KR102101344B1 - Photopolymerizable composition for roll-to-roll nanoimprint lithography replica mold, and replica mold containg the same - Google Patents

Abstract

The present invention relates to a photopolymerizable composition for producing a roll-to-roll nano-imprint replica mold, and a replica mold comprising the same, wherein the photo-polymerizable composition for producing a roll-to-roll nanoimprint replica mold according to the present invention has releasability, curability, pattern transferability, Since it has excellent adhesion to the substrate, chemical resistance, durability, permeability, etc., it can be manufactured not only as a fine pattern thin film with a pitch of 100 nm or less, but also as a nano-imprint replica mold, especially applied in a roll-to-roll process, 100 nm Below, it is possible to manufacture a fine pattern thin film of a pitch, which has a useful effect of providing a replica mold that can replace a conventional expensive master mold.

Description

Photopolymerizable composition for roll-to-roll nanoimprint lithography replica mold, and replica mold containg the same}

The present invention relates to a photopolymerizable composition for manufacturing a roll-to-roll nano-imprint replica mold, and a replica mold comprising the same.

Conventional patterns are formed by photolithography or laser direct depiction. In the photolithography method, since the uneven structure having a size smaller than the wavelength of light does not have a resolution, it is impossible to realize a microstructure of 100 nm or less. In addition, the laser depiction method is capable of processing less than 100 nm, but has a low processing rate that can be processed per hour, which is a problem.

Therefore, in recent years, it is also possible to process less than 100 nm and nanoimprint lithography technology has been studied as a method of improving the throughput. Nanoimprint lithography technology is a method of preparing a nanoimprint master mold in which a fine uneven pattern has been previously prepared, and transferring the unevenness of the nanoimprint master mold to the nanoimprint resin of the substrate by bonding the substrate coated with the nanoimprint resin. to be.

In nanoimprint technology, adhesion of a pattern obtained by curing a substrate surface and a coating film and releasability of a pattern and a mold are important. Regarding the releasability from the mold, a technique of imparting releasability through surface treatment with a fluorine-based treatment agent on the mold surface, and a technique of imprinting a fluorine-based gas such as pentafluoropropane gas at the interface between the photocurable composition and the mold are generally known.

However, when the nano-imprint process is repeatedly performed using a master mold, a mold pattern may be damaged or a pattern may be blocked due to repeated use of a curable resin. In order to prevent expensive mold damage and to facilitate the process, a nano-imprint process can be performed using the replica mold by making a replica mold from the master mold. For the production of a replica mold, a cured resin having different characteristics from the existing imprint resin is required, and the required characteristics may be more demanding than those of the imprint resin.

The cured resin for the replica mold should have excellent pattern formability and excellent mold release property as well as the resin for imprint. In addition, the produced replica mold should have excellent releasability with a nanoimprint resin (transfer pattern) after performing a nanoimprint process with an imprint resin. In the case of polydimethylsiloxane (PDMS) or hard PDMS (HPDMS), which is a material for thermosetting replication molds that has been widely used in the past, it is possible to manufacture flexible replication molds and is inexpensive, while nano imprint processes with a pitch of 200 nm or less impossible. In addition, resins for replica molds capable of forming a pattern with a pitch of 200 nm or less are difficult to find both photo-curable or thermosetting.

In addition, the conventional flat-panel nano-imprint technology makes it difficult to produce a continuous pattern by stamping a pattern several times with a single mold, such as step and repeat imprint, but using a round mold enables roll-based work. The roll-to-roll imprint technology is preferred because it can produce a large area pattern. Roll-to-Roll (Roll-to-Roll) is a web (web, film or paper, thin and long compared to the width of the material) using a number of drives and rolls (Roll) to continuously perform a number of processes It is a system.

The roll-to-roll nanoimprint process is an economical process, and if only one mold is secured, the microstructure can be processed for various research purposes. In the case of the nano-imprint process, the manufacture of a circular stamp of a nano-sized pattern, that is, a circular mold, is more difficult and more expensive than a flat plate mold. Therefore, the damage or damage of the mold during the nano-imprint process is very fatal, so it can be said that the use of the replica mold is essential.

In the manufacture of a replica mold suitable for a circular mold, the development of a resin for a replica mold is very important and can be said to be a core technology. It must satisfy the viscosity suitable for the roll-to-roll process, mold release and pattern formation. In addition, the fabricated replica mold is wound on a circular roll to perform a nano-imprint process. At this time, releasability with the resin for imprint can be said to be an essential condition. Development of a material for producing such a roll-to-roll nanoimprint replica mold has not been developed, and furthermore, it is necessary to develop a resin for a replica mold capable of implementing a pattern with a pitch of 100 nm.

Thus, the present inventors were studying to develop a composition for a replica mold capable of realizing a fine pattern at a level of 100 nm or less through a roll-to-roll nanoimprint process, while the photopolymerizable composition for roll-to-roll nanoimprint according to the present invention was releasable, Since it has excellent curability, pattern transferability, adhesion to a substrate, chemical resistance, durability, and permeability, it can be manufactured as a fine pattern thin film having a pitch of 100 nm or less through a roll-to-roll nanoimprint process, as well as a roll-to-roll nano imprint replica mold The present invention was completed by finding out that it can be usefully used.

KR 2013-0096242

Langmuir 2007, 23, 2898-2905

An object of the present invention is to provide a photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold.

Another object of the present invention is to provide a fine pattern thin film comprising a photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica mold.

Another object of the present invention is to provide a replica mold comprising a photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica mold.

Another object of the present invention is to provide a method for manufacturing a replica mold using the replica mold.

In order to achieve the above object,

In one aspect of the invention,

At least one compound selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 3; And

Provided is a photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold comprising an additive represented by the following Chemical Formulas 4 to 7:

[Formula 1]

(In the formula 1,

And, - R ¹ is - (CF ₂ OCF _{2) a}

Where a is independently an integer from 0-5);

[Formula 2]

(In the formula 2,

R ² is-(CF ₂ OCF ₂ ) _b- ,

Where b is independently an integer from 0-5);

[Formula 3]

(In the formula 3,

R ³ is-(CF ₂ OCF ₂ ) _c- ,

Where c is an integer from 0-5);

[Formula 4]

(In the above formula 4,

R ⁴ is-(CF ₂ CF ₂ ) _d- ,

d is an integer from 0-5);

[Formula 5]

(In the above formula 5,

e is independently an integer from 0-5);

[Formula 6]

(In the formula 6,

f, g, and h are independently integers of 0-20,

R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently

,

,

,

, 및

로 이루어진 군으로부터 선택되는 어느 1종이고,

,

,

,

, And

Any one selected from the group consisting of,

Where i, j, k and l are independently integers of 1-20); And

[Formula 7]

(In the above formula 7,

m is an integer from 1-20).

In addition, in another aspect of the invention,

A fine pattern thin film is provided comprising a photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica mold.

Furthermore, in another aspect of the invention,

A replica mold for nanoimprint is provided that includes a photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica mold.

In addition, in another aspect of the invention,

Coating a photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica mold on a substrate (step 1);

A molding step of pressing the master mold on the substrate coated with the photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica mold of step 1 (step 2); And

A method of manufacturing a replica mold for nano-imprint comprising the step (step 3) of releasing the mold and the substrate after irradiating light to the photopolymerizable composition for manufacturing a roll-to-roll nano-imprint replica mold molded in step 2 Is provided.

The photopolymerizable composition for manufacturing roll-to-roll nanoimprint replica mold according to the present invention is excellent in mold release, curability, pattern transferability, adhesion to a substrate, chemical resistance, durability, permeability, and the like, and is manufactured as a fine pattern thin film having a pitch of 100 nm or less Not only can it be made of a nano-imprint replica mold, it is particularly applicable to a roll-to-roll process to produce a fine pattern thin film with a pitch of 100 nm or less, a replica mold that can replace a conventional expensive master mold There is a useful effect provided.

1 is a SEM (Scanning Electron Microscope) image of a micropattern thin film prepared therefrom by performing a roll-to-roll nanoimprint process using a conventional expensive master mold on the photopolymerizable composition of the present invention (Example 20). As shown, fine patterns with a pitch of 100 nm or less are observed.
2 shows a SEM (Scanning Electron Microscope) image of a micropattern thin film prepared therefrom by performing a roll-to-roll nanoimprint process using a replica mold prepared according to the present invention, with a pitch of 100 nm or less Fine patterns are observed.

Hereinafter, the present invention will be described in detail.

In one aspect of the invention,

At least one compound selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 3; And

Provided is a photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold comprising an additive represented by the following Chemical Formulas 4 to 7:

[Formula 1]

(In the formula 1,

And, - R ¹ is - (CF ₂ OCF _{2) a}

Where a is independently an integer from 0-5);

[Formula 2]

(In the formula 2,

R ² is-(CF ₂ OCF ₂ ) _b- ,

Where b is independently an integer from 0-5);

[Formula 3]

(In the formula 3,

R ³ is-(CF ₂ OCF ₂ ) _c- ,

Where c is an integer from 0-5);

[Formula 4]

(In the above formula 4,

R ⁴ is-(CF ₂ CF ₂ ) _d- ,

d is an integer from 0-5);

[Formula 5]

(In the above formula 5,

e is independently an integer from 0-5);

[Formula 6]

(In the formula 6,

f, g, and h are independently integers of 0-20,

R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently

,

,

,

, 및

로 이루어진 군으로부터 선택되는 어느 1종이고,

,

,

,

, And

Any one selected from the group consisting of,

Where i, j, k and l are independently integers of 1-20); And

[Formula 7]

(In the above formula 7,

m is an integer from 1-20).

Hereinafter, the photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold according to the present invention will be described in detail.

In one aspect of the invention,

It can be understood that at least one compound selected from the group consisting of the compounds represented by Chemical Formulas 1 to 3 is a component that provides a function of excellent pattern transferability, curing speed, and shrinkage reduction during curing of the composition.

Although not limited to a specific theory, due to the high content of fluorine groups in the compounds represented by Chemical Formulas 1 to 3, the surface energy can be lowered, from which the release property of the photopolymerizable composition for manufacturing roll-to-roll nanoimprint replica mold of the present invention It can be understood to be more improved.

In one embodiment of the invention,

The compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 1a.

[Formula 1a]

In another embodiment of the invention,

The compound represented by Chemical Formula 2 may be a compound represented by Chemical Formula 2a.

[Formula 2a]

In another embodiment of the invention,

The compound represented by Chemical Formula 3 may be a compound represented by Chemical Formula 3a.

[Formula 3a]

In another aspect of the invention,

The at least one compound selected from the group consisting of the compounds represented by Formulas 1 to 3 is preferably included in 1 to 30% by weight, based on the total weight of the photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold, 5 to It is more preferably included at 25% by weight, and most preferably included at 10 to 25% by weight.

When included in less than 1% by weight, there is a problem that the mold release property of the photopolymerizable composition for producing roll-to-roll nanoimprint replica molds decreases. In particular, in the case of a replica mold produced using the composition of the present invention, another nanoimprint resin is used. In terms of releasability, problems may arise. On the other hand, when it is included in more than 30% by weight, the viscosity of the composition is too severe, a problem that is not suitable for the roll-to-roll nanoimprint process occurs.

In another aspect of the invention,

By selecting one compound among the compounds represented by Formulas 1 to 3, it may be included in the composition of the present invention, but alternatively, it may be preferable to include two or more compounds in the composition of the present invention by mixing, for example, When two types of compounds are mixed and included in the composition, the ratio of the two compounds is preferably mixed at 0.1 to 20 parts by weight, more preferably all three types of compounds may be mixed and included, in this case, Formula 1 Compound represented by: Compound represented by Formula 2: The weight ratio of the compound represented by Formula 3 is 0.1-1: 0.1-2: 1-3 It may be preferable in terms of properties of the composition.

In another aspect of the invention,

The additives represented by Formulas 4 to 7 may have a cross-linking structure by reacting with the polyfunctional acrylic system of the compounds represented by Formulas 1 to 3, and the composition of the present invention from the use of the additives, or It can be understood that the curing density of the replica mold is improved, and further, properties such as curability, chemical resistance and durability are improved.

In one embodiment of the invention,

The additive represented by Chemical Formula 4 may be a compound represented by Chemical Formula 4a.

[Formula 4a]

In another embodiment of the invention,

The additive represented by Chemical Formula 5 may be a compound represented by Chemical Formula 5a.

[Formula 5a]

In another embodiment of the invention,

The additive represented by Chemical Formula 6 may be any one or more selected from compounds represented by the following Chemical Formulas 6a to 6e.

[Formula 6a]

(In the above formula 6a,

n and o are independently integers of 1-20).

[Formula 6b]

(In the formula 6b,

p is an integer from 1-20).

[Formula 6c]

(In the formula 6c,

q, r, s, t and u are independently integers from 1-20).

[Formula 6d]

(In the formula 6d,

v and w are independently integers of 1-20).

[Formula 6e]

(In the formula 6e,

x and y are independently integers of 1-20).

In another embodiment of the invention,

The additive represented by Chemical Formula 7 may be a compound represented by Chemical Formula 7a.

[Formula 7a]

(In the formula 7a,

m is an integer from 5 to 15, the preferred molecular weight is 700 g / mol)

In another aspect of the invention,

The additives represented by Chemical Formulas 4 to 7 may be preferably 70 to 99% by weight based on the total weight of the photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold.

If, if the additive is contained in less than 70% by weight, the replica mold of the present invention produced therefrom occurs a problem that the mold release property is reduced with the resin for nanoimprint, while the additive is included in excess of 99% by weight, the composition There arises a problem of high viscosity, which is not suitable for silver roll-to-roll nanoimprint processes.

In another aspect of the invention,

The compound represented by Formula 4: The compound represented by Formula 5: The compound represented by Formula 6: The weight ratio of the compound represented by Formula 7 is preferably 2.5-3.0: 0.5-1.5: 2.6-3.6: 1.0-2.0 And 2.5-3.0: 0.5-1.0: 2.6-3.1: 1.0-1.5 may be more preferable.

Furthermore, in another aspect of the invention,

The photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold according to the present invention may further include a photoinitiator.

Here, the photoinitiator can be used without limitation, as long as it can promote the photocuring of the composition of the present invention, and in one aspect, particularly when applied to a roll-to-roll process, the composition of the present invention is photocured at a suitable rate for the process speed A photoinitiator that can promote photocuring to be used can be used.

In one embodiment of the invention,

The photoinitiator is, but is not limited to, phenyl glyoxylic acid methyl ester, 2-hydroxy-2-methyl-1-phenyl-1-propane, 1-hydroxy-cyclohexyl-phenyl-ketone, 2- Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, diphenyl (2,4,6- Trimethylbenzoyl) phosphine oxide or the like can be used alone or in combination, and phenyl glyoxylic acid methyl ester, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, or a combination thereof can be used. .

In one aspect, in the photopolymerizable composition for producing a roll-to-roll nanoimprint replica mold according to the present invention, the addition ratio of the photoinitiator, compared to one or more compounds selected from the compounds represented by Formulas 1 to 3, 0.05 to It is preferably 5 parts by weight, and more preferably 0.1 to 1 part by weight.

When included in less than 0.05 parts by weight, there is a problem that the photo-curing is not sufficiently promoted, and when it is included in more than 5 parts by weight, it exceeds the amount required for photo-curing, rather than the composition of the present invention, or a replica mold produced therefrom This can be a problem in terms of properties.

Meanwhile, in another aspect of the present invention,

The photopolymerizable composition for manufacturing roll-to-roll nanoimprint replica molds according to the present invention may preferably contain no separate solvent.

In one embodiment, when a solvent is included, there may be a problem that it is difficult to implement a pattern of the replication mold, particularly from a problem such as shrinkage due to solvent evaporation during the process of manufacturing the replication mold.

In addition, in another aspect of the invention,

A fine pattern thin film is provided comprising a photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica mold.

In one aspect of the fine pattern thin film of the present invention,

The fine patterned thin film of the present invention has excellent mold release properties, such as molds and substrates, and has little damage, and furthermore, even in terms of pattern pitch, a fine pattern of 100 nm or less, 90 nm or less, 80 nm or less, 60 nm or less, 50 nm or less There is an advantage that can be implemented.

In addition, in another aspect of the fine pattern thin film of the present invention,

The fine pattern thin film of the present invention has a high fluorine-containing surface energy, and thus has an advantage of excellent mold release property.

The roll-to-roll nanoimprint photopolymerizable composition for replica molding must be filled with the entire region of the mold to be used during the process for the production of a fine pattern, and for this, viscosity properties are very important.

In this aspect, the viscosity property of the photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold according to the present invention is advantageous, for example, may exhibit a viscosity of 150-250 cp (centi-poise) at 25 ° C, preferably It shows a viscosity of 180-220 cp.

When the viscosity is 150 cp or less, there is a problem that the composition flows down on the substrate, and when it is more than 250 cp, pattern transfer of the mold is difficult, and the photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica mold is difficult to be molded.

In particular, in terms of manufacturing a replica mold, the prior art could not achieve such a viscosity characteristic, and it was practically manufactured with a replica mold, so that it was not possible to transfer fine patterns. Further, since the implementation of a fine pattern of 100 nm or less was not possible with the prior art, it can be understood that the properties of the composition of the present invention, such as excellent releasability and pattern transferability, are particularly advantageous in terms of manufacturing a replica mold.

In addition, the photopolymerizable composition for manufacturing roll-to-roll nano-imprint replica molds according to the present invention is in a desirable viscosity range, and thus the fluid is excellent in fluidity, so that the composition in the cavity of the mold easily flows tightly and defects due to roll pressure, Since it does not cause bonding due to bubbles, it does not leave any residue due to the mold, and thus has excellent processability.

Furthermore, in another aspect of the fine pattern thin film of the present invention,

The fine pattern thin film of the present invention has an advantage of excellent light transmittance, moldability, and the like.

These properties, since the permeability of the composition of the present invention used in the fine pattern thin film is high, when light is irradiated, light is irradiated not only to the outside but also to the inside of the composition, and thus it can be understood to be achieved by uniformly curing. You can.

As described above, the advantage of the micropattern thin film of the present invention is that the roll-to-roll nano-imprint replica mold production photopolymerizable composition according to the present invention combines the functions exerted by each component constituting the mold and releasability with the mold. , It can be understood that the pattern transferability, adhesion to the substrate, chemical resistance, durability, permeability, and the like are attributable to remarkably excellent.

In one embodiment of the fine pattern thin film of the present invention,

Using a roll-to-roll process, it was confirmed that a fine pattern thin film having a pitch of 0.01-100 nm can be manufactured (see Experimental Example 2 and FIG. 1).

In another embodiment of the fine pattern thin film of the present invention,

In addition to confirming the micropattern implementation of the micropattern thin film by SEM image, it was shown that the prepared micropattern thin film can be finally used as a mold (see FIG. 2).

This shows that not only can an excellent micropattern thin film be produced from the composition of the present invention, but also that it can be used as a nano imprint mold again from the characteristics of the micropattern thin film. Even in the functional aspect as a mold such as transferability releasability, it was confirmed as excellent in FIG. 2.

Therefore, the micropattern thin film of the present invention can function as a mold for nanoimprint, and the present invention includes it. Preferably, the mold may be understood as a replica mold, and the replica mold of the present invention may be understood as a replica mold preferably applied to a roll-to-roll process.

Furthermore, in another aspect of the invention,

A replica mold for nanoimprint is provided that includes a photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica mold.

In one aspect of the replica mold for nanoimprints of the present invention,

The replica mold of the present invention has a high fluorine group and has a low surface energy, so it has an advantage of excellent releasability with a nanoimprint resin.

In general, in a nano-imprint process, when a process is repeatedly performed using a master mold, a master mold pattern is damaged or a pattern is blocked due to repeated use of a resin for nano-imprint. Therefore, by making a replica mold from the master mold, it is possible to perform an imprint process using the replica mold, and the properties required to be produced by the replica mold must have excellent releasability with the nanoimprint resin. In terms of aspect, the replication mold provided by the present invention achieves excellent releasability compared to the prior art and can be used continuously.

In addition, in another aspect of the replica mold for nanoimprints of the present invention,

The replica mold of the present invention has the advantage of exhibiting a uniform curing degree and excellent durability.

It will be understood that this is an advantage achieved from light-transmitting properties of the composition itself used for the production of the replica mold, and when light is cured, light is uniformly irradiated not only to the outside but also to the inside of the composition to induce curing uniformly as a whole. You can.

As described above, the replica mold for nanoimprint according to the present invention is a replica mold because it has excellent releasability, curability, pattern transferability, adhesion to a substrate, chemical resistance, durability, permeability, etc. with a resin for nanoimprint. It is a technology that can be applied to industrial sites in fact, as it demonstrates excellent functionality and is particularly capable of achieving micropattern transferability that cannot be achieved in the prior art as shown in FIG. 2.

In particular, in the roll-to-roll process, the functional requirements of the replica mold are more demanding, and in particular, for fine pattern transfer, there are many more required conditions such as mold release between the replica mold and the resin, pattern transferability, and durability of the mold. strict.

In the present invention, surprisingly, all of these requirements can be satisfied, and applied to a roll-to-roll process, to prepare a thin film with a transfer pattern of substantially less than 100 nm, and the results are verified as shown in FIG. 2 (Experimental Example) 3 and 2).

In addition, in another aspect of the invention,

Coating a photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica mold on a substrate (step 1);

A molding step of pressing the master mold on the substrate coated with the photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica mold of step 1 (step 2); And

A method of manufacturing a replica mold for nano-imprint comprising the step (step 3) of releasing the mold and the substrate after irradiating light to the photopolymerizable composition for manufacturing a roll-to-roll nano-imprint replica mold molded in step 2 Is provided.

Hereinafter, a method of manufacturing a replica mold according to the present invention will be described in detail step by step.

First, in the method for manufacturing a replica mold according to the present invention,

Step 1 is a step of applying a photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold on a substrate.

Specifically, in step 1, when the viscosity of the photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold is 25 ° C. or less than 150 cp, viscosity may be lowered when applied onto a substrate, so that a problem may occur, resulting in 150 ° C. at 150 ° C. Preference is given to applying a viscosity of -250 cp, preferably of 180-220 cp.

In the manufacturing method of the replica mold according to the present invention, step 2 is a molding step of pressing the master mold on the substrate coated with the photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica of step 1 above.

The forming step may be understood as a step of transferring a pattern to the composition of the present invention, for example, a step of transferring a fine pattern of 100 nm or less.

At this time, the master mold can be molded by simply pressing it on the composition, but applied to a roll-to-roll process to use a master mold (master roll) to transfer the pattern to the composition to be molded.

In particular, the excellent releasability and pattern transferability of the composition of the present invention serve as an advantageous advantage in this step.

Furthermore, in the method for manufacturing a replica mold according to the present invention, step 3 is a step of irradiating and curing light to the photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold formed in step 2, and then releasing the mold and the substrate to be.

In this step, the light used may be used without limitation, as long as it is light of a wavelength used in conventional light curing, and for example, in particular, if it is irradiated with light of at least a minimum condition capable of curing the composition of the present invention, It can be applied, for example, the light may be used ultraviolet rays (ultraviolet rays, UV), gamma rays (gamma ray), electron beams (electron beam), etc., it may be preferable to use ultraviolet rays.

On the other hand, in order to achieve rapid curing by light irradiation during light curing, a substrate used in the above manufacturing method may be used that is transparent, and in this aspect, the transparency of the composition of the present invention is rapid light curing and uniform curing of the entire composition This can be an advantage in terms of.

Hereinafter, the present invention will be described in detail by examples and experimental examples.

However, the following examples and experimental examples are merely illustrative of the present invention, and the contents of the present invention are not limited thereto.

<Production Example 1> Preparation of fluorinated siloxane compound 1

Step 1: After dissolving fluorinated triethylene glycol (5 g, 17.01 mmol) in tetrahydrofuran (25 mL) in a 3-neck flask, add sodium hydroxide (0.48 g, 11.91 mmol) and 30 min. While stirring. A solution of allyl bromide (1.44 g, 11.91 mmol) in tetrahydrofuran (20 mL) was slowly added dropwise to the mixed solution. After reacting at 40 DEG C for 12 hours in a nitrogen atmosphere, the reaction was terminated by cooling to room temperature, the precipitate was filtered, and the organic layer obtained by extraction with ethyl acetate was dried over magnesium sulfate and separated by column chromatography to obtain the target compound. It was obtained as a colorless liquid (F8OH) in% yield.

Step 2: Dissolve 1,1,3,3-tetramethyldisiloxane (1 g, 7.44 mmol) in toluene (20 mL) in a 3-neck flask, add Pt catalyst (1 mL) and stir for 30 minutes. To the mixed solution, a solution in which F8OH (5.47 g, 16.37 mmol) obtained in Step 1 was dissolved in toluene (20 mL) was slowly added dropwise. After reacting in a nitrogen atmosphere at 60 ° C. for 15 hours, the reaction was terminated by cooling to room temperature and stirred by adding charcoal. After filtering the charcoal precipitate and removing the solvent under reduced pressure, it was separated by column chromatography to obtain a colorless liquid (F8D ₂ OH) with a yield of 54%.

Step 3: F8D ₂ OH (5 g, 6.26 mmol) obtained in Step 2 was dissolved in tetrahydrofuran in a 3-neck flask, and then cooled to 0 ° C. Triethylamine (0.95 g, 9.4 mmol) was slowly added dropwise to the mixed solution and stirred for 30 minutes, and then acryloyl chloride (0.84 g, 9.4 mmol) was slowly added dropwise and reacted at room temperature for 15 hours. After filtering the precipitate, the organic layer obtained by extraction with ethyl acetate was dried over magnesium sulfate and separated by column chromatography to obtain the target compound as a colorless liquid (F8D ₂ Ac) in 64% yield.

¹ H NMR (300MHz, CDCl ₃ ): ppm 6.49-6.43 (d, 1H), 6.17-6.13 (q, 1H), 5.94-5.90 (d, 1H), 4.52-4.49 (t, 2H), 3.78-3.71 (t, 2H), 3.57-3.50 (t, 2H), 1.57-1.52 (t, 2H) 0.48-0.42 (m, 2H), 0.00 (s, 6H).

<Production Example 2> Preparation 2 of fluorinated siloxane compound

Step 1: Fluorinated triethylene glycol (5 g, 17.01 mmol) was dissolved in tetrahydrofuran (25 mL) in a 3-neck flask, and sodium hydroxide (0.48 g, 11.91mnol) was added and stirred for 30 minutes. Allyl bromide (1.44 g, 11.91 mmol) was dissolved in tetrahydrofuran (20 mL) and slowly added dropwise to the reaction solution. After reacting in a nitrogen atmosphere at 40 ° C. for 12 hours, the reaction was terminated by cooling to room temperature, and the precipitate was filtered, and then the organic layer obtained by extraction with ethyl acetate was dried over magnesium sulfate and separated by column chromatography to obtain the target compound. It was obtained as a colorless liquid (F8OH) in% yield.

Step 2: Dissolve 2,4,6,8-tetramethylcyclotetrasiloxane (2 g, 8.32 mmol) in toluene (20 mL) in a 3-neck flask, add Pt catalyst (1.5 mL) and stir for 30 minutes. . Compound F8OH of step 1 (12.23 g, 36.61 mmol) was dissolved in toluene (20 mL) and slowly added dropwise to the reaction. After reacting in a nitrogen atmosphere at 60 ° C. for 15 hours, the reaction was terminated by cooling to room temperature and stirred by adding charcoal. After filtering the charcoal precipitate and removing the solvent under reduced pressure, it was separated by column chromatography to obtain a colorless liquid (F8D ₄ OH) with a yield of 58%.

Step 3: F8D ₄ OH (2 g, 1.27 mmol) was dissolved in tetrahydrofuran in a three-necked flask and cooled to 0 ° C. Triethylamine (0.56 g, 5.58 mmol) was slowly added dropwise to the reaction solution, stirred for 30 minutes, and then acryloyl chloride (0.51 g, 5.58 mmol) was slowly added dropwise and reacted at room temperature for 15 hours. After filtering the precipitate, the organic layer obtained by extraction with ethyl acetate was dried over magnesium sulfate, and separated by column chromatography to obtain the target compound in the form of a colorless liquid (F8D ₄ Ac) with a yield of 42%.

¹ H NMR (300MHz, CDCl ₃ ): ppm 6.46-6.40 (d, 1H), 6.13-6.08 (q, 1H), 5.98-5.86 (d, 1H), 4.49-4.42 (t, 2H), 3.78-3.70 (t, 2H), 3.47-3.38 (t, 2H), 1.54-1.48 (t, 2H) 0.48-0.42 (m, 2H), 0.00 (s, 3H).

<Production Example 3> Preparation of fluorinated acrylic compound

Step 1: Fluorinated triethylene glycol (5 g, 17.01 mmol) was dissolved in tetrahydrofuran (25 mL) in a three-necked flask, and triethylamine (3.78 g, 37.42 mmol) was slowly added dropwise for 30 minutes. After stirring for a while, acryloyl chloride (3.39 g, 37.42 mmol) was slowly added dropwise and reacted at room temperature for 6 hours. After filtering the precipitate, the organic layer obtained by extraction with ethyl acetate was dried over magnesium sulfate, and separated by column chromatography to obtain the target compound in the form of a colorless liquid (F8Ac) with a 76% yield.

¹ H NMR (300 MHz, CDCl3): ppm 6.54-6.49 (d, 1H), 6.21-6.14 (q, 1H), 5.99-5.96 (d, 1H).

<Example 1-20> Preparation of photopolymerizable composition for manufacturing roll-to-roll nanoimprint replica mold according to the present invention

In order to prepare the roll-to-roll nanoimprint photopolymerizable composition according to the present invention, after mixing the compounds obtained in Preparation Examples 1 to 3 and the additives of A to F in the ratio of Table 1 below, to obtain a homogeneous solution In order to prepare a photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold by stirring at room temperature for 1 hour.

Example A B C D Preparation Example 1 Preparation Example 2 Preparation Example 3 E F One 30 10 31 (6a) 15 One 9 - 2 2 2 30 10 31 (6a) 15 2 8 - 2 2 3 30 10 31 (6a) 15 3 7 - 2 2 4 30 10 31 (6a) 15 4 6 - 2 2 5 30 10 31 (6a) 15 5 5 - 2 2 6 30 10 31 (6a) 15 6 4 - 2 2 7 30 10 31 (6a) 15 7 3 - 2 2 8 30 10 31 (6a) 15 8 2 - 2 2 9 30 10 31 (6a) 15 9 One - 2 2 10 30 10 31 (6a) 15 10 - - 2 2 11 30 10 31 (6a) 15 - 10 - 2 2 12 30 10 31 (6b) 15 - 10 - 2 2 13 30 10 31 (6c) 15 - 10 - 2 2 14 30 10 31 (6d) 15 - 10 - 2 2 15 30 10 31 (6e) 15 - 10 - 2 2 16 25 10 31 (6a) 10 5 5 10 2 2 17 25 10 31 (6a) 10 10 - 10 2 2 18 25 10 31 (6a) 10 - 10 10 2 2 19 30 5 31 (6a) 10 10 - 15 2 2 20 30 5 31 (6a) 10 - 10 15 2 2

(In Table 1 above

The unit is weight%,

A is Perfluorohexyl diacrylate,

B is Pentaerythritol triacrylate,

C is a siloxane-based urethane acrylate oligomer (Siloxane urethan acrylate oligomer),

(여기서, n 및 o는 독립적으로 1-20의 정수이다)이고;6a is

(Where n and o are independently integers of 1-20);

(여기서, p는 1-20의 정수이다)이고;6b is

(Where p is an integer from 1-20);

(여기서, q, r, s, t 내지 u는 독립적으로 1-20의 정수이다)이고;6c is

(Where q, r, s, t to u are independently integers of 1-20);

(여기서, v 및 w는 독립적으로 1-20의 정수이다)이고; 및6d

(Where v and w are independently integers of 1-20); And

(여기서, x 및 y는 독립적으로 1-20의 정수이다)이다6e is

(Where x and y are independently integers from 1-20)

D is Polyethylene glycol diacrylate,

E is phenyl glyoxylic acid methyl ester (trade name: Darocure MBF, manufacturer: BASF),

F is diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (trade name: Irgacure TPO, manufacturer: BASF).)

<Comparative Example 1-2> Preparation of photopolymerizable composition for manufacturing roll-to-roll nanoimprint replica mold not containing fluorinated triethylene glycol acrylate

After mixing the fluorinated triethylene glycol acrylate compounds obtained in Preparation Examples 1 to 3 in the ratio of Table 2 with A to F additives, and then stirring for 1 hour at room temperature to obtain a homogeneous roll A photopolymerizable composition for the production of a torrole nano imprint replica mold was prepared.

Comparative example A B C (6e) D E F One 30 15 36 15 4 - 2 30 10 36 20 2 2

(In Table 2 above,

A, B, C, D, E and F are the same as described in Table 1 above.)

<Experimental Example 1> Viscosity evaluation of the composition

In order to find out whether it can be suitably used in a roll-to-roll process, the viscosity properties of the photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold according to the present invention were evaluated.

Photopolymerizable composition for manufacturing roll-to-roll nano-imprint replica molds of Examples 1 to 20 including Preparation Examples 1 to 3, Light weight for production of roll-to-roll nano imprint replica molds of Comparative Examples 1 to 2 not including Production Examples 1 to 3 The synthetic composition was measured for viscosity using Micro VISC at 25 ° C, and the results are shown in Table 3 below.

Viscosity (cp), 25 ℃ Example 1 224.1 Example 2 223.8 Example 3 223.1 Example 4 222.7 Example 5 219.8 Example 6 217.2 Example 7 214.4 Example 8 211.7 Example 9 208.3 Example 10 206.5 Example 11 225.7 Example 12 200.4 Example 13 205.4 Example 14 217.7 Example 15 218.5 Example 16 218.7 Example 17 207.8 Example 18 224.3 Example 19 195.4 Example 20 197.6 Comparative Example 1 275.1 Comparative Example 2 263.7

As shown in Table 3, the roll-to-roll nano-imprint replica mold production photopolymerizable composition prepared in Examples 1 to 20 including Preparation Examples 1 to 3 has a viscosity of 150-250 cp suitable for the roll-to-roll nano imprint process (25 ° C) ). On the other hand, Comparative Examples 1 to 2 showed a viscosity of more than 250 cp, which was not suitable for the roll-to-roll nanoimprint process.

Therefore, it can be seen that the photopolymerizable composition for manufacturing a roll-to-roll nano-imprint replica mold according to the present invention has a viscosity suitable for a roll-to-roll nano-imprint process, and thus can be manufactured into an excellent fine pattern thin film through a roll-to-roll process. .

<Experimental Example 2> Pattern transferability and mold release evaluation

In order to evaluate the pattern transferability and releasability of the photopolymerizable composition for manufacturing a roll-to-roll nanoimprint replica mold according to the present invention, using the composition of Example 20, a nanoimprint process was performed as follows.

Specifically, a pressure was applied by placing the composition of Example 20 on a substrate using a master mold having a pitch of 100 nm, and irradiated with ultraviolet light for 1 minute to perform a nano-imprint process, and after processing, evaluating releasability with the master mold, In order to confirm the pattern transferability, it was shown as a picture as shown in FIG. 1 using a scanning electron microscope (SEM).

Referring to Figure 1, D1 = 57.44nm, D2 = 54.66nm, it can be seen that the pattern of the pitch of less than 100nm is implemented, in the fine pattern shape, there is no cracking, it can be seen a uniform and smooth shape.

From this, it can be seen that the photopolymerizable composition according to the present invention has excellent releasability with a mold, and in particular, when using the photopolymerizable composition of the present invention, it can be seen that a fine pattern of 100 nm or less can be successfully implemented. .

Thus, the roll-to-roll nano-imprint replica mold photopolymerizable composition can effectively produce a fine pattern thin film having a pitch of 100 nm or less, such as a polarizing film for a display, a semiconductor field, a hologram, a structure for a media, a precision sensor, a mechanical component, etc. It can be useful for fine structured applications.

<Experimental Example 3> Evaluation of pattern transferability and releasability using a replica mold

In order to evaluate whether the replica mold provided in the present invention can be used as a mold for an actual roll-to-roll nanoimprint process, a replica mold was prepared using the composition of the present invention, and the cured resin for nanoimprint, releasability, and pattern transferability were evaluated. .

Specifically, as in Experimental Example 2, a fine pattern thin film was prepared from the composition of Example 20 using a master mold having a pitch of 100 nm, and this was fixed as an epoxy resin in a roll-to-roll equipment to be used as a replica mold.

In the roll-to-roll process using the equipped replication mold, another nano-imprint resin (Example 20) is supplied on the substrate, the film is used as a substrate to control the stiffness, and the speed of the web is applied to the roll. The nano-imprint roll-to-roll process, which was cured with ultraviolet rays by setting the pressure, was performed, and as a result, the shape of the prepared fine pattern thin film was shown as a photograph in FIG. 2 using a scanning electron microscope (SEM).

Looking at Figure 2, even when the present invention using a replica mold, D1 = 53.18nm, D2 = 54.66nm, it is confirmed that the fine pattern thin film having a pitch of 100nm or less was successfully produced, excellent pattern transfer of the replica mold of the present invention Performance heterogeneity can be confirmed.

Therefore, as the result of this experiment, the replica mold of the present invention in which excellent function is confirmed as a mold capable of transferring fine patterns of 100 nm or less can be used not only for nanoimprint, but also particularly applicable to roll-to-roll processes. As the level of pattern transferability and releasability is proved to be excellent, it is possible to replace the conventional expensive master mold and master roll.

Claims (11)

One or more compounds selected from the group consisting of 10 to 25% by weight of the compounds represented by the following Chemical Formulas 1 to 3 relative to the photopolymerizable composition for manufacturing the entire roll-to-roll nanoimprint replica mold;
Additives represented by the following formulas 4 to 7 in an amount of 70 to 86% by weight with respect to the photopolymerizable composition for manufacturing a whole roll-to-roll nanoimprint replica mold; And
1 to 5% by weight of the photoinitiator with respect to the photopolymerizable composition for manufacturing the entire roll-to-roll nano-imprint replica mold;
Compound represented by the formula (4): Compound represented by the formula (5): Compound represented by the formula (6): The weight ratio of the compound represented by the formula (7) is characterized in that 2.5-3.0: 0.5-1.5: 2.6-3.6: 1.0-2.0 Photopolymerizable composition for manufacturing roll-to-roll nano imprint replica mold:
[Formula 1]

(In the formula 1,
And, - R ¹ is - (CF ₂ OCF _{2) a}
Where a is independently an integer from 0-5);

[Formula 2]

(In the formula 2,
R ² is-(CF ₂ OCF ₂ ) _b- ,
Where b is independently an integer from 0-5);

[Formula 3]

(In the formula 3,
R ³ is-(CF ₂ OCF ₂ ) _c- ,
Where c is an integer from 0-5);

[Formula 4]

(In the above formula 4,
R ⁴ is-(CF ₂ CF ₂ ) _d- ,
d is an integer from 0-5);

[Formula 5]

(In the above formula 5,
e is independently an integer from 0-5);

[Formula 6]

(In the formula 6,
f, g, and h are independently integers of 0-20,
R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently

,

,

,

, And

Any one selected from the group consisting of,
Where i, j, k and l are independently integers of 1-20); And

[Formula 7]

(In the above formula 7,
m is an integer from 1-20).
delete delete delete delete delete delete Applying a photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica mold of claim 1 on a substrate (step 1);
A molding step of pressing the master mold on the substrate coated with the photopolymerizable composition for manufacturing the roll-to-roll nanoimprint replica mold of step 1 (step 2); And
A method of manufacturing a replica mold for nano-imprint, comprising the step (step 3) of releasing the mold and the substrate after irradiating light to the photopolymerizable composition for manufacturing a roll-to-roll nano-imprint replica mold molded in step 2.
Claim 1 of the roll-to-roll nano-imprint replica mold comprising a photopolymerizable composition for producing a replica.
The method of claim 9,
The replica mold for nano-imprint, a replica mold for nano-imprint, characterized in that it can replace the master mold or a master roll in a roll-to-roll process.
The method of claim 9,
The nano-imprint replica mold, the nano-imprint replica mold, characterized in that by pressing the resin for nano-imprint to produce a fine pattern thin film of 0.01-100 nm pitch (pitch).

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