KR20210068854A - Resin composite, and laminate using the same - Google Patents

Abstract

A resin composition according to the present invention contains a vinyl ether group-containing monomer, first urethane acrylate having a weight average molecular weight (Mw) of 5,000 or less and a trifunctional or higher polyfunctionality, and an acrylate-based monomer, wherein the viscosity thereof may be 50 cps or less. By using the resin composition according to the present invention, it is possible to suppress pattern formation defects caused by an imprint lithography process.

Description

Resin composition and laminate using same {Resin composite, and laminate using the same}

The present invention relates to a resin composition and a laminate using the same.

Nanoimprint lithography is a technology that can fabricate nanostructures. It is a technology that transfers nanostructures having micropatterns by mechanically deforming them by pressing a stamp with nanopatterns on the surface of a resist applied on a substrate. means

In particular, roll-to-roll imprint lithography improves productivity by adding process continuity using roll equipment. Referring to FIG. 1 , on a substrate transferred from a backup roll, a nano-pattern is provided. A nanopattern can be formed with an imprinting roll.

In the roll-to-roll imprint lithography process, the entire area of the resin coated on the substrate is transferred in contact with the stamp at the same time as in the flat plate imprint lithography process, but the resin-coated substrate is transferred from the end according to the rotation of the backup roll. This is performed by sequentially contacting the printing roll in one direction, that is, the transfer may be sequentially performed from the contact surface of the resin on the substrate and the imprinting roll.

Therefore, during roll-to-roll imprinting, air bubbles may be generated by inflow of air into the bank between the contact surface of the resin on the substrate and the imprinting roll. When bubbles are generated, the formation of a complete pattern on the resin is prevented, which may cause a problem in that the finished product is defective. Therefore, in order to secure the reliability and uniformity of pattern transfer according to the roll-to-roll imprint lithography process, there is an urgent need to study for suppressing air bubbles.

In order to solve the above problems, the problem to be solved by the present invention is to provide a resin composition and a laminate. The technical problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

Since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and described in detail. However, this is not intended to limit the present invention to specific embodiments, and it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

In this application, when an element, such as a layer, region, or substrate, is referred to as being “on” another component, it may be directly on the other element or intervening elements may be present in between. You will understand.

Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used for the purpose of distinguishing one component from another.

Terms such as “comprise” or “have” are intended to designate that a feature, number, step, action, component, part, or combination thereof described in the specification is present, and includes one or more other features, numbers, or steps. , it should be understood that it does not preclude in advance the possibility of the existence or addition of an operation, component, part, or combination thereof.

The term “acrylate-based” means not only acrylates, but also methacrylates, or derivatives in which substituents are introduced into acrylates or methacrylates. In addition, "alkyl (group)" refers to an aliphatic hydrocarbon group, and may be a saturated alkyl group not containing multiple bonds or an unsaturated alkyl group containing at least one multiple bond. The alkyl group, whether saturated or unsaturated, may be branched, straight-chain or cyclic.

Furthermore, the description of a numerical range such as “x to y” or “x to carbon y” should be interpreted as describing not only x and y but also all numbers in between.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having meanings consistent with the meanings in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application does not

In an example related to the present application, the present application relates to a resin composition. The resin composition may include a vinyl ether group-containing monomer. The vinyl ether group-containing monomer may be a monomer containing a vinyl ether group at one terminal.

The vinyl ether group-containing monomer may be included in an amount of 5 to 25 parts by weight based on 100 parts by weight of the total resin composition. In some cases, it may mean a weight ratio between components of the composition. Specifically, the vinyl ether group-containing monomer may be included in, for example, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, or 10 parts by weight or more in the entire composition. In addition, it may be included in an amount of 24 parts by weight or less, 23 parts by weight or less, 22 parts by weight or less, 21 parts by weight or less, or 20 parts by weight or less. When the vinyl ether group-containing monomer is included in the above content range along with other components, it may be particularly advantageous to realize a low viscosity of the resin composition.

As an example, the vinyl ether group-containing monomer may be a monomer further comprising a (meth)acryloyloxy group at another terminal. In detail, the vinyl ether group-containing monomer may be represented by the following Chemical Formula 1 as an example. In Formula 1, n may be an integer of 1 to 10. R may be hydrogen or an alkyl group having 1 to 8 carbon atoms.

[Formula 1]

The vinyl ether group-containing monomer is, for example, 2(-2vinyloxyethoxy)ethyl acrylate (2-(2-vinyloxyethoxy)ethyl acrylate, VEEA), 2(-2vinyloxyethoxy)ethyl methacrylate (2-(2-vinyloxyethoxy)ethyl acrylate, VEEM), but is not limited thereto.

The resin composition may include a first urethane acrylate having a weight average molecular weight (Mw) of 5,000 or less and a polyfunctionality of trifunctional or more. The first urethane acrylate may be an oligomer.

The urethane acrylate may be a material formed by polymerization of an isocyanate-based compound and a polyol, and specifically, the urethane acrylate is obtained by polymerizing a compound such as isocyanate, alcohol, and acrylate according to a known method to obtain the following functional and/or It may be prepared to satisfy the molecular weight. For example, a polyisocyanate having 3 or more isocyanate groups is reacted with an acrylate having a hydroxyl group in a molecule and containing 3 or more acrylic groups under a metal catalyst and a radical polymerization inhibitor until the isocyanate (NCO) disappears. , urethane acrylate may be prepared by adding 5 to 30% by weight of an ultraviolet curable monomer. Alternatively, a urethane acrylate that satisfies the following functionalities and/or molecular weight may be selected from among commercially available products.

Since the first urethane acrylate is trifunctional or more polyfunctional, it is possible to implement a low viscosity of the resin composition including the same by using a somewhat low molecular weight one. As an example, the weight average molecular weight (Mw) of the first urethane acrylate may be 5,000 or less, and specifically, 4,500 or less, 4,000 or less, 3,500 or less, or 3,000 or less. In addition, the lower limit of the weight average molecular weight (Mw) of the first urethane acrylate may be 500 or more, 600 or more, 700 or more, 800 or more, 900 or more, or 1,000 or more.

On the other hand, the total weight of the first urethane acrylate having a weight and weight average molecular weight (Mw) of the vinyl ether group-containing monomer of 5,000 or less and having a trifunctional or higher polyfunctionality may be 20 to 50 parts by weight based on 100 parts by weight of the total resin composition. . For example, the lower limit of the total weight of the vinyl ether group-containing monomer and the first urethane acrylate may be 21 parts by weight or more, 22 parts by weight or more, 23 parts by weight or more, 24 parts by weight or more, or 25 parts by weight or more, The upper limit of the total weight may be, for example, 49 parts by weight or less, 48 parts by weight or less, 47 parts by weight or less, 46 parts by weight or less, or 45 parts by weight or less. When it has the above range, it may be advantageous to implement a low viscosity according to the present invention.

In addition, the first urethane acrylate may be included in an amount of 10 to 30 parts by weight based on 100 parts by weight of the total resin composition, and specifically, 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, or 15 parts by weight or more. more may be included. In addition, 29 parts by weight or less, 28 parts by weight or less, 27 parts by weight or less, 26 parts by weight or less, or 25 parts by weight or less may be included.

The resin composition may further include a monofunctional or bifunctional second urethane acrylate. The second urethane acrylate may be an oligomer.

The weight average molecular weight (Mw) of the second urethane acrylate may be 8,000 or more, and specifically, 9,000 or more, 9,500 or more, 10,000 or more, 10,500 or more, or 11,000 or more. That is, as the first urethane acrylate compared to the monofunctional or bifunctional second urethane acrylate, one having a relatively low molecular weight may be used.

The second urethane acrylate may be included in an amount of 10 to 30 parts by weight based on 100 parts by weight of the total resin composition, and specifically, 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, or 15 parts by weight or more. can In addition, 29 parts by weight or less, 28 parts by weight or less, 27 parts by weight or less, 26 parts by weight or less, or 25 parts by weight or less may be included.

In particular, the first urethane acrylate may be included in a high content compared to the content of the second urethane acrylate. That is, the resin composition containing the first urethane acrylate in a higher content than the second urethane acrylate together with other components may have a lower viscosity.

The resin composition may include an acrylate-based monomer. The acrylate-based monomer may include at least one of a monofunctional acrylate-based monomer, a bifunctional acrylate-based monomer, or a trifunctional acrylate-based monomer.

The monofunctional acrylate monomer is, for example, isobornyl acrylate (IBOA), benzyl acrylate, nonyl acrylate, isobutyl acrylate (isobutyl acrylate), isodecyl acrylic It may be isodecyl acrylate, lauryl acrylate, 2-Ethylhexyl acrylate, or Phenoxyethylacrylate (PEA). The bifunctional acrylate-based monomer is, for example, tricyclodecane dimethanol diacrylate (TCDDA), cyclohexane dimethanol diacrylate, 1,6-hexanediol diacrylate (1,6-hexanediol diacrylate, HDDA), tri ethylene glycol diacrylate, tetra ethylene glycol diacrylate, butylene glycol diacrylate, polyethylene It may be glycol diacrylate (polyethylene glycol diacrylate) or polypropylene glycol diacrylate (polypropylene glycol diacrylate). The trifunctional acrylate-based monomer is, for example, trimethylolpropane triacrylate (TMPTA), glycerine triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propylated trimethylolpropane triacrylate, glycerylpropylated triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate.

The acrylate-based monomer may be included in an amount of 25 to 45 parts by weight based on 100 parts by weight of the total resin composition. Specifically, the acrylate-based monomer may be included in an amount of 26 parts by weight or more, 27 parts by weight or more, 28 parts by weight or more, 29 parts by weight or more, or 30 parts by weight or more, and 44 parts by weight or less, 43 parts by weight or less, 42 It may be included in parts by weight or less, 41 parts by weight or less, 40 parts by weight or less.

In addition to the resin composition, an effective amount of an additive such as a photoinitiator or a silane coupling agent may be further included. For example, the additive may be included in an amount of about 10 parts by weight based on 100 parts by weight of the total resin composition.

By using the resin composition according to the present invention, it is possible to suppress pattern formation defects during the imprint lithography process. Specifically, the viscosity of the resin composition according to the present invention may represent 50 cps or less at 50 ℃. Therefore, by appropriately controlling the viscosity of the resin composition, high-speed curing is possible in a high-speed roll-to-roll imprint lithography process, particularly at 25 M/min or more, and furthermore, since the generation of bubbles formed in the bank can be suppressed, the obtained final Product reliability can be improved.

In another example related to the present application, the present application relates to a laminate.

2 is a cross-sectional view illustrating a laminate according to an embodiment of the present invention. Referring to FIG. 2 , the laminate may include a base layer 10 and a resin layer 20 that is formed on one surface of the base layer and is a cured layer of the resin composition.

The base layer 10 is a plastic film layer, and may be polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polymethyl methacrylate, polyester, vinyl chloride resin, polypropylene, polyethylene, and polyacrylate. It is not limited.

The resin layer 20 is a layer formed by photocuring the resin composition described above, and may be manufactured in a solvent-free type.

The resin layer 20 may form a concave-convex pattern on the opposite surface of one surface facing the substrate layer mass, and may be formed according to a UV-roll-to-roll imprint lithography process. The concave-convex pattern may be an embossed pattern or a fine pattern, and may be 1 µm to 20 µm concavo-convex.

The laminate, as described above, may be for a roll-to-roll imprint lithography process.

3 is a cross-sectional view showing a laminate according to an embodiment of the present invention. Referring to FIG. 3 , the laminate may further include a base layer 10 , a resin layer 20 , a metal layer 30 , and an adhesive layer 40 sequentially on one surface of the base layer. In addition to this, if necessary, the laminate according to the present invention may further include a layer that can be used in the art.

The metal layer 30 may be formed by depositing a metal such as tin, nickel, chromium, aluminum, indium, SUS, copper, silver, gold or platinum, and may serve as a finishing material having an aesthetic effect to give a metal texture. have. The metal layer may be formed by various methods such as vacuum deposition, thermal deposition, sputtering, and paste coating.

The adhesive layer 40 may include at least one selected from the group consisting of a polyester-based adhesive, a hydroxyl group-containing acrylic adhesive, a retane-based adhesive, and combinations thereof.

The adhesive composition constituting the adhesive layer 40 may include an isocyanate-based curing agent such as xylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), methylene diphenyl diisocyanate (MDI), and toluene diisocyanate (TDI). and the solvent may include methyl ethyl ketone, toluene, ethyl acetate, methyl isobutyl ketone, and the like.

As an example, the adhesive layer 40 may be formed by applying an adhesive such as polyester to a thickness of 3 to 15 μm by a comma coating method, and may produce a clearer three-dimensional effect by forming an opaque layer. In addition, when the adhesive layer 40 is formed as an opaque layer, a pigment may be added to the adhesive.

The laminate may be applied as a floor finishing material for finishing the floor by attaching an adhesive layer to the floor of a building, such as a building or a house.

By using the resin composition according to the present invention, it is possible to suppress pattern formation defects caused by the imprint lithography process. However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a schematic diagram illustrating a roll-to-roll imprint lithography process.
2 is a cross-sectional view illustrating a laminate according to an embodiment of the present invention.
3 is a cross-sectional view illustrating a laminate according to an embodiment of the present invention.
4A to 4E are photographs showing the results of the evaluation at room temperature on the eric phase of the laminates according to Examples 1-2 and Comparative Examples 1-3 of the present invention, respectively.
5A to 5E are photographs showing results of evaluation of eric phase hot water resistance of laminates according to Examples 1-2 and Comparative Examples 1-3 of the present invention, respectively.
6a to 6e are photographs showing the results of evaluation of the plate adhesion force of the laminate according to Examples 1-2 and Comparative Examples 1-3 of the present invention, respectively.

Hereinafter, a preferred experimental example (example) is presented to help the understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited by the following experimental examples.

<Production Example>

Examples 1-2; and Comparative Examples 1 to 3

Examples 1-2; and Comparative Examples 1 to 3, urethane acrylate, acrylate-based monomer, photoinitiator, and silane coupling agent were mixed in a weight ratio shown in Table 1 below, respectively, in order to prepare a resin composition. After applying the prepared resin composition to a thickness of 10 μm on a polyethylene terephthalate (PET) base layer having a thickness of 30 μm, it was transferred and cured using UV-roll-to-roll imprint lithography equipment as shown in FIG. 1 . In this case, as the imprinting roll, a 15 μm fine concavo-convex pattern was used. Next, an aluminum metal layer with a thickness of 500 nm is prepared on the surface on which the pattern of the resin layer is formed ^{using a vacuum thermal evaporation method at 10 -5} torr and 500° C., and an adhesive is applied to a thickness of 5 μm using a comma coating method. A pressure-sensitive adhesive layer was formed on the exposed surface of the pattern to obtain a laminate in which a polyethylene terephthalate film, a resin layer, and a metal layer were laminated.

Table 1 below summarizes the components of the resin compositions according to Examples and Comparative Examples of the present invention and their contents, in detail, parts by weight of the components relative to 100 weight of the total resin composition.

[Table 1]

Here, the first urethane acrylate is a trifunctional or more polyfunctional oligomer and has a weight average molecular weight of 3,000. The second urethane acrylate is a bifunctional oligomer and has a weight average molecular weight of 11,000. In addition, the third urethane acrylate is a trifunctional or more polyfunctional oligomer and has a weight average molecular weight of 11,500.

<Experimental example>

Table 2 below evaluates the workability and physical properties of the resin compositions or laminates according to Examples and Comparative Examples of the present invention.

[Table 2]

viscosity evaluation

Viscosity of the resin compositions according to Examples and Comparative Examples of the present invention is shown. In detail, the viscosity at 50 degreeC is measured.

Appearance evaluation

Appearances of the laminates according to Examples and Comparative Examples of the present invention were evaluated.

The evaluation criteria are whether the surface of the laminate is coated smoothly without foreign substances, lines, bubbles, or dents (if satisfactory, indicate “○”), and 20% or more of foreign substances, lines, bubbles, and dents on the surface. Whether it has occurred (indicated by “X” if satisfied).

Ericsson room temperature and hot water evaluation

Ericsson evaluation was performed on the laminates according to Examples and Comparative Examples of the present invention.

For the Ericsson room temperature evaluation, first, using a knife on the upper portion of the polyethylene terephthalate substrate layer of each laminate, a figure 11 shape having a 5 mm interval was cut to have a # shape crossed in the horizontal and vertical directions, respectively. Thereafter, a ball made of a spherical (SUS) material having a diameter of 8 mm and 10 mm was pressed 9 mm deep from the metal layer side, and the opposite # shape was visually observed. (Measuring device: Erichsen TEST device) FIGS. 4a to 4e are photographs showing the results of the room temperature evaluation of the eric phase of the laminate according to Examples 1-2 and Comparative Examples 1-3 of the present invention, respectively.

The evaluation of the Ericsson hot water resistance was performed by visually observing the cut surface after leaving the laminate sample, which had completed the Ericsson room temperature test, in a constant temperature bath containing 80°C water for 30 minutes. 5A to 5E are photographs showing results of evaluation of eric phase hot water resistance of laminates according to Examples 1-2 and Comparative Examples 1-3 of the present invention, respectively.

The evaluation criteria were whether there was no cross-out peeling and lifting (if satisfactory, marked with “○”), and whether all of the peeling affected by cross-out had been peeled off (if satisfied, marked with “X”).

Plate adhesion evaluation

The adhesion of the flat plate to the laminate according to Examples and Comparative Examples of the present invention was evaluated.

In order to evaluate the adhesion, the upper portion of the polyethylene terephthalate base layer of each laminate was applied with a knife inclined at an angle of about 45°, and the resin layer was cut to the extent that the resin layer was exposed. After that, a portion of the polyethylene terephthalate base layer was peeled off from the center of the portion cut with X with a knife, and the peeled base layer was torn off by applying force.

The evaluation criterion is based on whether the polyethylene terephthalate base layer peels off by 15 mm or more, and in the case of a good product, the polyethylene terephthalate base layer is torn without being peeled off. 6a to 6e are photographs showing the results of evaluation of plate adhesion strength of laminates according to Examples 1-2 and Comparative Examples 1-3 of the present invention, respectively.

10: base layer
20: coating layer
30: metal layer
40: adhesive layer

Claims (10)

vinyl ether group-containing monomers; A first urethane acrylate having a weight average molecular weight (Mw) of 5,000 or less and a trifunctional or higher polyfunctionality; and an acrylate-based monomer,
A resin composition having a viscosity of 50 cps or less. The method according to claim 1,
The total weight of the vinyl ether group-containing monomer and the first urethane acrylate is 20 to 50 parts by weight based on 100 parts by weight of the total resin composition, the resin composition. The method according to claim 1,
The vinyl ether group-containing monomer is included in an amount of 5 to 25 parts by weight based on 100 parts by weight of the total resin composition, the resin composition. The method according to claim 1,
The vinyl ether group-containing monomer is represented by the following formula (1), the resin composition:
[Formula 1]

Wherein n is an integer of 1 to 10, R is hydrogen or an alkyl group having 1 to 8 carbon atoms. The method according to claim 1,
The first urethane acrylate is included in an amount of 10 to 30 parts by weight based on 100 parts by weight of the total resin composition, the resin composition. The method according to claim 1,
A resin composition comprising at least one of the acrylate-based monomer, a monofunctional acrylate-based monomer, a bifunctional acrylate-based monomer, or a trifunctional acrylate-based monomer. The method according to claim 1,
A weight average molecular weight (Mw) of 8,000 or more, the resin composition further comprising a second urethane acrylate monofunctional or bifunctional. A base layer and a resin layer positioned on one surface of the base layer, which is a cured layer of a resin composition,
The resin composition may include a vinyl ether group-containing monomer; A first urethane acrylate having a weight average molecular weight (Mw) of 5,000 or less and a trifunctional or higher polyfunctionality; and an acrylate-based monomer, wherein the resin composition has a viscosity of 50 cps or less. 9. The method of claim 8,
The resin layer is a laminate in which a concave-convex pattern is formed on the opposite surface of one surface facing the base layer. 10. The method of claim 9,
The laminate further comprising at least one of a metal layer and an adhesive layer on the resin layer on which the uneven pattern is formed.

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