JP6318636B2 - Gas barrier film - Google Patents

Description

  The present invention is a method for producing a gas barrier film, which has good winding properties and does not produce a Newton ring pattern when contacting other members with a display or the like.

  Conventionally, various types of packaging materials having barrier properties related to permeation of oxygen and water vapor have been developed. Recently, metal oxide films such as silicon oxide and aluminum oxide are formed on a plastic substrate on a nano scale. Many gas barrier films have been proposed.

  In general, many gas barrier films using an aluminum foil are used, but when used in a display or the like, a high transmittance is required, and an aluminum foil cannot be used.

  In recent years, in display applications, gas barrier properties have been regarded as important as backlights using organic EL as a light source and protective films for wavelength conversion layers using phosphors, and Newton's when in contact with other plastic members There is a demand to prevent ring patterns.

  For example, as in Patent Document 1, there is an example in which a layer containing particles is formed on a polyethylene terephthalate film and anti-Newton ring characteristics are obtained, but since it is processed into a normal polyethylene terephthalate film, gas barrier properties There is no.

JP 2003-191393 A

  An object of the present invention is to produce a film having high transmittance and capable of achieving both anti-Newton ring characteristics and gas barrier properties with a single sheet.

As a means for solving the above-mentioned problems, the invention described in claim 1 is the vacuum film formation formed by the reaction of a silicon atom-containing layer made of SiO _X and a silanol group on at least one surface of the polymer film. A layer containing silicon atoms not formed in step 1 and an anti-Newton ring layer in which inorganic fine particles in contact with the layer containing silicon atoms not formed in the vacuum film formation are dispersed in a binder resin, and are laminated at 40 ° C. and 90% humidity. water vapor permeability of at is less 0.5g ^/ m 2 · day, the total light transmittance of 80% or more, Haze is Ru der 5 or more gas barrier film.

The invention described in claim 2 is the average particle diameter of the particles is 0.5μm or more, the gas barrier film of claim 1 wherein.

The invention according to claim 3 is the gas barrier film according to claim 1 or 2 , wherein the total thickness of the gas barrier film is 60 μm or less.

According to the present invention, it is a gas barrier film in which at least two layers containing silicon atoms are laminated on at least one surface of a polymer film, and the average particle size is 0.5 μm or more in addition to the layer containing silicon atoms. By having a layer containing particles, the water vapor permeability at 40 ° C. and 90% humidity is 0.5 g / m ² · day or less, the total light transmittance is 80% or more, and the haze is 5 or more, A film having both anti-Newton ring characteristics and gas barrier properties can be produced.

It is a section schematic diagram of one embodiment of a gas barrier film of the present invention. It is a section schematic diagram of other embodiments of the gas barrier film of the present invention.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view of a gas barrier laminate film in the present invention. The gas barrier film of the present invention comprises at least two layers (2) containing silicon atoms on at least one surface of a polymer film (1) made of a polymer material. Formed with a film.

Examples of the polymer film (1) used in the present invention include, but are not limited to, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, nylon, polycarbonate, polypropylene, triacetylcellulose, and cycloolefin. is not.
The thickness of the polymer film (1) is not limited, but the total thickness of the gas barrier film is more preferably 60 μm or less.

  The polymer film (1) may contain additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, and a slip agent as necessary. Further, the surface of the polymer film (1) may be subjected to a modification treatment such as a corona treatment, a frame treatment, a plasma treatment or an easy adhesion treatment, or an off-line anchor coat layer of an acrylic resin or a urethane resin. The substrate surface contributes to the denseness and adhesion in the initial growth stage of vacuum film formation, and is desirably smooth.

  It is necessary that at least one layer (2) containing silicon atoms used in the present invention is formed by vacuum film formation. In vacuum film formation, physical vapor deposition or chemical vapor deposition can be used. Examples of physical vapor deposition include, but are not limited to, vacuum vapor deposition, sputter vapor deposition, and ion plating. Examples of chemical vapor deposition include, but are not limited to, thermal CVD, plasma CVD, and photo CVD.

  Here, in particular, a resistance heating vacuum deposition method, an EB (Electron Beam) heating vacuum deposition method, an induction heating vacuum deposition method, a sputtering method, a reactive sputtering method, a dual magnetron sputtering method, a plasma chemical vapor deposition method ( PECVD method) is preferably used.

In the items after the above sputtering method, plasma is used, but DC (Direct
Examples thereof include plasma generation methods such as a current method, an RF (radio frequency) method, an MF (middle frequency) method, a DC pulse method, an RF pulse method, and a DC + RF superposition method.

In the case of the sputtering method, a negative potential gradient is generated in the target, which is a cathode, and Ar ⁺ ions receive potential energy and collide with the target. Here, even if plasma is generated, sputtering cannot be performed unless a negative self-bias potential is generated. Therefore, MW (Micro Wave) plasma is not suitable for sputtering because self-bias does not occur. However, in the PECVD method, a chemical reaction, deposition, and a process proceed using a gas phase reaction in plasma, so that a film can be generated without self-bias, and thus MW plasma can be used.

  As the layer (3) containing silicon atoms by vacuum film formation used in the present invention, a so-called metal oxide layer called SiOx can be used, but it may contain nitrogen or aluminum atoms.

  The layer (3) containing silicon atoms formed by vacuum film formation in the present invention is preferably 5 nm to 100 nm. If the film thickness is less than 5 nm, sufficient water vapor barrier performance cannot be obtained. On the other hand, if the cured film thickness is larger than 100 nm, cracks are generated due to an increase in curing shrinkage, and the water vapor barrier property is lowered. Furthermore, the cost increases due to an increase in the amount of material used, a longer film formation time, etc., which is not preferable from an economic viewpoint.

  In the case of the layer (4) containing silicon atoms that is not formed by vacuum film formation, it is desirable to use a coating method using a solution.

  As a coating method, a known method can be used. Specifically, wet film forming methods such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, and a die coater.

It is desirable that specific silicon atoms in the layer (4) containing silicon atoms not formed by vacuum film formation mainly form a film as a reaction of silanol groups, and generally R ¹ (Si-OR ² ). Examples of the raw material include silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane. In the case of an Al atom, R ¹ (Al—OR ² ) in which the metal atom is Al, specifically, tetramethoxyaluminum, tetraethoxyaluminum, tetraisopropoxyaluminum, tetrabutoxyaluminum, or the like can be used.

  In the layer (4) containing silicon atoms that is not formed by vacuum film formation, an aqueous resin may be added, and specific examples include acrylic resin, polyester resin, polyvinyl alcohol, and polyvinylpyrrolidone. There are no particular restrictions on the structure and the like as long as they are included in these series of compounds, but it is necessary to select a material that is compatible with a resin containing a silanol group.

The layer (4) containing silicon atoms which is not formed by vacuum film formation can be used by mixing the above materials. Further, other metal materials may be used for this layer. R ¹ (Ti—OR ² ) in which the metal atom is Ti, specifically, tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, and tetrabutoxytitanium can be given. R ¹ (Al—OR ² ) in which the metal atom is Al, specifically, tetramethoxyaluminum, tetraethoxyaluminum, tetraisopropoxyaluminum, tetrabutoxyaluminum, or R ¹ (Zr in which the metal atom is Zr) Examples of —OR ² ) include tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium and the like. Further, a leveling agent, an antifoaming agent, an ultraviolet absorber, an antioxidant, a silane coupling agent, a titanium chelating agent, etc. may be added as necessary.

  The film thickness of the layer (4) containing silicon atoms that is not formed by vacuum film formation is preferably in the range of 50 nm to 1000 nm, more preferably in the range of 100 nm to 600 nm. If it is too thin, it will not be formed as a film, and if it is too thick, it will cause cracking and curling.

  The method of curing the film of the layer (4) containing silicon atoms that is not formed by vacuum film formation is not particularly limited, and examples thereof include ultraviolet curing and thermal curing. In the case of UV curing, a polymerization initiator and a double bond are required. Moreover, you may perform a heating aging etc. as needed.

  As a method of providing an anti-Newton ring layer (5) to provide anti-Newton ring properties, it is necessary to form irregularities on the surface, and generally, a method of dispersing organic or inorganic fine particles in a binder resin and coating it, It may be formed by layer separation by spinodal decomposition.

  Examples of the organic or inorganic fine particles include inorganic particles and organic particles. As inorganic particles, silicon dioxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, zirconium oxide, calcium carbonate, barium sulfate, talc, kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate , Magnesium silicate, calcium phosphate, calcium sulfate and the like.

  Examples of the silicon dioxide fine particles include Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.), or 250, 250N, 256, 256N, 310. 320, 350, 358, 430, 431, 440, 450, 470, 435, 445, 436, 446, 456, 530, 540, 550, 730, 740, 770 (above, manufactured by Fuji Silysia Co., Ltd.) A commercial product having a trade name can be used.

  As the fine particles of zirconium oxide, for example, those commercially available under trade names such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.

  Organic particles include poly (meth) acrylate resins, silicon resins, polystyrene resins, polycarbonate resins, acrylic styrene resins, benzoguanamine resins, melamine resins, polyolefin resins, polyester resins, polyamide resins. Polyimide resin, polyfluorinated ethylene resin, etc. can be used.

  The particle diameter is not particularly limited, but generally about 0.1 μm to 10 μm is used. It is necessary to change according to the required film thickness. If the particle diameter is much smaller than the film thickness, it becomes difficult to form unevenness, and if it is much larger than the film thickness, a homogeneous film cannot be obtained.

  The binder used when organic or inorganic fine particles are used may be either a thermosetting resin or an actinic ray curable resin (curing that irradiates an active ray such as ultraviolet ray curing or electron beam curing to cause a crosslinking reaction).

  Examples of the thermosetting resin include acrylic resin, alkyd resin, epoxy resin, urethane resin, vinylidene chloride resin, acrylic / styrene copolymer resin, polyester resin, vinyl alcohol resin, ethylene vinyl alcohol resin, and silicon resin. A wide variety of acrylic and urethane resins are easy to use.

  If necessary, a curing agent such as isocyanate, an antistatic agent, a silane coupling agent, an ultraviolet absorber, an antioxidant, a leveling agent, a dispersing agent, or the like may be added to the thermosetting resin.

  Examples of actinic radiation curable resins include UV curable polyester acrylate resins, UV curable acrylic urethane resins, UV curable acrylate resins, UV curable methacrylate resins, and UV curable polyester acrylate resins. Examples thereof include resins and ultraviolet curable polyol acrylate resins.

  Further, in the case of UV curing, a photopolymerization initiator is required. Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, and the like.

If necessary, add photosensitizers such as n-butylamine, triethylamine, poly-n-butylphosphine, or antistatic agents, silane coupling agents, ultraviolet absorbers, antioxidants, leveling agents, dispersants, etc. It may be added.
The binder, fine particles and additives can be dissolved in a solvent and the solid content can be adjusted to 1 to 80% by weight, more preferably 3 to 60% by weight, and coated on the substrate.

In the case of formation by spinodal decomposition, a blend of two or more of a thermoplastic resin and a heat or actinic radiation curable resin is used.
Examples of the thermoplastic resin include styrene, acrylic, organic acid vinyl ester, vinyl ether, olefin-based, polycarbonate, polyester, polyamide, thermoplastic polyurethane, polysulfone, cellulose derivative, silicone, and rubber-based resin. These resins can be used alone or in combination of two or more. Moreover, you may have a polymeric functional group.

  The curable resin is a compound having a functional group that reacts with heat or actinic rays (such as ultraviolet rays or electron beams), and is a compound that is cured by crosslinking with heat or actinic rays. For example, in the case of thermosetting, it is a low molecular weight compound having an epoxy group, an isocyanate group, an alkoxysilyl group, a silanol group, etc., such as an epoxy resin, a polyester resin, a urethane resin, or a silicone resin.

  As the solvent, general-purpose solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexane non, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, butanol and the like can be used.

  Of the at least one thermoplastic component and the at least one thermosetting component, at least two components are used in combination that phase separate from each other near the processing temperature. Although it does not specifically limit as a combination which carries out phase separation, Usually, it is a combination of several thermoplastic resins, and is a combination of a thermoplastic resin and a thermosetting resin. If the compatibility of the two to be phase-separated is high, the layer is not effectively separated in the step of evaporating the solvent, and unevenness is not formed.

  The film thickness of the anti-Newton ring layer (5) is 0.5 μm to 10 μm, more preferably 1 to 5 μm. If it is too thin, the unevenness is small and the performance of the anti-Newton ring is not exhibited. If it is too thick, the particles do not come out on the surface, so that the performance of the anti-Newton ring does not come out, or curing failure and cost may increase.

  Since a thinner film is required in this field, the total thickness of the gas barrier film is desirably 60 μm or less after the formation of the gas barrier layer and the anti-Newton ring layer.

  FIG. 2 is a schematic cross-sectional view of another embodiment of the gas barrier film of the present invention, a layer (3) containing silicon atoms formed by vacuum film formation and a layer (4) containing silicon atoms not formed by vacuum film formation. It is a cross-sectional schematic diagram when there are two layers each.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

  The performance of the film was evaluated according to the following method.

  The water vapor transmission rate was measured by Percontram of MOCON using a method according to JIS-K7129, and the water vapor transmission rate of the film was measured under the conditions of 40 ° C. and 90 RH%.

  As for the anti-Newton ring characteristics, the surface subjected to the anti-Newton ring processing was pressed against the non-adhesive surface of the PET film A4100 100 μm film to confirm whether a Newton ring pattern appeared.

  Total light transmittance and Haze were measured according to JIS-K7105 using NDH-2000 made by Nippon Denshoku.

<Example 1>
[Production of substrate]
A polyester resin was applied on a 25 μm polyethylene terephthalate film substrate (T60, manufactured by Toray Industries, Inc.) by a bar coating method, and dried and cured at 80 ° C. for 1 minute to form a 100 nm film.
[Layer containing silicon atoms by vacuum deposition]
A silicon oxide material (SiO, manufactured by Canon Optron Co., Ltd.) is evaporated by electron beam heating using an electron beam heating vacuum deposition apparatus, and a cured film thickness is obtained when the pressure during film formation is 1.5 × 10 ⁻² Pa. A SiOx film having a thickness of 40 nm was formed. However, the deposition conditions at this time are acceleration voltage: 40 kV and emission current: 0.2 A.
[Layer containing silicon atoms not formed by vacuum film formation]
A coating solution obtained by mixing a hydrolyzate of tetraethoxysilane and polyvinyl alcohol at a 1/1 weight ratio was applied to the SiOx film by a bar coating method, cured at 120 ° C. for 1 minute, and processed to 400 nm.

Further, a coating solution in which silica particles having an average particle diameter of 1 μm and an ultraviolet curable resin are mixed at a solid content weight ratio of 1:10 is applied on the cured coating film by a bar coating method and cured with a metal halide lamp. I let you. The cured film thickness was 2 μm.
This film had a total light transmittance of 88%, a haze of 10, and a water vapor transmission rate of 0.3 g / m ² · day, and no Newton ring was generated in the Newton ring test.

<Example 2>
[Production of substrate]
A polyester resin was coated on a 50 μm polyethylene terephthalate film substrate (A4100, manufactured by Toyobo Co., Ltd.) by a bar coating method, and dried and cured at 80 ° C. for 1 minute to form a 100 nm film.
[Layer containing silicon atoms by vacuum deposition]
A silicon oxide material (SiO, manufactured by Canon Optron Co., Ltd.) is evaporated by electron beam heating using an electron beam heating vacuum deposition apparatus, and a cured film thickness is obtained when the pressure during film formation is 1.5 × 10 ⁻² Pa. A SiOx film having a thickness of 40 nm was formed. However, the deposition conditions at this time are acceleration voltage: 40 kV and emission current: 0.2 A.
[Layer containing silicon atoms not formed by vacuum film formation]
A coating solution obtained by mixing a hydrolyzate of tetraethoxysilane and polyvinyl alcohol at a 1/1 weight ratio was applied to the SiOx film by a bar coating method, cured at 120 ° C. for 1 minute, and processed to 400 nm.

Further, the above steps were repeated again.
On this coating film, a coating solution in which silica particles having an average particle diameter of 1 μm and an ultraviolet curable resin were mixed at a solid content weight ratio of 1:10 was applied by a bar coating method and cured with a metal halide lamp. The cured film thickness was 2 μm.
This film had a total light transmittance of 88%, a haze of 10, a water vapor transmission rate of 0.05 g / m ² · day, and no Newton ring was generated in the Newton ring test.

<Comparative Example 1>
[Creation of base material]
A polyester resin was applied on a 25 μm polyethylene terephthalate film substrate (T60, manufactured by Toray Industries, Inc.) by a bar coating method, and dried and cured at 80 ° C. for 1 minute to form a 100 nm film.
[Layer by vacuum deposition]
Using a resistance-type vacuum evaporation apparatus, the aluminum oxide material was evaporated by heating, and an AlOx film having a cured film thickness of 10 nm was formed at a pressure of 3.0 × 10 ⁻² Pa during film formation.
[Layer containing silicon atoms not formed by vacuum film formation]
A coating solution obtained by mixing a hydrolyzate of tetraethoxysilane and polyvinyl alcohol at a 1/1 weight ratio was applied to the SiOx film by a bar coating method, cured at 120 ° C. for 1 minute, and processed to 200 nm.
This film had a total light transmittance of 89%, a haze of 2, and a water vapor transmission rate of 0.03 g / m ² · day, and Newton rings were generated in the Newton ring test.

<Comparative example 2>
[Creation of base material]
A polyester resin was applied on a 25 μm polyethylene terephthalate film substrate (T60, manufactured by Toray Industries, Inc.) by a bar coating method, and dried and cured at 80 ° C. for 1 minute to form a 100 nm film.
[Layer containing silicon atoms by vacuum deposition]
A silicon oxide material (SiO, manufactured by Canon Optron Co., Ltd.) is evaporated by electron beam heating using an electron beam heating vacuum deposition apparatus, and a cured film thickness is obtained when the pressure during film formation is 1.5 × 10 ⁻² Pa. A SiOx film having a thickness of 40 nm was formed. However, the deposition conditions at this time are acceleration voltage: 40 kV and emission current: 0.2 A.
[Layer containing silicon atoms not formed by vacuum film formation]
A coating solution obtained by mixing a hydrolyzate of tetraethoxysilane and polyvinyl alcohol at a 1/1 weight ratio was applied to the SiOx film by a bar coating method, cured at 120 ° C. for 1 minute, and processed to 400 nm.

Furthermore, a coating solution in which silica particles having an average particle diameter of 1 μm and an ultraviolet curable resin are mixed at a solid content weight ratio of 4: 6 is applied onto the cured coating film by a bar coating method and cured with a metal halide lamp. I let you. The cured film thickness was 2 μm.
This film had a total light transmittance of 68%, a haze of 60, and a water vapor transmission rate of 0.3 g / m ² · day, and no Newton ring was generated in the Newton ring test.

<Comparative Example 3>
[Creation of base material]
A polyester resin was applied on a 100 μm polyethylene terephthalate film substrate (A4100, manufactured by Toyobo Co., Ltd.) by a bar coating method, and dried and cured at 80 ° C. for 1 minute to form a 100 nm film.
[Layer containing silicon atoms by vacuum deposition]
A silicon oxide material (SiO, manufactured by Canon Optron Co., Ltd.) is evaporated by electron beam heating using an electron beam heating vacuum deposition apparatus, and a cured film thickness is obtained when the pressure during film formation is 1.5 × 10 ⁻² Pa. A SiOx film having a thickness of 40 nm was formed. However, the deposition conditions at this time are acceleration voltage: 40 kV and emission current: 0.2 A.
[Layer containing silicon atoms not formed by vacuum film formation]
A coating solution obtained by mixing a hydrolyzate of tetraethoxysilane and polyvinyl alcohol at a 1/1 weight ratio was applied to the SiOx film by a bar coating method, cured at 120 ° C. for 1 minute, and processed to 400 nm.
On this coating film, a coating liquid in which silica particles having an average particle diameter of 0.1 μm and an ultraviolet curable resin are mixed at a solid content weight ratio of 1:10 is applied by a bar coating method and cured with a metal halide lamp. It was. The cured film thickness was 2 μm.
The total light transmittance of this film was 89%, the haze was 3, the water vapor transmittance was 0.3 g / m ² · day, and Newton rings were generated in the Newton ring test.

As shown in Table 1, it was possible to produce a film having high transmittance in the present invention and capable of achieving both anti-Newton ring characteristics and gas barrier properties with a single sheet.
The anti-Newton ring characteristics are effective when the average particle diameter is 1 μm in Example 1, Example 2 and Comparative Example 2, whereas the comparative example 3 is not effective when using 0.1 μm. It became clear.

DESCRIPTION OF SYMBOLS 1 ... Polymer film 2 ... Layer 3 containing silicon atoms ... Layer 4 containing silicon atoms formed by vacuum film formation ... Layer 5 containing silicon atoms not formed by vacuum film formation ...・ Anti-Newton ring layer

Claims (3)

A layer containing silicon atoms by vacuum deposition made of SiO _{X on} at least one surface of the polymer film, a layer containing silicon atoms not formed by vacuum film formation formed by reaction of silanol groups, and not formed by the vacuum film formation An anti-Newton ring layer in which inorganic fine particles in contact with a layer containing silicon atoms are dispersed in a binder resin is laminated, and the water vapor permeability at 40 ° C. and 90% humidity is 0.5 g / m ² · day or less. , the total light transmittance of 80% or more, the gas barrier film Ru der Haze is 5 or more.
The gas barrier film according to claim 1, wherein at least one layer containing silicon atoms is formed by vacuum film formation. The average particle diameter of the particles is 0.5μm or more, the gas barrier film of claim 1, wherein. The gas barrier film according to claim 1 or 2 , wherein the total thickness of the gas barrier film is 60 µm or less.