KR102165588B1 - Transparent photopolymer compositions which have high mositure-proof performance - Google Patents

Abstract

The present invention relates to a photocurable resin composition comprising a functional silica compound in a photocurable resin made of urethane acrylate, and the photocurable resin composition of the present invention may further include a dilution monomer for viscosity control.
The photocurable resin composition of the present invention drastically improves moisture barrier to smooth the next process without sticking to the equipment during the module process, and improves moisture permeability to reduce the defect rate due to moisture penetration, thereby reducing process time and cost. do.

Description

A transparent photocurable resin composition having excellent moisture permeability performance {TRANSPARENT PHOTOPOLYMER COMPOSITIONS WHICH HAVE HIGH MOSITURE-PROOF PERFORMANCE}

The present invention relates to a photocurable resin composition, and particularly to a photocurable resin composition having excellent moisture permeability and high transparency.

In the case of a photocurable resin applied to an existing display module, the resin itself has a limit in having a protective characteristic against moisture elements in an external environment. In order to resist moisture penetration, most of them are to form a coating layer by photo-curing the resin after coating the module by applying materials having water-repellent and moisture-proof properties.

However, due to the nature of organic materials, fluorine functional monomers and silicone compounds that are applied to increase water repellency and moisture-proof properties may change color such as yellowing and decrease the adhesion of the display module surface when coating it with a display module. Occurs. In addition, if the applied content is randomly increased, tacky of the uncured portion or the surface of the photocurable resin occurs. This is because when applied to thin-walled modules of new products, the module may be damaged due to the resin reaction heat and shrinkage rate generated when excessive photocuring energy is applied, reducing the light energy gradually. Due to the limitation of the application of these organic materials, conventional photocurable resins have a problem in which it is difficult to realize the moisture-permeable properties of less than 10^ ¹ g/m ² (thickness 300 μm).

Korean Patent Publication No. 10-2015-0079543 Japanese Patent Publication No. 2016-189102 Japanese Patent Publication No. 2016-187909

Accordingly, an object of the present invention is to dramatically improve the surface stickiness, color change, adhesion effect with the module, and moisture barrier, which are the problems of conventional photocurable resins, by using a non-soluble (insoluble) functional silica compound. It makes the next process smooth without sticking, and improves moisture-permeable properties to reduce the defect rate due to moisture penetration, thereby reducing process time and cost.

The object of the present invention is achieved by a photocurable resin composition comprising a functional silica compound in a photocurable resin made of urethane acrylate.

The photocurable resin composition of the present invention may further include a dilution monomer for viscosity control.

The photocurable resin composition of the present invention drastically improves moisture barrier to smooth the next process without sticking to the equipment during the module process, and improves moisture permeability to reduce the defect rate due to moisture penetration, thereby reducing process time and cost. do.

The photocurable resin composition of the present invention contains a urethane acrylate compound and a functional silica compound.

The urethane acrylate compound of the present invention may be a mixture of a plurality of urethane acrylate compounds, for example, a first urethane acrylate compound having a pencil hardness of 1H or more and having a polyfunctional group, and a polyether-based polyol as precursors. It may be a mixture of a second urethane acrylate compound having a polyfunctional group.

The photocurable resin composition according to an embodiment of the present invention is synthesized using 100 parts by weight of a first urethane acrylate compound having a pencil hardness of 1H or more and a polyfunctional group and a polyether-based polyol as a precursor, and a second having a polyfunctional group. It contains 20 to 50 parts by weight of a urethane acrylate compound.

The first urethane acrylate compound may include a plurality of types of urethane acrylate compounds having different numbers of functional groups. In addition, the second urethane acrylate compound may include 5 or less functional groups.

The second urethane acrylate compound may be synthesized using polyether, diisocyanate and hydroxy acrylate. As the hydroxy acrylate, hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxybutyl acrylate (HBA), etc. may be used, and the compounds may be used alone or as a mixture of two or more. .

The functional silica compound is, for example, a compound having a hydroxyl, methyl, vinyl, or glycidyl group on its surface and having the following structure. Substituents on the surface increase the bonding strength with the highly curable resin to improve moisture permeability.

The content of the functional silica compound may vary in composition ratio depending on the thickness required for the process application. The functional silica compound may be used in an amount of 0.1 to 15% by weight in the total photocurable resin composition.

The photocurable resin composition of the present invention is a solvent-free type that does not use a solvent.

The following monomers may be further included for dilution for viscosity control.

Where R1 is hydrogen or methyl.

Hereinafter, the present invention will be described in more detail with specific examples. However, the technical idea of the present invention is not limited by the following examples.

1. Urethane acrylate compound composition test

1.1) The first urethane acrylate compound is UV cured by applying urethane acrylates having various hard forms from branch type to dendrimer type and polybutadiene structure having hard properties including aromatic and cycloaliphatic structures. After that, the surface properties of the resin are maintained so that they do not collapse and have hard properties.

1.2) The second urethane acrylate compound is photocured using a polyfunctional urethane acrylate adjusted to the molecular length of the polyether-based polyol, and after photocuring, cracking of the resin occurs, and after surface coating of each equipment PET film, glass, polyimide film, etc. The phenomena such as film cracking, bending properties and yellowing are controlled as much as possible.

The final urethane acrylate compound has the best moisture permeability with WVTR 71 g/m ² .day at a thickness of 300 μm after film curing among several compositions in which the composition ratio of the first urethane and the second urethane compound is varied to have the respective required properties. The composition having characteristics was applied as shown in Table 1 and used in the test.

The composition of the urethane acrylate compound applied to the following examples is shown in Table 1 and is hereinafter referred to as UAC.

Urethane Acrylate Compound (UAC) Initiator First urethane acrylate
(1UA) Second urethane acrylate
(2UA) 1UA
2UA
Sum
weight
% 1st initiator
weight
% Kinds Functional group contain
ratio Application fee Kinds Functional group Application fee Kinds Applied amount MUA 6 10 80 Etheric 2 20 100 97 TPO 3 3 CAUA 2 90 * UAC: Urethane acrylate compound * UA: Urethane acrylate
* MUA: Polyfunctional urethane acrylate * CAUA: Cycloaliphatic urethane acrylate
* Curing :: UV Lamp 1.2J/cm2, WVTR measurement film thickness: 300um, WVTR mocon equipment used

2. Test of optimal content of dilution monomer

2.1) In order to increase moisture-permeable properties, use isobornyl acrylate (IBOA), an acrylate substituted with a hydrophobic structure using water-repellent properties, and adjust the composition ratio of IBOA and UAC as shown in Table 2 below to improve moisture-permeable properties and other physical properties. Was confirmed. The results are posted in Table 2 below.

Item Photocuring resin composition Test result Urethane acrylate Dilution monomer Initiator Coating properties surface WVTR Test Kinds
weight
% Kinds
weight
% Kinds
weight
% PET Glass PI Fairness Tacky g/㎡
·Day Example 1 UAC 97 IBOA 0 TPO 3 ◎ ◎ ○ ○ Tack Free 71.0 Example 2 UAC 87 IBOA 10 TPO 3 ◎ ◎ ○ ○ Tack Free 64.5 Example 3 UAC 77 IBOA 20 TPO 3 ◎ ◎ ○ ○ Tack Free 59.3 Example 4 UAC 67 IBOA 30 TPO 3 ◎ ◎ ○ ◎ Tack Free 56.8 Example 5 UAC 57 IBOA 40 TPO 3 ◎ ◎ ○ ◎ Tack Free 56.3 Example 6 UAC 47 IBOA 50 TPO 3 ◎ ◎ ○ ◎ Tack Free 57.3 Example 7 UAC 37 IBOA 60 TPO 3 △ ○ ○ ◎ Tack Free 62.2 Example 8 UAC 27 IBOA 70 TPO 3 △ △ ○ ○ Tack Free 69.1 Example 9 UAC 17 IBOA 80 TPO 3 △ △ △ △ Tacky Unreacted occurrence * UAC: Urethane acrylate compound (Table 1 optional composition) * UA: Urethane acrylate
* MUA: Polyfunctional urethane acrylate * CAUA: Cycloaliphatic urethane acrylate
* Curing :: UV Lamp 1.2J/cm2, WVTR measurement film thickness: 300um, WVTR mocon equipment used
* Coating: Good>◎>○>△> Poor Fairness: Good>◎>○>△> Very difficult to handle
* Tacky Free: No stickiness Tacky: Sticky

As the content of the diluent monomer decreases and the urethane acrylate oligomer content is relatively increased, the viscosity increase width according to the polymer properties becomes very large. Accordingly, the coating fairness of the display material is not easy to handle in the absence of a dilution monomer, so a temperature control device must be attached to the process equipment to maintain the coating fairness. In addition, it is confirmed that the reaction heat for the curing reaction of the polyfunctional reaction site is high, and the fume for the high reaction heat after curing is also confirmed.

On the contrary, as the content of the monomer for dilution increases, the viscosity decreases rapidly and the coating property improves, but the processability becomes more difficult to control. Accordingly, the curing rate of the material becomes very low due to the terminal monofunctional group, so when the same curing energy is used, unreacted It is also possible. The unreacted curing can be analyzed by increasing the amount of photoinitiator applied or by increasing the light energy required for curing to remove the unreacted, but the analysis of the uncured part was not conducted to confirm the characteristics under the same conditions.

2.2) In Table 2 above, it was confirmed that the optimal concentration of IBOA was around 40%, and the concentration from 35% to 45% was further subdivided into 1% units, and the composition ratio of IBOA and UAC was adjusted according to the composition shown in Table 3. , Moisture-permeable properties and other physical properties were confirmed when the IBOA content was finely adjusted. The test results are posted in Table 3.

Item Photocuring resin composition Test result Urethane acrylate Dilution monomer Initiator Coating properties surface WVTR Test Kinds weight
% Kinds weight
% Kinds weight
% PET Glass PI Fairness Tacky g/㎡
·Day Example 10 UAC 62 IBOA 35 TPO 3 ◎ ◎ ○ ◎ Tack Free 56.4 Example 11 UAC 61 IBOA 36 TPO 3 ◎ ◎ ○ ◎ Tack Free 56.0 Example 12 UAC 60 IBOA 37 TPO 3 ◎ ◎ ○ ◎ Tack Free 56.0 Example 13 UAC 59 IBOA 38 TPO 3 ◎ ◎ ○ ◎ Tack Free 56..1 Example 14 UAC 58 IBOA 39 TPO 3 ◎ ◎ ○ ◎ Tack Free 56.3 Example 5 UAC 57 IBOA 40 TPO 3 ◎ ◎ ○ ◎ Tack Free 56.3 Example 15 UAC 56 IBOA 41 TPO 3 ◎ ◎ ○ ◎ Tack Free 56.5 Example 16 UAC 55 IBOA 42 TPO 3 ◎ ◎ ○ ◎ Tack Free 56.4 Example 17 UAC 54 IBOA 43 TPO 3 ◎ ◎ ○ ◎ Tack Free 56.5 Example 18 UAC 53 IBOA 44 TPO 3 ◎ ◎ ○ ◎ Tack Free 56.7 Example 19 UAC 52 IBOA 45 TPO 3 ◎ ◎ ○ ◎ Tack Free 57.0 * UAC: Urethane acrylate compound (Table 1 optional composition) * UA: Urethane acrylate
* MUA: Polyfunctional urethane acrylate
* CAUA: Cycloaliphatic urethane acrylate
* IBOA: isobornyl acrylate
* TPO: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide
* Curing :: UV Lamp 1.2J/cm2, WVTR measurement film thickness: 300um, WVTR mocon equipment used
* Coating: Good>◎>○>△> Poor Fairness: Good>◎>○>△> Very difficult to handle
* Tacky Free: No stickiness Tacky: Sticky

3. Photoinitiator optimal content test

3.1) In order to confirm the characteristics according to the content of the TPO photoinitiator, a test was conducted with the composition shown in Table 4. The results of the physical property test by content of the photoinitiator are posted in Table 4 below.

Item Photocuring resin composition Test result Urethane acrylate Dilution monomer Initiator Coating properties surface WVTR Curing rate Test Kinds weight
% Kinds weight
% Kinds weight
% PET Glass PI Fairness Tacky g/㎡
·Day bottom Example 20 UAC 60 IBOA 38 TPO 2 ○ ◎ ○ ○ Tacky 58.6 73% Example 21 UAC 60 IBOA 37.5 TPO 2.5 ◎ ◎ ○ ○ Tack Free 57.2 81% Example 12 UAC 60 IBOA 37 TPO 3 ◎ ◎ ○ ○ Tack Free 56.0 88% Example 22 UAC 60 IBOA 36.5 TPO 3.5 ◎ ◎ ○ ◎ Tack Free 56.2 >95% Example 23 UAC 60 IBOA 36 TPO 4 ◎ ◎ ○ ◎ Tack Free 55.9 >95% * UAC: Urethane acrylate compound (Table 1 optional composition) * UA: Urethane acrylate
* MUA: Polyfunctional urethane acrylate * CAUA: Cycloaliphatic urethane acrylate
* IBOA: isobornyl acrylate * TPO: diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide
* Curing :: UV Lamp 1.2J/cm2, WVTR measurement film thickness: 300um, WVTR mocon equipment used
* Coating: Good>◎>○>△> Poor Fairness: Good>◎>○>△> Very difficult to handle
* Tacky Free: No stickiness Tacky: Sticky

After curing by applying more than 3% of TPO, the color of the coating film had to be applied to less than 3% due to the occurrence of yellowing, which is difficult to apply as a transparent display material.When the content of the photoinitiator decreases, the upper surface of the coating was confirmed to be tack-free, but It has been confirmed that the fast curing rate is low, and this can cause problems when out gassing and coming out in the display module process.

3.2) Accordingly, a mixed test was conducted by applying various types of photoinitiators that can increase fast curing, and 184 (1-hydroxy-cyclohexylphenyl ketone), which has good compatibility and properties with TPO, was used as the second photoinitiator as shown in Table 5. By additionally applying to the first photoinitiator TPO and the composition ratio differently tested to obtain the same results as in Example 26 having no problem in fast curing rate and film properties.

Item Photocuring resin composition Test result Urethane acrylate Dilution monomer Initiator Coating properties surface WVTR Curing rate Test Kinds weight
% Kinds weight
% Kinds Subsidy weight
% PET Glass PI Fairness Tacky g/㎡
·Day bottom Example 12 UAC 60 IBOA 37 TPO 100 3 ◎ ◎ ○ ◎ Tack Free 56.0 88% 184 0 Example 24 UAC 60 IBOA 37 TPO 90 3 ◎ ◎ ○ ◎ Tack Free 56.2 89% 184 10 Example 25 UAC 60 IBOA 37 TPO 80 3 ◎ ◎ ○ ◎ Tack Free 55.9 93% 184 20 Example 26 UAC 60 IBOA 37 TPO 70 3 ◎ ◎ ○ ◎ Tack Free 55.6 >95% 184 30 Example 27 UAC 60 IBOA 37 TPO 60 3 ◎ ◎ ○ ◎ Tacky 56.2 >95% 184 40 Example 28 UAC 60 IBOA 37 TPO 50 3 ◎ ◎ ○ ◎ Tacky Not measured surface
Uncured 184 50 Example 29 UAC 60 IBOA 37 TPO 40 3 ◎ ◎ ○ ◎ Tacky Not measured surface
Uncured 184 60 * UAC: Urethane acrylate compound (Table 1 optional composition) * UA: Urethane acrylate
* MUA: Polyfunctional urethane acrylate
* CAUA: Cycloaliphatic urethane acrylate
* IBOA: isobornyl acrylate
* TPO: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide
* 184: 1-hydroxy-cyclohexylphenyl ketone
* Curing :: UV Lamp 1.2J/cm2, WVTR measurement film thickness: 300um, WVTR mocon equipment used
* Coating: Good>◎>○>△> Poor Fairness: Good>◎>○>△> Very difficult to handle
* Tacky Free: No stickiness Tacky: Sticky

As the fast curing rate increased, it was confirmed that the photo-curing resin became more solid and the moisture-permeable properties were improved. A sufficient curing effect could not be exerted by the initiator alone, and tack and uncured portions were generated on the surface.

4. Diluting monomer selection and composition test

4.1) In order to control the viscosity of the urethane acrylate oligomer having high viscosity, a test was conducted by adding a dilution monomer as shown in Table 6 below.

Item Photocuring resin composition Test result Urethane acrylate Dilution monomer Initiator Coating properties surface WVTR Curing rate Test Kinds weight
% Kinds weight
% Kinds Subsidy weight
% PET Glass PI Fairness Tacky g/㎡
·Day bottom Example 26 UAC 60 IBOA 37 TPO 70 3 ◎ ◎ ○ ◎ Tack Free 55.6 >95% 184 30 Example 30 UAC 60 IBOMA 37 TPO 70 3 ◎ ◎ ○ ◎ Tacky 55.3 >95% 184 30 Example 31 UAC 60 DCPMA 37 TPO 70 3 ○ ◎ ◎ ◎ Tack Free 55.1 >95% 184 30 * UAC: Urethane acrylate compound (Table 1 optional composition) * UA: Urethane acrylate
* MUA: Polyfunctional urethane acrylate
* CAUA: Cycloaliphatic urethane acrylate
* IBOA: isobornyl acrylate
* TPO: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide
* 184: 1-hydroxy-cyclohexylphenyl ketone
* Curing :: UV Lamp 1.2J/cm2, WVTR measurement film thickness: 300um, WVTR mocon equipment used
* Coating: Good>◎>○>△> Poor Fairness: Good>◎>○>△> Very difficult to handle
* Tacky Free: No stickiness Tacky: Sticky

4.2) According to the results of each characteristic, the composition ratio of the two diluent monomers except IBOMA, which has a lower curing characteristic, was different to confirm the compatibility and the properties after curing as shown in Table 7.

Item Photocuring resin composition Test result Urethane acrylate Dilution monomer Initiator Coating properties surface WVTR Curing rate Test Kinds weight
% Kinds Subsidy
weight
% Kinds Subsidy
weight
% PET Glass PI Fairness Tacky g/㎡
·Day bottom Example 26 UAC 60 IBOA 100 37 TPO 70 3 ◎ ◎ ○ ◎ Tack Free 55.6 >95% DCPMA 0 184 30 Example 32 UAC 60 IBOA 90 37 TPO 70 3 ◎ ◎ ○ ◎ Tack Free 55.5 89% DCPMA 10 184 10 Example 33 UAC 60 IBOA 80 37 TPO 70 3 ◎ ◎ ○ ◎ Tack Free 55.3 93% DCPMA 20 184 30 Example 34 UAC 60 IBOA 70 37 TPO 70 3 ◎ ◎ ○ ◎ Tack Free 55.4 >95% DCPMA 30 184 30 Example 35 UAC 60 IBOA 60 37 TPO 70 3 ◎ ◎ ○ ◎ Tack Free 55.3 >95% DCPMA 40 184 30 Example 36 UAC 60 IBOA 50 37 TPO 70 3 ◎ ◎ ○ ◎ Tack Free 55.1 >95% DCPMA 50 184 30 Example 37 UAC 60 IBOA 40 37 TPO 70 3 ◎ ◎ ◎ ◎ Tack Free 55.2 >95% DCPMA 60 184 30 Example 38 UAC 60 IBOA 30 37 TPO 70 3 ◎ ◎ ◎ ◎ Tack Free 55.2 >95% DCPMA 70 184 30 Example 39 UAC 60 IBOA 20 37 TPO 70 3 ◎ ◎ ◎ ◎ Tack Free 55.1. >95% DCPMA 80 184 30 Example 40 UAC 60 IBOA 10 37 TPO 70 3 ○ ◎ ◎ ◎ Tack Free 55.2 >95% DCPMA 90 184 30 Example 31 UAC 60 IBOA 0 37 TPO 70 3 ○ ◎ ◎ ◎ Tack Free 55.1 >95% DCPMA 100 184 30 * UAC: Urethane acrylate compound (Table 1 optional composition) * UA: Urethane acrylate
* MUA: Polyfunctional urethane acrylate
* CAUA: Cycloaliphatic urethane acrylate
* IBOA: isobornyl acrylate
* TPO: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide
* 184: 1-hydroxy-cyclohexylphenyl ketone
* Curing :: UV Lamp 1.2J/cm2, WVTR measurement film thickness: 300um, WVTR mocon equipment used
* Coating: Good>◎>○>△> Poor Fairness: Good>◎>○>△> Very difficult to handle
* Tacky Free: No stickiness Tacky: Sticky

When the two dilution monomers were used in combination, there was no problem in solubility, and the optimum ratio was calculated in consideration of the coating characteristics of each dilution monomer for equipment. The best coating properties and moisture permeability to each material is Example 39, which will be used as a composition for adding various types of functional silica to be used later.

5. Functional silica compound addition test

5.1) In order to confirm the characteristics according to the silica type, the test was performed by varying by type of functional silica as shown in Table 8.

Item Photocuring resin composition Test result Mixed composition Functional silica Coating properties surface WVTR Test Kinds weight
% Kinds weight
% PET Glass PI Fairness Tacky g/㎡
·Day Example 41 Example
26 composition 95 Hydroxyl 5 ◎ ◎ ◎ ◎ Tack Free 2.25 Example 42 90 10 ◎ ◎ ◎ ◎ Tack Free 1.85 Example 43 85 15 ◎ ◎ ◎ ◎ Tacky Uncured part occurs Example 44 95 methyl 5 ◎ ◎ ◎ ◎ Tack Free 2.62 Example 45 90 10 ◎ ◎ ◎ ◎ Tack Free 2.08 Example 46 85 15 ◎ ◎ ◎ ◎ Tacky Uncured part occurs Example 47 95 vinyl 5 ◎ ◎ ◎ ◎ Tack Free 2.31 Example 48 90 10 ◎ ◎ ◎ ◎ Tack Free 0.98 Example 49 85 15 ◎ ◎ ◎ ◎ Tack Free 1.85 Example 50 95 Glycidyl 5 ◎ ◎ ◎ ◎ Tack Free 2.49 Example 51 90 10 ◎ ◎ ◎ ◎ Tack Free 1.65 Example 52 85 15 ◎ ◎ ◎ ◎ Tacky Uncured part occurs * UAC: Urethane acrylate compound (Table 1 optional composition)
* Mixed composition: urethane acrylate/diluting monomer/initiator
* Curing :: UV Lamp 1.2J/cm2, WVTR measurement film thickness: 300um, WVTR mocon equipment used
* Coating: Good>◎>○>△> Poor Fairness: Good>◎>○>△> Very difficult to handle
* Tacky Free: No stickiness Tacky: Sticky

5.2) As a photo-curing type resin according to the characteristics of the TPO photoinitiator, it was confirmed that the substitution of a vinyl-type functional group on silica has the best curing and moisture-permeable properties. I did.

Item Photocuring resin composition Test result Mixed composition Functional silica color Coating properties surface WVTR Test Kinds weight% Kinds weight% Compatibility After curing PET Glass PI Fairness Tacky g/㎡
·Day Example 39 Example
26 composition 100 vinyl 0 Good Transparency ◎ ◎ ◎ ◎ Tack Free 55.1 Example 53 99.5 0.5 Good Transparency ◎ ◎ ◎ ◎ Tack Free 48.8 Example 53 99.0 1.0 Good Transparency ◎ ◎ ◎ ◎ Tack Free 37.9 Example 54 98.0 2.0 Good Transparency ◎ ◎ ◎ ◎ Tack Free 29.3 Example 55 97.0 3.0 Good Transparency ◎ ◎ ◎ ◎ Tack Free 14.0 Example 56 96.0 4.0 Good Transparency ◎ ◎ ◎ ◎ Tack Free 6.45 Example 57 95.0 5.0 Good Transparency ◎ ◎ ◎ ◎ Tack Free 2.3 Example 58 94.0 6.0 Good Transparency ◎ ◎ ◎ ◎ Tack Free 1.5 Example 59 93.0 7.0 Good Transparency ◎ ◎ ◎ ◎ Tack Free 1.2 Example 60 92.0 8.0 Good Transparency ◎ ◎ ◎ ◎ Tack Free 0.98 Example 61 91.9 8.1 Good Transparency ◎ ◎ ◎ ◎ Tack Free 0.91 Example 62 91.8 8.2 Good Transparency ◎ ◎ ◎ ◎ Tack Free 0.93 Example 63 91.7 8.3 Good Transparency ◎ ◎ ◎ ◎ Tack Free 0.88 Example 64 91.6 8.4 Good Transparency ◎ ◎ ◎ ◎ Tack Free 0.88 Example 65 91.5 8.5 Good Transparency ◎ ◎ ◎ ◎ Tack Free 0.93 Example 66 91.4 8.6 Good Transparency ◎ ◎ ◎ ◎ Tack Free 0.98 Example 67 91.3 8.7 Good Transparency ◎ ◎ ◎ ◎ Tack Free 0.96 Example 68 91.2 8.8 Good Transparency ◎ ◎ ◎ ◎ Tack Free 0.94 Example 69 91.1 8.9 Good Transparency ◎ ◎ ◎ ◎ Tack Free 0.9 Example 70 91.0 9.0 Good Transparency ◎ ◎ ◎ ◎ Tack Free 1.01 Example 71 90.0 10.0 Good Transparency ◎ ◎ ◎ ◎ Tack Free 0.98 Example 72 89.0 11.0 opacity A little haze ◎ ◎ ◎ ○ Tack Free 1.19 Example 73 88.0 12.0. opacity Haze ◎ ◎ ◎ ○ Tack Free 1.4 Example 74 87.0 13.0 opacity Haze ◎ ◎ ◎ ○ Tack Free 1.7 Example 75 86.0 14.0 opacity Haze ◎ ◎ ◎ ○ Tack Free 2.0 Example 76 85.0 15.0 opacity Haze ◎ ◎ ◎ ○ Tacky 1.8 Example 77 80.0 20.0 opacity Haze Coty decreases due to silica drift phenomenon during coating N/D * UAC: Urethane acrylate compound (selective composition in Table 1) * Mixed composition: Urethane acrylate/diluting monomer/initiator
* Curing :: UV Lamp 1.2J/cm2, WVTR measurement film thickness: 300um, WVTR mocon equipment used
* Coating: Good>◎>○>△> Poor Fairness: Good>◎>○>△> Very difficult to handle
* Tacky Free: No stickiness Tacky: Sticky

As shown in each example, it was confirmed that the moisture-permeable properties were improved as functional silica was applied, and by applying it to the display module process, coating properties with various module equipment, bending and transparency were maintained, and the resin alone was exhibited. It was confirmed that the moisture-permeable properties, which cannot be achieved, are rapidly maintained to 10^-1 or less. From Example 72 onwards, compatibility was opaque due to a decrease in compatibility due to the polarity difference between the photocurable resin and functional silica contained in the composition, and haze gradually occurred in the coated resin after curing and the amount of functional silica was carried out. As shown in Example 72, it was confirmed that mixing and dispersibility became a problem, and coating property was degraded due to the occurrence of one side of the silica after curing.

Among the properties required for materials applied to display modules, conventionally, fluorine functional group monomers, silicone compounds, butadiene-based compounds with rubber properties applied to increase water repellency and moisture-proof properties due to the properties of organic materials are applied to display modules. In the case of coating, color change such as yellowing and adhesion performance on the surface of the display module may decrease, and if the applied content is recklessly increased, the uncured portion or surface stickiness occurs in the case of the photocurable resin. Due to the limitation of application of these organic materials, conventional photocurable resins have a problem that it is difficult to implement moisture-permeable properties. The photocurable resin composition of the present invention is made of functional silica capable of increasing the crosslinking density after curing, and is transparent, has no tacky surface, and has excellent moisture-permeable properties.

Claims (4)

A photocurable resin composition comprising a urethane acrylate compound and a functional silica compound of at least one of the following structures:

The photocurable resin composition of claim 1, wherein the photocurable resin composition further comprises one or more diluent monomers of the following structures:

Where R1 is hydrogen or methyl. The photocurable resin composition according to claim 1, wherein the urethane acrylate compound is a mixture of a plurality of urethane acrylate compounds. The method of claim 3, wherein the urethane acrylate compound is synthesized by using a first urethane acrylate compound having a polyfunctional group and a polyether-based polyol as precursors having a pencil hardness of 1H or more, and having a polyfunctional group. Photocurable resin composition, characterized in that the mixture.