KR101370149B1 - Adhesive composition for lamination and multi-layer or symmetrical structure plasic substrates using the same - Google Patents

Abstract

The present invention relates to a process for the preparation of a composition comprising at least one substance selected from glass flake and nano-sized silica; Epoxy resin; And it relates to a laminated adhesive composition comprising a photoinitiator and a plastic substrate of a multi-layer or symmetrical structure prepared using the same. The plastic substrate of the multi-layered or symmetrical structure manufactured by using the adhesive composition for lamination according to the present invention is transparent and satisfies a low coefficient of linear expansion (CTE), and has excellent gas barrier and moisture barrier properties.

Epoxy resin, glass flakes, nano-size inorganic particles, laminating adhesive

Description

Adhesive composition for lamination and a plastic substrate of a multi-layered or symmetrical structure manufactured using the same TECHNICAL FIELD

The present invention relates to a process for the preparation of a composition comprising at least one substance selected from glass flake and nano-sized silica; Epoxy resin; And it relates to a laminated adhesive composition comprising a photoinitiator and a plastic substrate of a multi-layer or symmetrical structure prepared using the same.

The glass substrate used for display devices, picture frames, crafts, containers and the like has various advantages such as small coefficient of linear expansion, excellent gas barrier property, high light transmittance, surface flatness, excellent heat resistance and chemical resistance, Is high and has a heavy drawback.

In recent years, interest in liquid crystal displays, organic light emitting display devices, and electronic paper has rapidly increased, and research has been actively conducted to replace substrates of these display devices with glass. That is, if the glass substrate is replaced with a plastic substrate, the overall weight of the display device can be reduced, flexibility in design can be imparted, and the manufacturing process can be economical compared to a glass substrate in a continuous process.

On the other hand, in order to be used in a display device, a plastic substrate is required to have a high glass transition temperature capable of withstanding the process temperature of the transistor device, the deposition temperature of the transparent electrode, oxygen and water vapor barrier properties to prevent aging of the liquid crystal and the organic light emitting material, A small coefficient of linear expansion and dimensional stability to prevent distortion of the substrate due to the change, high mechanical strength with compatibility with the processing equipment used in conventional glass substrates, chemical resistance that can withstand the etching process, high light transmittance and low birefringence, And scratch resistance of the surface.

However, since there is no high functional polymer substrate film including a polymer film and a polymer-inorganic composite film satisfying all of the above conditions, efforts have been made to satisfy the above properties by applying a functional coating of several layers to the polymer substrate film.

Examples of representative coating layers include organic planarization layers that reduce defects on the surface of polymers and impart flatness, gas barrier layers made of inorganic materials for blocking gases such as oxygen and water vapor, and organic or organic-inorganic hard coating layers for imparting scratch resistance to surfaces. Etc. can be mentioned.

In the case of many conventional multi-layer plastic substrates, a process of coating an inorganic gas barrier layer on a polymer substrate and forming a hard coating layer on the gas barrier layer is a problem. The deformation of the polymer base material and the cracking and peeling of the inorganic thin film may occur due to the difference in the coefficient of linear expansion between them. Therefore, it can be said that the design of the appropriate multilayer structure and the adhesion between the coating layer and the substrate to minimize the stress at the interface of each layer is very important.

Vitex Systems of the United States forms a thin film of a monomer on a polymer base film and irradiates it with ultraviolet rays to polymerize and form a coating layer by polymerizing (solidified organic layer) by PECVD, CVD and the like , And then an inorganic thin film was formed on the organic thin film by sputtering. Thus, a flexible substrate having various organic-inorganic layers and excellent gas barrier properties was prepared.

In addition, Korean Patent Publication No. 2004-0100907 discloses a sealant composition for a liquid crystal panel composed of an epoxy acrylate, a latent thermosetting agent, a photoinitiator, an inorganic filler for controlling viscosity, and the like. However, they have a disadvantage in that the viscosity is high and the shrinkage during ultraviolet curing is large, so that the adhesiveness and moisture resistance are weak.

In addition, Korean Patent Publication No. 2005-0014007 discloses an adhesive for sealing an organic electroluminescent device using [B (CF) ₆ ] ⁻ as a cationic photoinitiator and its application.

In addition, Korean Patent Publication No. 2000-0028332 discloses a latent curing agent of a heat and ultraviolet ray-initiated epoxy resin using a latent curing agent and an epoxy resin mixture, an epoxy resin composition containing the same, and an epoxy cured product. However, these epoxy resins are limited in heat resistance and low oxidation resistance.

Although the product having excellent gas barrier properties can be manufactured by the above method, it is not suitable for the use of a display requiring a low coefficient of linear expansion, and no solution has been proposed.

Accordingly, by using the adhesive composition for lamination according to the present invention on an existing plastic substrate, attempts to solve the above problems.

The present invention provides a transparent adhesive composition for laminating and satisfying a low coefficient of linear expansion (CTE) and increase gas barrier and water barrier properties, a plastic substrate having a multilayer or symmetrical structure manufactured using the same, and an electronic device including the same. It aims to do it.

The present invention provides a composition comprising (a) at least one material selected from glass flakes and nanosized silica;

(b) an epoxy resin; And

(c) It provides the adhesive composition for paper containing a photoinitiator.

The present invention also provides a method for laminating a plastic substrate of a multi-layered or symmetrical structure in which the adhesive composition for lamination is applied to at least one surface of two or more plastic substrates, and then the adhesive composition for lamination is cured with heat, UV, or ions. .

In addition, the present invention provides a plastic substrate of a multilayer or symmetrical structure in which two or more plastic substrates are laminated using the laminating adhesive composition.

In addition, the present invention provides a light emitter, a display device and a photovoltaic power generator comprising the plastic substrate of the multilayer or symmetrical structure.

The multi-layered or symmetrical plastic substrate prepared using the adhesive composition for lamination according to the present invention is transparent and satisfies a low coefficient of linear expansion (CTE), and has excellent gas barrier and moisture barrier properties.

Hereinafter, the present invention will be described in detail.

The adhesive composition for lamination according to the present invention comprises at least one material selected from glass flakes and nanosized silica; Epoxy resin; And photoinitiators.

The glass flake is excellent in the property of cutting off gas and moisture due to its large area. The glass flakes were classified into GF10 (0.1 mu m), GF35 (0.35 mu m), GF50 (0.5 mu m), GF70 (0.7 mu m), GF100 (1 mu m), GF300 (3 mu m), GF500 (7 mu m), unmilled glass flakes having 1700 to 150 mu m of 80% and 150 to 50 mu m of 20% depending on the particle size distribution of the glass flakes; A milled glass flake having 1000 to 300 占 퐉 of 10%, 300 to 50 占 퐉 of 65%, and 50 占 퐉 or less of 25%; Micronised glass flakes having a particle size of 150 mu m or more of 2%, a particle size of 150 to 50 mu m of 10%, and a size of 50 mu m or less of 88% or the like. Of these, one or more selected glass flakes can be used.

The refractive index of the glass flakes is not particularly limited but is preferably in the range of 1.50 to 1.60. According to the kind, it can be divided into E, C, A, S, D, NE and T glass, and S, T and NE glass are preferable.

The adhesive composition for lamination preferably further comprises one or more nano-size inorganic particles selected from nanoclay, glass beads, and Degussa Aerosil 300 including MMT.

The nano-size inorganic particles mean inorganic particles having a smaller size than the glass flakes, and the primary particle size range is preferably 1 nm to 100 nm, more preferably 7 nm to 16 nm.

The epoxy resin may further include at least one resin selected from a cycloaliphatic epoxy resin, a modified cycloaliphatic epoxy resin and an epoxy hybrid resin. In addition, the epoxy resin may be a resin containing 1 to 50% by weight of vinyl ethers.

Examples of the alicyclic epoxy resin include 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate (3,4-epoxycyclohexyl-methyl-3,4-, which is, for example, Celloxide 2021P (Daicel). epoxycyclohexane carboxylates, and derivatives thereof, can be used, which are stable, colorless, transparent, toughness, and have good adhesion and adhesion properties for high temperatures.

As the modified alicyclic epoxy resin, for example, Bis- (3,4-epoxycyclohexyl) Adipate, 3,4-epoxycyclohexylmethyl (3,4- Epoxycyclohexylmethyl) 3,4-epoxycyclohexanecarboxylate can be used, and they are colorless and transparent, have a high surface hardness and excellent adhesion to all substrates.

Examples of the epoxy hybrid resin include 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate, glycol, polyol, and the like. They can be used, and they have cationic & free radical mechanisms and can increase increased curing. It is also less susceptible to moisture during the curing reaction and can act as other cationic inhibitors.

The photoinitiator preferably includes at least one selected from sulfonium salts, ferrocenium salts, and the like.

The sulfonium salt may be triarylsulfonium hexafluoroantimonate salts (GE Silicones) or the like, and is preferably used for the curing rate and the degree of curing in the reaction.

In addition, the ferrocyanide salt is Ir 261 of Ciba specialty chemicals. When cumene hydroperoxide is used, the ferrosenium salt can lower the curing temperature, shorten the time, and have a coloring property.

In addition, the present invention can manufacture a plastic substrate of a multi-layered or symmetrical structure using the adhesive composition for the lamination.

In one embodiment, the multilayer plastic substrate comprises a plastic substrate layer; An organic-inorganic hybrid layer laminated on an upper surface of the plastic substrate layer; A gas barrier layer laminated on the organic-inorganic hybrid layer; And a polysilicon residue layer laminated on the upper surface of the gas barrier layer.

In another embodiment, the plastic substrate of the symmetrical structure may be formed in a structure in which two plastic substrates of the multilayer plastic substrate are bonded to each other by the adhesive composition for lamination.

Specifically, two or more multi-layered or symmetrical plastic substrates may be laminated using the adhesive composition for lamination according to the present invention. In this case, even if the adhesive composition for lamination comprises a small amount of glass flakes and nano-sized inorganic particles, the plastic substrate of the multi-layered or symmetrical structure prepared using the adhesive composition for the satisfactory transparent and low coefficient of linear expansion (CTE) Gas barrier and moisture barrier properties can be improved.

Applying the laminating adhesive composition to at least one surface of each layer constituting the multi-layer or symmetrical plastic substrate, and curing and laminating the laminating adhesive composition with heat, UV, or ions. Or it provides a method of laminating a plastic substrate of a symmetrical structure.

In addition, the adhesive composition for lamination includes glass flakes of different shapes and sizes, inorganic particles of nanosize or a mixture thereof, thereby providing a transparent and low coefficient of linear thermal expansion (CTE). In addition, it is possible to manufacture a plastic substrate having an oxygen transmittance rate (OTR) and a water vapor transmittance rate (WVTR), and increases gas barrier and water barrier properties.

In addition, the present invention provides a light emitter, a display device and a photovoltaic power generator comprising the plastic substrate of the multilayer or symmetrical structure.

Hereinafter, the present invention will be described in detail with reference to examples of the present invention. However, embodiments of the present invention may be modified in various forms, the scope of the present invention should not be construed in a way that is limited by the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

In Examples 1 to 16 and Comparative Examples 1 and 2, the water vapor permeability value represents a reduced amount compared to the standard by laminating two plastic substrates having a WVTR value of 1.0 g / m 2 · day as in the above-described composition, and the coefficient of linear expansion (CTE) ) Represents a reduced amount relative to the base by laminating two plastic substrates of 80 (ppm / ° C.) with the compositions of the following examples.

<Examples 1 to 4>

Celloxide 2021P (Daicel): Polyethylene glycol (Polyethylene glycol, Aldrich Mn 200): Photoinitiator (Triarylsulfonium hexafluoroantimonate salts in Propylene Carponate. 50 wt% solution) = 100: 15: 3 The laminating adhesive composition of Examples 1 to 4 was prepared by adding GF10 (nanoparticle thickness 100 nm of glass flakes, GLASSFLAKE Ltd.) to 5 parts by weight, 20 parts by weight, 40 parts by weight or 50 parts by weight, respectively. The laminated adhesive composition thus prepared was coated on two plastic substrates using a laminator, and then cured to 200 ° C. after UV irradiation at 600 (mJ / cm 2) using a metal halide lamp. The coefficient of linear expansion and the water vapor transmission rate of the plastic substrate prepared as described above were measured, and the results are shown in Table 1 below.

Glass Flake (GF10) CTE (ppm / ° C) WVTR (g / m ² · day) Example 1 (GF10-5) 5 76 0.43 Example 2 (GF10-20) 20 45 0.41 Example 3 (GF10-40) 40 38 0.42 Example 4 (GF10-50) 50 26 0.39

&Lt; Examples 5 to 8 >

Celloxide 2021P (Daicel Co., Ltd.): Polyethylene glycol (Polyethylene glycol; Aldrich Mn 200): Photoinitiator (Triarylsulfonium hexafluoroantimonate salts in Propylene Carbonate.50 wt% solution) 300 (Average Primary Particle Size 7nm: FUMED SILICA: DEGUSSA) was added to 1, 5, 10 or 20 parts by weight, respectively, to prepare the adhesive composition for lamination of Examples 5 to 8, and the lamination, curing and measuring methods were carried out as described above. It carried out similarly to Example 1, and described the result value in Table 2 below.

Ae300 CTE (ppm / ° C) WVTR (g / m ² · day) Example 5 (Ae300-1) One 79 0.42 Example 6 (Ae300-5) 5 77 0.39 Example 7 (Ae300-10) 10 68 0.31 Example 8 (Ae200-20) 20 62 0.21

<Examples 9 to 16>

Celloxide 2021P (Daicel Co., Ltd.): Polyethylene glycol (Polyethylene glycol; Aldrich Mn 200): Photoinitiator (Triarylsulfonium hexafluoroantimonate salts in Propylene Carbonate.50 wt% solution) = 100: 15: 3 The adhesive composition for lamination was prepared by mixing GF10 and Aerosil300, a nano-size inorganic material, in parts by weight shown in Table 3. After laminating in the same manner as in Example 1 and curing, a plastic substrate was prepared, and the linear expansion coefficient and water vapor permeability were measured, and the results are shown in Table 3 below.

Ae300 GF10 CTE (ppm / ° C) WVTR (g / m ² · day) Example 9 (GF10-20 / Ae300-1) One 20 43 0.42 Example 10 (GF10-20 / Ae300-5) 5 20 39 0.34 Example 11 (GF10-20 / Ae300-10) 10 20 35 0.22 Example 12 (GF10-20 / Ae300-20) 20 20 29 0.15 Example 13 (GF10-5 / Ae300-10) 10 5 55 0.43 Example 14 (GF10-20 / Ae300-10) 10 20 35 0.22 Example 15 (GF10-40 / Ae300-10) 10 40 27 0.21 Example 16 (GF10-50 / Ae300-10) 10 50 21 0.18

For Examples 1 to 4 using glass flakes alone, it was shown that CTE and WVTR decreased as the content of glass flakes increased.

In addition, in Examples 9 to 16 using nano-size silica, it was shown that the CTE and WVTR decreased as the content of the nano-size silica increased.

In addition, Examples 9 to 16 are intended to maximize the physical properties of the adhesive composition for lamination by uniformly dispersed in the lamination layer by using nano-size inorganic particles smaller than the glass flake together, first, the content of the glass flakes to the content of the adhesive solids The ratio of CTE and WVTR decreased significantly when the ratio was fixed to 20 parts by weight and added thereto while increasing the content of nano-sized inorganic particles.

&Lt; Comparative Example 1 &

Celloxide 2021P (Daicel): Polyethylene glycol (Polyethylene glycol, Aldrich Mn 200): Photoinitiator (Triarylsulfonium hexafluoroantimonate salts in Propylene Carbonate. Without the addition of flakes, the plastic substrate was produced by curing after curing under the conditions of Example 1 to measure the coefficient of linear expansion and water vapor transmission rate.

Glass Flake (GF10) CTE (ppm / ℃) WVTR (g / m ² · day) Comparative Example 1 (GF10-0) 0 80 0.44

Comparative Example 2

Except AEROSIL 300, the adhesive composition for lamination was prepared as in Example 2, and two plastic substrates were laminated under the same conditions as in Comparative Example 1, and then cured.

Ae300 CTE (ppm / ℃) WVTR (g / m ² · day) Comparative Example 2 (GF10-20) 0 45 0.41

Referring to Table 5, when the glass flakes were used, the CTE was improved, but the moisture permeability was not improved. Therefore, as shown in Comparative Examples 1 and 2, in order to satisfy the high moisture barrier properties and low linear expansion and coefficient at the same time, the improvement effect can be maximized by using the adhesive composition for lamination of the present invention.

Claims (14)

(a) glass flakes; (b) an epoxy resin; A plastic substrate of a multi-layered or symmetrical structure, comprising two or more plastic substrates laminated by a laminating adhesive composition comprising (c) a photoinitiator and (d) a nanosized inorganic particle smaller than the glass flakes. (a) glass flakes; (b) an epoxy resin; (c) a multilayer or symmetric comprising at least two plastic substrates comprising a photoinitiator and laminated by a laminating adhesive composition comprising at least 50 parts by weight of (a) the glass flakes relative to 100 parts by weight of (b) the epoxy resin; Plastic substrate of structure. (b) an epoxy resin; (c) a photoinitiator and (d) a nano-sized inorganic particle having a primary particle size of 1 nm to 100 nm, and comprises (d) inorganic particles at least 20 parts by weight relative to 100 parts by weight of the (b) epoxy resin. A plastic substrate of multilayer or symmetrical structure comprising two or more plastic substrates laminated by a laminating adhesive composition. The plastic substrate of claim 2, wherein the adhesive composition for lamination further comprises one or more nano-size inorganic particles selected from nanoclays and glass beads. The glass flakes of claim 1 or 2, wherein the glass flakes include GF10 (0.1 μm), GF35 (0.35 μm), GF50 (0.5 μm), GF70 (0.7 μm), GF100 (1 μm), GF300 (3 μm), and GF500 (5). Μm) and GF750 (7 μm) plastic substrate of a multi-layered or symmetrical structure comprising at least one selected from. The glass flakes of claim 1 or 2, wherein the glass flakes comprise an unmilled glass flake having a particle size of 1700 to 150 μm of 80% and a particle size of 150 to 50 μm of 20%; Milled glass flakes having a particle size of 1000 to 300 μm of 10%, a particle size of 300 to 50 μm of 65%, and a particle size of 50 μm or less of 25%; And at least one member selected from micronised glass flakes having a particle size of 150 μm or more, 2%, a particle size of 150 to 50 μm of 10%, and a particle size of 50 μm or less of 88%. Board. The plastic substrate of claim 1, wherein the glass flakes have a refractive index in the range of 1.50 to 1.60. The multilayer or symmetrical structure of claim 1, wherein the epoxy resin further comprises one or more selected from cycloaliphatic, modified cycloaliphatic, and hybrid resin systems. Plastic substrate. The plastic substrate according to any one of claims 1 to 3, wherein the epoxy resin contains 1 to 50 wt% of vinyl ethers. The plastic of claim 1, wherein the photoinitiator comprises one or more selected from sulfonium salts, ferrocenium salts, and diazonium salts. Board. Applying a laminating adhesive composition to at least one of the surfaces of each layer constituting the plastic substrate of the multilayer or symmetric structure; And A method of laminating a plastic substrate of any one of claims 1 to 3, comprising curing and bonding the laminating adhesive composition with heat, UV, or ions. Light emitter comprising a plastic substrate of any one of claims 1 to 3 multi-layered or symmetrical structure. A display device comprising the plastic substrate of any one of claims 1-3. A solar power plant comprising the plastic substrate of any one of claims 1 to 3 multi-layered or symmetrical structure.