Resin for Thermal Imprinting专利检索- 用在侧链中没有不饱和脂肪族基团的不饱和环状化合物的聚合物作为模制材料如苯并呋喃

Resin for Thermal Imprinting

申请号

US12086165

申请日

2006-07-12

公开(公告)号

US20100019410A1

公开(公告)日

2010-01-28

申请人

Takemori Toshifumi; Yoshiaki Takaya; Takahito Mita; Tetsuya Lizuka; Yuji Hashima; Takahisa Kusuura; Mitsuru Fujii; Takuji Taguchi; Anupam Mitra;

发明人

Takemori Toshifumi; Yoshiaki Takaya; Takahito Mita; Tetsuya Lizuka; Yuji Hashima; Takahisa Kusuura; Mitsuru Fujii; Takuji Taguchi; Anupam Mitra;

摘要

A cyclic-olefin-based thermoplastic resin for thermal imprint to be used in the production of a sheet or a film which contains at least one of skeletons represented by the following chemical equation 1 or the following chemical equation 2 in a main chain. The glass transition temperature Tg (° C.) and the value ([M]) of MFR at 260° C. satisfy the following equation 1, and [M] 219×log[M]−160 [Equation 1]

权利要求

1. A resin for thermal imprint and for producing a sheet or a film, the resin comprising a cyclic-olefin-based thermoplastic resin that contains at least one of skeletons represented by a following chemical equation 1 or a following chemical equation 2 in a main chain, and wherein:a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1; and

[M] <30; wherein
Tg(° C.)>219×log[M]−160 and further, wherein [Equation 1]

R¹to R²⁹in chemical equations 1, 2 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another; m and n are integers greater than or equal to 0; and, [M] in equation 1 represents a value of MFR at 260° C.

2. A resin for thermal imprint and for producing a sheet or a film, the resin comprising a cyclic-olefin-based thermoplastic resin that contains at least one of skeletons represented by a following chemical equation 3 or a following chemical equation 4 in a main chain, and wherein:a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1; and

[M]<20 and Tg>90° C.; wherein
Tg(° C.)>219×log[M]−160 and further, wherein [Equation 1]

R¹to R²⁹in chemical equations 3, 4 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another; m and n are integers greater than or equal to 0; and [M] in equation 1 represents a value of MFR at 260° C.

3. The resin for thermal imprinting of claim 2, wherein the cyclic-olefin-based thermoplastic resin comprises a copolymer of cyclic-olefin represented by a following chemical equation 5 and α-olefin, or a polymer produced by hydrogenation after ring-opening polymerization of the cyclic-olefin, wherein

and further wherein R³⁰to R⁴⁸in chemical equation 5 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another; and, m and n are integers greater than or equal to 0.

4. The resin for thermal imprint of claim 2, containing greater than or equal to one additive.

5. The resin for thermal imprint of claim 4, wherein the additive contains at least either one of an anti-oxidizing agent or a lubricant.

6. The resin for thermal imprint of claim 2, wherein a resin containing a skeleton represented by chemical equation 3 is a copolymer of cyclic-olefin represented by a following chemical equation 6 and ethylene; and wherein

and further wherein R³⁰to R⁴⁸in chemical equation 6 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another; and, m and n are integers greater than or equal to 0.

7. A thermal imprint method comprising:pressing a mold, which is heated to less than or equal to a glass transition temperature Tg (° C.) of a resin for thermal imprint+65° C., against a sheet or a film comprising the resin for thermal imprint of claim 1, thereby transferring a pattern of the mold.

8. A thermal imprint method comprising steps of:pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 1; and

releasing the mold from the resin for thermal imprint at a temperature greater than or equal to a glass transition temperature (Tg) of the resin for thermal imprint−25° C.

9. A thermal imprint method comprising:pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 1 at less than or equal to 2.5 MPa, thereby transferring a pattern of the mold.

10. A method of using a cyclic-olefin-based thermoplastic resin for an imprint process, the resin being used for producing a sheet or a film, and containing at least one of skeletons represented by a following chemical equation 7 or a following chemical equation 8 in a main chain, and wherein:a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1; and

[M]<30 wherein,
Tg(° C.)>219×log[M]−160 [Equation 1]

and further wherein R¹to R²⁹in chemical equations 7, 8 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another; m and n are integers greater than or equal to 0; and [M] in equation 1 represents a value of MFR at 260° C.

11. A method of using a cyclic-olefin-based thermoplastic resin for an imprint process, the resin being used for producing a sheet or a film, and containing at least one of skeletons represented by a following chemical equation 9 or a following chemical equation 10 in a main chain, and wherein:a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1; and

[M]<20 and Tg>90° C. wherein
Tg(° C.)>219×log[M]−160 [Equation 1]

and further wherein R¹to R²⁹in chemical equations 9, 10 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another; m and n are integers greater than or equal to 0; and, [M] in equation 1 represents a value of MFR at 260° C.

12. A thermal imprint method comprising:pressing a mold, which is heated to,less than or equal to a glass transition temperature Tg (° C.) of a resin for thermal imprint+65° C., against a sheet or a film comprising the resin for thermal imprint of claim 2 thereby transferring a pattern of the mold.

13. A thermal imprint method comprising steps of:pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 2; and

releasing the mold from the resin for thermal imprint at a temperature greater than or equal to a glass transition temperature (Tg) of the resin for thermal imprint−25° C.

14. A thermal imprint method comprising:pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 2 at less than or equal to 2.5 MPa, thereby transferring a pattern of the mold.

15. A thermal imprint method comprising:pressing a mold, which is heated to less than or equal to a glass transition temperature Tg (° C.) of a resin for thermal imprint+65° C., against a sheet or a film comprising the resin for thermal imprint of claim 3 thereby transferring a pattern of the mold.

16. A thermal imprint method comprising steps of:pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 3; and

releasing the mold from the resin for thermal imprint at a temperature greater than or equal to a glass transition temperature (Tg) of the resin for thermal imprint−25° C.

17. A thermal imprint method comprising:pressing a mold against a sheet or a4 film comprising the resin for thermal imprint of claim 3 at less than or equal to 2.5 MPa, thereby transferring a pattern of the mold.

18. A thermal imprint method comprising:pressing a mold, which is heated to less than or equal to a glass transition temperature Tg (° C.) of a resin for thermal imprint+65° C., against a sheet or a film comprising the resin for thermal imprint of claim 4 thereby transferring a pattern of the mold.

19. A thermal imprint method comprising steps of:pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 4; and

releasing the mold from the resin for thermal imprint at a temperature greater than or equal to a glass transition temperature (Tg) of the resin for thermal imprint−25° C.

20. A thermal imprint method comprising:pressing a mold against a sheet or a film comprising the resin for thermal imprint of claim 4 at less than or equal to 2.5 MPa, thereby transferring a pattern of the mold.

说明书全文

TECHNICAL FIELD

The present invention relates to a resin for thermal imprint. More specifically, the present invention relates to a cyclic-olefin-based thermoplastic resin which has a specific correlation between a glass transition temperature Tg (° C.) and MFR at 260° C., and can be used for producing a sheet or a film.

BACKGROUND ART

As the optical fields for optical communications, optical disks, displays, optical sensors, and the like dramatically develop, achieving both performance and cost becomes important for optical resin materials. Expectations for transparent resin materials which are easy to process become large in fields of biochips, micro reactors, and the like, in lieu of glasses. In all fields, processing of a base material surface, in particular, microprocessing becomes requisite, and the microprocessing becomes an important technology in a recent semiconductor field where integration becomes remarkable. Conventionally, to form a minute pattern on the surface of a transparent material, schemes of cutting the surface mechanically or of printing a pattern using a resist, a thermo, ultraviolet, or electron radiation curing resin, or the like are used. In particular, to cope up with the present trend and future need for miniaturization of various devices, several different patterning methods are under continuing development. Injection molding has its limitation below 500 μm of film thickness. However, various advanced devices including anti reflecting film or coating requires patterning on a sheet or a film with thickness much below the limit of injection molding.

According to the mechanical cutting, however, there is a problem such that an advanced and complex processing technique is required. According to the pattern printing using a resist or the like, steps thereof are complicated, and there is a problem in the durability, such as peeling of a printed pattern. Further, as patterns become minuter, a mechanism which controls a whole process highly precisely becomes requisite, so that the cost issue becomes not negligible.

To cope with such problems, there is proposed a thermal imprint method for forming a minute pattern at low cost. That is, this is a method of pressing a mold, having a minute pattern heated more than or equal to a glass transition temperature of a resin, against a resin substrate, and of transferring the minute pattern of the mold on the melted resin surface.

Disclosed so far to improve the thermal imprint characteristics (transferability, mold release characteristic, and the like) and the productivity (throughput) are a scheme of providing an insulator to shorten a cycle of temperature rising and cooling (see, for example, patent literature 1), and a scheme of providing an ultrasonic generation mechanism to reduce the melt viscosity by ultrasonic (see, for example, patent literature 2). However, there are few literatures which mentioned materials used for thermal imprint, and development of the materials for thermal imprint is desired.

In general, examples of materials used for thermal imprint are resin materials, glasses, metals, and the like. The resin materials can be molded at a lower temperature in comparison with imprinting to metals or glasses, thus advantageous for the manufacturing cost.

An example of resins is a (meta) acrylic resin represented by polymethacrylic acid (PMMA) or a polycarbonate resin, but have a problem such that the heat resistance is low and size distortion occurs due to water absorption. Further, controlling a balance between the fluidity and the solidification is difficult, so that it is difficult to maintain and use a minutely-transferred pattern (see, for example, patent literature 3).

On the other hand, as a resin having both heat resistance and dimension stability originating from the low water absorption coefficient, there are cyclic-olefin-based thermoplastic resins. In general, the cyclic-olefin-based thermoplastic resins are superior in the transparency, the chemical resistance property, and the low moisture absorption characteristic, and its heat resistance can be easily controlled by the structure of the cyclic-olefin or the contained amount of the cyclic-olefin in the resin. The resin has a low viscosity, and a short relaxation time (time necessary for filling the resin in the pattern of a mold), and is less adhered to the mold, and is superior in the transfer accuracy of a minute pattern, so that application as a thermal imprint material is expected as having a good productivity (see, for example, non-patent literature 1).

Patent Literature 1: Japanese Unexamined Patent Application Laid-open Publication No.2002-361500

Patent Literature 2: Japanese Unexamined Patent Application Laid-open Publication No.2004-288811

Patent Literature 3: Japanese Unexamined Patent Application Laid-open Publication No. 2000-158532

Non-patent Literature 1: J. Mater. Chem., 2000, volume 10, page 2634

Non-patent Literature 2: Nanoimprint Lithography in Topas, a highly UV-transparent and chemically resistant thrmoplast, T. Nielsen, D. Nilsson, et al.

DISCLOSURE OF INVENTION

Problems to be Solved by the Invention

However, conventional cyclic-olefin-based thermoplastic resins are not ones that the resin properties, such as a glass transition temperature Tg (° C.) and the fluidity are developed for the process of thermal nano-imprint, but require a high molding temperature and a large molding pressure, thus having insufficient thermal imprint characteristics (transferability, mold release characteristic, and the like). Moreover, a long molding time is required, so that the productivity (throughput) is low. For example, one disclosed in the foregoing non-patent literature 1 has a high molding temperature of 240° C., so that it takes a time to cool it down after the pattern of a mold is transferred, and the productivity (throughput) for manufacturing imprint products becomes low. In a non patent literature, as cited in 2, a polymer with a low Glass Transition temperature of 80° C. have been used however, the imprinting is performed at 90° C. above the glass transition temperature of the polymer for 5 min with a pressure of 2000N, making it a process with prolonged cooling time having a low practical or commercial impact, similar to that in citation 1. It is our experience that an optimized polymer for injection molding does not yield well in thermal nanoimprinting or, in other words, an ideal polymer film for thermal nanoimprinting would have to have a different characteristics that that of an ideal polymer for injection molding.

This is primarily because that a correlation between the resin properties, in particular, a glass transition temperature and MFR which becomes the barometer of the fluidity of the resin, and a correlation between an imprint conditions (molding temperature, molding pressure, mold release temperature, and the like) to the resin and the imprint characteristics (transferability, mold release characteristic, and the like) are not figured out.

Therefore, it is an object of the invention to provide a cyclic-olefin-based thermoplastic resin which can be used for manufacturing a sheet or a film like a substrate used for thermal imprint, is superior in thermal imprint characteristics (transferability, mold release characteristic, and the like), and improves a productivity (throughput), and a thermal imprint method using the same.

Means for Solving the Problems

To overcome the above mentioned problem, the present invention enables the development of an ideal polymer for nanoimprinting co-relating the glass transition temperature and MFR of the polymer.

That is, a cyclic-olefin-based thermoplastic resin of the invention is used for producing a sheet or a film, contains at least one of skeletons represented by the following chemical equation 1 or the following chemical equation 2 in a main chain, and wherein a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy the following equation 1, and [M]<30.

Tg(° C.)>219×log[M]−160 [Equation 1]

(R¹to R²⁹in the chemical equations 1, 2 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another. m and n are integers greater than or equal to 0. [M] in equation 1 represents a value of MFR at 260° C.)

Another resin for thermal imprint of the invention is used for producing a sheet or a film, comprises a cyclic-olefin-based thermoplastic resin that contains at least one of skeletons represented by the following chemical equation 3 or the following chemical equation 4 in a main chain, and wherein a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1, and [M] <20 and Tg>90° C.

Tg(° C.)>219×log[M]−160 [Equation 1]

(R¹to R²⁹in the chemical equations 3, 4 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another. m and n are integers greater than or equal to 0. [M] in equation 1 represents a value of MFR at 260° C.)

In this case, it is preferable that the cyclic-olefin-based thermoplastic resin should comprise a copolymer of cyclic-olefin represented by the following chemical equation 5 and x-olefin, or a polymer produced by hydrogenation after ring-opening polymerization of the cyclic-olefin.

(R³⁰to R⁴⁸in chemical equation 5 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another. m and n are integers greater than or equal to 0)

The resin for thermal imprint may contain greater than or equal to one additive. In this case, it is preferable that the additive should contain at least either one of an anti-oxidizing agent or a lubricant.

Further, it is preferable that a resin containing a skeleton represented by the chemical equation 3 is a copolymer of cyclic-olefin represented by the following chemical equation 6 and ethylene.

(R³⁰to R⁴⁸in the chemical equation 6 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another. m and n are integers greater than or equal to 0)

A thermal imprint method of the invention comprises: pressing a mold, which is heated to less than or equal to a glass transition temperature Tg (° C.) of a resin for thermal imprint+65° C., against a sheet or a film comprising the foregoing resin for thermal imprint, thereby transferring a pattern of the mold.

Another thermal imprint method of the invention comprises steps of: pressing a mold against an injection molded body comprising the foregoing resin for thermal imprint; and releasing the mold from the resin for thermal imprint at a temperature greater than or equal to a glass transition temperature (Tg) of the resin for thermal imprint−25° C.

Other thermal imprint method of the invention comprises: pressing a mold against a sheet or a film comprising the foregoing resin for thermal imprint at less than or equal to 2.5 MPa, thereby transferring a pattern of the mold.

The invention relates to a method of using a cyclic-olefin-based thermoplastic resin for an imprint process, the resin is used for producing a sheet or a film, and contains at least one of skeletons represented by the following chemical equation 7 or the following chemical equation 8 in a main chain, and wherein a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1, and [M]<30.

Tg(° C.)>219×log[M]−160 [Equation 1]

(R¹to R²⁹in the chemical equations 7, 8 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another. m and n are integers greater than or equal to 0. [M] in equation 1 represents a value of MFR at 260° C.)

The invention also relates to a method of using a cyclic-olefin-based thermoplastic resin for an imprint process, the resin is used for producing a sheet or a film, and contains at least one of skeletons represented by the following chemical equation 9 or the following chemical equation 10 in a main chain, and wherein a glass transition temperature Tg (° C.) of the resin and a value ([M]) of MFR at 260° C. satisfy a following equation 1, and [M]<20 and Tg>90° C.

Tg(° C.)>219×log[M]−160 [Equation 1]

(R¹to R²⁹in the chemical equations 9, 10 may differ or may be same, each of which is a substituent containing a hydrogen atom, a deuterium atom, a hydrocarbon radical having a carbon number of 1 to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the like, and may form a monocyclic or polycyclic structure with one another. m and n are integers greater than or equal to 0. [M] in equation 1 represents a value of MFR at 260° C.)

EFFECT OF THE INVENTION

Using a cyclic-olefin-based thermoplastic resin, which has a specific correlation between a glass transition temperature Tg (° C.) and MFR at 260° C., enables a thermal imprint at a low temperature and a low pressure, thereby improving the imprint characteristics (transferability, mold release characteristic, and the like) and the productivity (throughput).

Further, by applying imprint conditions (molding temperature, molding pressure, mold release temperature, and the like) to a cyclic-olefin-based thermoplastic resin having a specific correlation between a glass transition temperature Tg (° C.) and MFR at 260° C., the thermal imprint characteristics (transferability, mold release characteristic, and the like) and the productivity (throughput) can be further improved.

BEST MODE FOR CARRYING OUT THE INVENTION

An embodiment of the invention will be explained in detail with reference to the drawings.

A cyclic-olefin-based thermoplastic resin to which the invention is applied is a copolymer of cyclic-olefin and a-olefin, i.e., a copolymer with a-olefin containing a repeating unit indicated by a following chemical equation 11 and derived from cyclic-olefin, or a polymer that hydrogen is added to cyclic-olefin indicated by a chemical equation 12 undergone ring-opening polymerization.

R¹to R²⁹in the chemical equation 11 and the chemical equation 12 may differ, or may be same, and each of which is a substituent containing hydrogen atoms, deuterium atoms, hydrocarbon radical having carbon number of 1 to 15, halogen atoms, or hetero atoms, such as oxygen, or sulfur, and forms a monocyclic or polycyclic structure with one another. Note that m and n are integers greater than or equal to zero.

Cyclic-olefin monomer which constitutes the foregoing resin has a structure indicated by a chemical equation 13, and examples of preferable monomer are, for example, bicyclo[2,2,1]hept-2-ene(norbornene), 5-methylbicyclo[2,2, 1]hept-2-ene, 7-methybicyclo[2,2,1]hept-2-ene, 5-ethylbicyclo[2,2,1]hept-2-ene, 5-propylbicyclo[2,2,1]hept-2-ene, 5-n-butylbicyclo[2,2,1]hept-2-ene, 5-isobutylbicyclo[2,2,1]hept-2-ene 1,4-dimnethylbicyclo[2,2,1]hept-2-ene, 5-bromobicyclo[2,2,1]hept-2-ene, 5-chlorobicyclo[2,2,1]hept-2-ene, 5-fluorobicyclo[2,2,1]hept-2-ene, 5,6-dimethylbicyclo[2,2,1]hept-2-ene, dicyclopentadiene, tricyclopentadiene, tetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 5,10-dimethyltetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 2,10-dimethyltetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 11,12-dimethyltetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 2,7,9-trimethyltetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 9-ethyl-2,7-dimethyltetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 9-isobutyl-2,7-dimetyltetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 9-isobutyl-2,7-dimethyltetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 9,11,12-triethyltetmcyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 9-ethyl-11,12-dimethyltetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 9-isobutyl-11,12-dimethyltetmcyclo[4,4,0,1^2.5, 1^7.10]-3-dodecene, 5,8,9,10-tetramethyltetracyclo[4,4,0,1^2.5, 1^7.10]-3-dodecene, 8-hexyltetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 8-stearyltetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 8-methyl-9-ethyltetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 8-cyclohexyltetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 8-ethylidenetetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 8-chlorotetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 8-bromotetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 8-fluorotetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 8,9-dichlorotetmcyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, hexacyclo[6,6,1,1^3.6,1^10.13,0^2.7, 0^9.14]-4-deptadecene, 12-methylhexacyclo[6,6,1,1^3.6,1^10.13,0^2.7, 0^9.14])-4-deptadecene, 12-ethylhexacyclo[6,6,1,1^3.6,1^10.13,0^2.7, 0^9.14]-4-deptadecene, 12-isobutylhexacyclo[6,6,1,1^3.6, 1^10.13,0^2.7,0^9.14]-4-deptadecene, 1,6,10-trimethyl-12-isobutylhexacyclo[6,6,1,1^3.6,1^10.13,0^2.7,0^9.4]-4-deptadecene, 5-methyl-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-ethyl-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-n-propyl-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-n-butyl-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5,6-dimethyl-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-methyl-6-ethyl-5-phenylbicyclo[2,2,1]hept-2-ene, 5,6,6-trimethyl-5-phenyl-bicyclo[2,2,1]hept-2-ene, 1,4,5-trimethylbicyclo[2,2,1]hept-2-ene, 5,6-diethyl-5-phenylbicyclo[2,2,1]hept-2-ene, 5-bromo-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-chloro-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-fluoro-5-phenyl-bicyclo[2,2,1]hept-2-ene, 5-methyl-5-(tert-butylphenyl)-bicyclo[2,2,1]hept-2-ene, 5-methyl-5-(bromophenyl)-bicyclo[2,2,1]hept-2-ene, 5-methyl-5-(chlorophenyl)-bicyclo[2,2,1]hept-2-ene, 5-methyl-5-(fluorophenyl)-bicyclo[2,2,1]hept-2-ene, 5-methyl-5-(a-naphthyl)-bicyclo[2,2,1]hept-2-ene, 5-methyl-5-antracenyl-bicyclo[2,2,1]hept-2-ene, 8-methyl-8-phenyl-tetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 8-ethyl-8-phenyl-tetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 8-n-propyl-8-phenyl-tetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 8-n-butyl-8-phenyl-tetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 8-chloro-8-phenyl-tetracyclo[4,4,0,1^2.5,1^7.10]-3-dodecene, 11-methyl-11-phenyl-hexacyclo[6,6,1, 1^3.6,1^10.13,0^2.7,0^9.14]-4-heptadecene, 1,4-methano-4a,9,9-trimethyl-1,4,9a-trihydrofluorene. Such various monomers can be basically made by a thermal Diels-Alder reaction of corresponding dienes and olefins, and adding hydrogen or the like appropriately makes it possible to produce a desired monomer.

R³⁰to R⁴⁸in the chemical equation 13 may differ or may be same, and each of which is a substituent including hydrogen atoms, deuterium atoms, hydrocarbon radical having carbon number of 1 to 15, halogen atoms, or hetero atoms, such as oxygen and sulfur, and forms a monocyclic or polycyclic structure with each other. Note that m and n are integers greater than or equal to zero.

An example of α-olefin suitably used for the copolymer indicated by the chemical equation 11 is α-olefin having a carbon number of 2 to 20, preferably, a carbon number of 2 to 10, and includes, for example, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and those can be used individually or combined. Ethylene and propylene are preferable in those, and ethylene is particularly preferable from the standpoint of practical aspects, such as copolymer characteristic, and economic efficiency.

In the copolymer indicated by the chemical equation 11, the preferable mole ratio (α-olefin/cyclic-olefn) between the α-olefin and the cyclic-olefin is within a range from 10/90 to 90/10, and further preferably, with in a range from 30/70 to 70/30. The mole ratio in copolymer is decided based on ¹³C-NMR (400 MHz, temperature: 120° C./solvent: 1,2,4-trichlorobenzene/1,1,2,2-deuterated tetrachloroethane mixing system).

The thermal imprint resin of the invention is adjusted in such a way that the glass transition temperature Tg (° C.) thereof and a value ([M]) of MFR at 260° C. satisfy the following equation 1.

Tg(° C.)>219×log[M]−160 [Equation 1]

The weight average molecular weight Mw of the cyclic-olefin-based thermoplastic resin indicated by the chemical equation 11 or the chemical equation 12 is within 10,000 to 1,000,000, preferably, 20,000 to 500,000, and further preferably, 50,000 to 300,000, and the value [M] of MFR at 260° C. is less than or equal to 30, preferably, less than or equal to 20, and further preferably, less than or equal to 10. Accordingly, the strength of the resin becomes high, so that the imprint characteristics (transferability, mold release characteristic, and the like) can be improved without deteriorating the fluidity of the resin.

In considering the application of the resin on which a minute pattern is transferred by thermal imprint, it is preferable that the heat resistance of the resin should be high, and the glass transition temperature should be greater than or equal to 80° C., preferably, greater than or equal to 90° C., and further preferably, higher than the boiling temperature of water, i.e., beyond 100° C. in view of the practicality.

A polymerization method for producing the resin is not limited to any particular ones, and well-known methods, such as a method of coordination polymerization using Ziegler-Natta catalyst or single-site catalyst, and further, causing a copolymer to be subjected to hydrogen addition in accordance with necessity, and a method of adding hydrogen after ring-opening polymerization using metathesis polymerization catalyst. As a method of adding hydrogen, well-known methods can be employed, and this can be carried out using a catalyst containing metal components, such as nickel, and palladium. Examples of the single-site catalyst used for producing the copolymer indicated by, for example, the chemical equation 11 are various kinds of metallocene compounds, and methylene(cyclopentadienyl)(tetracyclopentadienyl)zirconiumdichloride or the like disclosed in, for example, Japanese Unexamined Patent Application Laid-open Publication No. 2003-82017 can be preferably used. A promoter used for a polymerization reaction is not limited to any particular one, but methyl aluminoxanes can be used preferably, and other organic aluminum compounds may coexist and polymerize in accordance with a reaction. Such a polymerization reaction can be preferably carried out within a range from a room temperature (25° C. or so) to 200° C., but it is desirable to carry out such a reaction within a range from 40 to 150° C. in view of the reactivity and the stability of a catalyst. An organic solvent used for a polymerization reaction is not limited to any particular one, and for example, aromatic solvents, such as benzene, toluene, xylene, and ethyl benzene, saturated hydrocarbon solvents, such as hexane, cyclohexane, heptane, methyl cyclohexane, and octane, or a mixed solvent thereof can be preferably used. After the resin is produced, hetero atoms, such as oxygen atoms and sulfur atoms can be arbitrarily introduced by a radical reaction.

In accordance with necessity, greater than or equal to one of additives, such as an anti-oxidizing agent, a heat resistance stabilizer, a weathering stabilizer, a light stabilizer, an antistatic agent, a slipping agent, anti-blocking agent, an anti-fog additive, a lubricant, a color, a pigment, a natural oil, a synthetic oil, and a wax, can be added and mixed, and the mix ratio thereof can be set arbitrarily. Additives (anti-oxidizing agent, lubricant, and the like) are not limited to any particular ones, and well-known compounds can be used preferably.

Additionally, additives like fluorine containing non-ionic surfactant or silocone containing leveling material could be used to reduce surface roughness of a sheet or a film.

According to the invention, addition of an oxidizing agent prevents an oxidization of the resin when heated, a creation of a gel originating from the staining of the resin and a bridge formation of the resin molecular chain, and a deterioration of physical property due to a disconnection of the resin molecular chain.

According to the invention, addition of a lubricant improves the mold release characteristic, after imprint, and the productivity (throughput) of imprint products. Furthermore, there is an effectiveness such that the resin can be easily put into a pattern on a mold when fabricating the resin.

Further, without deteriorating the physical properties required in the application fields of an imprint product, a rubber component can be added to improve the durability of the resin plate, and a well-known compound can be used.

Examples of the applications of the imprint product are optical devices, such as an optical waveguide, a light guiding plate, and a diffraction grating, biochips, fluidic devices, such as a micro flow channel, and a micro reactor, media for saving data, and circuit substrates.

The method of manufacturing a sheet or a film is not limited to any particular one, and a well-known method of the extrusion molding, dipping method, solution casting, spin coating method, or the like can be applied. The thickness can be arbitrarily selected in accordance with an application of an imprint product, and molding is possible if the thickness is less than or equal to 500 μm. The sheet or the film using the thermal imprint resin of the invention can be formed in any shapes, it is preferable that the thickness is less than or equal to 300 μm, and more preferably less than or equal to 150 μm.

Various products can be used as a device for imprinting, and can be selected arbitrarily. Various sizes, such as less than or equal to 100 μm, less than or equal to 50 μm, less than or equal to 10 μm, less than or equal to 1 μm, and less than or equal to 500 nm can be selected as the size of a transferred pattern for the thermal imprint resin of the invention.

Next, an explanation will be given of a method of performing imprinting on a sheet or a film comprising the resin of the invention.

To realize a process having the improved imprint characteristics (transferability, mold release characteristic, and the like), it is preferable to reduce a molding pressure and to shorten the retention time at molding. This is because that if the molding pressure when performing imprinting is too high and the retention time of a pressure is too long, the resin adheres to the mold, so that the pattern is elongated or damaged in mold releasing, and the transfer precision of the pattern is reduced. Specifically, in using a sheet or a film of the resin of the invention, the molding pressure in performing imprinting should be less than or equal to 3.0 MPa, and more preferably, less than or equal to 2.5 MPa. Further, the retention time in performing molding should be less than or equal to 1000 seconds, more preferably, less than or equal to 600 seconds.

The polymer film or sheet could be supported by a substrate of a polymer like poly carbonates, poly acryls, poly imides or graphite or metal like aluminum, stainless steel, etc, during the imprinting process. In case a polymer substrate is used as a support, the glass transition temperature of the said polymer should be higher than the temperature at which the imprinting is performed. In case a film is cast on a substrate of aluminum or silicon, etc, the film on substrate could be used directly.

Further, to realize a process having the improved productivity (throughput), it is preferable to reduce the temperature of the mold, and to shorten the retention time in performing molding. This is because that if the mold temperature is low, the cooling time can be shortened, and if the retention time at which the mold and the sheet or the film are pressed is short, then the molding time can be shortened.

Specifically, it is preferable to use a sheet or a film comprised of the resin of the invention, and to set the temperature in performing molding to less than or equal to the glass transition temperature Tg+80° C., and more preferably, less than or equal to Tg+65° C. It is preferable that the temperatures of the mold in mold releasing and the sheet or the film should be greater than or equal to Tg−40° C., and more preferably, greater than or equal to Tg−25° C.

Examples

Examples of the invention will be explained below, but the invention should not be limited to the following examples.

Regarding the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight fractionation (Mw/Mn) of the resin to be used, an GPC device manufactured by Wasters was used by the gel permeation chromatography method (GPC), and those were measured under a condition such that column: K-805L/K-806L manufactured by Shodex, column temperature: 40° C., solvent: chloroform, flow rate: 0.8 ml/minute. The glass transition temperature Tg (° C.) of the resin used was acquired from the heat absorption peak in heat up using a differential scanning calorimeter (model: EXSTAR 6000, DSC 6200) manufactured by SEIKO. Further, regarding the value [M] of MFR at 260° C., the MELT INDEXER (model: L248-2531) manufactured by TECHNOL SEVEN Co., Ltd. was used, and a value measured at a loading of 2.16 kgf.

Film or sheet could be fabricated either by the usage of Labo Plastomill D-2025 from Toyoseiki or by spin coating in a SC-300 spin coater from E.H.C Corporation or by casting using an applicator on a glass plate followed by baking, drying and annealing.

For imprint evaluations, an imprint device (VX-2000N-US) manufactured by SCIVAX was used, and the evaluations were carried out under condition described in the examples, respectively, using a mold of 30 mm by 30 mm. Table 1 shows imprint characteristics inherent to presence/absence of correlations (represented by equation 1) between a structure of a resin or a glass transition temperature Tg (° C.) and MFR at 260° C. For evaluation of imprint characteristics, acquired minute bumpy patterns were observed through an electronic microscope, and if a pattern similar to a mold was well transferred, a circular mark is filled, if a resin adhered to a mold, and a deficit of a pattern was formed, then a triangle mark is filled, and if a pattern failure (insufficient filling, elongation, deficit) was confirmed, then a cross mark is filled. if a resin adhered to a mold and there is a deficit or film peeling or overstretch, then a cross mark is filled.

First, an explanation will be given of the production method of a sheet or a film used in the examples and comparative examples. Samples 1 to 8 were sheets or films made of resins which satisfied the foregoing equation 1, and samples 9 and 10 were sheets or films made of resins which did not satisfy the equation 1. Note that polymers used for sheets or films contained an anti-oxidizing agent and a lubricant, as long as any particular explanations will be given for product examples.

Product Example 1

Production of a Sheet or a Film

Ethylene/norbornene copolymer (Tg=134° C., MFR=11 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 1) having a thickness of 100 μm was produced.

Product Example 2

Production of a Sheet or a Film

Ethylene/norbornene copolymer (Tg=135° C., MFR=10 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 2) having a thickness of 90 μm was produced.

Product Example 3

Production of a Sheet or a Film

Ethylene/norbornene copolymer (Tg=109° C., MFR=16 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 3) having a thickness of 100 μm was produced.

Product Example 4

Production of a Sheet or a Film

Hydrogeneration of cyclic-olefin based ring-opening polymer (Tg=138° C., MFR=8 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 4) having a thickness of 110 μm was produced.

Product Example 5

Production of a Sheet or a Film

Hydrogeneration of cyclic-olefin based ring-opening polymer (Tg=136° C., MFR=7 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 5) having a thickness of 110 μm was produced.

Product Example 6

Production of a Sheet or a Film

Hydrogeneration of cyclic-olefin based ring-opening polymer (Tg=105° C., MFR=9 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 6) having a thickness of 100 μm was produced.

Product Example 7

Production of a Sheet or a Film

A solution containing 15wt % of ethylene/norbornane type copolymer (Tg=135° C., MFR=10@260° C.) in diethyl benzene solvent is spin coated on a silicon wafer (400 rpm×5 s 2000 rpm×20 s) followed by baking (100° C.×15 min, 150° C.×30 min) and annealing (110° C.×30 min) to produce 1.3 μm thick coating (sample 7)

Product Example 8

Production of a Sheet or a Film

Ethylene/norbornene copolymer (Tg=135° C., MFR=59 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 8) having a thickness of 100 μm was produced.

Product Example 9

Production of a Sheet or a Film

Ethylene/norbornene copolymer (Tg=132° C., MFR=51 @ 260° C.) was molded by the film molding machine, and a transparent molded body (sample 9) having a thickness of 90 Jim was produced.

Example 1