KR20230058923A - Solventless Coating Compositions of Organic/Inorganic Hybrid Materials with Imprinting Processability and its Manufacturing Method - Google Patents

Abstract

The present invention relates to a solvent-free organic-inorganic hybrid imprinting coating composition, and a method for manufacturing the same. More specifically, the present invention relates to: a solvent-free organic-inorganic hybrid imprinting coating composition which satisfies the characteristics of the high-speed imprinting process by maintaining fluidity to enable molding without the use of solvents even though a high content of high-purity silica sol is dispersed in an acrylic resin composition that is cured at high speed by UV irradiation at low temperature; and a nano-scale imprinting process technology using the same.

Description

Solventless Coating Compositions of Organic/Inorganic Hybrid Materials with Imprinting Processability and its Manufacturing Method}

The present invention relates to a solvent-free organic-inorganic hybrid imprinting coating composition and a method for preparing the same, and more particularly, to an acrylic resin composition that is cured at a high speed by UV irradiation at a low temperature even when a high-purity silica sol is dispersed in a high content, and the solvent is not The present invention relates to an organic-inorganic hybrid coating composition that satisfies characteristics of a high-speed imprinting process by maintaining a viscosity capable of being molded without use, and a nanoscale imprinting process technology using the same.

Various liquid acrylic monomers are used as raw materials for photocuring coatings, and rapid curing reactions are possible through UV light irradiation, so the commercial importance of the technology of forming nanostructures on the surface layer through roll-to-roll coating and imprinting processes is increasing. .

Recently, with the improvement of nanohybrid material technology and wet nanoimprinting process technology, it is becoming possible to secure the material characteristics of the surface nanostructure.

The production of functional surface nanostructures by the wet material imprinting method can secure excellent price competitiveness, but in order to satisfy high-speed photocurable moldability, it is necessary to control the viscosity of the acrylic resin without using a solvent, and the imprinted surface nanostructures has a disadvantage in that it is vulnerable to mechanical damage and has a large cure shrinkage, resulting in excessive curling. In other words, it is required to develop nanoimprint materials that can overcome the limitations of mechanical durability and dimensional stability of fast-curing organic materials. It is a thin film type product with innovative functionality and can be used for manufacturing various parts and devices.

In order for products with nanostructures on the surface of materials such as transparent films, plastics, and glass to be commercially used, mechanical properties that do not break under various external forces (excellent high toughness/high stiffness materials with hardness and impact/tensile/abrasion strength) ), and must have formability capable of the imprinting process while satisfying material properties such as chemical stability (yellowing durability), transparency, and heat resistance. In order to enable imprinting using nano-level molds, acrylic resins with low viscosity (low molecular weight) having fluidity are mainly used. In the process of solidification through curing reaction, there is a lot of volume reduction, resulting in severe curling and nanopatterning on flexible base materials. It lacks mechanical flexibility for molding, and development of new complementary technologies is required, such as yellowing.

In addition, coating agents formulated with transparent oligomers to secure flexibility and toughness have relatively low viscosity even at room temperature and can be rapidly cross-linked by UV irradiation, so they are widely used as coating molding materials for continuous roll-to-roll processes, but curing shrinkage (7-10) 8%), it lacks dimensional stability, is easily contaminated, and has weak flexibility and impact strength, which limits its use as an imprinting material.

The organic-inorganic hybrid material in which colloidal ceramics are dispersed in an organic medium has a slight increase in viscosity compared to the ceramic content, and the reinforcement of ceramics reduces shrinkage during hardening and greatly improves the hardness of the material, so it is used as an imprinting molding coating agent. this is possible

Korean Patent Publication No. 2009-0053155 Korea Patent No. 1965624 Korean Patent Publication No. 2019-0036166 Korean Patent Publication No. 2011-0134546

The present invention provides an organic-inorganic hybrid imprinting coating composition that satisfies material characteristics while having fluidity by dispersing nano-sized silica sol in a solvent-free form in a photocurable acrylic resin liquid prescription material and an imprinting molding process using the same will be.

On the one hand, the present invention

photocurable acrylic resin;

a surface-modified silica sol dispersed in the acrylic resin; and

Including; one or more oligomers or additives;

Provided is a solvent-free organic-inorganic hybrid imprinting coating composition characterized in that it exhibits imprinting moldability and flexibility and hardness characteristics after molding.

On the other hand, the present invention

synthesizing a surface-modified silica sol;

Preparing a hybrid dispersion by removing the solvent by adding an acrylic monomer; and

Adding a photocurable resin to the hybrid dispersion to prepare an organic-inorganic hybrid imprinting coating composition; of an organic-inorganic hybrid imprinting coating composition that satisfies molding characteristics and flexibility and strength after molding. A manufacturing method is provided.

The coating composition according to the present invention requires the elimination of internal stress (reduced bending/curling deformation) due to curing shrinkage in an acrylic resin and silica sol hybrid material, as well as bending durability during bending. Surface treatment of silica sol, silicon-modified acrylic resin, and fluorine-based compound formulation improve fluidity, flatness, and releasability of liquid materials to secure nano-level imprinting process moldability and improve the contact angle of the molded solid surface to achieve super water repellency ( It is possible to secure surface properties such as antifouling/fingerprint, slip/lubricity).

In addition, in order to secure the dispersion stability of the silica sol constituting the coating composition of the present invention, organic silane treatment is required continuously after the synthesis of the silica sol. When the solvent and the low boiling point solvent are removed, a silica sol having excellent storage stability dispersed in an organic medium is obtained. When silanes are diluted with an organic solvent and added during organic silane treatment, there is an advantage in that the surface treatment efficiency and storage stability of silica are improved.

In addition, according to the production method of the present invention, in synthesizing silica sol from a precursor, in the initial reaction, the hydrolysis and condensation reactions occur stably through securing uniform solubility of the reaction medium, and in the intermediate reaction step with increased hydrophilicity, water It is possible to synthesize dense silica particles of a small particle size in a short time without aggregation while increasing the temperature while adding the silica growth reaction at a rapid rate.

1 is a flow chart showing manufacturing steps of an organic-inorganic hybrid imprinting coating composition according to the present invention.
Figure 2 is a conceptual diagram of the synthesis of silica sol, silane surface treatment, and organic-inorganic hybrid materials according to the present invention.
3 is a nanoimprint process step diagram of an organic-inorganic hybrid material according to an embodiment of the present invention.
4 is a view showing an example of a nanostructure molded using the composition for imprinting according to the present invention.
5 is a surface on which a pencil hardness test was performed on the case of UV curing using the composition for imprinting according to the present invention (a, b, c) and the nanostructured surface (d, e, f) subjected to heat treatment after UV curing It is a drawing showing the evaluation result.
6 is a view showing evaluation results of cracks (a) of a commercially available high-hardness resin and bendability (b) of a resin for imprint by a bending test according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

A solvent-free organic-inorganic hybrid imprinting coating composition according to an embodiment of the present invention,

photocurable acrylic resin;

a surface-modified silica sol dispersed in the acrylic resin; and

Including; one or more oligomers or additives;

It is characterized by showing imprinting moldability and flexibility and hardness characteristics after molding.

The coating composition according to the present invention is a solvent-free state in which silanized silica sol is dispersed in curable acrylic resin, and even when a high content of silica sol is mixed, there is little increase in viscosity, and compared to the acrylic resin alone, the coating composition has thermal, mechanical, optical, and electrical properties. Due to its excellent properties, it can be widely used commercially as a liquid coating material.

In order to form a nano-level surface structure through the imprinting process, it is important to secure fluidity along with transparency, so a very small 10-20 nm size silica sol is synthesized and acrylic resins are refined through sophisticated silica sol surface modification with organic functional silane materials. It should be possible to manufacture it as a low-viscosity liquid material with excellent storage stability by being dispersed in a high content in The nano-hybrid imprinting coating composition composed of a highly transparent silica sol and a photocurable acrylic resin has excellent properties such as heat resistance, chemical stability, transparency, high toughness (softness and high hardness), abrasion resistance, slipperiness, and antifouling property, and has excellent volume during curing and molding. Since the shrinkage is small, it can be used as a molding material for imprinting nanostructures.

Dense particulate organosilane-treated silica sol can be dispersed in high content in low-viscosity acrylic monomers without using an organic solvent. The increase in viscosity is negligible, the curing shrinkage is greatly reduced, and it greatly contributes to the improvement of material properties such as hardness and flexibility. . High-purity silica sol can be synthesized using basic catalysts such as ammonia or amines with high catalytic activity. It is possible to synthesize silica sol with a small particle size at a high speed by adjusting factors such as the amount of water, type/amount of catalyst, and reaction temperature.

In order to utilize the synthesized silica sol, the surface of the silica sol is modified with non-reactive and reactive organosilanes. Through this, the surface energy of the silica sol can be controlled as well as organic reactive groups can be provided, thereby improving the dispersion stability in the organic medium and The chemical reaction of the period proceeds, and molding into a solid material is possible. Therefore, effective surface treatment of the silica particles by organosilane is required to enable dispersion in a relatively high content in the liquid acrylic monomer, and the organic-inorganic hybrid material prepared in this way has imprinting moldability and can be used as a stable hybrid material.

One embodiment of the present invention relates to a method for preparing a solvent-free organic-inorganic hybrid imprinting coating composition and imprinting molding method,

synthesizing a surface-modified silica sol;

Preparing a hybrid dispersion by removing the solvent by adding an acrylic monomer; and

and adding a photocurable resin and an additive to the hybrid dispersion to prepare an organic-inorganic hybrid imprinting coating composition.

Hereinafter, a method for preparing the solvent-free organic-inorganic hybrid imprinting coating composition of the present invention will be described in detail.

(a) Synthesis of surface-modified silica sol

A colloidal ultrafine silica sol can be synthesized from a silica precursor (TMOS, TEOS), and a surface-modified silica sol can be synthesized by treating non-reactive/reactive and chain-type organosilane.

Specifically, when ammonia water is added to an alcohol solution in which the precursor is dissolved and reacted with stirring at 45 to 60 ° C. for 18 hours, silica sol is synthesized. It is well known.

In the final step of synthesizing silica sol, as the particle size increases, aggregation between particles sometimes proceeds. To prevent this, when organosilane diluted in an organic solvent is added as soon as possible after sol synthesis is completed, silane treatment can proceed effectively without aggregation.

As the silica precursor, tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS) is mainly used, but various tetraalkoxy silanes can be used. As the alcohol, methanol, ethanol, IPA, n-propanol, etc. may be used, but is not limited thereto.

In synthesizing the above silica sol, it is preferable that the content ratio of alcohol to 1M of the silica precursor is 2 to 10M. If it is less than 2M, the precursor and the number of catalysts are not uniformly dissolved, so the reaction proceeds in a heterogeneous system. The reaction rate is slow and the solid content is too low, so there is little commercial significance.

The organosilane used for surface modification of the silica sol may be a compound represented by Formula 1 below.

[Formula 1]

(R ¹ ) _n Si(OR ² ) _m

In the above formula,

n is an integer from 0 to 3;

m is an integer from 1 to 4;

The silica sol is surface-modified with an organosilane containing 10 to 95 wt% of one or more types of non-reactive silane, 5 to 90 wt% of a reactive silane, and 0 to 15 wt% of a chain silane modified with urethane, thereby improving dispersion stability and molding in the acrylic resin. It can contribute to improving the flexibility of the material.

In the organic silane R ¹ _{0 to 3} Si(OR ² ) _{1 to 4} , R ¹ is a non-reactive group, and is an alkyl group (methyl-methyltrimethoxysilane, ethyl, propyl-propyltrimethoxysilane, isobutyl-isobutyltrimethoxysilane, fluorine alkyl group) or a phenyl group-phenyltrimethoxysilane, And silane materials having an acrylic group, a methacrylic group, an allyl group, a vinyl group, an amino group, an epoxy group, a thiol group, and an NCO group as reactive groups. At least one silane having a reactive group is selected and non-reactive silanes are also used in combination. R ² is at least one selected from methyl, ethyl, iso-propyl, n-propyl, or n-butyl, but is not limited thereto. Table 1 below shows examples of organosilanes according to the present invention.

In this patent, it is difficult to secure excellent flexibility and toughness in prescription materials of silica sol treated with commercially available low molecular weight silane, so silane, a long chain molecule, is synthesized and used. One side is reacted with a silane having a reactive group and the other side is reacted with a compound having an acrylic reactive group to synthesize a chain-type modified silane, and the chain-type silane is grafted onto the surface of the silica sol to secure the flexibility of the material. did

An example of the chemical structure of the synthesized chain-like silane is shown in Formula 2 below, but it is not limited to this structure, and various combinations of materials are possible and some of the simplest synthesized materials are presented as shown in Table 2 below.

[Formula 2]

(RO) ₃ Si(CH ₂ ) ₃ X ⁺ NCO ^- Y ^- NCO ⁺ HO(CH ₂ ) ₂ OOCCH=CH ₂

In the above formula,

RO is methoxy or ethoxy;

X is SH or NH ₂ ;

Y is a di-NCO compound.

In one embodiment of the present invention, Y in Formula 2 is a di-NCO compound, and materials shown in Table 2 may be used as the di-NCO compound.

The amount of silane used in the silica sol treatment is preferably 5 to 50% of the weight of the solid content of the silica sol. If it is less than 5%, the silica sol surface is not sufficiently treated and aggregation proceeds, making it unstable. If it is more than 50%, the surface is treated Since the remaining silane reacts independently to create a new by-product, a problem of not forming a flat film occurs.

(b) Preparation of Silica Sol Hybrid Dispersion

Solvent-free hybrid by adding the surface-modified silica sol to 1-4 functional group monomers with excellent dispersion characteristics among low-viscosity acrylic monomers and removing solvents such as water and alcohol used in the synthesis of the sol through concentration under reduced pressure. Dispersions can be prepared. At this time, since the viscosity and storage stability of the hybrid dispersion differ depending on the degree of aggregation of the silica sol, the type of treated silane, the surface modification effect, and the type of acrylic resin, countermeasures are required.

The acrylic monomer may use the materials shown in Table 3 (organic-inorganic hybrid liquid prescription material composition summary) below, but is not limited thereto.

(c) Preparation of organic-inorganic hybrid imprinting coating composition

Bifunctional oligomer acrylate, 6, 9, 10 functional oligomer acrylate, curing agent, leveling agent, etc. are added to the hybrid dispersion to prepare a solvent-free organic-inorganic hybrid imprinting coating composition considering material properties and imprinting molding characteristics. can

The bifunctional oligomer acrylate has excellent transparency (yellowing durability) and flexibility, and can be cured in a short time by UV light irradiation, and silicone acrylate may be used in consideration of abrasion resistance and releasability, but is not limited thereto. no.

The composition according to the present invention is characterized in that it has a viscosity of 100 to 3,000 cps even when formulated with a plurality of oligomer acrylates, silicone acrylates, and fluorine acrylates.

The 6,9,10 functional oligomer acrylate is used to impart hardness and flexibility at the same time, and can be synthesized in various ways with glycol and Di-NCO materials, and usually has a high viscosity because the molecular weight is 1,000 or more, so it is a solvent-free type. The usage is limited in the prescription of They have low volume reduction and excellent adhesive strength during crosslinking, so when heated after photocrosslinking to a thermal state of 120 to 180 ° C, the curing process is further progressed to realize improved heat resistance and mechanical properties.

Reactive groups of silica sol surface-treated silane also cause crosslinking reactions with monomers, which contribute to the improvement of thermal/mechanical properties as they are chemical reactions between organic and inorganic materials.

A peroxide-based curing agent is mainly used as an additive for the crosslinking reaction, and various materials are commercialized, and 0.5 to 3 wt% of the total solid content may be used, but is not limited thereto.

In addition, a leveling agent can be used as the additive, and the leveling agent is a silicon-modified acrylate, and various BYK-based materials have been developed. It can be, but is not limited thereto.

One embodiment of the present invention relates to a process for forming a nano-patterned imprinting molding structure using the organic-inorganic hybrid imprinting coating composition,

As a method for forming a nanostructure using an imprinting coating composition,

coating the coating composition on a base material to be formed with nanopatterns;

inducing flattening by applying heat/vibration to the coating composition to improve fluidity;

inducing the coating composition to form a structure by contacting the imprinting mold; and

It is characterized by including; UV-curing the composition in a state of contact with the imprinting mold and demolding it from the imprinting mold.

Specifically, the imprinting coating composition is coated on a base material and heat is applied to improve fluidity to induce flattening, and after making a pattern shape through mold contact so that molding by an imprinting mold is possible, UV is irradiated to After rapid photocuring, the imprinting structure may be molded through a process of demolding.

The base material may use a film, plastic sheet, glass, metal, etc., but is not limited thereto.

In this way, the imprinting pattern of the nanoconcave-convex structure has a solid structure form by the photocuring reaction, but as the reaction proceeds rapidly, it is difficult for the internal molecular chains to be in a thermally stable alignment state, making it easy to become a solid material with high internal stress. When the solid material molded by this imprinting method is gradually heated to 130~180℃, the internal stress is relieved and additional thermal curing is accompanied to stabilize the thermal and mechanical properties of the material, resulting in an imprinted material having flexibility at the same time. . In order for the imprinted nanostructure to be demolded from the mold, the surface tension of the molding must be low. It is possible to secure demolding moldability by adding acrylic resin modified with silicon or fluorine. Not only is it easy to mold, but it can also have excellent fingerprint resistance and water repellency.

The nanoimprint technology using the organic-inorganic hybrid material according to the present invention can be divided into a process of forming a nanostructure through UV irradiation and a thermal curing process of securing mechanical properties through an additional curing reaction by heat.

Prescribing oligomers/polymers helps to improve flexibility and toughness (stiffness), but the amount of addition is extremely limited because the viscosity increases significantly.

Wet imprinting molding proceeds in the process of forming a pattern with a mold while coating a liquid material made of photocurable acrylic resin on one side of a film/transparent plastic sheet/foil, etc., and releasing it after photocrosslinking. In order to rapidly form a nanoscale mold for imprinting, the viscosity of the liquid material must be low (less than 1000 cps), but when diluted with a solvent, the burden on the drying process (drying energy, clean environment, process speed reduction, bubble generation, etc.) arises. Therefore, the coating composition is formulated with low-viscosity central monomers. When imprinting molding is performed with these materials, curing shrinkage is severe, making it difficult to form an elaborate nano-patterned structure, and curl may occur, so that the impact durability of the nanostructure may be weakened.

Therefore, the present invention synthesizes a nano-grade silica sol with a high mechanical reinforcing effect and an insignificant increase in viscosity, and surface-modifies it with an acrylic reactor, an organic group with low surface tension, and a chain-type urethane-modified silane to form an acrylic resin capable of photocrosslinking. It is intended to develop an imprinting moldable nanohybrid liquid material capable of rapid photocuring by UV irradiation while having a relatively low viscosity that enables imprinting molding even when a high content of silica sol is prescribed in the manufacture of nanohybrid liquid material.

In this way, in order to satisfy the roll-to-roll continuous imprinting molding process of the organic-inorganic hybrid liquid coating having a certain viscosity (200 cps) with a high content of silica sol prescribed even in a solvent-free state, the coating method, heat treatment conditions, UV light source intensity, and light Imprinting molding process conditions that enable continuous molding were established by securing UV imprint and heat treatment process conditions in which demolding effectively proceeds under conditions such as irradiation time (line speed and light irradiation length).

Hereinafter, the present invention will be described in more detail by examples. These examples are only for explaining the present invention, it is apparent to those skilled in the art that the scope of the present invention is not limited to these examples.

Example 1: Preparation of silanized silica sol

350 g of TEOS, 1000 g of ethanol (EtOH), 8 g of 9.8 wt% aqueous ammonia, and 400 g of distilled water were added and stirred at 50 ° C for 20 hours to obtain a transparent 15-20 nm colloidal silica sol.

MTMS, IBTMS, and AcTMS were used as silane surface treatment agents to secure the stability of the colloidal silica sol obtained above. After adding 8 to 12 g of the mixture at room temperature for 20 hours, a colloidal silica sol whose surface was modified with several kinds of silanes was prepared. Among the silanes used at this time, AcTMS is a silane having an acrylic reactive group capable of crosslinking with an acrylic resin, and silica sol was prepared by prescribing 20 to 40 wt% of the total silane.

Acrylic resins were added to the surface-modified silica sol solution, and ethanol/methanol/water was removed under reduced pressure to obtain a silica sol solution dispersed in 20-30% of the acrylic resin.

Comparative Example 1: Preparation of Organic Resin Imprinting Coating Composition

Similar to the prescription of photocurable high-hardness acrylic resins without the prescription of silica sol, 2, 3, and 4 functional group acrylic resins, types of oligomers, and additives were prescribed in the composition shown in Table 4 below. They were coated on a PET film substrate with a thickness of 8 μm to evaluate various material properties.

Classification of Prescription Ingredients Composition ratio (wt%) Prescription details acrylic monomers 65 1)HDDA/TEGDA(10/15) : 25
2)TMPTA/PETA(15/15) : 30
3)PE044 : 10 Silanized Silica Sol - - oligomeric acrylate 30 1) PED400DA : 10
2) PETA+HDI+PETA : 15
3)PU6510 : 5 Other Additives 5 1) Photocuring agent (Igacure 186): 3
2) Leveling agent (TEGO CP7602): 2

Example 2: Preparation of hybrid imprinting coating composition

The silane-treated silica sol (20wt%) synthesized in Example 1 was formulated with 2-, 3-, and 4-functional acrylic resins, types of oligomers, and additives in the composition shown in Table 5 below. They were coated on a PET film substrate with a thickness of 8 μm to evaluate various material properties.

Classification of Prescription Ingredients Composition ratio (wt%) Prescription details acrylic monomers 54 1) HEA : 8
2)HDDA/TEGDA(6/8) : 14
3)TMPTA/PETA(11/11) : 22
4)PE044: 10 Silanized Silica Sol 20 1) Colloidal Silica 13
2)MTMS 8+IBTMS 2+AcTMS 4
(Silanes react and shrink to 50%) oligomeric acrylate 21 1)PED400DA : 6
2) PETA+HDI+PETA : 11
3)PU6510 : 4 Other Additives 5 1) Photocuring agent (Igacure 186): 3
2) Leveling agent (TEGO CP7602): 2

Example 3: Preparation of Imprinting Coating Composition

The silane-treated silica sol (25wt%) synthesized in Example 1 was formulated with 2-, 3-, and 4-functional acrylic resins, types of oligomers, and additives in the composition shown in Table 6 below. They were coated on a PET film substrate with a thickness of 8 μm to evaluate various material properties.

Classification of Prescription Ingredients Composition ratio (wt%) Prescription details acrylic monomers 50 1) HEA : 8
2)HDDA/TEGDA(4/6) : 10
3)TMPTA/PETA(11/11) : 22
4)PE044: 10 Silanized Silica Sol 25 1) Colloidal Silica 18
2)MTMS 8+IBTMS 2+AcTMS 4
(Silanes react and shrink to 50%) oligomeric acrylate 20 1) PED400DA : 5
2) PETA+IPDI+PETA : 10
3)PU6510 : 5 Other Additives 5 1) Photocuring agent (Igacure 186): 3
2) Leveling agent (TEGO CP7602): 2

Example 4: Preparation of Imprinting Coating Composition

The silane-treated silica sol (30wt%) synthesized in Example 1 was formulated with 2, 3, and 4 functional group acrylic resins, silicon-modified acrylate oligomer, and additives in the composition shown in Table 7 below. They were coated on a PET film substrate with a thickness of 8 μm to evaluate various material properties.

Classification of Prescription Ingredients Composition ratio (wt%) Prescription details acrylic monomers 48 1) HEA : 9
2)HDDA/TEGDA(5/6) : 11
2)TMPTA/PETA(9/9) : 18
3)PE044 : 10 Silanized Silica Sol 30 1) Colloidal Silica 23
2)MTMS 8+IBTMS 2+AcTMS 4
(Silanes react and shrink to 50%) oligomeric acrylate 17 1) PED400DA : 5
2) PETA+IPDI+PETA : 10
3) Silicone modified acrylate: 2 Other Additives 5 1) Photocuring agent (Igacure 186): 2
2) Leveling agent (TEGO CP7602): 2
3) Antioxidant ( Tinuvin ) : 1

Example 5: Preparation of Imprinting Coating Composition

The silane-treated silica sol (30 wt%) synthesized in Example 1 was formulated with 2, 3, and 4 functional group acrylic resins, silicon-modified acrylate/fluorine compound acrylate oligomers, and additives in the composition shown in Table 8 below. They were coated on a PET film substrate with a thickness of 8 μm to evaluate various material properties.

Classification of Prescription Ingredients Composition ratio (wt%) Prescription details acrylic monomers 50 1) HEA : 10
2)HDDA/TEGDA(10/15) : 15
2)TMPTA/PETA(15/15) : 15
3)PE044 : 10 Silanized Silica Sol 30 1) Colloidal Silica 23
2)MTMS 8+IBTMS 2+AcTMS 4
(Silanes react and shrink to 50%) oligomeric acrylate 15 1) PED400DA : 5
2) PETA+IPDI+PETA : 7
3) Silicone modified acrylate: 2
4) Fluorine compound acrylate: 1 Other Additives 5 1) Photocuring agent (Igacure 186): 2
2) Leveling agent (TEGO CP7602): 2
3) Antioxidant ( Tinuvin ) : 1

For the coating compositions for imprinting molding prepared in the above examples, physical properties such as pencil hardness, contact angle, bendability, imprintability, discoloration, and light transmittance were measured in the following manner.

Experimental Example 1: Evaluation of physical properties

Nanostructures having a size of hundreds of nanometers were molded using the coating compositions of Examples 2 to 5 and Comparative Example 1, and it was confirmed that moldability and releasability were easy (see FIG. 4). In the case of molding the nanostructure using the coating composition prepared according to the example, when heat treatment was performed at 110 ° C. compared to the case where only UV curing was performed, it was confirmed that the hardness of the surface decreased rapidly and the scratch resistance of the surface decreased. could (see FIG. 5).

For bendability, the curvature radius at which cracks occur was measured by coating 10um of the imprinting coating material on a 250um PMMA film. For comparison, commercially available high-hardness resin products were compared. In the case of general high-hardness resins, cracks occurred at the initial stage of bending, but when the proposed coating composition was cured, it was confirmed that no cracks occurred even at a radius of about 3 mm (see FIG. 6). .

Table 9 below shows the results of evaluating the physical properties of the nanopatterned molded structure.

Comparative Example 1 Example 2 Example 3 Example 4 Example 5 prescription key points

Core Specifications high hardness acrylic
(2,3,4,6 functional groups) High hardness acrylic aliphatic urethane silica sol 20% High hardness acrylic alicyclic urethane silica sol 25% High hardness acrylic silicone urethane silica sol 30% High hardness acrylic silicone urethane
Fluorine Silane Coated Silica Sol 30% Pencil Hardness (H) 3 3.5 4 4.7 4.5 contact angle 98 105 110 130 140 bendability
(radius of curvature, mm) 3 1.5 1.2 1.0 0.8 imprinting dysplasia error commonly Good Good Good discoloration pale yellow pale yellow Transparency Transparency Transparency Light transmittance (%) 90 91 94 95 96

Having described specific parts of the present invention in detail above, it is clear that these specific techniques are only preferred embodiments for those skilled in the art to which the present invention belongs, and the scope of the present invention is not limited thereto. do. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above information.

Accordingly, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims (14)

photocurable acrylic resin;
a surface-modified silica sol dispersed in the acrylic resin; and
Including; one or more oligomers or additives;
A solvent-free organic-inorganic hybrid imprinting coating composition, characterized in that it exhibits imprinting moldability and flexibility and hardness characteristics after molding. The method of claim 1, wherein the coating composition is composed of a solvent-free type by removing the solvent contained in the surface-modified silica sol through concentration under reduced pressure after adding the acrylic monomers, characterized in that the non-solvent type organic-inorganic hybrid imprinting coating composition. The method of claim 1, wherein the silica sol is surface-modified with organosilane containing 10 to 95 wt% of one or more non-reactive silanes, 5 to 90 wt% of reactive silanes, and 0 to 15 wt% of chain silane modified with urethane to obtain the acrylic A non-solvent type organic-inorganic hybrid imprinting coating composition, characterized in that it contributes to improving the dispersion stability in the resin and the flexibility of the molding material. The solvent-free organic-inorganic hybrid imprinting coating composition according to claim 1, wherein the coating composition is formulated with a plurality of oligomer acrylates, silicone acrylates and fluorine acrylates and has a viscosity of 100 to 3,000 cps. The solvent-free organic-inorganic hybrid imprinting coating composition according to claim 1, wherein the coating composition satisfies imprinting molding processability by further including a curing agent, an antioxidant or a leveling agent. The method of claim 1, wherein the coating composition is coated on the surface of the base material and then nanostructures are formed through an imprinting process to satisfy hardness / abrasion resistance, flexibility or anti-fingerprint (super water repellency) properties and photofunctional properties, characterized in that, Solvent-free organic-inorganic hybrid imprinting coating composition. The method of claim 1, wherein the coating composition comprises 40 to 70 wt% of a photocurable acrylic resin, 5 to 50 wt% of a surface-modified silica sol, 15 to 40 wt% of one or more oligomers, and 0.5 to 5 additives, based on 100 wt% of the total solid content. A non-solvent type organic-inorganic hybrid imprinting coating composition comprising wt%. One side of Di-NCO, which becomes urethane, is reacted with silane having a reactive group, and the other side is reacted with a compound having an acrylic reactive group to synthesize chain-type modified silane,
A non-solvent type organic-inorganic hybrid imprinting coating composition, characterized in that the flexibility of the material is improved by grafting the chain-type modified silane to the surface of the silica sol. The coating composition according to claim 8, wherein the coating composition is prepared by mixing a plurality of acrylic monomers, reactive/non-reactive silane surface treatment, silica sol in which chain-type silane is grafted and dispersed, a plurality of silicon/fluorine-modified oligomer acrylates, and additives. A non-solvent type organic-inorganic hybrid imprinting coating composition characterized by having storage stability. synthesizing a surface-modified silica sol;
Preparing a hybrid dispersion by removing the solvent by adding an acrylic monomer; and
A method for preparing a solvent-free, low-viscosity organic-inorganic hybrid imprinting coating composition comprising the step of preparing an organic-inorganic hybrid imprinting coating composition by adding a photocurable resin and an additive to the hybrid dispersion. A nano-patterned imprinting molded structure manufactured using the coating composition according to any one of claims 1 to 9. The nano-patterned imprinting molding structure according to claim 11, characterized in that the molding structure has processability such as continuous wet coating, imprinting molding, rapid light curing or demolding of the molding. As a method for forming a nanostructure using an imprinting coating composition,
Coating the coating composition according to any one of claims 1 to 9 on a base material to be nanopatterned;
inducing flattening by applying heat/vibration to the coating composition to improve fluidity;
inducing the coating composition to form a structure by contacting the imprinting mold; and
UV-curing the composition in contact with the imprinting mold and demolding it from the imprinting mold; characterized in that it comprises a nano-patterned imprinting molding structure molding process using a solvent-free organic-inorganic hybrid imprinting coating composition . [Claim 14] The process of claim 13, wherein the base material is a film, plastic sheet, glass or metal.

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