal curing is not limited, and includes cases where thermal curing is performed after photocuring, photocuring is performed after thermal curing, and photocuring and thermal curing are performed simultaneously.

[Heat curing]
In the case of curing by heat, the heating atmosphere and the heating temperature are not particularly limited. For example, the curable composition 1 can be heated in the range of 40 ° C. or higher and 200 ° C. or lower under an inert atmosphere or under reduced pressure. Moreover, when heating the to-be-shaped transfer layer (coating film 4), a hot plate, oven, furnace, etc. can be used.

2-4. Step [4] (Release step; FIG. 1 (d))
Next, the mold 3 is separated from the cured film 5, and a process of forming a cured film having a predetermined pattern shape on the substrate 2 (mold release process, FIG. 1D) is performed. This step is a step of peeling the mold 3 from the cured film 5, and a reverse pattern of the fine pattern formed on the mold 3 in the previous step (curing step) is obtained as the pattern of the cured film 5.

The method of separating the cured film 5 and the mold 3 is not particularly limited as long as a part of the cured film 5 is not physically damaged when being separated, and various conditions are not particularly limited. For example, the substrate 2 (substrate to be processed) may be fixed and the mold 3 may be moved away from the substrate 2 to be separated, or the mold 3 may be fixed and the substrate 2 moved away from the mold to be separated. Alternatively, both of them may be peeled by pulling in the opposite direction.

In addition, when the mold contact process is performed in a condensable gas atmosphere, when the cured film and the mold are separated in the mold release process, condensation occurs as the pressure at the interface between the cured film and the mold decreases. When the property gas is vaporized, the release force reducing effect tends to be exhibited.

A cured film having a desired concavo-convex pattern shape (pattern shape due to the concavo-convex shape of the mold 3) can be obtained by the series of steps (manufacturing process) from the steps [1] to [4] described above. The obtained cured film can also be used, for example, as an optical member (including a case where it is used as one member of an optical member) such as a Fresnel lens or a diffraction grating. In such a case, it can be set as the optical member which has the board | substrate 2 and the cured film 5 which has the pattern shape arrange | positioned on this board | substrate 2 at least.

From the above, the curable composition of the present invention has a high curing rate, and thus has high productivity and is excellent for imprinting. Particularly, it is remarkably excellent for nanoimprinting for forming a nano-sized (1 to 100 nm) pattern.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the technical scope of the present invention is not limited to the examples described below.

[Polymerizable compound]
For use in preparing the curable composition, the polymerizable compounds shown in Examples 1 to 5, Comparative Examples 1 to 3, and Reference Example 1 described below were prepared.

[Polymerization initiator]
As polymerization initiators, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (Lucrin TPO, hereinafter also referred to as LTPO) and 4,4′-diethylaminobenzophenone (hereinafter also referred to as DABP) are shown below. Prepared).

1. Curing Rate of Curable Composition The curing rate of the curable composition of the present invention was evaluated by the following examples.

[Measurement method of curing rate]
The curable composition was put into a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Co., Ltd., model, X-DSC7000), and then irradiated with ultraviolet rays using an ultraviolet irradiation device (manufactured by Hayashi Watch Co., Ltd., model, LA-410UV). At this time, the irradiation light had a wavelength of 365 nm and an illuminance of 100 mW / cm ² . Based on the following calculation formula, the calorific value when irradiated for 180 seconds (H ₁₈₀ ) is defined as the total calorific value, and the reaction rate after irradiation for 18 seconds from the ratio of the calorific value for 18 seconds after the start of irradiation (H ₁₈ ) to the total calorific value. (%) Was calculated and the curing rates were compared. Since the photocuring reaction is an exothermic reaction, the higher the reaction rate, the higher the curing rate.

[Example 1]
The polymerizable compound [A] and the polymerization initiator [B] shown below were mixed at a composition ratio shown in parentheses to prepare a curable composition (a-1).
<Polymerizable compound [A]>
4-HFIP-phenyl acrylate represented by the formula (1a), 30.4 mass% (19.2 mol%) (Japanese Patent Laid-Open No. 2011-164345 describes a synthesis method)
Benzyl acrylate, 62.7% by mass (76.8 mol%)
<Polymerizable initiator [B]>
・ Lucirin TPO, 5.3 mass% (3.0 mol%)
・ 4,4′-diethylaminobenzophenone, 1.6% by mass (1.0 mol%)

Table 1 shows the composition ratio of the curable composition (a-1). Table 1 also shows the curable compositions (a-2) to (a-5) used in Examples 2 to 5 described later and the curable compositions (b-1) used in Comparative Examples 1 to 3. (B-3) and the composition ratio of the curable composition (c-1) used in Reference Example 1 are also shown. In these curable compositions, the ratio of the total mol% of the polymerizable compound [A] to the total mol% of the polymerization initiator [B] is 96: 4.

The reaction rate of the curable composition (a-1) calculated by the above method was 95.6%. The results are shown in Table 1. This value was larger than 88.5% of the curable composition (b-1) of Comparative Example 1 described later and 86.3% of the curable composition (b-2) of Comparative Example 2.

[Example 2]
In Example 1, 4-HFIP-phenyl acrylate was changed to 3,5-bis-HFIP-phenyl acrylate represented by the formula (1b) (the synthesis method is described in JP-A-2004-83900). A curable composition (a-2) was prepared in the same manner as in Example 1 except that.

<Polymerizable compound [A]>
-3,5-bis-HFIP-phenyl acrylate represented by the formula (1b), 40.0 mass% (19.2 mol%)
Benzyl acrylate, 54.1% by mass (76.8 mol%)
<Polymerizable initiator [B]>
・ Lucirin TPO, 4.5 mass% (3.0 mol%)
・ 4,4′-diethylaminobenzophenone, 1.4% by mass (1.0 mol%)
When the curing rate of the curable composition (a-2) was evaluated by the above method in the same manner as in Example 1, the reaction rate was 98.3%. The results are shown in Table 1. This value was larger than 88.5% of the curable composition (b-1) of Comparative Example 1 described later and 86.3% of the curable composition (b-2) of Comparative Example 2. That is, the curable composition (a-1) and the curable composition (a-2) have a shorter ultraviolet irradiation time than the curable composition (b-1) and the curable composition (b-2). Since the composition is sufficiently cured, the nanoimprint using the curable composition (a-1) and the curable composition (a-2) has high productivity.

[Example 3]
A polymerizable compound [A] and a polymerization initiator [B] shown below were mixed at a composition ratio shown in parentheses to prepare a curable composition (a-3).
<Polymerizable compound [A]>
-4-HFIP-styrene represented by the formula (2a), 95.0 mass% (96 mol%) (Chem. Mater. 2003.15.1512-1517 describes the synthesis method)
<Polymerizable initiator [B]>
・ Lucirin TPO, 3.8% by mass (3 mol%)
・ 4,4′-diethylaminobenzophenone, 1.2% by mass (1 mol%)

When the curing rate of the curable composition (a-3) was evaluated in the same manner as in Example 1, the reaction rate was 10.7%. The results are shown in Table 1. Since this example is a polymerization of a styrene-based polymerizable compound, the curing rate is small compared to the values of other examples, but the curable composition (b-3) of Comparative Example 3 described later is 5. Compared to 6%. That is, the improvement in the curing rate by introducing the HFIP group into the side chain is also apparent in this example.

[Example 4]
In Example 3, 4-HFIP-styrene is a polymerizable compound represented by the formula (1c), 4,4,4-trifluoro-3-hydroxy-1-methyl-3- (trifluoromethyl) butyl-2 A curable composition (a-4) was prepared in the same manner as in Example 3, except that it was changed to -acrylate (the synthesis method is described in JP-A-2005-239710).

<Polymerizable compound [A]>
Compound represented by formula (1c), 95.2% by mass (96 mol%)
<Polymerizable initiator [B]>
・ Lucirin TPO, 3.7% by mass (3 mol%)
・ 4,4′-diethylaminobenzophenone, 1.1% by mass (1 mol%)
When the curing rate of the curable composition (a-4) was evaluated by the above method in the same manner as in Example 1, the reaction rate was 98.3%. The results are shown in Table 1. The curing rate of the curable compositions of Example 1 and Example 2 and equivalent results were obtained.

[Example 5]
In Example 3, 4-HFIP-styrene was changed to a polymerizable compound represented by the formula (1d) (4,4,4-trifluoro-3-hydroxy-1-methyl-3- (trifluoromethyl) butyl-2. A curable composition (a-5) was prepared in the same manner as in Example 3 except that the method was changed to -methacrylate) and JP-A-2005-239710, whose synthesis method is described.

When the curing rate of the curable composition (a-5) was evaluated by the above method in the same manner as in Example 1, the reaction rate was 31.6%. The results are shown in Table 1. As a methacrylic monomer, which is said to have low polymerizability compared to an acrylic monomer, it has a relatively high curing rate.

[Comparative Example 1]
A curable composition (b-1) was prepared in the same manner as in Example 1 except that 4-HFIP-phenyl acrylate was changed to phenyl acrylate represented by the following formula in the description of Example 1.

When the curing rate of the curable composition (b-1) was evaluated by the above method in the same manner as in Example 1, the reaction rate was 88.5%. The results are shown in Table 1.

[Comparative Example 2]
In the description of Example 1, the curable composition (b-2) was prepared in the same manner as in Example 1 except that 4-HFIP-phenyl acrylate was changed to 4-hydroxy-phenyl acrylate represented by the following formula. Prepared.

When the curing rate of the curable composition (b-2) was evaluated by the above method in the same manner as in Example 1, the reaction rate was 86.3%. The results are shown in Table 1.

[Comparative Example 3]
In the description of Example 3, a curable composition (b-3) was prepared in the same manner as in Example 3 except that 4-HFIP-styrene was changed to styrene represented by the following formula.

When the curing rate of the curable composition (b-3) was evaluated in the same manner as in Example 1, the reaction rate was 5.6%. The results are shown in Table 1.

[Reference Example 1]
In the description of Example 3, a curable composition (c-1) was prepared in the same manner as in Example 3 except that 4-HFIP-styrene was changed to “diacrylate 1” represented by the following formula. .

When the curing rate of the curable composition (c-1) was evaluated in the same manner as in Example 1, the reaction rate was 81.0%. The results are shown in Table 1.

2. Release property of cured film The following example evaluated the release property in the "release process" after hardening the curable composition of this invention.

[Measurement of mold release force]
The release force was measured according to the procedure shown below.
<Arrangement process>
A droplet of the curable composition was dropped on the silicon wafer on which the adhesion promoting layer was formed.
<Mold contact process>
Next, with respect to the curable composition on the silicon wafer, a quartz mold (24 mm in length, having a surface treatment with a fluorine-based coating agent for nanoimprinting (product name, OPTOOL HD-1100, manufactured by Daikin Industries, Ltd.) 24 mm wide) was brought into contact.
<Irradiation process>
Next, after contacting the quartz mold, UV light was irradiated to the curable composition through the quartz mold for 120 seconds. As the light source, a halogen light source (Mortex Co., Ltd., model, MUV351U) was used.
<Mold release process>
Next, the quartz mold was separated from the photocured film at a speed of 0.0125 mm / s. The force required for mold release was measured using a tension / compression dual-use compact load cell (manufactured by Kyowa Denki Co., Ltd., model, LUR-A-1KNSA1). When actually performing the measurement, the release force measurement was performed five times under the same conditions, and the average value was calculated from the measurement data of each time.

[Example 6]
A polymerizable compound [A] and a polymerization initiator [B] shown below were mixed at a composition ratio shown in parentheses to prepare a curable composition (a-6).
<Polymerizable compound [A]>
4-HFIP-phenyl acrylate (polymerizable compound represented by formula (1a)) (40 parts by mass)
・ Isobornyl acrylate (10 parts by mass)
・ Neopentyl diacrylate (45 parts by mass)
<Polymerizable initiator [B]>
・ Lucirin TPO (4 parts by mass)
・ 4,4'-diethylaminobenzophenone (1 part by mass)

The average mold release force of the cured product obtained from the curable composition (a-6) was measured by the above method, and found to be 54.2 N. The curable composition (b-4) of Comparative Example 4 described below. The average release force 73.2N of the cured product obtained from (1) and the average release force 66.3N of the cured product obtained from the curable composition (b-5) of Comparative Example 5 were lower. .

[Example 7]
In Example 6, except that 4-HFIP-phenyl acrylate was changed to 3,5-bis-HFIP-phenyl acrylate represented by the formula (1b), the curable composition (a -7) was prepared.
When the average mold release force of the cured product obtained from the curable composition (a-7) was measured in the same manner as in Example 6, the average mold release force was 54.1 N. This value was obtained from the average release force 73.2N of the cured product obtained from the curable composition (b-4) of Comparative Example 4 described later and the curable composition (b-5) of Comparative Example 5. The average release force of the cured product was lower than 66.3N. That is, the cured product obtained from the curable composition (a-6) and the curable composition (a-7) was obtained from the curable composition (b-4) and the curable composition (b-5). The mold can be released with a release force lower than that of the cured product, and in the nanoimprint method, pattern defects can be reduced and alignment accuracy can be improved.

[Example 8]
A polymerizable compound [A] and a polymerization initiator [B] shown below were mixed at a composition ratio shown in parentheses to prepare a curable composition (a-8).
<Polymerizable compound [A]>
-Polymerizable compound represented by formula (1c) (20 parts by mass)
・ Isobornyl acrylate (10 parts by mass)
・ Benzyl acrylate (20 parts by mass)
・ Neopentyl diacrylate (45 parts by mass)
<Polymerizable initiator [B]>
・ Lucirin TPO (4 parts by mass)
・ 4,4'-diethylaminobenzophenone (1 part by mass)
When the average mold release force of the cured product obtained from the curable composition (a-8) was measured in the same manner as in Example 6, the average mold release force was 68.3 N.

[Comparative Example 4]
A curable composition (b-4) was prepared in the same manner as in Example 6, except that 4-HFIP-phenyl acrylate was changed to phenyl acrylate in Example 6.
When the average mold release force of the cured product obtained from the curable composition (b-4) was measured by the above method in the same manner as in Example 6, the average mold release force was 73.2 N.

[Comparative Example 5]
A curable composition (b-5) was prepared in the same manner as in Example 6 except that 4-HFIP-phenyl acrylate was changed to 4-hydroxy-phenyl acrylate in Example 6.
When the average mold release force of the cured product obtained from the curable composition (b-5) was measured in the same manner as in Example 6, the average mold release force was 66.3 N.

[Reference Example 2]
A polymerizable compound [A] and a polymerization initiator [B] shown below were mixed at a composition ratio shown in parentheses to prepare a curable composition (c-2).
<Polymerizable compound [A]>
・ Diacrylate 1 (45 parts by mass)
・ Isobornyl acrylate (10 parts by mass)
・ Benzyl acrylate (40 parts by mass)
<Polymerizable initiator [B]>
・ Lucirin TPO (4 parts by mass)
・ 4,4'-diethylaminobenzophenone (1 part by mass)
When the average mold release force of the cured product obtained from the curable composition (c-2) was measured in the same manner as in Example 6, the average mold release force was 56.6 N.

Thus, the average mold release force of the cured product obtained by curing the curable composition of the present invention is a numerical value (equivalent level) that is comparable to that of the conventional polymerizable composition having no HFIP group (Comparative Example). It was found that the material was excellent in releasability.

Since the curable composition containing the polymerizable compound represented by the formula (1) or (2) obtained by the present invention has a property of a high curing rate, it is a semiconductor sealing material, underfill material, organic It can be used as a sealing material or bank material for EL elements and organic EL displays.

1: curable composition, 2: substrate, 3: mold, 4: coating film, 5: cured film, 6: irradiation light

Claims (7)

1. At least one polymerizable compound represented by the following formula (1) or formula (2);
   A polymerization initiator;
   A curable composition comprising:
   

   

   Wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a divalent or trivalent linear, branched or cyclic aliphatic hydrocarbon group, or a divalent or trivalent aromatic group. R ³ is a divalent or trivalent aromatic group, and m and n are integers of 1 to 2.)
2. 2. The polymerizable compound according to claim 1, wherein the polymerizable compound is any polymerizable compound represented by the following formula (1a), formula (1b), formula (1c), formula (1d), or formula (2a): Curable composition.
   

   

   

   

   

   
3. The curable composition according to claim 1 or 2, wherein the polymerization initiator is a photopolymerization initiator.
4. The curable composition according to any one of claims 1 to 3, wherein the curable composition is an optical nanoimprint composition.
5. The manufacturing method of the member with a pattern which arranged the cured film which has a pattern shape on the board | substrate including the following each process.
   Arrangement process: The process of arrange | positioning the curable composition of any one of Claim 1 thru | or 4 on a board | substrate.
   Mold contact step: a step of bringing a mold having a pattern shape into contact with the curable composition disposed on the substrate.
   Curing step: a step of curing the curable composition in contact with the mold with light or heat to form a cured film.
   Mold release step: a step of separating the mold from the cured film to obtain the patterned member.
6. The method for producing a patterned member according to claim 5, wherein the mold contact step is performed in a gas atmosphere containing a condensable gas.
7. The condensable gas in the contacting step is 1,1,1,3,3-pentafluoropropane (HFC-245fa), trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)) Cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1 The method for producing a patterned member according to claim 6, comprising one or more of, 3,3,3-tetrafluoropropene (HFO-1234ze (Z)).

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