JP2009073809A - Ultraviolet-sensitive compound containing thiol group and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet-sensitive compound having an action such as development of adhesiveness by ultraviolet irradiation, an adhesive for nanoimprint technology having excellent adhesiveness between a metallic thin film and a thermoplastic polymer, a substrate having a fine metal thin film pattern and a method for producing the substrate. <P>SOLUTION: The ultraviolet-sensitive compound is expressed by formula (I). The adhesive contains the compound, and the substrate has a metallic thin film pattern having a line width of 0.01-10 μm and useful as a wire grid polarization plate, a diffraction grating, a metal-wired substrate for electronic device, etc. In the formula, a specific group in R<SP>1</SP>to R<SP>6</SP>is -X-(CH<SB>2</SB>)<SB>m</SB>-SH (X is O, OCO, COO, NH or NHCO; and m is 1-20) and the other groups are each a hydrogen atom, a 1-6C hydrocarbon group or a 1-6C hydrocarbon group connected through an oxygen atom or a nitrogen atom. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an ultraviolet-sensitive compound, an adhesive for nanoimprinting using the same, a substrate having a metal thin film pattern, and a method for producing the same.

In recent years, the amount of information distributed to society has increased dramatically, and there is an increasing expectation for downsizing and multi-functioning information equipment for processing this information. In order to meet this demand, it is indispensable to improve the information recording density and the information processing speed. Therefore, higher integration of semiconductor integrated circuits constituting information equipment is being promoted. With the high integration of this semiconductor integrated circuit, the miniaturization of the wiring pattern has progressed, and now a fine structure of 100 nm or less is formed. In the future, further miniaturization is required, and according to the ITRS 2006 version, a DRAM half pitch of 65 nm in 2007, 45 nm in 2010, and 32 nm in 2013 is required.
In response to these miniaturization requirements, an immersion lithography process using a high refractive index liquid and an EUV lithography process using extreme ultraviolet light as a light source have been proposed. However, since a polar solvent or an organic solvent is used in the immersion lithography process, there is a problem of contamination of the stepper lens due to elution of the photodegradation product of the photoacid generator. Further, in EUV lithography, the amount of capital investment related to each elemental technology is extremely increased.

Therefore, according to Non-Patent Document 1 and Patent Document 1, a nanoimprint lithography process was proposed by Professor Chou et al. At Princeton University. Since this process is simpler than photolithography, the amount of capital investment can be suppressed, and the manufacturing cost can be greatly reduced. Therefore, it is expected to be a mass production technique that replaces photolithography.
The nanoimprint lithography process can be broadly classified into thermal nanoimprint lithography and optical nanoimprint lithography. The former forms a thermoplastic polymer film on the substrate to be imprinted, then heats and softens it, presses the mold patterned in a concavo-convex shape from above, releases it after cooling and molds the concavo-convex shape of the mold. This is a process of transferring to a film made of a thermoplastic polymer on a substrate. In the former thermal nanoimprint lithography, it is possible to easily form a concavo-convex shape on the thermoplastic polymer by pressing the mold against a self-supporting thermoplastic polymer film having a film thickness of several tens of μm or more. However, if the uneven height difference is greater than the thickness of the thermoplastic polymer, for example, if the mold is pressed against a thin film of thermoplastic polymer formed by spin coating on a solid substrate, the convexity of the formed pattern There is a problem that a part of the part is peeled off from the substrate without being released from the mold, resulting in a structural defect. In order to overcome this problem, optimization of molding conditions such as molding temperature, cooling temperature, holding time, mold release speed, etc. depending on the thermoplastic polymer and selection of a mold release agent on the mold surface, Attempts have been made to reduce the residual stress that occurs at the boundary of this, but it is still not sufficient.

  According to Patent Document 2, a mold whose surface is treated with a reactive release agent such as perfluoropolyether having a functional group that chemically reacts with the surface of the mold material is proposed in order to suppress the above-described structural defects. Has been. However, since the patterning material and the mold always come into contact with each other during the nanoimprint process, the mold release agent on the mold surface falls off as the number of times of pattern transfer increases. As a result, the releasability of the patterning material is lowered, and pattern peeling becomes a problem. In particular, when a patterning material made of a thermoplastic polymer is formed on a metal thin film and thermal nanoimprinting is performed, peeling of the pattern becomes remarkable because the adhesion of the thermoplastic polymer to the metal thin film is low. Therefore, it is necessary to perform resurface treatment of the mold after a certain area or a certain number of nanoimprints. However, such a process has an effect on productivity, and a mold cleaning process is added, resulting in a problem that the life of the mold is shortened.

According to Non-Patent Document 2, a thermoplastic polymer thin film is provided on a substrate having a gold layer, irregularities are transferred by thermal nanoimprint, gold is removed by wet chemical etching after RIE (reactive ion etching) process, Finally, a method for forming a fine gold pattern by removing a thermoplastic polymer with oxygen plasma and its substrate have been reported. However, since the adhesion between the metal and the thermoplastic polymer resin is generally low, the polymer pattern is peeled off during nanoimprinting, and the gold pattern is lost, deformed, or thinned by the penetration of the etching solution when etching gold.
According to Non-Patent Document 3, a substrate having a SiO ₂ surface is modified with a silane coupling agent having a benzophenone group, and then a polymer layer having a hydrocarbon group is provided and irradiated with ultraviolet rays, whereby the polymer and benzophenone are combined. A method for covalent bonding has been reported. This method is effective for substrates and fine particles made of a metal oxide having a hydroxyl group on the surface. However, the metal surface such as gold cannot be expected to have an anchor effect, and it is not assumed to be applied to the nanoimprint process.
According to Non-Patent Document 4, photoenolization by intramolecular hydrogen transfer by irradiating light after adsorbing a thiol group having 2-methylbenzophenone on the gold cluster surface has been reported. However, since the alkyl group is substituted at the 2-position of benzophenone, the hydrogen abstraction reaction by radicals is limited within the molecule, and a covalent bond cannot be formed between benzophenone and the resin. For this reason, the adhesiveness of the resin to the gold cluster is not sufficient.

  Further, in thermal nanoimprint lithography, it takes time for thermal cycles such as heating, holding, and cooling, and therefore, improvement in throughput is desired. In order to solve this problem, development of a high-performance heater / cooler, roller nanoimprint described in Non-Patent Document 5, and room temperature nanoimprint using a sol-gel material described in Non-Patent Documents 6 and 7 Has been proposed. In Non-Patent Document 8, the effect of molecular weight is studied, and when a low molecular weight polymer is used, the viscosity is lower than that of a high molecular weight polymer, and the possibility of shortening the holding time is described. However, the weight average molecular weights of the thermoplastic resins studied in Non-Patent Document 8 are 58000 and 353000, and the effect when using a thermoplastic polymer of 58000 or less has not been studied.

On the other hand, as a conventional method for forming a metal thin film pattern on a substrate, an etching resist layer is formed on a substrate having a metal thin film such as copper by a printing method such as screen printing or ink jet printing or a photolithography method, and then wet etching. There is known a subtractive method for removing a metal layer by the above method. There is also known an additive method in which a plating resist layer is formed on a substrate by a printing method or a photolithography method, and a conductive metal layer is formed by electroless plating or electrolytic plating. These have been put into practical use by a method for forming a conductor line width of 10 μm or more, but cannot cope with fine processing of 10 μm or less, and further formation of a conductor line width of 1 μm or less.
Therefore, according to Non-Patent Document 9, a metal wiring method by electroless plating using patterning of a self-assembled film having a film thickness of nanometer has been reported. However, electroless plating alone has low metal adhesion and problems with durability, low metal density and the need for electrolytic plating, and conductivity due to the effects of impurities such as organic substances and metal oxides generated by photolysis. There is a problem that the wiring edge shape is not uniform.
US Pat. No. 5,772,905 JP 2004-351893 A SY Chou, et al., Applied Physics Letters, 67, 3114-3116 (1995) Ch. Pannemann, T. Diekmann, U. Hilleringman Microelectronic Engineering, 67-68, 845-852 (2003) O. Prucker, et al., J. Am. Chem. Soc., 121, 8766-8770 (1999) AJ Kell, CC Montcalm, MS Workentin, Can. J. Chem. 81, 484-494 (2003) H. Tan, A. Gilbertson and SY Chou: J. Vac. Sci. Technol. B 16, 3926 (1998) S. Matsui, Y. Igaku, H. Ishigaki, J. Fugita, M. Ishida, Y. Ochiai, H. Namatsu, M. Komuro and H. Hiroshima; J. Vac. Sci. Technol. B 19, 2801 (2001 ). Y. Igaku, S. Matsui, H. Ishigaki, J. Fugita, M. Ishida, Y. Ochiai, M. Komuro and H. Hiroshima; J. Vac. Sci. Technol. B 19, 2801 (2001). J. Appl. Vac. Phys. 41, 4198 (2002)). H. Schulz, M. Wissen, N. Bogdanski, H.-C. Scheer, K. Mattes, Ch. Friedrich; Microelect. Eng. 83, 259 (2006) P. Zhu, Y. Masuda, K. Koumoto, J. Mater. Chem., 14, 976-981 (2004)

An object of the present invention is to provide a novel ultraviolet-sensitive compound that exhibits an action such as exhibiting adhesiveness by ultraviolet irradiation, and to firmly bond a metal thin film on a substrate surface and a thermoplastic polymer using the compound. It is to provide a nanoimprint adhesive.
Another subject of the present invention is to produce a substrate having a metal thin film pattern as designed, which can suppress the disappearance and deformation of the metal thin film pattern, firmly bonding the metal thin film on the substrate surface and the thermoplastic polymer. Another object of the present invention is to provide a method for manufacturing a substrate having a metal thin film pattern that can be used, and a substrate obtained by the method.

According to the present invention, an ultraviolet-sensitive compound represented by the formula (I) is provided.
(Wherein two groups with one group one group selected from R ¹ to R ³ is, or is selected from R ¹ to R ³ one group and which are selected from R ⁴ to R ⁶ _{-X- (CH 2) m-SH} ( wherein, X is indicated O, OCO, COO, NH or NHCO, m is an integer of 1 to 20), and hydrogen remaining groups, alone respectively An atom, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms linked by an oxygen atom or a nitrogen atom is shown.)

Moreover, according to this invention, the adhesive for nanoimprint containing the said ultraviolet sensitive compound is provided.
Further, according to the present invention, there is provided a substrate (hereinafter sometimes referred to as substrate (a1)) comprising a metal thin film layer, a cured film layer of the above-mentioned UV-sensitive compound, and a film layer of a thermoplastic polymer in this order. Provided.
Furthermore, according to the present invention, there is provided a substrate (hereinafter sometimes referred to as substrate (a2)) comprising a metal thin film layer and a film layer containing a cured product of the above-mentioned UV-sensitive compound and a thermoplastic polymer. .
Further, according to the present invention, there is provided a substrate (hereinafter sometimes referred to as substrate (b)) in which irregularities are formed on the film layer of the substrate (a1) or substrate (a2) by a thermal nanoimprint method.
Furthermore, according to the present invention, in the substrate (b), the step of removing the residual thermoplastic polymer film in the concave portion by dry etching, the step of removing the metal thin film in the concave portion by wet etching, and the heat in the convex portion There is provided a method for producing a substrate having a metal thin film pattern, comprising a step of peeling a plastic polymer, wherein a metal thin film pattern having a line width of 0.01 μm to 10 μm is formed on the substrate (b).
Furthermore, according to the present invention, there is provided a substrate (hereinafter sometimes referred to as substrate (c)) having a metal thin film pattern having a line width of 0.01 μm to 10 μm manufactured by the above manufacturing method.

The ultraviolet-sensitive compound of the present invention is useful as an adhesive component that firmly bonds the surface of a metal thin film and the surface of a thermoplastic polymer by ultraviolet irradiation, and can be used for a nanoimprint method or the like.
Since the nanoimprint adhesive of the present invention contains the ultraviolet-sensitive compound of the present invention, the metal thin film surface and the thermoplastic polymer surface can be firmly bonded.
In the method for producing a substrate (c) of the present invention, since the adhesive of the present invention is used, peeling of the thermoplastic polymer in the thermal nanoimprint or between the metal thin film and the thermoplastic polymer in the etching solution in wet etching. Invasion of the metal thin film pattern can be suppressed, the disappearance and deformation of the metal thin film pattern can be prevented, and a substrate (c) having a fine metal thin film pattern as designed can be obtained. In addition, this method is far more productive than electron beam lithography, and is superior in resolution and quality of metal thin film patterns compared to the conventional thermal nanoimprint method. Is excellent. The substrate (c) of the present invention having a metal fine pattern thus obtained is useful for a wire grid polarizer, a diffraction grating, a metal wiring substrate for electronic devices, and the like.

Hereinafter, the contents of the present invention will be described in detail.
<Ultraviolet sensitive compound>
The ultraviolet-sensitive compound of the present invention is a compound represented by the above formula (I).
Wherein, R ¹ to R is one group selected from ^3, or two groups with one group selected from a single group and R ⁴ to R ⁶ is selected from R ¹ to R ³ - X— (CH ₂ ) m —SH, and the remaining groups are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a carbon atom having 1 to 6 carbon atoms linked by an oxygen atom or a nitrogen atom. Indicates a hydrogen group. When the hydrocarbon group has 7 or more carbon atoms, the adsorption density of the benzophenone group on the substrate surface decreases, so the amount of ultraviolet irradiation needs to be increased.
Here, X represents O, OCO, COO, NH, or NHCO, and OCO, COO, and NHCO are preferable because of the ease of the synthesis reaction. m represents an integer of 1 to 20, and is preferably 5 to 12 because of easy availability of raw materials and photoreactivity with thermoplastic polymers. When m exceeds 20, the flexibility of the molecular chain increases, the amount of adsorption of the compound decreases, and the adhesion function may be reduced.
In the formula (I), R ² alone or two groups of R ² and R ⁵ are —X— (CH ₂ ) m —.
A compound that is SH is preferably mentioned, and X in this case is preferably O, OCO, NH, or NHCO (such a compound may be hereinafter referred to as compound (A)). OCO and NHCO are preferred because of the ease of the synthesis reaction. Such a compound (A) can adhere the metal thin film surface and the thermoplastic polymer surface more firmly. Moreover, productivity can be improved by suppressing the amount of ultraviolet irradiation. As said hydrocarbon group in a compound (A), a C1-C6 alkyl group, a C3-C6 cycloalkyl group, and a phenyl group are mentioned, for example.

Examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, isobutyl group, sec-butyl group, pentyl group, isopentyl group, and cyclopentyl group. Hexyl group, cyclohexyl group, and phenyl group. A methyl group, an ethyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, and a phenyl group are preferable because of photoreactivity caused by steric hindrance and adhesion to a gold substrate.
Preferred examples of the hydrocarbon group having 1 to 6 carbon atoms connected by an oxygen atom or a nitrogen atom preferably include groups in which the exemplified groups of the above hydrocarbon group having 1 to 6 carbon atoms are connected by an oxygen atom or a nitrogen atom. be able to.

Examples of the ultraviolet-sensitive compound in which one group of R ^{1 to} R ^{3 in} the above formula (I) is —X— (CH ₂ ) m —SH and the remaining group is a hydrogen atom include 3- (2 -Mercaptoethyloxy) benzophenone, 3- (6-mercaptohexyloxy) benzophenone, 3- (8-mercaptooctyloxy) benzophenone, 3- (10-mercaptodecyloxy) benzophenone, 3- (12-mercaptododecyloxy) benzophenone 3- (18-mercaptooctadecyloxy) benzophenone, 4- (2-mercaptoethyloxy) benzophenone, 4- (6-mercaptohexyloxy) benzophenone, 4- (8-mercaptooctyloxy) benzophenone, 4- (10- Mercaptodecyloxy) benzophenone, 4- (12-mercaptododecyloxy) benzophenone, 4- ( 18-mercaptooctadecyloxy) benzophenone, 3- (3-mercaptopropionyloxy) benzophenone, 3- (6-mercaptohexanoyloxy) benzophenone, 3- (8-mercaptooctanoyloxy) benzophenone, 3- (11-mercaptoun) Decanoyloxy) benzophenone, 4- (3-mercaptopropionyloxy) benzophenone, 4- (6-mercaptohexanoyloxy) benzophenone, 4- (8-mercaptooctanoyloxy) benzophenone, 4- (11-mercaptoundecanoyl) Oxy) benzophenone, 3- (2-mercaptoethyloxycarbonyl) benzophenone, 3- (6-mercaptohexyloxycarbonyl) benzophenone, 3- (8-mercaptooctyloxycarbonyl) benzophenone, 3- ( 0-mercaptodecyloxycarbonyl) benzophenone, 4- (2-mercaptoethyloxycarbonyl) benzophenone, 4- (6-mercaptohexyloxycarbonyl) benzophenone, 4- (8-mercaptooctyloxycarbonyl) benzophenone, 4- (10- Mercaptodecyloxycarbonyl) benzophenone, 3- (2-mercaptoethylamino) benzophenone, 3- (6-mercaptohexylamino) benzophenone, 3- (8-mercaptooctylamino) benzophenone, 3- (10-mercaptodecylamino) benzophenone 3- (12-mercaptododecylamino) benzophenone, 3- (18-mercaptooctadecylamino) benzophenone, 4- (2-mercaptoethylamino) benzophenone, 4- (6-mercaptohexyl) Mino) benzophenone, 4- (8-mercaptooctylamino) benzophenone, 4- (10-mercaptodecylamino) benzophenone, 4- (12-mercaptododecylamino) benzophenone, 4- (18-mercaptooctadecylamino) benzophenone, 3- (3-mercaptopropionylamino) benzophenone, 3- (6-mercaptohexanoylamino) benzophenone, 3- (8-mercaptooctanoylamino) benzophenone, 3- (11-mercaptododecanoylamino) benzophenone, 4- (3- Mercaptopropionylamino) benzophenone, 4- (6-mercaptohexanoylamino) benzophenone, 4- (8-mercaptooctanoylamino) benzophenone, 4- (11-mercaptododecanoylamino) benzophenone. But not limited to these.

Examples of the ultraviolet-sensitive compound in which one group of R ^{1 to} R ^{3 in} the above formula (I) is —X— (CH ₂ ) m —SH and the remaining group includes a group other than a hydrogen atom include 3 -Methyl-4- (2-mercaptoethyloxy) benzophenone, 3-methoxy-4- (2-mercaptoethyloxy) benzophenone, 3,5-dimethyl-4- (4-mercaptobutyloxy) benzophenone, 4- (2 -Mercaptoethyloxy) -4'-methylbenzophenone, 4- (4-mercaptobutyloxy) -4'-butylbenzophenone, 4- (6-mercaptohexyloxy) -4'-cyclohexylbenzophenone, 4- (8-mercapto Octyloxy) -4'-methoxybenzophenone, 4- (8-mercaptooctyloxy) -3 ', 5'-dimethoxybenzophenone, 4- (10-mercaptodecyloxy) 3 ′, 4 ′, 5′-trimethoxybenzophenone, 4- (10-mercaptodecyloxy) -4′-dimethylaminobenzophenone, 4- (10-mercaptodecyloxy) -4′-phenylbenzophenone, 4- (10 -Mercaptodecyloxy) -4'-phenoxybenzophenone, 3-methyl-4- (3-mercaptopropionyloxy) benzophenone, 3-methoxy-4- (3-mercaptopropionyloxy) benzophenone, 3,5-dimethyl-4- (6-mercaptohexanoyloxy) benzophenone, 4- (3-mercaptopropionyloxy) -4′-methylbenzophenone, 4- (6-mercaptohexanoyloxy) -4′-butylbenzophenone, 4- (6-mercaptohexa Noyloxy) -4'-cyclohexylbenzophenone, 4- (6-merca) Tohexanoyloxy) -4′-methoxybenzophenone, 4- (6-mercaptohexanoyloxy) -3 ′, 5′-dimethoxybenzophenone, 4- (6-mercaptohexanoyloxy) -3 ′, 4 ′, 5 '-Trimethoxybenzophenone, 4- (8-mercaptooctanoyloxy) -4'-dimethylaminobenzophenone, 4- (11-mercaptoundecanoyloxy) -4'-phenylbenzophenone, 4- (11-mercaptoundeca Noyloxy) -4'-phenoxybenzophenone, 3-methyl-4- (2-mercaptoethyloxycarbonyl) benzophenone, 3-methoxy-4- (2-mercaptoethyloxycarbonyl) benzophenone, 3,5-dimethyl-4- (6-mercaptohexyloxycarbonyl) benzophenone, 4- (2-mercapto Tyloxycarbonyl) -4'-methylbenzophenone, 4- (6-mercaptohexyloxycarbonyl) -4'-butylbenzophenone, 4- (8-mercaptooctyloxycarbonyl) -4'-cyclohexylbenzophenone, 4- (8- Mercaptooctyloxycarbonyl) -4′-methoxybenzophenone, 4- (8-mercaptooctyloxycarbonyl) -3 ′, 5′-dimethoxybenzophenone, 4- (10-mercaptodecyloxycarbonyl) -3 ′, 4 ′, 5 '-Trimethoxybenzophenone, 4- (10-mercaptodecyloxycarbonyl) -4'-dimethylaminobenzophenone, 4- (10-mercaptodecyloxycarbonyl) -4'-phenylbenzophenone, 4- (10-mercaptodecyloxycarbonyl) ) -4'-phenoxybenzof Non, 3-methyl-4- (2-mercaptoethylamino) benzophenone, 3-methoxy-4- (2-mercaptoethylamino) benzophenone, 3,5-dimethyl-4- (6-mercaptohexylamino) benzophenone, 4 -(2-mercaptoethylamino) -4'-methylbenzophenone, 4- (6-mercaptohexylamino) -4'-butylbenzophenone, 4- (8-mercaptooctylamino) -4'-cyclohexylbenzophenone, 4- ( 8-mercaptooctylamino) -4′-methoxybenzophenone, 4- (8-mercaptooctylamino) -3 ′, 5′-dimethoxybenzophenone, 4- (10-mercaptodecylamino) -3 ′, 4 ′, 5 ′ -Trimethoxybenzophenone, 4- (10-mercaptodecylamino) -4'-dimethylaminobenzopheno 4- (10-mercaptodecylamino) -4′-phenylbenzophenone, 4- (10-mercaptodecylamino) -4′-phenoxybenzophenone, 3-methyl-4- (3-mercaptopropionylamino) benzophenone, 3- Methoxy-4- (3-mercaptopropionylamino) benzophenone, 3,5-dimethyl-4- (6-mercaptohexanoylamino) benzophenone, 4- (3-mercaptopropionylamino) -4′-methylbenzophenone, 4- ( 6-mercaptohexanoylamino) -4′-butylbenzophenone, 4- (8-mercaptooctanoylamino) -4′-cyclohexylbenzophenone, 4- (11-mercaptododecanoylamino) -4′-methoxybenzophenone, 4- (8-mercaptooctanoylamino) -3 ', 5'-dimethoxy Cibenzophenone, 4- (11-mercaptododecanoylamino) -3 ′, 4 ′, 5′-trimethoxybenzophenone, 4- (11-mercaptododecanoylamino) -4′-dimethylaminobenzophenone, 4- (11- Examples include, but are not limited to, mercaptododecanoylamino) -4′-phenylbenzophenone and 4- (11-mercaptododecanoylamino) -4′-phenoxybenzophenone.

Two groups of one group selected from R ^{1 to} R ³ and one group selected from R ^{4 to} R ^{6 in the} above formula (I) are —X— (CH ₂ ) m —SH. Examples of the UV-sensitive compound include 3,3′-bis (2-mercaptoethyloxy) benzophenone, 3,3′-bis (6-mercaptohexyloxy) benzophenone, and 3,3′-bis (8-mercaptooctyloxy). ) Benzophenone, 3,3′-bis (10-mercaptodecyloxy) benzophenone, 3,3′-bis (12-mercaptododecyloxy) benzophenone, 3,3′-bis (18-mercaptooctadecyloxy) benzophenone, 4, 4'-bis (2-mercaptoethyloxy) benzophenone, 4,4'-bis (6-mercaptohexyloxy) benzophenone, 4,4'-bis (8-mercaptooctyloxy) benzopheno 4,4′-bis (10-mercaptodecyloxy) benzophenone, 4,4′-bis (12-mercaptododecyloxy) benzophenone, 4,4′-bis (18-mercaptooctadecyloxy) benzophenone, 3,3 '-Bis (3-mercaptopropionyloxy) benzophenone, 3,3'-bis (6-mercaptohexanoyloxy) benzophenone, 3,3'-bis (8-mercaptooctanoyloxy) benzophenone, 3,3'-bis (11-mercaptoundecanoyloxy) benzophenone, 4,4′-bis (3-mercaptopropionyloxy) benzophenone, 4,4′-bis (6-mercaptohexanoyloxy) benzophenone, 4,4′-bis (8 -Mercaptooctanoyloxy) benzophenone, 4,4'-bis (11-mercaptoundecanoyl) Oxy) benzophenone, 3,3′-bis (2-mercaptoethyloxycarbonyl) benzophenone, 3,3′-bis (6-mercaptohexyloxycarbonyl) benzophenone, 3,3′-bis (8-mercaptooctyloxycarbonyl) Benzophenone, 3,3′-bis (10-mercaptodecyloxycarbonyl) benzophenone, 4,4′-bis (2-mercaptoethyloxycarbonyl) benzophenone, 4,4′-bis (6-mercaptohexyloxycarbonyl) benzophenone, 4,4′-bis (8-mercaptooctyloxycarbonyl) benzophenone, 4,4′-bis (10-mercaptodecyloxycarbonyl) benzophenone, 3,3′-bis (2-mercaptoethylamino) benzophenone, 3,3 '-Bis (6-mercaptohexylamino) ben Phenone, 3,3′-bis (8-mercaptooctylamino) benzophenone, 3,3′-bis (10-mercaptodecylamino) benzophenone, 3,3′-bis (12-mercaptododecylamino) benzophenone, 3,3 '-Bis (18-mercaptooctadecylamino) benzophenone, 4,4'-(2-mercaptoethylamino) benzophenone, 4,4'-bis (6-mercaptohexylamino) benzophenone, 4,4'-bis (8- Mercaptooctylamino) benzophenone, 4,4′-bis (10-mercaptodecylamino) benzophenone, 4,4′-bis (12-mercaptododecylamino) benzophenone, 4,4′-bis (18-mercaptooctadecylamino) benzophenone 3,3′-bis (3-mercaptopropionylamino) benzophenone, 3, 3′-bis (6-mercaptohexanoylamino) benzophenone, 3,3′-bis (8-mercaptooctanoylamino) benzophenone, 3,3′-bis (11-mercaptododecanoylamino) benzophenone, 4,4 ′ -Bis (3-mercaptopropionylamino) benzophenone, 4,4'-bis (6-mercaptohexanoylamino) benzophenone, 4,4'-bis (8-mercaptooctanoylamino) benzophenone, 4,4'-bis ( 11-mercaptododecanoylamino) benzophenone, but is not limited to.

  Preferred examples of the ultraviolet-sensitive compound of the present invention include 3-methyl-4- (2-mercaptoethyloxy) benzophenone, 3-methoxy-4- (2-mercaptoethyloxy) benzophenone, 3,5-dimethyl- 4- (4-mercaptobutyloxy) benzophenone, 4- (2-mercaptoethyloxy) -4′-methylbenzophenone, 4- (4-mercaptobutyloxy) -4′-butylbenzophenone, 4- (6-mercaptohexyl) Oxy) -4'-cyclohexylbenzophenone, 4- (8-mercaptooctyloxy) -4'-methoxybenzophenone, 4- (8-mercaptooctyloxy) -3 ', 5'-dimethoxybenzophenone, 4- (10-mercapto Decyloxy) -3 ', 4', 5'-trimethoxybenzophenone, 4- (1 0-mercaptodecyloxy) -4′-dimethylaminobenzophenone, 4- (10-mercaptodecyloxy) -4′-phenylbenzophenone, 4- (10-mercaptodecyloxy) -4′-phenoxybenzophenone, 3-methyl- 4- (3-mercaptopropionyloxy) benzophenone, 3-methoxy-4- (3-mercaptopropionyloxy) benzophenone, 3,5-dimethyl-4- (6-mercaptohexanoyloxy) benzophenone, 4- (3-mercapto Propionyloxy) -4'-methylbenzophenone, 4- (6-mercaptohexanoyloxy) -4'-butylbenzophenone, 4- (6-mercaptohexanoyloxy) -4'-cyclohexylbenzophenone, 4- (6-mercapto) Hexanoyloxy) -4'-methoxybe Nzophenone, 4- (6-mercaptohexanoyloxy) -3 ′, 5′-dimethoxybenzophenone, 4- (6-mercaptohexanoyloxy) -3 ′, 4 ′, 5′-trimethoxybenzophenone, 4- (8 -Mercaptooctanoyloxy) -4'-dimethylaminobenzophenone, 4- (11-mercaptoundecanoyloxy) -4'-phenylbenzophenone, 4- (11-mercaptoundecanoyloxy) -4'-phenoxybenzophenone, 3-methyl-4- (2-mercaptoethyloxycarbonyl) benzophenone, 3-methoxy-4- (2-mercaptoethyloxycarbonyl) benzophenone, 3,5-dimethyl-4- (6-mercaptohexyloxycarbonyl) benzophenone, 4- (2-mercaptoethyloxycarbonyl) -4 ' Methylbenzophenone, 4- (6-mercaptohexyloxycarbonyl) -4′-butylbenzophenone, 4- (8-mercaptooctyloxycarbonyl) -4′-cyclohexylbenzophenone, 4- (8-mercaptooctyloxycarbonyl) -4 ′ -Methoxybenzophenone, 4- (8-mercaptooctyloxycarbonyl) -3 ', 5'-dimethoxybenzophenone, 4- (10-mercaptodecyloxycarbonyl) -3', 4 ', 5'-trimethoxybenzophenone, 4- (10-mercaptodecyloxycarbonyl) -4′-dimethylaminobenzophenone, 4- (10-mercaptodecyloxycarbonyl) -4′-phenylbenzophenone, 4- (10-mercaptodecyloxycarbonyl) -4′-phenoxybenzophenone, 3- Til-4- (2-mercaptoethylamino) benzophenone, 3-methoxy-4- (2-mercaptoethylamino) benzophenone, 3,5-dimethyl-4- (6-mercaptohexylamino) benzophenone, 4- (2- Mercaptoethylamino) -4'-methylbenzophenone, 4- (6-mercaptohexylamino) -4'-butylbenzophenone, 4- (8-mercaptooctylamino) -4'-cyclohexylbenzophenone, 4- (8-mercaptooctyl) Amino) -4′-methoxybenzophenone, 4- (8-mercaptooctylamino) -3 ′, 5′-dimethoxybenzophenone, 4- (10-mercaptodecylamino) -3 ′, 4 ′, 5′-trimethoxybenzophenone 4- (10-mercaptodecylamino) -4′-dimethylaminobenzopheno 4- (10-mercaptodecylamino) -4′-phenylbenzophenone, 4- (10-mercaptodecylamino) -4′-phenoxybenzophenone, 3-methyl-4- (3-mercaptopropionylamino) benzophenone, 3 -Methoxy-4- (3-mercaptopropionylamino) benzophenone, 3,5-dimethyl-4- (6-mercaptohexanoylamino) benzophenone, 4- (3-mercaptopropionylamino) -4'-methylbenzophenone, 4- (6-mercaptohexanoylamino) -4′-butylbenzophenone, 4- (8-mercaptooctanoylamino) -4′-cyclohexylbenzophenone, 4- (11-mercaptododecanoylamino) -4′-methoxybenzophenone, 4 -(8-mercaptooctanoylamino) -3 ' 5′-dimethoxybenzophenone, 4- (11-mercaptododecanoylamino) -3 ′, 4 ′, 5′-trimethoxybenzophenone, 4- (11-mercaptododecanoylamino) -4′-dimethylaminobenzophenone, 4- (11-mercaptododecanoylamino) -4′-phenylbenzophenone, 4- (11-mercaptododecanoylamino) -4′-phenoxybenzophenone, 4,4′-bis (2-mercaptoethyloxy) benzophenone, 4,4 '-Bis (6-mercaptohexyloxy) benzophenone, 4,4'-bis (8-mercaptooctyloxy) benzophenone, 4,4'-bis (10-mercaptodecyloxy) benzophenone, 4,4'-bis (12 -Mercaptododecyloxy) benzophenone, 4,4'-bis (18-merca) Tooctadecyloxy) benzophenone, 4,4′-bis (3-mercaptopropionyloxy) benzophenone, 4,4′-bis (6-mercaptohexanoyloxy) benzophenone, 4,4′-bis (8-mercaptooctanoyloxy) ) Benzophenone, 4,4′-bis (11-mercaptoundecanoyloxy) benzophenone, 4,4′-bis (6-mercaptohexylamino) benzophenone, 4,4′-bis (8-mercaptooctylamino) benzophenone, 4,4′-bis (10-mercaptodecylamino) benzophenone, 4,4′-bis (12-mercaptododecylamino) benzophenone, 4,4′-bis (18-mercaptooctadecylamino) benzophenone, 4,4′- Bis (3-mercaptopropionylamino) benzophenone, 4, Examples include 4'-bis (6-mercaptohexanoylamino) benzophenone, 4,4'-bis (8-mercaptooctanoylamino) benzophenone, and 4,4'-bis (11-mercaptododecanoylamino) benzophenone. It is not limited to.

In the ultraviolet-sensitive compound of the present invention, R ¹ is preferably a hydrogen atom because of easy availability of raw materials, ease of synthesis, photoreactivity with a thermoplastic polymer, and adhesion to a gold substrate. R ² is a 10-mercaptodecylamino group or 6-mercaptohexanoylamino group, R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, R ⁵ is a methoxy group, 10-mercaptodecylamino 4- (10-mercaptodecylamino) -4′-methoxybenzophenone, 4,4′-bis (10-mercaptodecylamino), which is a group or 6-mercaptohexanoylamino group and R ⁶ is a hydrogen atom Benzophenone, 4- (6-mercaptohexanoylamino) -4′-methoxybenzophenone, or 4,4′-bis (6-mercaptohexanoylamino) benzopheno It is.

The production of the UV-sensitive compound of the present invention is, for example, first by hydroxybenzophenone by Friedel-Crafts reaction in which each of benzoic acid chloride and phenol, benzoic acid chloride and benzoic acid, benzoic acid chloride and nitrobenzene are reacted in the presence of aluminum chloride. Carboxybenzophenone and nitrobenzophenone are obtained. The desired UV-sensitive compound can be obtained by haloalkylation and sulfidation of hydroxybenzophenone and carboxybenzophenone.
Aminobenzophenone can be obtained by reducing nitrobenzophenone, and the desired UV-sensitive compound can be obtained by haloalkylation and sulfidation thereof.
Benzoic acid chloride, phenol, benzoic acid, and nitrobenzene, which are the benzophenone reaction raw materials, may be nucleus-substituted with an alkyl group, a cycloalkyl group, an alkoxyl group, a phenyl group, or a phenoxy group. The 2nd, 6th, 2 'and 6' positions need to be hydrogen atoms.

Hereinafter, synthesis examples of ultraviolet-sensitive compounds will be described more specifically.
Synthesis of 3- (8-mercaptooctyloxy) benzophenone using hydroxybenzophenone as a raw material was obtained by reacting 3-hydroxybenzophenone and 1,8-dibromooctane in the presence of an alkali to obtain 8-bromooctyl ether, After the reaction, it can be carried out by hydrolysis with alkali and hydrochloric acid treatment.
Similarly, the synthesis of 4- (8-mercaptoheptylcarbonyloxy) benzophenone using hydroxybenzophenone as a raw material involves the reaction of 4-hydroxybenzophenone and 8-bromooctanoic acid chloride in the presence of triethylamine to form 8-bromooctanoic acid ester. It can be obtained by reacting with thiourea followed by hydrolysis with alkali and hydrochloric acid treatment.
Synthesis of 4- (8-mercaptooctyloxycarbonyl) benzophenone using carboxybenzophenone as a raw material was conducted by reacting an acid chloride of 4-carboxybenzophenone with 1-hydroxy-8-bromooctane in the presence of triethylamine. Bromooctyl ester can be obtained and reacted with thiourea, followed by hydrolysis with alkali and treatment with hydrochloric acid.
Synthesis of 4- (8-mercaptooctylamino) benzophenone using nitrobenzophenone as raw material is obtained by catalytic reduction of 4-nitrobenzophenone to obtain 4-aminobenzophenone, which is reacted with 1,8-dibromooctane in the presence of alkali. 8-bromooctylamine can be obtained and reacted with thiourea, followed by hydrolysis with alkali and treatment with hydrochloric acid.
Similarly, the synthesis of 4- (8-mercaptooctanoylamino) benzophenone using nitrobenzophenone as a raw material was obtained by catalytic reduction of 4-nitrobenzophenone to obtain 4-aminobenzophenone and 8-bromooctanoic acid chloride in the presence of triethylamine. It can be reacted to obtain 8-bromooctanoic acid amide, reacted with thiourea, and then subjected to hydrolysis with alkali and hydrochloric acid treatment.

  The ultraviolet-sensitive compound of the present invention can be used as a nanoimprint adhesive containing the compound or a nanoimprint adhesive containing the compound and a thermoplastic polymer. By applying these nanoimprint adhesives, an adsorption film of the compound can be formed on a substrate having a metal thin film. The following is a nanoimprint adhesive containing an ultraviolet-sensitive compound (hereinafter referred to as adhesive (a1)), and a nanoimprint adhesive containing both the compound and a thermoplastic polymer (hereinafter referred to as adhesive (a2)). Will be described.

<Adhesive (a1)>
The adhesive (a1) is a solution having the ultraviolet-sensitive compound of the present invention, and may further contain an additive for promoting the photochemical reaction of benzophenone.
The solvent may be any solvent that dissolves the UV-sensitive compound, for example, alcohols such as methanol, ethanol, isopropyl alcohol, propanol, and butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; acetic acid Esters such as ethyl, butyl acetate, methoxyethyl acetate, methoxypropyl acetate, ethoxypropyl acetate and ethyl lactate; ethers such as tetrahydrofuran; alkyl halides such as chloroform and butyl chloride; aromatic hydrocarbons such as benzene, toluene and xylene; Examples include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone. These may be a mixed solvent of two or more. Ethanol is preferred from the viewpoint of the working environment.
The additive is preferably a compound having a role of promoting the progress of the photochemical reaction of benzophenone, and examples thereof include alkylthiols having 6 to 20 carbon atoms.
In the adsorption film formed on the surface of the metal thin film, the benzophenone parts contributing to the photochemical reaction are dense due to intermolecular interaction. Therefore, it is easy to deactivate due to light energy transfer between benzophenones. A thiol compound having no benzophenone structure may be added as a diluent in order to reduce the density of benzophenone in the adsorption film and efficiently generate bisradicals of the benzophenone part by photoexcitation. A sensitizer that promotes photoexcitation of benzophenone may be added.
In the adhesive (a1), the concentration of the ultraviolet-sensitive compound is usually in the range of 0.0001 to 1 mol / dm ³ , preferably 0.001 to 0.1 mol / dm ³ . When the concentration is lower than 0.0001 mol / dm ³ , the adsorption film may not be formed uniformly on the surface of the metal thin film. There is no difference in effect even at concentrations higher than 1 mol / dm ³ .

<Adhesive (a2)>
Adhesive (a2) is a solution containing both the ultraviolet-sensitive compound of the present invention and a thermoplastic polymer, and further contains a diluent and a sensitizer additive for promoting the photochemical reaction of benzophenone. May be.
The solvent may be any solvent that dissolves the ultraviolet-sensitive compound and the thermoplastic polymer. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; ethyl acetate, butyl acetate, ethoxypropyl acetate, Esters such as ethyl lactate; Ethers such as tetrahydrofuran; Alkyl halides such as chloroform and butyl chloride; Aromatic hydrocarbons such as benzene, toluene and xylene; Non-protons such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone A polar solvent.
The thermoplastic polymer may be a polymer having a weight average molecular weight of 1,000 to 10,000,000, a glass transition temperature of room temperature or higher, soluble in a solvent, and insoluble in an etching solution used for wet etching. More preferably, a thermoplastic resin having a hydrocarbon group in the molecule is preferable. In particular, the weight average molecular weight is more preferably 1000 to 50000, and most preferably 1000 to 10000. Here, it is preferable to reduce the weight-average molecular weight of the thermoplastic polymer because the retention time in the thermal nanoimprint condition during the production of the substrate (b) described later can be shortened.
Here, examples of the hydrocarbon group include a methyl group, a methylene group, and a methine group. Examples of the thermoplastic polymer include polymethyl methacrylate, polystyrene (PSt), polycarbonate, and polyvinyl chloride when an aqueous etching solution is used.
In addition, a surfactant, a leveling agent and the like can be added to improve the coating properties on the substrate. Examples of these additives include ionic or nonionic surfactants, silicone derivatives, and fluorine derivatives.
In the adhesive (a2), the concentration of the ultraviolet-sensitive compound is usually in the range of 0.0001 to 1 mol / dm ³ , preferably 0.001 to 0.1 mol / dm ³ . When the concentration is lower than 0.0001 mol / dm ³ , the adsorption film may not be formed uniformly on the surface of the metal thin film. There is no difference in effect even at concentrations higher than 1 mol / dm ³ .
The concentration of the thermoplastic polymer is usually in the range of 0.1 to 10% by mass. When the concentration is lower than 0.1% by mass, spots may appear on the thermoplastic polymer film, and a homogeneous film may not be obtained. When the concentration is higher than 10% by mass, the film thickness may exceed 1 μm, and during wet etching, the etching pattern may not be easily supplied or replaced due to the high aspect ratio of the resist pattern. Structural defects may occur in the patterning of the metal thin film.

<Substrate (a1) and Substrate (a2)>
In the present invention, the substrate (a1) is a substrate provided with a metal thin film layer, a cured film layer of the UV-sensitive compound, and a film layer of a thermoplastic polymer in this order, and the adhesive (a1). Can be used.
The substrate (a2) is a substrate provided with a metal thin film layer and a film layer containing a cured product of an ultraviolet-sensitive compound and a thermoplastic polymer, and can be produced using the adhesive (a2). .

In the substrate (a1) and the substrate (a2), the metal thin film layer is not particularly limited as long as the metal thin film layer has a surface on which the thiol group of the ultraviolet-sensitive compound is adsorbed. As a metal which forms a metal thin film, Au, Pt, Ag, Cu, Ni, Ti, or Fe is mentioned, for example, Au, Ag, Cu, Ni, or Fe in which the metal surface is not oxidized is mentioned preferably. Au that does not oxidize the metal surface even in the atmosphere is particularly preferable.
The thickness of the metal thin film layer corresponds to the wiring thickness of the metal thin film pattern to be formed, and is preferably 5 nm to 20 μm. If the thickness is less than 5 nm, unevenness may occur in the volume resistivity in the substrate surface. If it is more than 20 μm, the film forming time becomes long and the production cost of the metal thin film becomes expensive. In addition, when the adhesive (a1) or the adhesive (a2) is formed on the surface of the Ag, Cu, Ni, Ti or Fe metal thin film as described later, the surface of the metal thin film may be reduced in advance. preferable.
The metal thin film is formed on a substrate. The substrate material is not particularly limited as long as it is a material having a glass transition temperature higher than that of a thermoplastic polymer molded by thermal nanoimprint lithography. For example, silicon, glass, quartz, alumina, barium titanate, etc. Inorganic oxides: epoxy resins, phenol resins, polyimide resins, polyester resins, or laminates and composites thereof. When the finally obtained substrate is used as a wiring substrate for electronics, it is a substrate made of an inorganic material such as silicon, glass or quartz, or a heat resistant organic material such as polyimide, in terms of smoothness, low thermal expansion coefficient, and insulation. Is preferred.
In order to improve the adhesion between the substrate and the metal thin film, an adhesion layer such as chromium can be formed in advance on the substrate surface with a normal film thickness of 0.5 nm to 10 nm.
Examples of the method for forming a metal thin film on a substrate include sputtering methods such as DC (direct current) sputtering, RF (high frequency) sputtering, magnetron sputtering, and ion beam sputtering; resistance heating vapor deposition method, electroless plating method, electrolytic plating method, A method by heat fusion of metal nanoparticles or a method of attaching a rolled metal foil can be used.

  In the substrate (a1) and the substrate (a2), on the metal thin film formed on the substrate, a cured film layer of an ultraviolet-sensitive compound or a film layer containing a cured product of an ultraviolet-sensitive compound and a thermoplastic polymer is laminated. First, apply the adhesive (a1) or adhesive (a2) on a substrate having a metal thin film by spin coating, dipping, etc., and evaporate the solvent under air blowing, heating or under reduced pressure. To form an adsorption film layer.

Next, in the case of the substrate (a1), a thermoplastic polymer film is further formed on the formed adsorption film layer. Examples of the thermoplastic polymer include those similar to the thermoplastic polymer used for the adhesive (a2).
The thermoplastic polymer film is formed by, for example, laminating a solution in which a thermoplastic polymer is dissolved in a solvent by spin coating, dipping, spray coating, flow coating, roll coating, or the like on the adsorption film. Furthermore, it can be carried out by evaporating the solvent under blowing, heating or reduced pressure. As the solvent, those exemplified in the above-mentioned adhesive (a2) can be used. Further, the solution in which the thermoplastic polymer is dissolved in a solvent may contain, for example, an ionic or nonionic surfactant; a leveling agent such as a silicone derivative or a fluorine derivative in order to improve coating properties. it can.
Under the present circumstances, the density | concentration of a thermoplastic polymer is the range of 0.1-10 mass% normally. When the concentration is lower than 0.1% by mass, spots may appear on the thermoplastic polymer film, and a homogeneous film may not be obtained. When the concentration is higher than 10% by mass, the film thickness may exceed 1 μm, and during wet etching, the etching pattern may not be easily supplied or replaced due to the high aspect ratio of the resist pattern. Structural defects may occur in the patterning of the metal thin film.

Next, the substrate (a1) and the substrate (a2) are usually produced by irradiating and curing the adsorption film layer and the thermoplastic polymer film formed as described above with ultraviolet rays having a wavelength of 200 nm to 400 nm. be able to.
As a light source for ultraviolet irradiation, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, an Hg-Xe lamp, or a halogen lamp can be used. Can be used. Ultraviolet light of less than 200 nm is not preferred because of its low transmittance with respect to the thermoplastic polymer and the light source is expensive, and light exceeding 400 nm is not preferred because of the low efficiency of benzophenone photoinduced radical formation.
The irradiation energy of ultraviolet rays is usually 10 to 250 J / cm ² . If it is less than 10 J / cm ² , the photochemical reaction of benzophenone may not sufficiently proceed and the adhesion function may not be exhibited. If it exceeds 250 J / cm ² , the photooxygen oxidation reaction, the photochemical reaction of the thermoplastic polymer film itself, etc. Deterioration of the film caused by the change in the thermophysical properties of the thermoplastic polymer may cause cracks on the surface of the film.

  By the ultraviolet irradiation, the carbonyl group of benzophenone in the ultraviolet sensitive compound is excited to generate a biradical. The radical generated on the oxygen atom of benzophenone quickly changes the alcohol from the hydrocarbon group of the thermoplastic polymer. The radical generated on the carbon of one benzophenone forms a covalent bond by recombination with the radical generated on the hydrocarbon of the thermoplastic polymer. Based on this principle, the layers in the substrate (a1) and the substrate (a2) are firmly bonded by adsorption of thiol on the metal thin film and covalent bond of benzophenone on the thermoplastic polymer.

The substrate (b) of the present invention is a substrate in which irregularities are formed by thermal nanoimprinting on the substrate (a1) or the substrate (a2). The unevenness can usually be formed using a thermal nanoimprint mold and a thermal nanoimprint apparatus.
<Description of mold for thermal nanoimprint>
The mold for thermal nanoimprinting is a mold for molding a thermoplastic polymer film on a substrate into irregularities by the thermal nanoimprinting method, and the material is mainly surface oxide silicon, synthetic silica, fused silica, quartz, silicon Nickel.
The mold for thermal nanoimprinting can be obtained by forming a desired concavo-convex pattern on the surface of the molding material using a known technique. The concave portion of the mold corresponds to the pattern of the metal thin film finally remaining after the wet etching process.
Since the chemical composition of the surface silica layer, synthetic silica, fused silica, and quartz of the surface silicon oxide is almost the same SiO ₂ , the concave and convex pattern is formed by processing the flat plate of the above material using a known semiconductor microfabrication technology can do. For example, a negative electron beam resist is applied to the flat plate having a smooth surface, and an electron beam is drawn on the electron resist by an electron beam drawing apparatus. Thereafter, when development is performed, the resist in the electron beam non-irradiated portion is removed, and the resist film remains in the electron beam irradiated portion on the flat plate. SiO ₂ is etched by using a negative image of the electron beam resist as an etching mask for dry etching by dry etching such as CHF ₃ / O ₂ plasma. Then, a recess can be produced on the surface of the flat plate by immersing in a stripping solution to remove the negative image of the electron beam resist and washing. In order to accelerate the release of the thermoplastic polymer, a treatment with a release agent such as a fluorocarbon-containing silane coupling agent may be performed.
The mold manufactured in this way can be used as a mold as it is, but after forming a metal film such as nickel on the surface of the mold, the nickel layer is further coated and peeled off using an electroforming process technique. It can also be a mold. In addition, after a metal film such as nickel is formed by sputtering on the surface of the flat plate made of the above material or a polyimide or polyester polymer resin, an organic image is formed using a photoresist or an electron beam resist. The nickel layer can be further thickened by a casting process technique, and can be used as a less expensive nickel mold by surface polishing and resist removal.

<Configuration of thermal nanoimprint apparatus>
The thermal nanoimprint apparatus includes a heating / cooling unit, a pressurizing unit, and a decompressing unit. The heating / cooling section is composed of a stage including a heater and a water cooling structure, and a substrate on which a thermoplastic polymer such as the substrate (a1) or the substrate (a2) is formed is installed and heated to soften the thermoplastic polymer film. This is the part to be cooled.
The pressurizing portion is a press that presses the concave-convex mold onto the substrate on which the thermoplastic polymer is formed, and is a portion that transfers the fine concave-convex structure of the mold to the substrate on which the thermoplastic polymer film has been softened. The decompression part is a part that efficiently keeps the substrate and the mold in a decompressed state when the mold is in a pressurized state with respect to the substrate and efficiently fills the concavo-convex part with the thermoplastic polymer.

<Manufacture of substrate (b)>
The production of the substrate (b) can be obtained, for example, by the following method.
First, the substrate (a1) or the substrate (a2) is placed on the heating / cooling stage of the thermal nanoimprint apparatus. Next, the substrate (a1) or the substrate (a2) is heated at a temperature 10 to 50 ° C. higher than the glass transition temperature of the thermoplastic polymer. When the temperature is lower than 10 ° C., the thermoplastic polymer does not become rubbery, and therefore, the edge portion of the transferred pattern may be rounded without being sufficiently softened. When the temperature is higher than 50 ° C., there is a problem that shrinkage during cooling after pattern transfer is large and the line width of some patterns is reduced.
Next, the above-described mold having a fine uneven pattern is pressed, and the unevenness of the mold is transferred to the thermoplastic polymer thin film of the substrate. Although it depends on the shape of the concavo-convex pattern of the mold, the thickness of the thermoplastic polymer film on the substrate (a1) or the substrate (a2) is generally 10 nm to 10 μm, preferably 50 nm to 500 nm. If the aspect ratio of the thermoplastic polymer molding by thermal nanoimprinting is large, it becomes difficult for the etching solution to enter between the concave and convex molding parts during etching, and it becomes difficult to exchange the etching solution before the reaction with the etching solution after the reaction. Etching may take time.
The pressing pressure is generally 10 to 1,000 bar (1 to 100 MPa), preferably 50 to 200 bar (5 to 20 MPa), and the pressing time is generally 0.1 to 10 minutes, preferably 15 to 120 seconds. By maintaining a reduced pressure between the mold and the substrate (a1) or the substrate (a2) during the pressing, the thermoplastic polymer can efficiently enter the fine irregularities of the mold.
Thereafter, the temperature of the substrate is lowered below the glass transition temperature of the thermoplastic polymer, and the mold is released from the substrate. After transferring the uneven pattern of the mold, the substrate (b) can be obtained by peeling the mold from the substrate to obtain a resin pattern.

<Manufacture of substrate (c)>
The method for producing the substrate (c) of the present invention includes a step of removing the remaining thermoplastic polymer film in the concave portion by dry etching in the substrate (b), a step of removing the metal thin film in the concave portion by wet etching, And a step of peeling the thermoplastic polymer in the convex portion, and forming a metal thin film pattern having a line width of 0.01 to 10 μm on the substrate (b).
In the production of the substrate (b), when the resin pattern is finally obtained by peeling the mold from the substrate, the thermoplastic polymer remains in the portion corresponding to the convex portion of the mold, that is, the portion corresponding to the concave portion of the resin pattern. It remains as a film. In that case, the remaining film is removed by etching with UV / ozone or oxygen reactive etching. The metal thin film portion is removed by etching the substrate on which the finely patterned thermoplastic polymer is formed. At this time, the thermoplastic polymer functions as an etching resist.

As an etching method, an etching solution used in a conventional subtractive method can be used. As the kind of etching liquid, it is used according to the kind of metal. When the metal is gold, there are aqua regia system and iodine system of mixed acid of concentrated nitric acid and concentrated hydrochloric acid, and iodine system is preferably used for fine processing. Specifically, a substrate having a gold thin film subjected to thermal nanoimprinting and dry etching is immersed in an iodine-based etching solution in which iodine is dissolved in an aqueous potassium iodide solution at room temperature, and the thermoplastic polymer on the substrate is immersed. Etch the gold in the recess. In that case, you may mix and use an organic solvent. When the metal is copper, an aqueous solution containing ferric chloride (FeCl ₃ ), cupric chloride (CuCl ₂ ), and Cu (NH ₃ ) ₄ Cl ₂ is preferably used as the etching solution.
Finally, the substrate (c) on which the metal thin film pattern is formed can be obtained by washing and removing the thermoplastic polymer formed on the metal thin film pattern with a solvent.
In that case, it is preferable to use the solvent used when dissolving said thermoplastic polymer as a solvent which can be used. Moreover, in order to make it peel efficiently, it can implement in an ultrasonic cleaner. In addition to peeling with a solvent, the portion can be removed by etching with UV / ozone or oxygen reactive etching.
The line width of the metal thin film pattern in the substrate (c) of the present invention is 0.01 to 10 μm or less. Further, the cross-sectional shape of the metal thin film pattern can be patterned not only in a rectangular shape but also in a semicircle according to the pattern shape of the mold.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these examples.
Example 1-1
Synthesis of 3- (8-mercaptooctyloxy) benzophenone
(Etherification reaction)
To a eggplant-shaped flask equipped with a condenser, 5.9 g of 3-hydroxybenzophenone, 1.68 g of potassium hydroxide, 150 mL of tetrahydrofuran and 20 mL of water were added, and magnetically stirred for 1 hour in an argon atmosphere. After 1 hour, 24.4 g of 1,8-dibromooctane was added and refluxed for 24 hours. After 24 hours, the reaction mixture was cooled to room temperature and tetrahydrofuran was removed by concentration under reduced pressure. Chloroform was added to the residue for extraction and washing. Magnesium sulfate was added to the organic layer, dried and filtered. The filtrate was concentrated under reduced pressure and purified by silica gel chromatography to obtain 3- (8-bromooctyloxy) benzophenone in a yield of 6.1 g and a yield of 52%.
(Thiolation reaction)
To an eggplant-shaped flask equipped with a condenser, 0.18 g of thiourea and 20 mL of ethanol were added to 1.0 g of 3- (8-bromooctyloxy) benzophenone, and the mixture was heated to reflux for 3 hours. After 3 hours, the disappearance of the raw materials was confirmed, an aqueous sodium hydroxide solution in which 0.14 g of sodium hydroxide was dissolved in 20 mL of water was added, and the mixture was heated to reflux for 3 hours. After 3 hours, the reaction mixture was acidified with dilute sulfuric acid. Chloroform was added to the reaction mixture and extracted. The extracted organic layer was washed with water, and after washing, magnesium sulfate was added to the organic layer, dried and filtered, and the filtrate was concentrated under reduced pressure to give 0.70 g and 80% yield of 3- (8-mercaptooctyl). Oxy) benzophenone was obtained. The two-stage yield was 42%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (12H) 2.5 ppm, m, C H ₂ —SH (2H) 4.0 ppm, t, O—C H ₂ ( 2H) 7.0 ppm, d, Ar (1H) 7.2-7.7 ppm, m, Ar (8H)

Example 1-2
Synthesis of 3- (10-mercaptodecyloxy) benzophenone The same procedure as in Example 1-1 was performed except that 1,10-dibromodecane was used instead of 1,8-dibromooctane, and 3- (10-mercapto Decyloxy) benzophenone was obtained. The yield for the two stages was 40%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (16H) 2.5 ppm, m, C H ₂ —SH (2H) 4.0 ppm, t, O—C H ₂ ( 2H) 7.0 ppm, d, Ar (1H) 7.3-7.7 ppm, m, Ar (8H)

Example 1-3
Synthesis of 4- (8-mercaptooctyloxy) benzophenone The same operation as in Example 1-1 was performed except that 4-hydroxybenzophenone was used instead of 3-hydroxybenzophenone, and 4- (8-mercaptooctyloxy) benzophenone was used. Got. The yield for the two stages was 44%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (12H) 2.5 ppm, m, C H ₂ —SH (2H) 4.0 ppm, t, O—C H ₂ ( 2H) 6.9 ppm, d, Ar (2H) 7.3-7.7 ppm, m, Ar (7H)

Example 1-4
Synthesis of 4- (10-mercaptodecyloxy) benzophenone Example 1 except that 1,10-dibromodecane was used instead of 1,8-dibromooctane and 4-hydroxybenzophenone was used instead of 3-hydroxybenzophenone The same operation as 1 was performed to obtain 4- (10-mercaptodecyloxy) benzophenone. The yield for the two stages was 38%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (16H) 2.5 ppm, m, C H ₂ —SH (2H) 4.0 ppm, t, O—C H ₂ ( 2H) 6.9 ppm, d, Ar (2H) 7.3-7.7 ppm, m, Ar (7H)

Example 1-5
Synthesis of 4- (6-mercaptopentylcarbonyloxy) benzophenone
(Esterification reaction)
To a two-necked eggplant-shaped flask equipped with a calcium chloride tube and a dropping funnel, 2.1 g of 6-bromohexanoyl chloride, 1.2 g of triethylamine and 50 mL of dichloromethane were added and cooled to 0 ° C. 4-hydroxybenzophenone 1.9g was melt | dissolved in 20 mL of dichloromethane, and it was dripped over 15 minutes with the dropping funnel. After completion of dropping, the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the organic layer was extracted and washed with a saturated aqueous sodium bicarbonate solution and water. Magnesium sulfate was added to the organic layer, dried and filtered. The filtrate was concentrated under reduced pressure and purified by silica gel chromatography to obtain 4- (6-bromopentylcarbonyloxy) benzophenone in a yield of 3.2 g and a yield of 89%.
(Thiolation reaction)
The same procedure as in Example 1-1 (thiolation reaction) was carried out except that 4- (6-bromopentylcarbonyloxy) benzophenone was used instead of 3-hydroxybenzophenone, and 4- (6-mercaptopentylcarbonyl) was obtained. Oxy) benzophenone was obtained. The two-stage yield was 71%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.6 ppm, m, C H ₂ (6H) 2.2 ppm, t, CO—C H ₂ (2H) 2.5 ppm, m, C H ₂ —SH ( 2H) 7.2-7.7 ppm, m, Ar (9H)

Example 1-6
Synthesis of 4- (8-mercaptooctyloxycarbonyl) benzophenone
(Acid chloride reaction)
To a eggplant-shaped flask equipped with a calcium chloride tube, 2.3 g of 4-benzoylbenzoic acid, 1.5 g of oxalyl chloride, 50 mL of chloroform, and a very small amount of N, N-dimethylformamide were added and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure to obtain 4-benzoylbenzoic acid chloride in a yield of 2.4 g and a yield of 98%.
(Esterification reaction)
To a eggplant-shaped flask equipped with a calcium chloride tube and a dropping funnel were added 1.2 g of 4-benzoylbenzoic acid chloride, 0.76 g of triethylamine and 50 mL of dichloromethane, and the mixture was cooled to 0 ° C. 1.1 g of 8-bromo-1-octanol was dissolved in 10 mL of dichloromethane and added dropwise using a dropping funnel over 15 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the organic layer was extracted and washed with an aqueous sodium bicarbonate solution and water. Magnesium sulfate was added to the organic layer, dried and filtered. The filtrate was concentrated under reduced pressure and purified by silica gel chromatography to obtain 4- (8-bromooctyloxycarbonyl) benzophenone in a yield of 1.8 g and a yield of 90%.
(Thiolation reaction)
4- (8-Mercaptooctyloxycarbonyl) was treated in the same manner as in (Thiolation reaction) of Example 1-1 except that 4- (8-bromooctyloxycarbonyl) benzophenone was used instead of 3-hydroxybenzophenone. ) Benzophenone was obtained. The three-stage yield was 71%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.8 ppm, m, C H ₂ (12H) 2.5 ppm, m, C H ₂ —SH (2H) 4.3 ppm, t, O—C H ₂ ( 2H) 7.3-7.5 ppm, m, Ar (3H) 7.7 ppm, d, Ar (2H) 7.8 ppm, d, Ar (2H) 8.1 ppm, d, Ar (2H)

Example 1-7
Synthesis of 4- (10-mercaptodecyloxycarbonyl) benzophenone The same procedure as in Example 1-6 was performed, except that 10-bromo-1-decanol was used instead of 8-bromo-1-octanol. 10-mercaptodecyloxycarbonyl) benzophenone was obtained. The yield for the three stages was 68%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.8 ppm, m, C H ₂ (16H) 2.5 ppm, m, C H ₂ —SH (2H) 4.3 ppm, t, O—C H ₂ ( 2H) 7.3-7.5 ppm, m, Ar (3H) 7.7 ppm, d, Ar (2H) 7.8 ppm, d, Ar (2H) 8.1 ppm, d, Ar (2H)

Example 1-8
Synthesis of 4- (8-mercaptooctylamino) benzophenone
(Amination reaction)
To an eggplant-shaped flask equipped with a condenser, 2.0 g of 4-aminobenzophenone and 0.84 g of sodium hydrogen carbonate dissolved in 1 mL of water were added, and the mixture was heated and stirred at 80 ° C. To the reaction mixture, 8.1 g of 1,8-dibromooctane was gradually added over 30 minutes and stirred for 4 hours. The reaction mixture was cooled to room temperature, washed with chloroform and water. Magnesium sulfate was added to the organic layer, dried and filtered. The filtrate was concentrated under reduced pressure and purified by silica gel chromatography to give 4- (8-bromooctylamino) benzophenone in a yield of 1.3 g and a yield of 34%.
(Thiolation reaction)
4- (8-mercaptooctylamino) benzophenone was prepared in the same manner as in (Thiolation reaction) of Example 1-1 except that 4- (8-bromooctylamino) benzophenone was used instead of 3-hydroxybenzophenone. Got. The yield for the two stages was 28%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (12H) 2.5 ppm, m, C H ₂ —SH (2H) 3.0 ppm, t, NH—C H ₂ ( 2H) 6.5 ppm, d, Ar (2H) 7.3-7.7 ppm, m, Ar (7H)

Example 1-9
Synthesis of 4- (10-mercaptodecylamino) benzophenone The same operation as in Example 1-8 was carried out except that 10-bromo-1-decanol was used instead of 8-bromo-1-octanol, and 4- (10 -Mercaptodecylamino) benzophenone was obtained. The two-stage yield was 29%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (16H) 2.5 ppm, m, C H ₂ —SH (2H) 3.0 ppm, t, NH—C H ₂ ( 2H) 6.5 ppm, d, Ar (2H) 7.3-7.7 ppm, m, Ar (7H)

Example 1-10
Synthesis of 4- (6-mercaptohexanoylamino) benzophenone The same procedure as in Example 1-5 was carried out except that 4-aminobenzophenone was used instead of 4-hydroxybenzophenone. ) Benzophenone was obtained. The two stage yield was 75%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (6H) 2.2 ppm, t, CO—C H ₂ (2H) 2.5 ppm, m, C H ₂ —SH ( 2H) 7.3-7.8 ppm, m, Ar (9H)

Example 1-11
Synthesis of 4,4'-bis (8-mercaptooctyloxycarbonyl) benzophenone Benzophenone-4,4'-dicarboxylic acid is used instead of 4-benzoylbenzoic acid, and oxalyl chloride, 8-bromo-1-octanol, triethylamine The same operation as in Example 1-6 was carried out except that a double amount of thiourea and aqueous sodium hydroxide solution was used to obtain 4,4′-bis (8-mercaptooctyloxycarbonyl) benzophenone. The three-stage yield was 70%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.8 ppm, m, C H ₂ (24H) 2.5 ppm, m, C H ₂ —SH (4H) 4.3 ppm, t, O—C H ₂ ( 4H) 7.8 ppm, d, Ar (4H) 8.1 ppm, d, Ar (4H)

Example 1-12
Synthesis of 4,4′-bis (10-mercaptodecyloxycarbonyl) benzophenone The same procedure as in Example 1-11 was performed, except that 10-bromo-1-decanol was used instead of 8-bromo-1-octanol. 4,4′-bis (10-mercaptodecyloxycarbonyl) benzophenone was obtained. The three-stage yield was 69%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.8 ppm, m, C H ₂ (32H) 2.5 ppm, m, C H ₂ —SH (4H) 4.3 ppm, t, O—C H ₂ ( 4H) 7.8 ppm, d, Ar (4H) 8.1 ppm, d, Ar (4H)

Example 1-13
Synthesis of 3-methyl-4- (10-mercaptodecyloxy) benzophenone Using 3-methyl-4-hydroxybenzophenone instead of 3-hydroxybenzophenone and 1,10-dibromodecane instead of 1,8-dibromooctane The same operation as in Example 1-1 was performed, except that it was used, to obtain 3-methyl-4- (10-mercaptodecyloxy) benzophenone. The two-stage yield was 35%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (16H) 2.4 ppm, s, C H ₃ (3H) 2.5 ppm, m, C H ₂ —SH (2H) 4.0 ppm, t, O—C H ₂ (2H) 6.8 ppm, d, Ar (1H) 7.4-7.7 ppm, m, Ar (7H)

Example 1-14
Synthesis of 4- (8-mercaptooctyloxy) -4′-methoxybenzophenone The same operation as in Example 1-1 was performed except that 4-hydroxy-4′-methoxybenzophenone was used instead of 3-hydroxybenzophenone. 4- (8-Mercaptooctyloxy) -4'-methoxybenzophenone was obtained. The yield for the two stages was 40%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (12H) 2.5 ppm, m, C H ₂ —SH (2H) 3.7 ppm, s, OC H ₃ (3H) 4.0 ppm, t, O—C H ₂ (2H) 6.9 ppm, m, Ar (4H) 7.7 ppm, m, Ar (4H)

Example 1-15
Synthesis of 4- (10-mercaptodecyloxy) -3 ′, 4 ′, 5′-trimethoxybenzophenone
(Etherification reaction)
2.8 g of phenol, 1.68 g of potassium hydroxide, 80 mL of tetrahydrofuran, and 10 mL of water were added to an eggplant-shaped flask equipped with a condenser, and magnetically stirred for 1 hour in an argon atmosphere. After 1 hour, 24.4 g of 1,10-dibromodecane was added and refluxed for 24 hours. After 24 hours, the reaction mixture was cooled to room temperature and tetrahydrofuran was removed by concentration under reduced pressure. Chloroform was added to the residue for extraction and washing. Magnesium sulfate was added to the organic layer, dried and filtered. The filtrate was concentrated under reduced pressure and purified by silica gel chromatography to obtain 10-bromodecane phenyl ether in a yield of 4.6 g and a yield of 49%.
(Friedel-Crafts reaction)
An anhydrous aluminum chloride powder was suspended in carbon tetrachloride in an eggplant-shaped flask equipped with a calcium chloride tube, and cooled to 0 ° C. To this, 3,4,5-trimethoxybenzoyl chloride was added little by little with stirring. 10-Bromodecane phenyl ether was added dropwise to the reaction mixture over 1 hour, and the mixture was stirred for 1 hour after completion of the addition. Ice was added to the reaction mixture to terminate the reaction, petroleum ether was added, and the organic layer was extracted and washed with dilute hydrochloric acid, aqueous sodium carbonate, and water. Magnesium sulfate was added to the organic layer, dried and filtered. The filtrate was concentrated under reduced pressure and purified by silica gel chromatography to give 4- (bromodecyloxy) -3 ′, 4 ′, 5′-trimethoxybenzophenone.
(Thiolation)
Except that 4- (bromodecyloxy) -3 ′, 4 ′, 5′-trimethoxybenzophenone was used instead of 3-hydroxybenzophenone, the same operation as in (Thiolation reaction) of Example 1-1 was performed, 4- (10-mercaptodecyloxy) -3 ', 4', 5'-trimethoxybenzophenone was obtained. The yield for the three stages was 15%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (16H) 2.5 ppm, m, C H ₂ —SH (2H) 3.7 ppm, s × 3, OC H ₃ ( 9H) 4.0 ppm, t, O—C H ₂ (2H) 6.7 ppm, s × 2, Ar (2H) 6.9 ppm, d, Ar (2H) 7.5 ppm, d, Ar (2H)

Example 1-16
Synthesis of 4- (10-mercaptodecyloxy) -4'-phenylbenzophenone And 3-methyl-4- (10-mercaptodecyloxy) benzophenone was obtained. The yield of the three stages was 18%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (16H) 2.5 ppm, m, C H ₂ —SH (2H) 4.0 ppm, t, O—C H ₂ ( 2H) 6.9 ppm, d, Ar (2H) 7.2-7.8 ppm, m, Ar (11H)

Example 1-17
Synthesis of 4,4'-bis (8-mercaptooctyloxy) benzophenone 4,4'-dihydroxybenzophenone is used instead of 3-hydroxybenzophenone, and 1,8-dibromooctane, potassium hydroxide, thiourea, hydroxylated The same operation as in Example 1-1 was performed except that sodium was used in an amount twice as much to obtain 4,4′-bis (8-mercaptooctyloxy) benzophenone. The yield for the two stages was 39%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (24H) 2.5 ppm, m, C H ₂ —SH (4H) 4.0 ppm, t, O—C H ₂ ( 4H) 6.9 ppm, d, Ar (4H) 7.7 ppm, d, Ar (4H)

Example 1-18
Synthesis of 4,4′-bis (10-mercaptodecyloxy) benzophenone The same operation as in Example 1-17 was carried out except that 1,10-dibromodecane was used instead of 1,8-dibromooctane. 4′-bis (10-mercaptodecyloxy) benzophenone was obtained. The two-stage yield was 35%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (32H) 2.5 ppm, m, C H ₂ —SH (4H) 4.0 ppm, t, O—C H ₂ ( 4H) 6.9 ppm, d, Ar (4H) 7.7 ppm, d, Ar (4H)

Example 1-19
Synthesis of 4- (6-mercaptopentylcarbonyloxy) -4′-methoxybenzophenone The same operation as in Example 1-5 was performed except that 4-hydroxy-4′-methoxybenzophenone was used instead of 4-hydroxybenzophenone. 4- (6-mercaptopentylcarbonyloxy) -4'-methoxybenzophenone was obtained. The two stage yield was 75%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (6H) 2.2 ppm, t, CO—C H ₂ (2H) 2.5 ppm, m, C H ₂ —SH ( 2H) 3.7 ppm, s, OC H ₃ (3H) 6.9 ppm, d, Ar (2H) 7.2 ppm, d, Ar (2H) 7.5-7.7 ppm, m, Ar (4H)

Example 1-20
Synthesis of 4,4'-bis (6-mercaptopentylcarbonyloxy) benzophenone 4,4'-dihydroxybenzophenone is used instead of 4-hydroxybenzophenone, and 6-bromohexanoyl chloride, triethylamine, thiourea, sodium hydroxide The same operation as in Example 1-5 was carried out except that the aqueous solution was used in an amount twice as much to obtain 4,4′-bis (6-mercaptopentylcarbonyloxy) benzophenone. The two-stage yield was 71%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (12H) 2.2 ppm, t, CO—C H ₂ (4H) 2.5 ppm, m, C H ₂ —SH ( 4H) 7.2 ppm, d, Ar (4H) 7.7 ppm, d, Ar (4H)

Example 1-21
Synthesis of 4- (10-mercaptodecylamino) -4'-methoxybenzophenone 4-amino-4'-methoxybenzophenone instead of 4-aminobenzophenone and 10-bromo-1 instead of 8-bromo-1-octanol The same operation as in Example 1-8 was carried out except that -decanol was used to obtain 4- (10-mercaptodecylamino) -4′-methoxybenzophenone. The two-stage yield was 26%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (16H) 2.5 ppm, m, C H ₂ —SH (2H) 3.0 ppm, t, NH—C H ₂ ( 2H) 3.7 ppm, s, OC H ₃ (3H) 6.5 ppm, d, Ar (2H) 6.9 ppm, d, Ar (2H) 7.5-7.6 ppm, m, Ar (4H)

Example 1-22
Synthesis of 4,4′-bis (8-mercaptooctylamino) benzophenone 4,4′-diaminobenzophenone was used instead of 4-aminobenzophenone, and 1,8-dibromooctane, sodium bicarbonate, thiourea, water The same operation as in Example 1-8 was carried out except that 2 times amount of sodium oxide was used, and 4,4′-bis (8-mercaptooctylamino) benzophenone was obtained. The yield for the two stages was 24%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (24H) 2.6 ppm, t, C H ₂ —SH (4H) 3.0 ppm, t, NH—C H ₂ ( 4H) 6.5 ppm, d, Ar (4H) 7.5 ppm, d, Ar (4H)

Example 1-23
Synthesis of 4,4′-bis (10-mercaptodecylamino) benzophenone 4′-bis (10-mercaptodecylamino) benzophenone was obtained. The two-stage yield was 25%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (32H) 2.5 ppm, m, C H ₂ —SH (4H) 3.0 ppm, t, NH—C H ₂ ( 4H) 6.5 ppm, d, Ar (4H) 7.5 ppm, d, Ar (4H)

Example 1-24
Synthesis of 4- (6-mercaptohexanoylamino) -4′-methoxybenzophenone The same procedure as in Example 5 was performed except that 4-amino-4′-methoxybenzophenone was used instead of 4-hydroxybenzophenone. -(6-Mercaptohexanoylamino) -4'-methoxybenzophenone was obtained. The two-stage yield was 70%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (6H) 2.2 ppm, t, CO—C H ₂ (2H) 2.5 ppm, m, C H ₂ —SH ( 2H) 3.7 ppm, s, OC H ₃ (3H) 6.9 ppm, d, Ar (2H) 7.4-7.8 ppm, m, Ar (6H)

Example 1-25
Synthesis of 4,4′-bis (6-mercaptohexanoylamino) benzophenone 4,4′-bis (6-mercaptohexanoylamino) benzophenone was obtained. The two-stage yield was 69%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (12H) 2.2 ppm, t, CO—C H ₂ (4H) 2.5 ppm, m, C H ₂ —SH ( 4H) 7.7 ppm, d, Ar (4H) 7.4 ppm, d, Ar (4H)

The compounds prepared in Examples 1-1 to 1-25 are shown in Table 1. Table R ¹ to R ⁶ in 1 indicates the R ¹ to R ⁶ in the in the formula (I), X and m are in the formula (I) -X- a (CH ₂₎ m-SH X and m Show.

Synthesis example 1
Synthesis of 2- (10-mercaptodecyloxy) benzophenone Example 1 except that 2-hydroxybenzophenone was used instead of 3-hydroxybenzophenone and 1,10-dibromodecane was used instead of 1,8-dibromooctane The same operation as 1 was performed to obtain 2- (10-mercaptodecyloxy) benzophenone. The yield for the two stages was 39%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (16H) 2.5 ppm, m, C H ₂ —SH (2H) 4.0 ppm, t, O—C H ₂ ( 2H) 6.9 ppm, m, Ar (2H) 7.3-7.7 ppm, m, Ar (7H)

Synthesis example 2
Synthesis of 4- (10-mercaptodecyloxy) -2′-methylbenzophenone Then, 4- (10-mercaptodecyloxy) -2′-methylbenzophenone was obtained. The yield for the three stages was 14%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (16H) 2.4 ppm, s, C H ₃ (3H) 2.5 ppm, m, C H ₂ —SH (2H) 4.0 ppm, t, O—C H ₂ (2H) 6.9 ppm, d, Ar (2H) 7.1-7.6 ppm, m, Ar (6H)

Synthesis example 3
Synthesis of 4- (10-mercaptodecyloxy) -2′-methoxybenzophenone The same procedure as in Example 1-15 was performed except that 2-methoxybenzoyl chloride was used instead of 3,4,5-trimethoxybenzoyl chloride. This gave 4- (10-mercaptodecyloxy) -2′-methoxybenzophenone. The yield for the three stages was 16%. The measurement result of ¹ H NMR is shown below.
¹ H NMR (CDCl ₃ ): 1.2-1.7 ppm, m, C H ₂ (16H) 2.5 ppm, m, C H ₂ —SH (2H) 3.7 ppm, s, O C H ₃ (3H ) 4.0 ppm, t, O—C H ₂ (2H) 6.8-7.0 ppm, m, Ar (4H) 7.3-7.6 ppm, m, Ar (4H)

<Example of etching resist pattern formation>
Example 2-1
Pattern formation of PSt etching resist 3.7 mg of the compound of Example 1-4 was dissolved in 100 mL of ethanol to prepare an adhesive for nanoimprinting. DC (direct current) sputter deposition was performed on a 1 mm thick fused silica substrate in the order of 0.5 nm thick chromium and 100 nm thick gold. Thereafter, dicing was performed to obtain six gold substrates having a length of 15 mm, a width of 15 mm, and a thickness of 1 mm. Six gold substrates (contact angle with water <5 °) washed by UV / ozone treatment were immersed in the nanoimprint adhesive for 24 hours. Subsequently, it was washed with clean ethanol to form an adsorption film made of the compound of Example 1-4 on a gold substrate. Toluene solution containing 2% by mass of PSt (manufactured by Aldrich, Mw = 45000, Tg = 93 ° C.) on a gold substrate having an adsorption film of the compound of Example 1-4 showing a contact angle with water of 75 ± 2 ° Was spin-coated under the conditions of 500 rpm, 3 seconds, 2000 rpm, and 30 seconds to form a PSt film having a thickness of about 60 nm. Next, using a 200W of Hg-Xe lamp (Sun-ei, Supercure 202S) , each exposure amount of the ultraviolet at ^{365nm 30J / cm 2, 60J /} cm 2, 120J / cm 2, 180J / cm 2, 240 J / cm ^2, was irradiated to each gold substrate such that 300 J / cm ^2. An ultraviolet-irradiated PSt layer / adsorbed film of the compound of Example 1-4 / gold substrate was placed on the stage of a thermal nanoimprint apparatus (NM-0400, manufactured by Myeongchang Kiko), and a 100 nm line and space (hereinafter abbreviated as L & S). ), Thermal nanoimprinting was performed under the conditions consisting of the five stages shown in Table 2 using a mold made of surface-oxidized silicon having a height difference of 200 nm of convex and concave portions having L & S of 200 nm, L & S of 500 nm, and L & S of 1000 nm.

Six PSt moldings obtained by thermal nanoimprinting and the mold after use were observed with an optical microscope (OM) and a scanning electron microscope (SEM) to evaluate the shape. Table 3 shows the irradiation energy required for molding a PSt pattern in which no collapse or structural defect was observed. FIG. 1 shows a copy of an SEM photographic image of a PSt molded body having an L & S of 100 nm on a gold substrate irradiated with ultraviolet rays having an irradiation energy of 240 J / cm ² . It can be seen that the PSt thin film is formed into irregularities with 100 nm L & S. Further, from the OM image, it was confirmed that PSt did not adhere to the mold.

Example 2-2
Pattern formation of PSt etching resist The same process as in Example 2-1 was performed except that the compound of Example 1-5 was used, and the shape was evaluated. The results are shown in Table 3. From the SEM photographic image, it was found that the PSt thin film was formed into irregularities by L & S of 100 nm. Further, from the OM image, it was confirmed that PSt did not adhere to the mold.

Examples 2-3 to 2-14
Pattern formation of PSt etching resist Examples 1-6, 1-9, 1-12, 1-13, 1-15, 1-18, 1-19, 1-20, 1-21, 1-23, 1 The shape was evaluated by the same treatment as in Example 2-1, except that the compound of -24 or 1-25 was used. The results are shown in Table 3. From the SEM photographic image, it was found that the PSt thin film was formed into irregularities by L & S of 100 nm. Further, from the OM image, it was confirmed that PSt did not adhere to the mold.

Comparative Example 1
PSt etching resist pattern formation (no compound adsorption film of Example 1-4)
Except not using the adhesive for nanoimprint containing the compound of Example 1-4, it processed similarly to Example 2-1 and evaluated the shape. The results are shown in Table 4. Although 300 J / cm ² of ultraviolet rays were irradiated, it was found from the copy of the SEM photograph of the 100 nm L & S PSt molding shown in FIG. 2 that a part of the PSt molding was collapsed. Further, from the OM image, it was confirmed that PSt was adhered to the mold.

Comparative Example 2
PSt etching resist pattern formation (no UV irradiation)
PSt spin coating and thermal nanoimprinting were applied to the gold substrate on which the compound adsorption film of Example 1-4 was formed in the same manner as in Example 2-1, except that 240 J / cm ² ultraviolet irradiation at 365 nm was not performed. And evaluated. The results are shown in Table 4. From the SEM image, it was found that there was a structural defect in a part of the 100 nm L & S molded product of PSt. Further, it was confirmed from the OM image that PSt adhered to the mold.

Comparative Example 3
PSt etching resist pattern formation (with compound adsorption film of Synthesis Example 1)
The treatment was performed in the same manner as in Example 2-1, except that the compound of Synthesis example 1 was used instead of the compound of Example 1-4. The results are shown in Table 4. From the SEM image, it was found that there was a structural defect in a part of the 100 nm L & S molded product of PSt. Further, it was confirmed from the OM image that PSt adhered to the mold.

Comparative Example 4
PSt etching resist pattern formation (with compound adsorption film of Synthesis Example 2)
The treatment was performed in the same manner as in Example 2-1, except that the compound of Synthesis Example 2 was used instead of the compound of Example 1-4. The results are shown in Table 4. From the SEM image, it was found that there was a structural defect in a part of the 100 nm L & S molded product of PSt. Further, it was confirmed from the OM image that PSt adhered to the mold.

Comparative Example 5
PSt etching resist pattern formation (with compound adsorption film of Synthesis Example 3)
The treatment was performed in the same manner as in Example 2-1, except that the compound of Synthesis example 3 was used instead of the compound of Example 1-4. The results are shown in Table 4. From the SEM image, it was found that there was a structural defect in a part of the 100 nm L & S molded product of PSt. Further, it was confirmed from the OM image that PSt adhered to the mold.

Comparative Example 6
PSt etching resist pattern formation (with 1-decanethiol adsorption film)
The treatment was performed in the same manner as in Example 2-1, except that 1-decanethiol (manufactured by Aldrich) was used instead of the compound of Example 1-4. The results are shown in Table 4. From the SEM image, it was found that there was a structural defect in a part of the 100 nm L & S molded product of PSt. Further, it was confirmed from the OM image that PSt adhered to the mold.

From the results in Table 3, it was found that a PSt pattern having no defects was obtained at an irradiation dose of 240 J / cm ² or less due to the effect of the adhesive containing the thiol group-containing UV-sensitive compound of the present invention. On the other hand, from the results shown in Table 4, only PSt patterns with collapse or structural defects were obtained even at an irradiation dose of 300 J / cm ² or more.

<Example of gold thin film pattern formation>
Example 3-1
Gold thin film pattern formation (with the compound adsorption film of Synthesis Example 4, with UV irradiation)
In a stainless steel chamber of a 172 nm excimer light irradiation device (USHIO Inc., P0032), the PSt molded body produced in Example 2-1 was irradiated with vacuum ultraviolet radiation at 172 nm for 60 seconds under a reduced pressure of 1000 Pa, and UV / ozone. The resin film which remained in the recessed part of the PSt molded object was removed by processing. After dissolving 1.33 g of potassium iodide in 500 mL of deionized water, 0.33 g of iodine was dissolved to prepare an iodine-based etching solution. The film was immersed in the etching solution at room temperature for 30 seconds, washed with deionized water, and further washed with acetone to remove PSt of the etching resist. Subsequently, it was put into a UV / ozone treatment apparatus (manufactured by Nippon Laser Electronics Co., Ltd., NL-UV42S), subjected to UV / ozone treatment for 3 minutes, and photocrosslinked PSt and the compound adsorption film of Example 1-4 were removed. The pattern of the gold thin film formed on the substrate was observed with an SEM to evaluate the pattern shape. FIG. 3 shows a copy of a 100 nm L & S SEM photographic image obtained after wet etching. It can be seen that the white portion of this copy is gold, and a pattern of a 100 nm L & S gold thin film is formed.

Comparative Example 7
Gold Thin Film Pattern Formation A gold thin film pattern was formed in the same manner as in Example 3-1, except that the PSt molded body produced in Comparative Example 1 was used. 5 shows a copy of a 100 nm L & S SEM photographic image obtained after the wet etching shown in FIG. From this copy, it can be seen that a gold thin film pattern different from the shape of the etching resist of PSt is formed.

Comparative Example 8
Gold Thin Film Pattern Formation A gold thin film pattern was formed in the same manner as in Example 3-1, except that the PSt molded body produced in Comparative Example 2 was used. FIG. 6 shows a copy of a 100 nm L & S SEM photographic image obtained after the wet etching shown in FIG. From this copy, it can be seen that a gold thin film pattern different from the shape of the etching resist of PSt is formed.

Example 4-1
(Formation of etching resist pattern: Mw = 4000, with ultraviolet irradiation, holding time 60 s)
With Mw = 4000 of PSt (Aldrich Co.) instead of PSt of Mw = 45000 in Example 2-1 of the formation of the etching resist pattern, except that the 240 J / cm ² exposure amount of ultraviolet rays in Example 2- The same operation as 1 was performed. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film of the recess of 100 nm L & S was 8 nm.

Example 4-2
(Formation of etching resist pattern: Mw = 4000, with UV irradiation, holding time 40 s)
The same operation was performed except that the thermal nanoimprint conditions in Example 4-1 were changed to the conditions shown in Table 5. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film of the recess of 100 nm L & S was 8 nm.

Example 4-3
(Formation of etching resist pattern: Mw = 4000, with UV irradiation, holding time 20 s)
The same operation was performed except that the thermal nanoimprint conditions in Example 4-1 were changed to the conditions shown in Table 6. The PSt molding obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM to evaluate the shape. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film in the recess of 100 nm L & S was 9 nm.

Example 4-4
(Formation of etching resist pattern: Mw = 35000, UV irradiation, holding time 60s)
The same operation was carried out except that PSt having Mw = 35000 (manufactured by Aldrich) was used instead of PSt having Mw = 4000 in Example 4-1. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film of the recess of 100 nm L & S was 8 nm.

Example 4-5
(Formation of etching resist pattern: Mw = 35000, with UV irradiation, holding time 40s)
The same operation was carried out except that PSt having Mw = 35000 (manufactured by Aldrich) was used instead of PSt having Mw = 4000 in Example 4-2. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement showed that the remaining film of the 100 nm L & S recess was 11 nm.

Example 4-6
(Formation of etching resist pattern: Mw = 35000, UV irradiation, holding time 20s)
The same operation was carried out except that PSt having Mw = 35000 (manufactured by Aldrich) was used instead of PSt having Mw = 4000 in Example 4-3. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film in the recess of 100 nm L & S was 23 nm.

Example 4-7
(Formation of etching resist pattern: Mw = 90000, UV irradiation, holding time 60 s)
The same operation was performed except that PSt with Mw = 90,000 (manufactured by Aldrich) was used instead of PSt with Mw = 4000 in Example 4-1. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film in the recess of 100 nm L & S was 10 nm.

Example 4-8
(Formation of etching resist pattern: Mw = 90000, UV irradiation, holding time 40s)
The same operation was carried out except that PSt with Mw = 90,000 (manufactured by Aldrich) was used instead of PSt with Mw = 4000 in Example 4-2. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film in the recess of 100 nm L & S was 20 nm.

Example 4-9
(Formation of etching resist pattern: Mw = 90,000, UV irradiation, holding time 20 s)
The same operation was performed except that PSt with Mw = 90,000 (manufactured by Aldrich) was used instead of PSt with Mw = 4000 in Example 4-3. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film of the 100 nm L & S recess was 42 nm.

Comparative Example 9-1
(Formation of etching resist pattern: Mw = 4000, no UV irradiation, holding time 60 s)
The same operation was performed except that ultraviolet irradiation was not performed in Example 4-1. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, disintegration and structural defects were observed as in the pattern shown in FIG.

Comparative Example 9-2
(Formation of etching resist pattern: Mw = 4000, no UV irradiation, holding time 40 s)
The same operation was performed except that ultraviolet irradiation was not performed in Example 4-2. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, disintegration and structural defects were observed as in the pattern shown in FIG.

Comparative Example 9-3
(Formation of etching resist pattern: Mw = 4000, no UV irradiation, holding time 20 s)
The same operation was performed except that ultraviolet irradiation was not performed in Example 4-3. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, disintegration and structural defects were observed as in the pattern shown in FIG.

Comparative Example 9-4
(Formation of etching resist pattern: Mw = 35000, no UV irradiation, holding time 60s)
The same operation was performed except that ultraviolet irradiation was not performed in Example 4-4. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film in the recess of 100 nm L & S was 9 nm.

Comparative Example 9-5
(Formation of etching resist pattern: Mw = 35000, no UV irradiation, holding time 40s)
The same operation was performed except that ultraviolet irradiation was not performed in Example 4-5. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film in the recess of 100 nm L & S was 10 nm.

Comparative Example 9-6
(Formation of etching resist pattern: Mw = 35000, no UV irradiation, holding time 20 s)
The same operation was performed except that ultraviolet irradiation was not performed in Example 4-6. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film in the recess of 100 nm L & S was 22 nm.

Comparative Example 9-7
(Formation of etching resist pattern: Mw = 90000, no UV irradiation, holding time 60s)
The same operation was performed except that the ultraviolet irradiation in Example 4-7 was not performed. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film in the recess of 100 nm L & S was 10 nm.

Comparative Example 9-8
(Formation of etching resist pattern: Mw = 90000, no UV irradiation, holding time 40s)
The same operation was performed except that ultraviolet irradiation was not performed in Example 4-8. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film in the recess of 100 nm L & S was 22 nm.

Comparative Example 9-9
(Formation of etching resist pattern: Mw = 90000, no UV irradiation, holding time 20 s)
The same operation was performed except that ultraviolet irradiation was not performed in Example 4-9. The PSt molded body obtained by thermal nanoimprinting and the mold after use were observed by OM and SEM, and the shape was evaluated. As a result, like the pattern shown in FIG. 1, no collapse or structural defect was observed. AFM measurement revealed that the remaining film in the recess of 100 nm L & S was 40 nm.

Example 5-1
(Gold thin film pattern formation: Mw = 4000, with UV irradiation, holding time 60 s)
The same operation was performed except that the PSt molded body produced in Example 4-1 was used instead of the PSt molded body produced in Example 2-1 in Example 3-1 of gold thin film pattern formation. Gold thin film pattern formation was performed. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, a 100 nm L & S gold thin film pattern was formed in the same manner as the gold thin film pattern shown in FIG.

Example 5-2
(Gold thin film pattern formation: Mw = 4000, with UV irradiation, holding time 40 s)
The same operation was performed except that the PSt molded body produced in Example 4-2 was used instead of the PSt molded body produced in Example 2-1 in Example 3-1 of pattern formation of the gold thin film. A thin film pattern was formed. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, a 100 nm L & S gold thin film pattern was formed in the same manner as the gold thin film pattern shown in FIG.

Example 5-3
(Gold thin film pattern formation: Mw = 4000, with UV irradiation, holding time 20 s)
The same operation was performed except that the PSt molded body produced in Example 4-3 was used instead of the PSt molded body produced in Example 2-1 in Example 3-1 of gold thin film pattern formation. A thin film pattern was formed. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, a 100 nm L & S gold thin film pattern was formed in the same manner as the gold thin film pattern shown in FIG.

Example 5-4
(Pattern formation of gold thin film: Mw = 35000, with UV irradiation, holding time 60s)
The same operation was performed except that the PSt molded body produced in Example 4-4 was used instead of the PSt molded body produced in Example 2-1 in Example 3-1 of pattern formation of the gold thin film. A thin film pattern was formed. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, a 100 nm L & S gold thin film pattern was formed in the same manner as the gold thin film pattern shown in FIG.

Example 5-5
(Pattern formation of gold thin film: Mw = 35000, with UV irradiation, holding time 40s)
The same operation was performed except that the PSt molded body produced in Example 4-5 was used instead of the PSt molded body produced in Example 2-1 in Example 3-1 of pattern formation of the gold thin film. A thin film pattern was formed. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, a 100 nm L & S gold thin film pattern was formed in the same manner as the gold thin film pattern shown in FIG.

Example 5-6
(Gold thin film pattern formation: Mw = 90,000, UV irradiation, holding time 60 s)
The same operation was performed except that the PSt molded body produced in Example 4-7 was used in place of the PSt molded body produced in Example 2-1 in Example 3-1 of gold thin film pattern formation. A thin film pattern was formed. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, a 100 nm L & S gold thin film pattern was formed in the same manner as the gold thin film pattern shown in FIG.

Comparative Example 10-1
(Gold thin film pattern formation: Mw = 4000, no UV irradiation, holding time 60 s)
The same operation was performed except that the PSt molded body produced in Comparative Example 9-1 was used in place of the PSt molded body produced in Example 2-1 in Example 3-1 of gold thin film pattern formation. A thin film pattern was formed. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, similarly to the gold thin film pattern shown in FIG. 5, a gold thin film pattern different from the shape of the PSt etching resist was formed.

Comparative Example 10-2
(Gold thin film pattern formation: Mw = 4000, no UV irradiation, holding time 40 s)
The same operation was performed except that the PSt molded body produced in Comparative Example 9-2 was used instead of the PSt molded body produced in Example 2-1 in Example 3-1 of gold thin film pattern formation. A thin film pattern was formed. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, similarly to the gold thin film pattern shown in FIG. 5, a gold thin film pattern different from the shape of the PSt etching resist was formed.

Comparative Example 10-3
(Gold thin film pattern formation: Mw = 4000, no UV irradiation, holding time 20 s)
The same operation was performed except that the PSt molded body produced in Comparative Example 9-3 was used instead of the PSt molded body produced in Example 2-1 in Example 3-1 of gold thin film pattern formation. A thin film pattern was formed. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, similarly to the gold thin film pattern shown in FIG. 5, a gold thin film pattern different from the shape of the PSt etching resist was formed.

Comparative Example 10-4
(Pattern formation of gold thin film: Mw = 35000, no UV irradiation, holding time 60 s)
The same operation was performed except that the PSt molded body produced in Comparative Example 9-4 was used instead of the PSt molded body produced in Example 2-1 in Example 3-1 of gold thin film pattern formation. A thin film pattern was formed. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, similarly to the gold thin film pattern shown in FIG. 5, a gold thin film pattern different from the shape of the PSt etching resist was formed.

Comparative Example 10-5
(Pattern formation of gold thin film: Mw = 35000, no UV irradiation, holding time 40s)
The same operation was carried out except that the PSt molded body produced in Comparative Example 9-5 was used in place of the PSt molded body produced in Example 2-1 in Example 3-1 of gold thin film pattern formation. A thin film pattern was formed. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, similarly to the gold thin film pattern shown in FIG. 5, a gold thin film pattern different from the shape of the PSt etching resist was formed.

Comparative Example 10-6
(Pattern formation of gold thin film: Mw = 35000, no UV irradiation, holding time 20 s)
In the same manner as in Example 3-1 for patterning a gold thin film, the PSt molded body produced in Comparative Example 9-6 was used in place of the PSt molded body produced in Example 2-1. The remaining film of the recess was removed. However, since the remaining film of the recess before the ultraviolet irradiation was thick, it could not be removed in 60 seconds. Vacuum ultraviolet irradiation was performed until the remaining film disappeared, followed by etching and UV / ozone treatment to form a gold thin film pattern. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, similarly to the gold thin film pattern shown in FIG. 5, a gold thin film pattern different from the shape of the PSt etching resist was formed.

Comparative Example 10-7
(Pattern formation of gold thin film: Mw = 90000, no UV irradiation, holding time 60 s)
The same operation was performed except that the PSt molded body produced in Comparative Example 9-7 was used in place of the PSt molded body produced in Example 2-1 in Example 3-1 of gold thin film pattern formation. A thin film pattern was formed. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, similarly to the gold thin film pattern shown in FIG. 5, a gold thin film pattern different from the shape of the PSt etching resist was formed.

Comparative Example 10-8
(Pattern formation of gold thin film: Mw = 90000, no UV irradiation, holding time 40 s)
In the same manner as in Example 3-1 for forming a gold thin film, the PSt molded body produced in Comparative Example 9-8 was used instead of the PSt molded body produced in Example 2-1. The remaining film of the recess was removed. However, since the remaining film of the recess before the ultraviolet irradiation was thick, it could not be removed in 60 seconds. Vacuum ultraviolet irradiation was performed until the remaining film disappeared, followed by etching and UV / ozone treatment to form a gold thin film pattern. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, similarly to the gold thin film pattern shown in FIG. 5, a gold thin film pattern different from the shape of the PSt etching resist was formed.

Comparative Example 10-9
(Gold thin film pattern formation: Mw = 90,000, no UV irradiation, holding time 20 s)
In the same manner as in Example 3-1 for patterning a gold thin film, the PSt molded body produced in Comparative Example 9-9 was used in place of the PSt molded body produced in Example 2-1, and the PSt molded body was similarly subjected to vacuum ultraviolet irradiation. The remaining film of the recess was removed. However, since the remaining film of the recess before the ultraviolet irradiation was thick, it could not be removed in 60 seconds. Vacuum ultraviolet irradiation was performed until the remaining film disappeared, followed by etching and UV / ozone treatment to form a gold thin film pattern. The pattern of the 100 nm L & S gold thin film formed on the substrate was observed by SEM to evaluate the pattern shape. As a result, similarly to the gold thin film pattern shown in FIG. 5, a gold thin film pattern different from the shape of the PSt etching resist was formed.

It is a copy of the SEM photograph image of a PSt molded object with L & S of 100 nm on the gold substrate which irradiated the ultraviolet-ray of the irradiation energy of 240 J / cm < ² > in Example 2-1. 4 is a copy of an SEM photographic image of a PSt molded body having an L & S of 100 nm on a gold substrate irradiated with ultraviolet rays having an irradiation energy of 300 J / cm ² in Comparative Example 1. It is a copy of a 100 nm L & S SEM photograph image obtained after wet etching in Example 3-1. 10 is a copy of a 100 nm L & S SEM photographic image obtained after wet etching in Comparative Example 7. 10 is a copy of a 100 nm L & S SEM photographic image obtained after wet etching in Comparative Example 8.

Claims (13)

An ultraviolet-sensitive compound represented by the formula (I).
(Wherein two groups with one group one group selected from R ¹ to R ³ is, or is selected from R ¹ to R ³ one group and which are selected from R ⁴ to R ⁶ _{-X- (CH 2) m-SH} ( wherein, X is indicated O, OCO, COO, NH or NHCO, m is an integer of 1 to 20), and hydrogen remaining groups, alone respectively An atom, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms linked by an oxygen atom or a nitrogen atom is shown.) The compound according to claim 1, wherein in the formula (I), R ² alone or two groups of R ² and R ⁵ are -X- (CH ₂ ) m -SH. -X- (CH ₂₎ X of m-SH is, O, OCO, compound of claim 2, wherein the NH or NHCO.   The adhesive for nanoimprint containing the compound in any one of Claims 1-3.   The adhesive of claim 4, further comprising a thermoplastic polymer.   The board | substrate provided with the metal thin film layer, the cured film layer of the compound in any one of Claims 1-3, and the film layer of the thermoplastic polymer in this order.   The board | substrate provided with the metal thin film layer and the film layer containing the hardened | cured material of the compound in any one of Claims 1-3, and a thermoplastic polymer.   The substrate according to claim 6 or 7, wherein the metal of the metal thin film layer is selected from the group consisting of Au, Pt, Ag, Cu, Ni, Ti or Fe.   The substrate according to any one of claims 6 to 8, wherein the thermoplastic polymer is a thermoplastic polymer having a hydrocarbon group.   The weight average molecular weight of a thermoplastic polymer is 1000-50000, The board | substrate in any one of Claims 6-9.   The board | substrate which formed the unevenness | corrugation in the film | membrane layer of the board | substrate in any one of Claims 6-10 by the thermal nanoimprint method.   12. The substrate according to claim 11, wherein the step of removing the remaining thermoplastic polymer film in the concave portion by dry etching, the step of removing the metal thin film in the concave portion by wet etching, and the removal of the thermoplastic polymer in the convex portion. A method for producing a substrate having a metal thin film pattern, comprising forming a metal thin film pattern having a line width of 0.01 μm to 10 μm on the substrate according to claim 11.   The board | substrate which has a metal thin film pattern with the line | wire width of 0.01 micrometer-10 micrometers manufactured by the manufacturing method of Claim 12.