KR102327593B1 - The barrier film and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a barrier film and a method for manufacturing the same, and specifically to a barrier film having improved handling and uniformity, and a method for manufacturing the same.

Description

Barrier film and manufacturing method thereof

The present invention relates to a barrier film and a method for manufacturing the same.

Quantum dots are semiconductor materials with a crystal structure of several nanometers, and have different wavelengths depending on their size. Or it is known that it can be used as a display itself. On the other hand, the quantum dots are used, for example, combined in a small amount in a polymer optical sheet that enters the backlight unit (BLU).

However, when the quantum dots are exposed to moisture and oxygen in the air, there is an oxidation problem due to surface oxidation. In general, the optical sheet is disposed on the light guide plate of the blue BLU module (on-surface method). On the other hand, the optical sheet can respond to various display screen sizes from small to large.

On the other hand, the optical sheet as described above has a certain degree of barrier performance against moisture and oxygen due to the barrier film, but there is a problem in that the barrier performance of the barrier film rapidly decreases when exposed to high temperature and high humidity conditions. There is a problem in that the luminance cannot be stably maintained.

In addition, the inorganic layer, which is the main component of the barrier film, is generally produced through ALD, PE-CVD, sputter, thermal evaporation, etc., and researches to improve the performance of the inorganic layer and lower the price have been conducted during sample production through the Roll to Roll process. is losing In particular, since the film is formed in a vacuum, the thickness of the substrate is thin and the film formation speed is set high to increase the yield. Characteristics are required, and research to solve them is urgently needed.

Accordingly, an object of the present invention is to provide a barrier film having improved handleability and uniformity, and a method for manufacturing the same.

A first preferred embodiment of the present invention for solving the above problems is a barrier layer consisting of a substrate layer and an inorganic material layer; And an adhesive layer and a base layer are laminated on any one surface of the barrier layer, and the order in which the adhesive layer and the base layer are laminated is to provide a barrier film comprising a laminated adhesive layer and a base layer sequentially from the barrier layer.

It is characterized in that the adhesive layer and a separate barrier layer are sequentially laminated on the other surface of the barrier layer on which the adhesive layer and the base layer are laminated.

It is characterized in that the overcoat layer is laminated on the other surface of the barrier layer on which the adhesive layer is not laminated.

The base layer is a cyclic olipine-based resin, polystyrene-based resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polymethacrylic resin, polycarbonate-based resin, polyethylene A polyester-based resin including terephthalate and polyethylene naphthalate, a polyamide-based resin including nylon, a polyurethane-based resin, an acetal-based resin, and any one or more selected from the group consisting of a cellulose-based resin do it with

The inorganic material layer is silicon (Si), aluminum (Al), indium (In), tin (Sn), zinc (Zn), zirconium (Zr), titanium (Ti), copper (Cu), cerium (Ce), At least one metal selected from the group consisting of yttrium (Yt), lanthanum (La), barium (Ba), magnesium (Mg), fluorine (F2), antimony (Sb), strontium (Sr), and tantalum (Ta); It is characterized in that it contains any one or more inorganic substances selected from the group consisting of oxides, nitrides, carbides, oxidized carbides, oxidized carbides, nitrided carbides, and oxynitride carbides.

The adhesive layer is characterized in that it comprises a UV curable resin and a photoinitiator.

The adhesive layer is characterized in that it contains 0.5 to 25 parts by weight of a photoinitiator based on 100 parts by weight of the UV curable resin.

The UV curable resin includes epoxy, epoxy acrylate, lauryl acrylate, norborene, polystyrene, ethylene-styrene, acrylate containing bisphenol A and bisphenol A derivatives, acrylate containing fluorene derivatives, and isobornyl acrylic. Late, polyphenylalkylsiloxane, urethane acrylate oligomer, dipentaerythritol pentaacrylate, and trihydroxyethyl isocyanurate triacrylate comprising any one or more selected from the group consisting of.

The photoinitiator is characterized in that it is selected from the group consisting of benzophenone series, thioxanthone series, hydroxy ketone and alpha amino ketone series.

The adhesive layer is characterized in that 0.1 to 100㎛.

The adhesive layer is characterized in that the refractive index value is 1.3 to 2.1.

The overcoat layer is characterized in that it comprises a UV curable resin, a thermoplastic resin, and a photoinitiator.

The UV curable resin comprises at least one selected from the group consisting of an epoxy resin, an unsaturated polyester resin, a polyurethane resin, a polycarbonate polyurethane, a polyester polyurethane, a phenol resin, a melamine resin, a urea resin, and a silicon resin characterized in that

The thermoplastic resin is any one selected from the group consisting of a urethane-based resin, a copolymer of a urethane-based resin and a polyether-based resin, a copolymer of a urethane-based resin and a polyester-based resin, a polyester-based resin, and a polyvinylbutyltloride-based resin It is characterized in that it includes the above.

The overcoating layer is characterized in that it contains 50 to 500 parts by weight of the thermoplastic resin and 0.5 to 20 parts by weight of the photoinitiator based on 100 parts by weight of the UV curable resin.

In addition, a second preferred embodiment of the present invention comprises the steps of forming a barrier layer by laminating an inorganic material layer on any one surface of the base layer (S1); And after forming an adhesive layer by wet coating the adhesive layer composition on any one surface of the formed barrier layer, laminating a substrate layer on top of the formed adhesive layer (S2). will do

forming an overcoat layer by wet coating the overcoat layer composition on the other surface of the barrier layer formed in step S1 (S3).

After wet coating the adhesive layer on the other surface of the barrier layer formed in step S1, laminating a separate barrier layer on top of the coated adhesive layer (S4). The adhesive layer composition includes a UV curable resin and a photoinitiator.

According to the present invention, handleability and barrier performance are improved, and when applied to a QD sheet, the adhesive strength between the QD Lay (quantum dot layer) and the barrier sheet is improved.

1 schematically shows a preferred example of a barrier film according to the present invention.
2 schematically shows another preferred example of a barrier film according to the present invention.
3 schematically shows another preferred example of a barrier film according to the present invention.
4 schematically shows another preferred example of a barrier film according to the present invention.
5 schematically shows an example in which the barrier film according to the present invention is applied to a QD sheet.

According to an aspect of the present invention, a barrier layer comprising a substrate layer and an inorganic material layer; And an adhesive layer and a substrate layer are laminated on any one surface of the barrier layer, and the order in which the adhesive layer and the substrate layer are laminated is sequentially from the barrier layer.

1 schematically shows a preferred example of a barrier film according to the present invention.

When the barrier film according to the present invention is described in detail with reference to FIG. 1, an adhesive layer and a substrate layer are sequentially laminated on one side of the barrier layer (A) consisting of a substrate layer and an inorganic layer based on the barrier layer. include For example, it is to include a structure in which the substrate layer, the inorganic layer, the adhesive layer and the substrate layer are sequentially laminated from above, or the inorganic layer, the substrate layer, the adhesive layer and the substrate layer are sequentially laminated from above.

In addition, the barrier film according to the present invention includes an adhesive layer and a separate barrier layer sequentially laminated on the other surface of the barrier layer on which the adhesive layer and the base layer are laminated.

2 schematically shows another preferred example of a barrier film according to the present invention. When the barrier film including the structure is described in detail with reference to FIG. 2 , an adhesive layer and a base layer are sequentially laminated with respect to the barrier layer on one surface of the barrier layer (A) consisting of a base layer and an inorganic layer, and the other An adhesive layer and a separate barrier layer (A') different from the barrier layer may be further laminated on one surface. For example, sequentially laminated with a base layer, an inorganic layer, an adhesive layer, an inorganic layer, a base layer, an adhesive layer and a base layer from above, or an inorganic layer, a base layer, an adhesive layer, an inorganic layer, a base layer, an adhesive layer, and a base layer sequentially from above It is to be laminated as or to include a structure in which the inorganic layer, the substrate layer, the adhesive layer, the substrate layer, the inorganic layer, the adhesive layer and the substrate layer are sequentially laminated from above.

In the present invention, as described above, by including one or more barrier layers consisting of a base layer and an inorganic material layer, and by laminating an adhesive layer and a base layer on any one surface of the barrier layer, the crack resistance of the inorganic layer is improved. , it is possible to obtain the effect of increasing the uniformity of the barrier characteristics. In addition, it is possible to obtain the effect of further increasing the barrier properties by further including one or more barrier layers composed of a base layer and an inorganic material layer.

In addition, in the barrier film according to the present invention, it is preferable that an overcoat layer is laminated on the other surface of the barrier layer on which the adhesive layer is not laminated. In particular, when the barrier film is applied to the QD sheet, it is preferable to include an overcoating layer on the barrier film.

3 and 4 schematically show another preferred example of a barrier film including an overcoat layer according to the present invention. 3 and 4, if described in detail, the adhesive layer and the base layer are sequentially laminated on one side of the barrier layer consisting of the substrate layer and the inorganic layer, and the overcoat layer is laminated on the other side of the barrier layer. can For example, the overcoat layer, the substrate layer, the inorganic layer, the adhesive layer and the substrate layer are sequentially laminated from above, or the overcoat layer, the inorganic layer, the substrate layer, the adhesive layer and the substrate layer are sequentially laminated from above.

In addition, an adhesive layer and a substrate layer are sequentially laminated on one side of the barrier layer (A) made of a substrate layer and an inorganic layer based on the barrier layer, and on the other side, an adhesive layer and a separate barrier layer different from the barrier layer (A') ) in the additionally laminated structure, the overcoat layer may be laminated on one surface on which the adhesive layer of the separate barrier layer (A') is not laminated. For example, the overcoat layer, the substrate layer, the inorganic layer, the adhesive layer, the inorganic layer, the substrate layer, the adhesive layer, and the substrate layer are sequentially laminated from above, or the overcoat layer, the inorganic layer, the substrate layer, the adhesive layer, the inorganic layer, the substrate sequentially from above It is laminated as a layer, an adhesive layer and a base layer, or includes a structure in which an overcoat layer, an inorganic layer, a base layer, an adhesive layer, a base layer, an inorganic layer, an adhesive layer, and a base layer are sequentially stacked from above.

In the present invention, as described above, by laminating the overcoating layer, it is possible to obtain the effect of increasing the adhesion with the QD resin and the high-temperature, high-humidity reliability characteristics when manufacturing the final product, the QD sheet.

For the base layer, a base material generally used in the art may be used, and a cyclic olipine-based resin, a polystyrene-based resin, an acrylonitrile-styrene copolymer (AS resin), an acrylonitrile-butadiene-styrene copolymer (ABS) resin), polymethacrylic resin, polycarbonate resin, polyester resin including polyethylene terephthalate and polyethylene naphthalate, polyamide resin including nylon, polyurethane resin, acetal resin, cellulose resin It is preferable to include any one or more selected from the group consisting of.

The inorganic material layer is silicon (Si), aluminum (Al), indium (In), tin (Sn), zinc (Zn), zirconium (Zr), titanium (Ti), copper (Cu), cerium (Ce), At least one metal selected from the group consisting of yttrium (Yt), lanthanum (La), barium (Ba), magnesium (Mg), fluorine (F2), antimony (Sb), strontium (Sr), and tantalum (Ta); It is preferable to include any one or more inorganic substances selected from the group consisting of oxides, nitrides, carbides, oxidized carbides, oxidized carbides, nitrided carbides, and oxynitride carbides.

The adhesive layer may include a UV curable resin and a photoinitiator, and the content thereof is preferably 0.5 to 25 parts by weight, preferably 1 to 10 parts by weight, of the photoinitiator based on 100 parts by weight of the UV curable resin. When the amount of the photoinitiator is less than 0.5 parts by weight, there is a problem that UV curing cannot be performed properly, and when it exceeds 25 parts by weight, the polymer chain is shortened and there is a problem that the adhesive force may decrease.

Examples of the UV curable resin include epoxy, epoxy acrylate, lauryl acrylate, norborene, polystyrene, ethylene-styrene, acrylates containing bisphenol A and bisphenol A derivatives, acrylates containing fluorene derivatives, and isobornyl. It is preferable to include any one or more selected from the group consisting of acrylate, polyphenylalkylsiloxane, urethane acrylate oligomer, dipentaerythritol pentaacrylate, and trihydroxyethyl isocyanurate triacrylate.

At this time, the content of the bisphenol diacrylate-based derivative in the UV-curable resin may be appropriately adjusted according to the refractive index required for the cured resin layer, and is 5 to 99.5% by weight based on the solid content of the adhesive layer composition, preferably 10 to 50% by weight is preferred. If it is less than 5% by weight, the refractive index value may be too low (less than 1.3), and if it exceeds 99.5% by weight, it may be a refractive index value (greater than 2.1), but the viscosity of the adhesive layer composition increases and the film formed from this adhesive layer composition is broken It is easy to brittle and the flexibility may be lowered.

The photoinitiator is preferably at least one selected from the group consisting of benzophenone series, thioxanthone series, hydroxy ketone series and alpha amino ketone series.

The adhesive layer according to the present invention is preferably 0.1 to 100 μm, preferably 1 to 50 μm. If the thickness of the adhesive layer is less than 0.1㎛, the thickness of the adhesive? Adhesion may be reduced, and when it exceeds 100 μm, the flexibility of the film may deteriorate.

In addition, the above-mentioned adhesive layer preferably has a refractive index value of 1.3 to 2.1, preferably 1.5 to 1.8. When the refractive index value of the adhesive layer is less than 1.3 or exceeds 2.1, there is a problem in that the transmittance of the barrier film is lowered due to the interference effect of light.

The overcoating layer includes a UV curable resin, a thermoplastic resin, and a photoinitiator, and a UV curable resin for maintaining adhesion with the inorganic layer even under high temperature/high humidity conditions and QD (quantum dot) resin under high temperature/high humidity conditions. It contains a mixed composition of the thermoplastic resin to maintain the. The QDI resin means QDI resin commonly used in the field to which the present invention belongs.

The UV curable resin included in the overcoating layer is selected from the group consisting of an epoxy resin, an unsaturated polyester resin, a polyurethane resin, a polycarbonate polyurethane, a polyester polyurethane, a phenol resin, a melamine resin, a urea resin, and a silicon resin. It is preferable to include one or more.

The thermoplastic resin is any one selected from the group consisting of a urethane-based resin, a copolymer of a urethane-based resin and a polyether-based resin, a copolymer of a urethane-based resin and a polyester-based resin, a polyester-based resin and a polyvinylbutyltloride-based resin It is preferable to include the above.

The photoinitiator preferably includes at least one selected from the group consisting of benzophenone series, thioxanthone series, hydroxy ketone series, and alpha amino ketone series. The overcoating layer is preferably included in 50 to 500 parts by weight, preferably 100 to 400 parts by weight, of the thermoplastic resin based on 100 parts by weight of the UV curable resin in terms of adhesion to QD resin and reliability of high temperature and high humidity.

When the amount of the thermoplastic resin is less than 50 parts by weight, the adhesive strength with the QD resin is low, and the QD resin cannot be protected. 60℃, 90%, 1000hr) there is a problem that may drop.

The overcoating layer is preferably included in an amount of 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight of the photoinitiator based on 100 parts by weight of the UV curable resin. When the amount of the photoinitiator is less than 0.5 parts by weight, there is a problem that UV curing is not performed, and when it exceeds 20 parts by weight, the polymer chain is shortened and the adhesive force may be lowered. In this case, the overcoat layer may further include a silane coupling agent, and the silane coupling agent is included in an amount of 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the UV curable resin. In the case of the silane coupling agent, an effect of improving adhesion between the overcoating layer and the inorganic layer may be obtained through the reaction of the silane coupling agent with the hydroxyl group present on the surface of the inorganic layer laminated in contact with the overcoating layer.

As the silane coupling agent, a silane coupling agent commonly used in the field to which the present invention belongs may be arbitrarily selected and used, for example, a vinyl group, an epoxy group, a styryl group, a methacrylate group, an acrylate group, an amino group, and compounds containing a chloropropyl group, a mercapto group, a sulfido group, an isocyanato group, and the like.

The barrier film including the laminate structure as described above can be applied to a QD sheet, and FIG. 5 schematically shows an example in which the barrier film according to the present invention is applied to the QD sheet. . As shown in FIG. 5 , a QD sheet may be manufactured by stacking a QD layer (QD Lay; quantum dot layer) between the barrier films according to the present invention. At this time, the QD layer is preferably laminated in contact with the overcoat layer located at the outermost portion of the barrier film of the present invention. When the QD layer is laminated between the overcoat layer located on the outermost side of the barrier film of the present invention, the adherend has an adhesive force that destroys it, and the adhesive force can be maintained even at high temperature and high humidity (60 ℃ 90%). When the adhesive strength as described above is obtained, it is possible to protect the QD resin from moisture or oxygen, and has the advantage of extending the lifespan.

The above-described barrier film may be manufactured by a manufacturing method according to another aspect described below.

According to another aspect of the present invention, forming a barrier layer by laminating an inorganic layer on any one surface of the base layer (S1); And after forming an adhesive layer by wet coating the adhesive layer composition on any one surface of the formed barrier layer, laminating a substrate layer on top of the formed adhesive layer (S2) It provides a method of manufacturing a barrier film comprising: will be.

First, a barrier layer is formed by laminating an inorganic material layer on any one surface of the base layer (S1).

The base layer is the same as described above, and after plasma pretreatment is performed on any one surface of the base layer, an inorganic material is dry-coated to laminate the inorganic material layer.

The inorganic material is silicon (Si), aluminum (Al), indium (In), tin (Sn), zinc (Zn), zirconium (Zr), titanium (Ti), copper (Cu), cerium (Ce), yttrium Contains at least one metal selected from the group consisting of (Yt), lanthanum (La), barium (Ba), magnesium (Mg), fluorine (F2), antimony (Sb), strontium (Sr), and tantalum (Ta) It is preferable to include any one or more selected from the group consisting of oxides, nitrides, carbides, oxidized carbides, oxidized carbides, nitrided carbides, and oxynitrided carbides.

In this case, the inorganic material layer is preferably formed to a thickness of 0.5 to 110 nm, preferably 1 to 80 nm.

Then, the adhesive layer composition is wet-coated on one surface of the formed barrier layer to form an adhesive layer, and then a base layer is laminated on the formed adhesive layer (S2).

The adhesive layer composition may include a UV curable resin and a photoinitiator, and the content thereof is 0.5 to 25 parts by weight, preferably 1 to 10 parts by weight of the photoinitiator based on 100 parts by weight of the UV curable resin. When the amount of the photoinitiator is less than 0.5 parts by weight, there is a problem that UV curing cannot be performed properly, and when it exceeds 25 parts by weight, the polymer chain is shortened and there is a problem that the adhesive force may decrease.

Examples of the UV curable resin include epoxy, epoxy acrylate, lauryl acrylate, norborene, polystyrene, ethylene-styrene, acrylates containing bisphenol A and bisphenol A derivatives, acrylates containing fluorene derivatives, isobornyl It is preferable to include any one or more selected from the group consisting of acrylate, polyphenylalkylsiloxane, urethane acrylate oligomer, dipentaerythritol pentaacrylate, and trihydroxyethyl isocyanurate triacrylate.

The photoinitiator is preferably at least one selected from the group consisting of benzophenone series, thioxanthone series, hydroxy ketone series and alpha amino ketone series.

The lamination process may be performed by selecting a lamination method commonly used in the field to which the present invention pertains.

Meanwhile, in the present invention, the overcoating composition may be wet coated on the other surface of the barrier layer formed in step S1 to form an overcoating layer (S3). The barrier film including the overcoat layer is preferable when applied to a QD (QD) sheet.

The overcoating layer composition includes a UV curable resin, a thermoplastic resin, and a photoinitiator.

The UV curable resin included in the overcoating layer is selected from the group consisting of an epoxy resin, an unsaturated polyester resin, a polyurethane resin, a polycarbonate polyurethane, a polyester polyurethane, a phenol resin, a melamine resin, a urea resin, and a silicon resin. It is preferable to include one or more.

The thermoplastic resin is any one selected from the group consisting of a urethane-based resin, a copolymer of a urethane-based resin and a polyether-based resin, a copolymer of a urethane-based resin and a polyester-based resin, a polyester-based resin, and a polyvinylbutyltloride-based resin more preferably.

The photoinitiator is preferably at least one selected from the group consisting of benzophenone series, thioxanthone series, hydroxy ketone series, and alpha amino ketone series.

The overcoating layer is preferably included in an amount of 50 to 500 parts by weight of the thermoplastic resin, preferably 100 to 400 parts by weight, based on 100 parts by weight of the UV curable resin. When the amount of the thermoplastic resin is less than 50 parts by weight, the adhesive strength with the QD resin is low, and the QD resin cannot be protected. 60℃, 90%, 1000hr) there is a problem that may drop.

The overcoating layer is preferably included in an amount of 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight of the photoinitiator based on 100 parts by weight of the UV curable resin. When the amount of the photoinitiator is less than 0.5 parts by weight, there is a problem that UV curing is not performed, and when it exceeds 20 parts by weight, the polymer chain is shortened and the adhesive force may be lowered.

In this case, the overcoat layer may further include a silane coupling agent, and the silane coupling agent is included in an amount of 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the UV curable resin. In the case of the silane coupling agent, an effect of improving adhesion between the overcoating layer and the inorganic layer may be obtained through the reaction of the silane coupling agent with the hydroxyl group present on the surface of the inorganic layer laminated in contact with the overcoating layer.

The silane coupling agent is the same as described above.

The barrier film manufactured including step S3 has adhesive strength with QD resin, serves to protect moisture and oxygen from the outside, and the ease of handling of the barrier film improves the uniformity of barrier properties, so that QD It can solve the black spot problem caused by death, so it can be effective as a protective layer of QD resin.

In addition, in the present invention, after wet coating an adhesive layer on the other side of the barrier layer formed in step S1, laminating a separate barrier layer on top of the coated adhesive layer (S4) It is preferable to include do.

It means that the separate barrier layer is a barrier layer manufactured by the same method in step S1 described above.

The barrier film produced including the step S4 may have better barrier performance by further introduction of the inorganic layer, have an adhesive force with QD resin and protect moisture and oxygen from the outside, and handleability of the barrier film This facilitates the improvement of the uniformity of the barrier properties, so it is possible to solve the black spot problem caused by the QD dying after the QD sheet is manufactured, thereby obtaining the effect of the QD resin as a protective layer.

Example

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention in more detail, and the present invention is not limited thereto.

Example 1

Preparation of barrier layer

After plasma pretreatment using a roll-to-roll evaporator on one side of polyethylene terephthalate (KOLON's U43R grade) with a thickness of 25㎛, dry coating with a total thickness of 70nm of AlOx 10nm / SiOx 60nm and then an inorganic layer is formed Thus, a barrier layer was prepared.

Adhesive layer composition preparation

After diluting 100 parts by weight of a urethane acrylate resin (Tesk, A-2697 grade) with a methyl ethyl ketone solvent, a photoinitiator (Igacure 184) was added in an amount of 3 parts by weight based on 100 parts by weight of the urethane acrylate resin After that, it was sufficiently dissolved to prepare an adhesive layer composition having a solid content of 20 wt%.

Barrier film production

Wet coating the adhesive layer composition to a thickness of 5 μm on the upper surface of the inorganic material layer of the prepared barrier layer, drying in an oven at 80° C. for 3 minutes to form an adhesive layer, and then a base layer on the upper surface of the formed adhesive layer After roll lamination, a type-D bulb was mounted on an ultraviolet irradiator (Fusion) and irradiated with an exposure dose of 500 mJ/cm 2 to prepare a barrier film.

Manufacture of optical sheet

A crude urethane acrylic resin polymer solution in which non-cadmium-based quantum dots are dispersed between the two barrier films prepared above was applied to a thickness of 100 μm and UV cured under exposure conditions of 1000 mJ/cm 2 to prepare an optical sheet.

Example 2

Preparation of barrier layer

After plasma pretreatment using a roll-to-roll evaporator on one side of polyethylene terephthalate (KOLON's U43R grade) with a thickness of 25㎛, dry coating with a total thickness of 70nm of AlOx 10nm / SiOx 60nm and then an inorganic layer is formed Thus, a barrier layer was prepared.

Adhesive layer composition preparation

After diluting 100 parts by weight of a urethane acrylate resin (Tesk, A-2697 grade) with a methyl ethyl ketone solvent, a photoinitiator (Igacure 184) was added in an amount of 3 parts by weight based on 100 parts by weight of the urethane acrylate resin After that, it was sufficiently dissolved to prepare an adhesive layer composition having a solid content of 20 wt%.

Preparation of overcoating composition

Polyurethane (Ellas/KOLON) as a thermoplastic resin and urethane acrylate (8BR/Taisei Fine Chemical) as a UV curable resin are added in 100 parts by weight of the thermoplastic resin based on 100 parts by weight of the UV curable resin, and these are added as a solvent MEK After mixing with (Methyl Ethyl Ketone), 10 parts by weight of a silane coupling agent (OFS6020/DOW) as an additive based on 100 parts by weight of a UV curable resin, and a hydrolysis resistant agent (ALTFONA5151/Green Chem) with a UV curable resin Based on 100 parts by weight, 1 part by weight of the photoinitiator (Irgacure184/CIBA) was added in an amount of 7.5 parts by weight based on 100 parts by weight of the UV curable resin, and stirred to prepare.

Barrier film production

Wet coating the adhesive layer composition to a thickness of 5 μm on the upper surface of the substrate layer of the prepared barrier layer, drying in an oven at 80° C. for 3 minutes to form an adhesive layer, and then a substrate layer on the upper surface of the formed adhesive layer After roll lamination, a type-D bulb was mounted on an ultraviolet irradiator (Fusion) and irradiated with an exposure amount of 500 mJ/cm 2 . Thereafter, an overcoating layer was formed by M/G coating (Micro Gravure Coating) of the overcoating composition on the upper surface of the inorganic material layer of the barrier layer.

Manufacture of optical sheet

A crude urethane acrylic resin polymer solution in which non-cadmium-based quantum dots are dispersed between the two barrier films prepared above was applied to a thickness of 100 μm and UV cured under exposure conditions of 1000 mJ/cm 2 to prepare an optical sheet.

Example 3

A barrier film and an optical sheet were prepared in the same manner as in Example 1, except for the following examples.

Preparation of first and second adhesive layer compositions

After diluting 100 parts by weight of a urethane acrylate resin (Tesk, A-2697 grade) with a methyl ethyl ketone solvent, a photoinitiator (Igacure 184) was added in an amount of 3 parts by weight based on 100 parts by weight of the urethane acrylate resin After that, it was sufficiently dissolved to prepare an adhesive layer composition having a solid content of 20 wt%. At this time, the first and second adhesive layer compositions were prepared in the same manner as described above.

Barrier film production

Wet coating the adhesive layer composition to a thickness of 5 μm on the upper surface of the base layer of the prepared barrier layer, drying in an oven at 80° C. for 3 minutes to form a first adhesive layer, and then forming the first After roll lamination of the base layer on the upper surface of the adhesive layer, a type-D bulb was mounted on an ultraviolet irradiator (Fusion) and irradiated with an exposure amount of 500 mJ/cm 2 . Thereafter, a separate adhesive layer composition is wet coated on the upper surface of the inorganic material layer of the barrier layer to a thickness of 5 μm, dried in an oven at 80° C. for 3 minutes to form a second adhesive layer, and then the formed The barrier layer prepared in the same manner as described above was laminated on the upper surface of the adhesive layer of Step 2, and the inorganic layer of the barrier layer was laminated so as to be in contact with the second adhesive layer.

Example 4

A barrier film and an optical sheet were prepared in the same manner as in Example 2, except for the following examples.

Preparation of first and second adhesive layer compositions

After diluting urethane acrylate resin (Tesk, A-2697 grade) with methyl ethyl ketone solvent, add 3 parts of photoinitiator (Igacure 184) to the solid content of the acrylate resin and dissolve it sufficiently to make an adhesive layer composition with a solid content of 20 wt% was prepared. The first and second adhesive layer compositions were prepared in the same manner as described above.

Barrier film production

Wet coating the adhesive layer composition to a thickness of 5 μm on the upper surface of the base layer of the barrier layer prepared above, drying in an oven at 80° C. for 3 minutes to form a first adhesive layer, and then the upper surface of the formed adhesive layer After roll lamination of the substrate layer, a type-D bulb was mounted on an ultraviolet irradiator (Fusion) and irradiated with an exposure amount of 500 mJ/cm 2 . Thereafter, a separate adhesive layer composition is wet coated on the upper surface of the inorganic material layer of the barrier layer to a thickness of 5 μm, dried in an oven at 80° C. for 3 minutes to form a second adhesive layer, and then the formed The barrier layer prepared in the same manner as above was laminated on the upper surface of the adhesive layer of No. 2, and the substrate layer of the barrier layer was laminated so as to be in contact with the second adhesive layer. Thereafter, the overcoating composition was M/G coated on the upper surface of the inorganic material layer of the barrier layer laminated on the second adhesive layer to form an overcoating layer.

Example 5

A barrier film and an optical sheet were prepared in the same manner as in Example 4, except for the following examples.

Preparation of first and second adhesive layer compositions

After diluting 100 parts by weight of a urethane acrylate resin (Tesk, A-2697 grade) with a methyl ethyl ketone solvent, a photoinitiator (Igacure 184) was added in an amount of 10 parts by weight based on 100 parts by weight of the urethane acrylate resin After that, it was sufficiently dissolved to prepare an adhesive layer composition having a solid content of 20 wt%. The first and second adhesive layer compositions were prepared in the same manner as described above.

Example 6

A barrier film and an optical sheet were prepared in the same manner as in Example 4, except for the following examples.

Preparation of first and second adhesive layer compositions

After diluting 100 parts by weight of a urethane acrylate resin (Tesk, A-2697 grade) with a methyl ethyl ketone solvent, a photoinitiator (Igacure 184) was added in an amount of 20 parts by weight based on 100 parts by weight of the urethane acrylate resin After that, it was sufficiently dissolved to prepare an adhesive layer composition having a solid content of 20 wt%. The first and second adhesive layer compositions were prepared in the same manner as described above.

Example 7

A barrier film and an optical sheet were prepared in the same manner as in Example 4, except for the following examples.

Preparation of first and second adhesive layer compositions

After diluting 100 parts by weight of an epoxy acrylate resin (Test, A-2699 grade) with a methyl ethyl ketone solvent, a photoinitiator (Igacure 184) was added in an amount of 3 parts by weight based on 100 parts by weight of the urethane acrylate resin After that, it was sufficiently dissolved to prepare an adhesive layer composition having a solid content of 20 wt%. The first and second adhesive layer compositions were prepared in the same manner as described above.

Example 8

A barrier film and an optical sheet were prepared in the same manner as in Example 4, except for the following examples.

Preparation of overcoating composition

Polyurethane (Ellas/KOLON) as a thermoplastic resin and urethane acrylate (8BR/Taisei Fine Chemical) as a UV curable resin are added in 300 parts by weight of a thermoplastic resin based on 100 parts by weight of the UV curable resin, and these are added as a solvent MEK After mixing with (Methyl Ethyl Ketone), 10 parts by weight of a silane coupling agent (OFS6020/DOW) as an additive based on 100 parts by weight of a UV curable resin, and a hydrolysis resistant agent (ALTFONA5151/Green Chem) with a UV curable resin Based on 100 parts by weight, 1 part by weight of the photoinitiator (Irgacure184/CIBA) was added in an amount of 7.5 parts by weight based on 100 parts by weight of the UV curable resin, and stirred to prepare.

Comparative Example 1

The same procedure was performed except that in Example 1, an adhesive layer and a base layer were not laminated on top of the barrier layer.

Comparative Example 2

The same procedure was performed except that in Example 2, an adhesive layer and a base layer were not laminated on top of the barrier layer.

The physical properties were measured in the following manner, and the results are shown in Tables 1 and 2.

(1) Thickness of adhesive layer: To measure the thickness of the coated adhesive, it was measured using a thickness meter (Mitutoyo, IP65).

(2) Refractive index of the adhesive layer: To measure the refractive index of the adhesive layer, the adhesive layer is coated with a certain thickness on the substrate, dried and UV cured to form a coating layer, and then measured using an ellipsometer (Ellipso Technology, Ellip-SE) equipment. did.

(3) Barrier property measurement of barrier film: In order to measure the WVTR value, the barrier property was measured at a temperature of 37.8° C. and a humidity of 100% using a MOCON Permatran-W700 equipment.

(4) Barrier uniformity measurement of barrier film: Measure the barrier properties of the first, middle, and end samples in the MD direction of the roll sample at 37.8℃ and 100% humidity using the MOCON Permatran-W700 equipment to measure the uniformity (%) , the formula = ((MAX-MIN)/2*Average)*100) was checked.

(5) Measurement of optical properties of barrier film: Transmittance and haze values were specified using a haze-meter (HM-150).

(6) Flexural resistance check: After applying a load of 500 g to both sides of the barrier film, attach it to a rod with a diameter of 4 mm, bend it for 1 minute, and check the barrier properties.

Structure of barrier film adhesive layer refractive index Example 1 write adhesive layer inorganic layer write - - - - 1.56 Example 2 write adhesive layer write inorganic layer OC - - 1.56 Example 3 write adhesive layer write inorganic layer adhesive layer inorganic layer write - 1.56 Example 4 write adhesive layer write inorganic layer adhesive layer write inorganic layer OC 1.56 Example 5 write adhesive layer write inorganic layer adhesive layer write inorganic layer OC 1.56 Example 6 write adhesive layer write inorganic layer adhesive layer write inorganic layer OC 1.56 Example 7 write adhesive layer write inorganic layer adhesive layer write inorganic layer OC 1.56 Example 8 write adhesive layer write inorganic layer adhesive layer write inorganic layer OC 1.56 Comparative Example 1 write inorganic layer - - - - - - - Comparative Example 2 write inorganic layer OC - - - -

Adhesion with QD resin, Peel Test (gf/25mm) Adhesion Peel Test between substrate and substrate or inorganic layer and substrate (gf/25mm) Barrier properties (WVTR, g/㎡*day) Barrier characteristic uniformity (%) optical properties
(Tt, %) Barrier properties after bending resistance (WVTR, g/m2*day) Example 1 22 destruction 0.1 5 88 0.1 Example 2 destruction destruction 0.1 4 88 0.1 Example 3 20 destruction 0.05 6 90 0.05 Example 4 destruction destruction 0.05 5 91 0.05 Example 5 destruction destruction 0.04 5 91 0.04 Example 6 destruction destruction 0.05 4 90 0.05 Example 7 destruction destruction 0.05 6 90 0.05 Example 8 destruction destruction 0.06 4 91 0.06 Comparative Example 1 22 '- 5 to 0.1 20 88 '- Comparative Example 2 destruction '- 0.9 to 0.1 10 88 '-

* In the case of uniformity (%), the lower the value, the better the uniformity.

As can be seen from the results of Tables 1 and 2, in the case of Examples 1 to 8, the adhesion between the substrate and the substrate is at the level of adhesion failure, the uniformity is 10% or less, and the optical characteristic has a characteristic of 88% or more, It can be seen that the barrier properties are maintained even after flexibility. In the case of Examples 3 to 8, the difference from Examples 1 to 2 is that the barrier performance is improved due to the presence of one more inorganic layer, and it can be seen that the thickness of the adhesive is thinly coated to exhibit higher transmittance characteristics. .

However, in the case of Comparative Example 1, there is no adhesive layer or substrate supporting the inorganic layer, so it has a range of barrier properties, and it can be seen that the uniformity is also high as 20%. Although it has the adhesive force of , it had the same characteristics as Comparative Example 1.

A, A': barrier layer

Claims (19)

a barrier layer comprising a substrate layer and an inorganic material layer; and an adhesive layer and a substrate layer are laminated on any one surface of the barrier layer, and the order in which the adhesive layer and the substrate layer are laminated includes that the adhesive layer and the substrate layer are sequentially laminated from the barrier layer,
An adhesive layer, a separate barrier layer and an overcoat layer are sequentially laminated on the other side of the barrier layer on which the adhesive layer and the base layer are laminated,
The adhesive layer is a UV curable resin; and 0.5 to 25 parts by weight of a photoinitiator based on 100 parts by weight of the UV curable resin. delete delete According to claim 1, wherein the base layer is a cyclic olipine-based resin, polystyrene-based resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polymethacrylic resin, Any one selected from the group consisting of a polycarbonate-based resin, a polyester-based resin including polyethylene terephthalate and polyethylene naphthalate, a polyamide-based resin including nylon, a polyurethane-based resin, an acetal-based resin, and a cellulose-based resin A barrier film comprising the above. According to claim 1, wherein the inorganic layer is silicon (Si), aluminum (Al), indium (In), tin (Sn), zinc (Zn), zirconium (Zr), titanium (Ti), copper (Cu) , cerium (Ce), yttrium (Yt), lanthanum (La), barium (Ba), magnesium (Mg), fluorine (F2), antimony (Sb), strontium (Sr) and tantalum (Ta) selected from the group consisting of A barrier film comprising at least one inorganic material selected from the group consisting of oxides, nitrides, carbides, oxynitrides, oxidized carbides, nitrided carbides, and oxynitrided carbides containing one or more metals. delete delete The method of claim 1, wherein the UV curable resin includes epoxy, epoxy acrylate, lauryl acrylate, norborene, polystyrene, ethylene-styrene, bisphenol A and bisphenol A derivatives, including acrylates and fluorene derivatives. Acrylate, isobornyl acrylate, polyphenylalkylsiloxane, urethane acrylate oligomer, dipentaerythritol pentaacrylate, comprising any one or more selected from the group consisting of trihydroxyethyl isocyanurate triacrylate barrier film. The barrier film according to claim 1, wherein the photoinitiator is selected from the group consisting of benzophenone series, thioxanthone series, hydroxy ketone series, and alpha amino ketone series. The barrier film according to claim 1, wherein the adhesive layer has a thickness of 0.1 to 100 µm. The barrier film according to claim 1, wherein the adhesive layer has a refractive index value of 1.3 to 2.1. The barrier film according to claim 1, wherein the overcoat layer comprises a UV curable resin, a thermoplastic resin, and a photoinitiator. 13. The method of claim 12, wherein the UV curable resin is selected from the group consisting of an epoxy resin, an unsaturated polyester resin, a polyurethane resin, a polycarbonate polyurethane, a polyester polyurethane, a phenol resin, a melamine resin, a urea resin, and a silicon resin. A barrier film comprising any one or more. 13. The method of claim 12, wherein the thermoplastic resin is a urethane-based resin, a copolymer of a urethane-based resin and a polyether-based resin, a copolymer of a urethane-based resin and a polyester-based resin, a polyester-based resin, and a polyvinylbutyltloride-based resin. A barrier film comprising any one or more selected from the group. The barrier film according to claim 12, wherein the overcoating layer comprises 50 to 500 parts by weight of the thermoplastic resin and 0.5 to 20 parts by weight of the photoinitiator based on 100 parts by weight of the UV curable resin. forming a barrier layer by laminating an inorganic material layer on any one surface of the base layer (S1);
Wet coating an adhesive layer composition on one surface of the formed barrier layer to form an adhesive layer, and then laminating a base layer on the formed adhesive layer (S2);
After wet coating the adhesive layer on the other side of the barrier layer formed in step S1, laminating a separate barrier layer on top of the coated adhesive layer (S4); and
Including a step (S3) of forming an overcoat layer by wet coating an overcoating layer composition on top of the separate barrier layer formed in step S4;
The adhesive layer composition is a UV curable resin; and 0.5 to 25 parts by weight of a photoinitiator based on 100 parts by weight of the UV curable resin. delete delete delete

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