KR20220043001A - Low refractive thermosetting composition, optical material and display device formed therefrom - Google Patents

Abstract

The present invention relates to a thermosetting composition, an optical member formed therefrom, and a display device. The thermosetting composition comprises a thermosetting resin, air-containing particles, and a monomer or an oligomer having two or more thermosetting functional groups and has optical effects such as a low refractive of 1.40 or less, high light transmittance, and low haze for the light of a wavelength of 450 nm.

Description

Low refractive index thermosetting composition, optical member and display device formed therefrom

The present invention relates to a thermosetting composition having a low refractive index, an optical member and a display device formed therefrom.

Technology to improve light efficiency in organic light-emitting diode (OLED), QD-OLED (Quantum dot - Organic Light-Emitting Diode), QNED (quantum nano-emitting diode), Micro-LED and image sensor The needs are continuously increasing. The technology for improving the light efficiency is an essential technology for reducing the reflectance of the display, improving the lifespan of the OLED, and increasing the battery efficiency, and R&D has been actively conducted in recent years.

In order to improve the light efficiency, a technique for lowering the refractive index of light at the boundary of the medium is required, and the lower limit of the refractive index range that can be adjusted using an organic compound as a medium is theoretically known to be about 1.40 sec. is insufficient to improve it. Therefore, in order to realize an optical member having a refractive index of 1.40 or less at the boundary of a medium, a hybrid technology including hollow silica in addition to an organic compound is required.

However, when the hollow silica is mixed, the refractive index is lowered, but there are issues such as transmittance, haze lowering, and upper and lower film adhesion due to compatibility problems with organic compounds, and there are many technical limitations.

Due to all the problems of the prior art, while exhibiting low refractive properties, the decrease in transmittance and increase in haze are suppressed, and the development of a technology that enables the formation of an optical film exhibiting excellent adhesion and heat resistance continues. is being requested

It is an object of the present invention to provide a thermosetting composition having a low refractive index of light, excellent light transmittance, and excellent adhesion and heat resistance while suppressing haze increase.

Another object of the present invention is to provide an optical member including a cured film including the thermosetting composition.

Another object of the present invention is to provide a display device including the optical member.

In order to achieve the above object, the thermosetting composition according to an embodiment of the present invention is a thermosetting resin; air-containing particles; and a monomer or oligomer having two or more thermosetting functional groups.

In order to achieve the above object, an optical member according to another embodiment of the present invention includes a cured film including a substrate and the thermosetting composition.

In order to achieve the above object, a display device according to another embodiment of the present invention includes the optical member.

When the thermosetting composition of the present invention is cured to form a cured film, it has a low refractive index of 1.40 or less with respect to light having a wavelength of 450 nm, has excellent light transmittance, and has optical properties of low haze, while having excellent adhesion and curing on the surface of the cured film There is an effect of having excellent heat resistance of the film itself.

The display device according to an embodiment of the present invention includes an optical member using the thermosetting composition, and has an excellent effect in improving light efficiency.

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Accordingly, the configurations shown in the embodiments and manufacturing examples described in this specification are only the most preferred embodiment of the present invention, and do not represent all of the technical spirit of the present invention, so they cannot be replaced at the time of the present application. It should be understood that there may be various equivalents and variations that exist.

The thermosetting composition according to an embodiment of the present invention includes a thermosetting resin, air-containing particles, and a monomer or oligomer having a thermosetting functional group, wherein the monomer or oligomer has two or more thermosetting functional groups.

The monomer or oligomer having two or more thermosetting functional groups improves the degree of thermosetting between the resin and the air-containing particles, thereby providing an effect of further improving the thermosetting properties of the composition.

The thermosetting resin may be a resin containing at least one or more of an epoxy group, an oxetane group, or a hydroxyl group (OH) for thermosetting, for example, a thermosetting resin containing an epoxy group.

The thermosetting resin may specifically have a weight average molecular weight of 1,000 to 200,000. If the weight average molecular weight of the thermosetting resin is less than 1,000, problems may occur in upper and lower adhesive strength of the low-refractive thermosetting layer, inkjet processability, and slit coating properties. may occur.

The air-containing particles have an internal space (void) cut off from the outside inside the solid particle, and the internal space refers to particles filled with air. And the particle diameter of the air-containing particles means the length of the diameter based on the outer surface of the air-containing particles.

The air-containing particles serve to significantly lower the refractive index of the composition due to the internal space (voids). However, since the air-containing particles have poor compatibility with organic compounds, an appropriate content range is important. Accordingly, the thermosetting composition according to an embodiment of the present invention may include the air-containing particles in an amount of 30 to 80% by weight based on the total weight, thereby implementing a thermosetting composition having a refractive index of 1.40 or less with respect to light having a wavelength of 450 nm. When the air-containing particles are included in less than 30% by weight based on the total weight of the composition, it may be difficult to implement a refractive index of 1.40 or less, and when it is included in more than 80% by weight, compatibility with other organic compounds in the composition This may cause a problem in that the transmittance and haze are lowered, and the adhesive strength is lowered after curing.

More specifically, when the air-containing particles are included in an amount of 50 to 80% by weight based on the total weight of the thermosetting composition, a thermosetting composition having a lower refractive index of 1.25 or less with respect to light having a wavelength of 450 nm can be implemented.

The air-containing particles may be hollow organic or inorganic particles, for example, porogen or hollow silica, and hollow silica may be used as an embodiment of the present invention.

The air-containing particles can improve the dispersibility of the particles by preventing aggregation of the particles through the surface treatment process. When the air-containing particles are agglomerated, compatibility with other organic compounds in the composition may decrease, so that transmittance and haze may be lowered, and there may be problems in that adhesive strength after curing is lowered.

The air-containing particles may be specifically surface-treated with one or more functional groups selected from the group consisting of an alkyl group, an acryl group, a methacrylic group, an epoxy group, and a vinyl group.

In the process of surface treatment of the air-containing particles, if the surface treatment thickness is less than 3 nm, the surface treatment effect is lowered, and aggregation between the air-containing particles may occur and a problem of increased haze may occur. Conversely, if the surface treatment thickness is less than 50 nm If it is thick, there may be a problem in that the refractive index of the composition is deteriorated. Therefore, the air-containing particles are preferably surface-treated to a thickness of 3 to 50 nm, and may be surface-treated to a thickness of 3 to 30 nm to realize a lower refractive index.

The D50 particle diameter of the air-containing particles is preferably 30 to 150 nm, specifically, 30 to 150 nm based on the D50 particle diameter measured by the DLS Litesizer 500 (Anton Paar). If the D50 particle size is less than 30 nm, a problem of a decrease in refractive index may occur, and if it exceeds 150 nm, a problem of a decrease in transmittance and haze may occur due to a decrease in the dispersion margin, and a lack of crosslinking with the resin may cause upper and lower There may be a problem in that adhesion to the film is lowered.

When air-containing particles are included in the composition, since it is insufficient to secure the degree of curing of the composition with only the thermosetting resin, the degree of curing can be improved by additionally applying a monomer and/or oligomer containing a thermosetting functional group, and furthermore, the upper and lower layers of the low refractive index layer It is possible to improve adhesion with the The monomer or oligomer having the thermosetting functional group may specifically include an alicyclic epoxy structure with excellent reactivity to ensure thermosetting.

As a specific example, the monomer or oligomer having the thermosetting functional group may have one of the chemical structures represented by the following Chemical Formulas 1 to 24.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

In Formulas 4 and 6, R each independently represents a hydrocarbon group having 1 to 10 carbon atoms, R in Formula 6 is one of an alkyl, alkenyl and alkoxy group, and Formulas 2 to 4, 11 to 13 and 20 In to 21, l, m, n and o are each independently an integer from 1 to 30.

In this case, in place of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol used as a precursor of Formula 19, the following Formulas 25 to 32 A compound having a chemical structure selected from may be used.

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

In order to form a cured film having excellent upper and lower adhesive strength and to realize excellent optical properties of the thermosetting composition, the specific composition ratio is 1 to 69 wt% of the thermosetting resin, 30 to 80 wt% of the air-containing particles, and a monomer having a thermosetting functional group Or it is preferred that the oligomer is included in an amount of 1 to 60% by weight.

Formation of a cured film having excellent upper and lower adhesive strength and excellent optical properties of the thermosetting composition are related to the total weight ratio of the thermosetting resin and the monomer or oligomer having a thermosetting functional group, and the total weight of the thermosetting resin and the monomer or oligomer having a thermosetting functional group is Specifically, it may be included in an amount of 20 to 70% by weight based on the total composition.

The thermosetting composition may further include one or more additives selected from the group consisting of a silane coupling agent, an adhesive having an alkoxy group as a cross-linking site, and a surfactant to further improve the adhesion to the upper and lower portions of the low-refractive layer. there is.

Specifically, the silane coupling agent may be included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the thermosetting resin, and when it is less than 0.1 parts by weight, a problem of lowering the adhesive strength margin may occur, and when it exceeds 30 parts by weight, storage stability is a problem. may occur.

The silane coupling agent is, for example, (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3- Glycideoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3-trie oxysily-N-(1,3 dimethyl-butylidene)propylamine, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane; at least one selected from the group consisting of N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and (3-isocyanatepropyl)triethoxysilane; It may be included, but is not limited to the above examples and may be used.

In addition, the adhesive having the alkoxy group as the crosslinking site may be specifically included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the thermosetting resin. If it exceeds parts by weight, a problem may occur in storage stability.

And the surfactant may be specifically included in an amount of 0.0001 to 5 parts by weight based on 100 parts by weight of the thermosetting resin, if it is less than 0.0001 parts by weight, a problem in coating properties may occur, and if it exceeds 5 parts by weight, coating bubbles may occur. can occur

The thermosetting composition may further include at least one dispersant selected from the group consisting of an acrylic dispersant, an epoxy dispersant, and a silicone dispersant to improve dispersibility.

In addition, the thermosetting composition may further include at least one crosslinking accelerator selected from the group consisting of a thermal acid generator and a thermal base generator to accelerate curing.

The thermosetting composition may include a solvent, but may be a solvent-free type that does not include a solvent. When a solvent is included, it serves to improve the compatibility or coatability of the thermosetting resin and the air-containing particles. At this time, in order to facilitate the coating of the thermosetting composition, the solvent is diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether pro. Cypionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, diphoropylene glycol di Ethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene glycol Dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tertiary butyl ether, tetraethylene glycol dimethyl ether, diethylene glycol ethylhexyl ether, diethylene glycol methylhexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl At least one solvent selected from the group consisting of ether and dipropylene glycol methylhexyl ether may be included.

By controlling the content of the solvent, the viscosity of the thermosetting composition may be adjusted, and in order to realize both fairness and excellent optical properties, the viscosity may be specifically 3 to 30 cP.

The optical member according to an embodiment of the present invention includes a substrate and a cured film, and the cured film is cured including the thermosetting composition according to the embodiment of the present invention.

The optical member may implement excellent optical properties having a refractive index of 1.40 or less and a haze of 3% or less based on light having a wavelength of 450 nm.

The optical member may be, for example, a light extraction layer or a refractive index adjusting layer, but is not limited thereto.

The display device according to an embodiment of the present invention includes the optical member, and may be, for example, an OLED, QLED, or microLED display device having excellent luminance, but is not limited thereto.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the examples and examples described herein.

[Preparation Example 1: Synthesis of thermosetting resin]

As an embodiment of the thermosetting resin of the thermosetting composition according to an aspect of the present invention, a resin including an epoxy group, an oxetane group, a hydroxyl group, and the like was used. Synthesis examples of the thermosetting resin included in the thermosetting composition are shown in Synthesis Examples 1 to 10 below, and the synthesis of the thermosetting resin for comparing the effect difference with the Synthesis Examples is shown in Reference Synthesis Examples 1 to 3 below.

[Synthesis Example 1]

In a flask equipped with a cooling tube and a stirrer, 500 parts by weight of tetrahydroxyfuran and 100 parts by weight of glycidyl methacrylate based on 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) were put , and then gently stirred after nitrogen substitution. The reaction solution was heated to 60° C. to prepare a polymer solution including an acrylic copolymer while maintaining this temperature for 24 hours.

100 parts by weight of the polymer solution containing the acrylic copolymer was precipitated with respect to 1,000 parts by weight of n-hexane. Then, after removing the waste liquid through a filtering process using a mesh, vacuum drying at 30 ° C. or less

A thermosetting resin including an epoxy group having a weight average molecular weight of 10,000 was prepared.

At this time, the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with the e2695 Alliance Separation Module of Waters.

The weight average molecular weight is a polystyrene reduced average molecular weight measured using GPC.

[Synthesis Example 2]

In Synthesis Example 1, in the same manner as in Synthesis Example 1, except that 80 parts by weight of meta glycidyl methacrylate and 20 parts by weight of styrene were used instead of 100 parts by weight of glycidyl methacrylate, including an epoxy group A thermosetting resin was prepared.

The weight average molecular weight of the thermosetting resin including an epoxy group synthesized according to Synthesis Example 2 was 8,000.

In this case, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Separation Module. did

[Synthesis Example 3]

In Synthesis Example 1, 60 parts by weight of 3-ethyl 3-oxatanyl methyl methacrylate and 40 parts by weight of ethoxy ethoxy ethyl acrylate were used instead of 100 parts by weight of glycidyl methacrylate. A thermosetting resin including an oxetane group was prepared in the same manner as in Synthesis Example 1.

The weight average molecular weight of the thermosetting resin including an oxetane group synthesized according to Synthesis Example 3 was 5,000.

In this case, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Separation Module. did

[Synthesis Example 4]

In Synthesis Example 1, 1.1 parts by weight was used instead of 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) as an initiator, and the reaction solution was heated to 60° C. and this temperature for 20 hours. A thermosetting resin including an epoxy group was prepared in the same manner as in Synthesis Example 1 except for maintaining the .

The weight average molecular weight of the thermosetting resin including an epoxy group synthesized according to Synthesis Example 4 was 200,000.

In this case, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Separation Module. did

[Synthesis Example 5]

In Synthesis Example 1, in place of 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) as an initiator, 29 parts by weight was used, and the reaction solution was heated to 60° C. for 6 hours at this temperature. A thermosetting resin including an epoxy group was prepared in the same manner as in Synthesis Example 1 except for maintaining the .

The weight average molecular weight of the thermosetting resin including an epoxy group synthesized according to Synthesis Example 5 was 1,000.

At this time, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Separation Module. did.

[Synthesis Example 6]

In Synthesis Example 1, 60 parts by weight of 2-hydroxyethyl acrylate and 40 parts by weight of perfluorooctylethyl acrylate were used instead of 100 parts by weight of glycidyl methacrylate, and 2,2'-azo was used as an initiator. The same method as in Synthesis Example 1, except that 5 parts by weight was used instead of 10 parts by weight of bis(2,4-dimethylvaleronitrile), and the reaction solution was heated to 60° C. and maintained at this temperature for 24 hours. to prepare a thermosetting resin containing a hydroxyl group.

The weight average molecular weight of the hydroxyl group-containing thermosetting resin synthesized according to Synthesis Example 6 was 52,000.

In this case, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Separation Module. did

[Synthesis Example 7]

In Synthesis Example 1, 60 parts by weight of 3,4-epoxy cyclohexyl methyl methacrylate and 40 parts by weight of lauryl methacrylate were used instead of 100 parts by weight of glycidyl methacrylate, and 2,2' as an initiator -Azobis(2,4-dimethylvaleronitrile) was replaced with 10 parts by weight, 3 parts by weight was used, and the reaction solution was heated to 60° C. and this temperature was maintained for 24 hours, except that the same as in Synthesis Example 1 A thermosetting resin including an epoxy group was prepared in the same manner.

The weight average molecular weight of the thermosetting resin including an epoxy group synthesized according to Synthesis Example 7 was 106,000.

In this case, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Separation Module. did

[Synthesis Example 8]

In a flask equipped with a cooling tube and a stirrer, 80 parts by weight of 3-glycidoxypropyl trimethoxysilane and 20 parts by weight of tetraethoxysilane were added as reactive silanes, and after nitrogen substitution, the mixture was gently stirred. In addition, 50 parts by weight of ultrapure water and 4 parts by weight of oxalic acid as a catalyst were added to the reaction solution, and then gently stirred again. After 1 hour, the reaction solution was heated to 60° C., maintained at this temperature for 10 hours for polymerization, and then cooled to room temperature to terminate the reaction. A thermosetting resin containing an epoxy group and a hydroxyl group having a weight average molecular weight of 3,000 was prepared by vacuum drying at 30° C. or less to remove the water and alcohol components generated during the reaction.

In this case, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Separation Module. did

[Synthesis Example 9]

In Synthesis Example 8, in place of 80 parts by weight of 3-glycidoxypropyl trimethoxysilane and 20 parts by weight of tetraethoxysilane, 40 parts by weight of 3-glycidoxypropyl trimethoxysilane, 60 parts by weight of tetraethoxysilane A thermosetting resin including an epoxy group and a hydroxyl group was prepared in the same manner as in Synthesis Example 1, except that the part was used.

The weight average molecular weight of the thermosetting resin including an epoxy group and a hydroxyl group synthesized according to Synthesis Example 9 was 15,000.

In this case, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Separation Module. did

[Synthesis Example 10]

In Synthesis Example 8, in place of 80 parts by weight of 3-glycidoxypropyl trimethoxysilane and 20 parts by weight of tetraethoxysilane, 20 parts by weight of 2-(3,4 epoxycyclohexyl)ethyl trimethoxysilane, A thermosetting resin including an epoxy group and a hydroxyl group was prepared in the same manner as in Synthesis Example 1, except that 80 parts by weight of tetramethoxysilane was used.

The weight average molecular weight of the thermosetting resin including an epoxy group and a hydroxyl group synthesized according to Synthesis Example 10 was 46,000.

In this case, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Separation Module. did

[Reference Synthesis Example 1]

In Synthesis Example 1, 30 parts by weight was used instead of 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) as the initiator, and the reaction solution was heated to 60° C. and this temperature for 6 hours. A thermosetting resin including an epoxy group was prepared in the same manner as in Synthesis Example 1 except for maintaining the .

The weight average molecular weight of the thermosetting resin including an epoxy group synthesized according to Reference Synthesis Example 1 was 900.

In this case, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using a standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Seperation Module. did

[Reference Synthesis Example 2]

In Synthesis Example 1, 1 part by weight was used instead of 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) as the initiator, and the reaction solution was heated to 60° C. and this temperature for 24 hours. A thermosetting resin including an epoxy group was prepared in the same manner as in Synthesis Example 1 except for maintaining the .

The weight average molecular weight of the thermosetting resin including an epoxy group synthesized according to Reference Synthesis Example 2 was 201,000.

At this time, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Separation Module. did

[Reference Synthesis Example 3]

In Synthesis Example 8, in place of 80 parts by weight of 3-glycidoxypropyl trimethoxysilane and 20 parts by weight of tetraethoxysilane as reactive silane, 30 parts by weight of 3-glycidoxypropyl trimethoxysilane, tetraethoxy A thermosetting resin including an epoxy group and a hydroxyl group was prepared in the same manner as in Synthesis Example 7, except that 70 parts by weight of silane was used.

The weight average molecular weight of the thermosetting resin including an epoxy group and a hydroxyl group synthesized according to Reference Synthesis Example 3 is 250,000.

At this time, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Separation Module. did

[Comparative Synthesis Example 1]

In Synthesis Example 1, in the same manner as in Synthesis Example 1, except that 100 parts by weight of lauryl methacrylate was used instead of 100 parts by weight of glycidyl methacrylate, a thermosetting group having a weight average molecular weight of 9,000 was not included. A non-resin was prepared.

In this case, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Seperation Module. did

[Comparative Synthesis Example 2]

In Synthesis Example 1, 50 parts by weight of lauryl methacrylate and 50 parts by weight of styrene were used instead of 100 parts by weight of glycidyl methacrylate, and 2,2'-azobis(2,4-dimethyl) was used as an initiator. Valeronitrile), a resin having a weight average molecular weight of 135,000 and not including a thermosetting group was prepared in the same manner as in Synthesis Example 1, except that 1.5 parts by weight was used instead of 10 parts by weight.

In this case, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Seperation Module. did.

[Comparative Synthesis Example 3]

In Synthesis Example 1, 50 parts by weight of lauryl methacrylate and 50 parts by weight of ethyl methacrylate were used instead of 100 parts by weight of glycidyl methacrylate, and 2,2'-azobis(2,4) was used as an initiator. -Dimethylvaleronitrile) A resin having a weight average molecular weight of 25,000 and not including a thermosetting group was prepared in the same manner as in Synthesis Example 1, except that 5 parts by weight was used instead of 10 parts by weight.

In this case, the weight average molecular weight was the polystyrene equivalent weight average molecular weight measured using GPC, and the weight average molecular weight was measured using the standard analysis method of gel permeation chromatography (GPC) used with Waters' e2695 Alliance Seperation Module. did

[Preparation Example 2: Preparation of low refractive index thermosetting composition and optical film]

Using the resin synthesized in the Synthesis Examples, Reference Synthesis Examples and Comparative Synthesis Examples, the thermosetting compositions of Examples 1 to 64, Comparative Examples 1 to 6 and Reference Examples 1 to 15 with the compositions shown in Tables 1 to 3 below Each was prepared. this? As the air-containing particles, hollow silica was used, and an epoxy monomer was used as a monomer having a thermosetting functional group.

At this time, a composition containing an epoxy resin, an epoxy monomer or oligomer and hollow silica is added to the inkjet equipment and the slit coater equipment, and then applied to the SiOx film, pre-baked, and then single to a thickness of 2.5 μm. A film was formed.

Then, in a convection oven (Convection Oven), 180 ℃ / 30min heat treatment to prepare a cured film of the low refractive index thermosetting composition. At this time, the thickness of the formed cured film was maintained at 2㎛.

The epoxy monomer structures of Tables 1 to 3 are as follows.

(The detailed structure of Formula 2 used in Examples of the present invention is a structure in which n is 2.)

[Experimental example: of optical film Measurement of physical properties]

With respect to the optical films of Reference Examples and Examples prepared by Preparation Example 2, physical properties such as refractive index, haze, and viscosity were measured by the following method, and the results are shown in Tables 5 to 7.

[Experimental Example 1: Measurement of Light Refractive Index of Optical Film]

With respect to the optical film, refractive index (450 ± 20 nm average) was measured using an ellipsometer, and indicated in Tables 5 to 7 with symbols according to the following standards.

◎: When the measurement value of the refractive index of the optical film is 1.25 or less

○: When the refractive index measurement value of the optical film is 1.26 ~ 1.40

Δ: When the measurement value of the refractive index of the optical film is 1.41 ~ 1.45

X: When the measurement value of the refractive index of the optical film exceeds 1.45

[Experimental Example 2: Measurement of light transmittance of optical film]

For the optical film, the average transmittance at 450 ± 20 nm was measured using a UV-VIS spectrophotometer (Cary4000, Agilent), and it was indicated in Tables 5 to 7 with symbols according to the following standards.

○: When the average transmittance value is 90% or more

Δ: When the average transmittance value is greater than 80 and less than 90%

X: When the average transmittance value is less than 80%

[Experimental Example 3: Measurement of haze of optical film]

The haze was measured using a haze meter COH 400 manufactured by NIPPON DENSHOKU, and indicated in Tables 5 to 7 with symbols according to the following standards.

○: When the haze measurement value is 3.0 or less

Δ: When the haze measurement value is greater than 3.0 and less than or equal to 4.0

X: When the haze measurement value is over 4.0

[Experimental Example 4: Measurement of Viscosity (Absolute Viscosity) of Composition]

For each of the photopolymerizable compositions and olefinic monomers of the Reference Examples and Examples, each absolute viscosity was measured using a viscometer (trade name: Brook Field viscometer) at a temperature of 25 ° C. It is indicated in Tables 5 to 7.

◎: When the absolute viscosity value is 5 to 20 cP or less

○: When the absolute viscosity value exceeds 20 to 30 cP or less

Δ: When the absolute viscosity value exceeds 30 to 40 cP or less

X: When the absolute viscosity value is out of the above range

[Experimental Example 5: Evaluation of Inkjet Fairness]

It was confirmed whether the surface was formed by changing the nozzle temperature of the inkjet equipment, and indicated in Tables 5 to 7 with symbols according to the following standards.

Surface formation at nozzle temperature 25~45℃ = ○

Surface formation at nozzle temperature >45°C to 50°C = Δ

No face formation (Uncoating) = X at nozzle temperature 25~50℃

[Experimental Example 6: Evaluation of slit coating properties]

The coating property was confirmed using the slit coater equipment, and the thickness distribution was indicated in Tables 5 to 7 as symbols according to the following standards.

Within 5% of thickness distribution = ○

Thickness distribution within 10% = Δ

Thickness spread over 10% = X

[Experimental Example 7: Evaluation of lower adhesiveness of the optical film]

100 cells were cross-cut at intervals of 1 mm ² to the cured film formed on the lower SiOx film, and adhesive strength with the lower SiOx film was compared using a tape.

According to the classification criteria of the adhesion test results of Table 4, the lower adhesive properties of the optical film were shown in Tables 5 to 7 as 0 to 5B.

[Experimental Example 8: Evaluation of the upper adhesiveness of the optical film]

With respect to the optical film, a 0.2 μm SiOx film was further deposited through a CVD process. 100 cells were cross-cut at intervals of 1 mm ² on the upper SiOx, and the adhesive strength with the lower low refractive optical film was compared using a tape.

According to the classification criteria of the adhesion test results of Table 3, the lower adhesive properties of the optical film were 0 to 5B, and are shown in Tables 5 to 7 below.

[Experimental Example 9: Evaluation of heat resistance of optical film]

Heat resistance was measured using TGA (equipment name: Discovery TGA-55, TA KOREA) equipment. After sampling the pattern film formed during the sensitivity measurement, it was measured while raising the temperature from room temperature to 900 °C at a rate of 10 °C per minute using TGA equipment.

○ : TGA 5wt% Weight loss Temp. 300℃ or higher

Δ : TGA 5wt% Weight loss Temp. In case of 270℃ or more and less than 300℃

X : TGA 5wt% Weight loss Temp. Below 270℃

Through the results of Experimental Examples 1 to 9 shown in Tables 5 to 7, the optical film according to the present invention has a very small refractive index, a very high average transmittance, a small haze measurement value, a high viscosity of the composition, and an inkjet device. It can be confirmed that the surface is formed at a nozzle temperature of 25~50℃, the surface is formed even when coated using a slit coater equipment, the upper and lower adhesive properties of the optical film are very excellent, and the heat resistance of the optical film itself is also excellent. there was.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will understand that the present invention may be implemented in a modified form without departing from the essential characteristics of the present invention. will be able Therefore, the disclosed embodiments are to be considered in an illustrative rather than a restrictive sense. The scope of the present invention is indicated in the claims rather than the foregoing description, and all differences within the scope equivalent thereto should be construed as being included in the present invention.

Claims (22)

thermosetting resin;
air-containing particles; and
Including a monomer or oligomer having a thermosetting functional group,
The monomer or oligomer is a thermosetting composition having two or more thermosetting functional groups. According to claim 1,
The thermosetting resin is a thermosetting composition comprising at least one of an epoxy group, an oxetane group, or a hydroxyl group (OH). According to claim 1,
The thermosetting resin has a weight average molecular weight of 1,000 to 200,000. According to claim 1,
A thermosetting composition comprising 30 to 80% by weight of the air-containing particles based on the total weight. According to claim 1,
A thermosetting composition comprising 50 to 80% by weight of the air-containing particles based on the total weight. The method of claim 1,
The air-containing particles are porogen or hollow silica thermosetting composition. The method of claim 1,
The air-containing particle is a thermosetting composition surface-treated with at least one functional group selected from the group consisting of an alkyl group, an acryl group, a methacrylic group, an epoxy group, and a vinyl group. According to claim 1,
The thermosetting composition wherein the air-containing particles are surface-treated to a thickness of 3 to 50 nm. The method of claim 1,
The D50 particle diameter of the air-containing particles is 30 to 150nm thermosetting composition. According to claim 1,
The monomer or oligomer having a thermosetting functional group is a thermosetting composition comprising an alicyclic epoxy structure. The method of claim 1,
The monomer or oligomer having a thermosetting functional group is a thermosetting composition comprising a compound having one chemical structure selected from the group consisting of the following Chemical Formulas 1 to 24:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

In Formulas 4 and 6, R each independently represents a hydrocarbon group having 1 to 10 carbon atoms, R in Formula 6 is one of an alkyl, alkenyl and alkoxy group, and Formulas 2 to 4, 11 to 13 and 20 In to 21, l, m, n and o are each independently an integer from 1 to 30. According to claim 1,
1 to 69% by weight of the thermosetting resin;
30 to 80% by weight of the air-containing particles; and
Thermosetting composition comprising a; 1 to 60% by weight of the monomer or oligomer having the thermosetting functional group. According to claim 1,
The thermosetting resin and the total weight of the monomer or oligomer having a thermosetting functional group is 20 to 70% by weight based on the total composition of the thermosetting composition. The method of claim 1,
A thermosetting composition further comprising at least one additive selected from the group consisting of a silane coupling agent, an adhesive having an alkoxy group as a crosslinking site, and a surfactant. According to claim 1,
A thermosetting composition further comprising at least one dispersant selected from the group consisting of an acrylic dispersant, an epoxy dispersant, and a silicone dispersant. According to claim 1,
A thermosetting composition further comprising at least one crosslinking accelerator selected from the group consisting of a thermal acid generator and a thermal base generator. According to claim 1,
Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl Ether propionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, diphoropylene glycol diethyl ether, butylene glycol monomethyl ether, butylene glycol monomethyl ether Ethyl ether, dibutylene glycol dimethyl ether, dibutylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol ether Sherry butyl ether, tetraethylene glycol dimethyl ether, diethylene glycol ethyl hexyl ether, diethylene glycol methyl hexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethyl hexyl ether and dipropylene glycol methyl hexyl ether selected from the group consisting of A thermosetting composition comprising at least one solvent. According to claim 1,
A solvent-free thermosetting composition that does not contain a solvent. The method of claim 1,
A thermosetting composition having a viscosity of 3 to 30 cP. write; and
[Claim 20] An optical member comprising a; a cured film comprising the thermosetting composition of any one of claims 1 to 19. 21. The method of claim 20,
The cured film is an optical member having a haze of 3% or less based on light of a wavelength of 450 nm. A display device comprising the optical member of claim 20 .