KR101784286B1 - Gas barrier resin composition and gas barrier film using thereof - Google Patents

Abstract

The present invention relates to a gas barrier resin composition and a barrier film using the same, which comprises an ester compound obtained by polymerizing an organic polymer and a silane compound; Inorganic nanoparticles; And a solvent; And the inorganic nanoparticles are dispersed in the ester compound.
Disclosed is a gas barrier resin composition which is excellent in mechanical properties, high gas barrier property, printability, transparency and the like, and can be recycled without being discarded after being buried or incinerated after use, and a barrier film using the same .

Description

TECHNICAL FIELD [0001] The present invention relates to a gas barrier resin composition and a gas barrier film using the gas barrier resin composition.

The present invention relates to a gas barrier resin composition and a barrier film using the same, and more particularly, to a gas barrier resin composition having excellent gas barrier properties and recyclability including an organic-inorganic composite material and a barrier film .

Various kinds of foods, medicines and cosmetics have been developed along with the development of industry, and packaging films which can block the permeation of oxygen, moisture and foreign substances for their quality maintenance and packaging are widely used in the industry in general.

In particular, the demand for packaged food such as retort food, packaged rice, frozen food and the like is increasing in proportion to the increase of the working age, the aged and the elderly living alone, and the packaging film used for packaging such foods has a suitable mechanical property, Transparency, oxygen barrier properties, moisture barrier properties, heat resistance, and impact resistance.

Generally, such packaging films are formed by coating Al ₂ O ₃ or SiO ₂ on the surface of synthetic resin based films such as polypropylene (PP), polyvinyl chloride (PVC), and polyethylene terephthalate (PET) And a vapor deposition layer is formed by vapor deposition of a metal or an inorganic compound such as palladium or the like on the surface of a substrate. Such a packaging film having such a vapor deposition layer can produce a film having gas barrier properties excellent in barrier properties against oxygen, water vapor, In order to form a vapor deposition layer, an expensive vacuum deposition equipment is required, and therefore, the entire amount is imported from abroad.

Further, in the case of the barrier film formed with such a deposition layer, flexibility is usually low, and a phenomenon such as cracks and pinholes occurs on the surface or the inner surface of the packaging film in an after-treatment process in an inorganic state, There has been a problem that the printing property, which is an important characteristic of the film, is inferior.

In addition, in order to solve such a problem, research and development have been made on a packaging film using a wet coating which is conventionally carried out continuously at normal pressure. However, in addition to the problems such as formation of a creator on a coating surface during coating drying It can not be used for high oxygen or high water content blocking with a low barrier rate, and this problem is not effectively solved.

On the other hand, there are many opinions that such packaging materials or packaging films are the main cause of environmental problems such as generation of greenhouse gases.

Recently, according to the 'Fourth National Waste Statistics Survey' conducted by the Ministry of Environment, about 70% of the municipal solid waste excluding food waste has been disposed of with the disposal of 2.7 million tons of wrapping paper annually. The environmental problems are serious.

Such environmental problems usually arise from the recyclability of the packaging film. In general, the packaging film is composed of a composite material or a synthetic resin having a complicated structure, which makes it difficult to recycle, and a considerable amount of harmful gas is generated when incinerated. Development of a coating resin composition and packaging film excellent in gas barrier property at the present time and at the same time recyclable and capable of reducing enormous amount of greenhouse gas can be achieved due to difficulty in processing such as overburden occupying capacity and years of processing time It is an urgent time.

DISCLOSURE OF THE INVENTION Accordingly, the present invention has been made to solve the above problems and to provide a gas barrier resin composition which is excellent in mechanical properties, And a barrier film using the same.

In order to accomplish the above-mentioned object, the present invention relates to an ester compound produced by polymerization reaction of an organic polymer and a silane compound; Inorganic nanoparticles; And a solvent; And the inorganic nanoparticles are dispersed in the ester compound.

Preferably, 5 to 100 parts by weight of the silane compound is added to 100 parts by weight of the organic polymer; 1 to 25 parts by weight of layered inorganic nanoparticles; . ≪ / RTI >

Preferably, the organic polymer may be at least one member selected from the group consisting of modified polyvinyl alcohol (PVA), unmodified polyvinyl alcohol (PVA), polyacrylonitrile, and cellulose.

Preferably, the organic polymer may have a degree of saponification of 70 to 99%.

Preferably, the silane compound may be at least one selected from the group consisting of an alkoxysilane having an amino group, a hydrolyzate of an alkoxysilane having an amino group, and a partial condensate of an alkoxysilane having an amino group.

Preferably, the silane compound may be 3-aminopropyltriethoxysilane (APTES) or 3-aminopropyltrimethoxysilane (APTMS) or a mixture thereof.

Preferably, the inorganic nanoparticles are selected from the group consisting of bentonite, hectorite, lapolyte, montmorillonite, vitelite, sapphire, miica, fluorinated miica, calcium sulfate, calcium carbonate, magnesium carbonate, talc, kaolin, silica, Zeolite, titanium oxide, and alumina.

Preferably, the average particle size of the inorganic nanoparticles may be 100 nm to 20,000 nm.

Preferably, the solvent may be a mixed solvent of water and a lower alcohol having 1 to 5 carbon atoms in a weight ratio of 1:10 to 5: 5.

Preferably, the inorganic nanoparticles dispersed in the esterified compound can be dispersed by a centrifugal bead mill method using beads.

Preferably, the beads may be selected from zirconia, zirconia silicates and mixtures thereof having a diameter of from 0.01 mm to 1.0 mm.

Preferably, the viscosity of the resin composition may be 430 to 930 cps.

A gas barrier film according to an embodiment of the present invention includes a support layer; And a gas barrier layer formed by coating the gas barrier resin composition of the present invention on at least one surface of the support layer; .

Preferably, the support layer comprises at least one of polyethylene terephthalate (PET), polyethylene (PE), low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polyamide (PA), nylon And may be at least one selected from the group consisting of propylene (PP), biaxially oriented polypropylene (BOPP), and lead-free polypropylene (CPP).

Preferably, the support layer may have a thickness of 7 to 250 [mu] m.

Preferably, the gas barrier layer may have a thickness of 0.1 to 30 占 퐉.

Preferably, a primer layer is formed on at least one surface of the support layer; Can be formed.

According to the gas barrier resin composition of the present invention constructed as described above and the barrier film using the same, it is possible to provide a packaging film which can be recycled while maintaining excellent gas barrier properties through the resin composition containing the organic-inorganic composite material There is an effect that can be done.

Further, the packaging film using the resin composition of the present invention has an excellent appearance, printability and transparency.

Further, the packaging film using the resin composition of the present invention can be directly printed on the surface thereof, so that the complex layer structure of the packaging film can be reduced.

Further, it has an effect of exhibiting excellent adhesion under high temperature and high humidity conditions.

On the other hand, even if the effects are not explicitly mentioned here, the effects expected by the technical features of the present invention described in the following specification and its provisional effects can be handled as described in the specification of the present invention.

1 is a schematic view of a gas barrier film according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG.

The terms described below are not intended to be limiting or to be construed in a conventional or dictionary sense and the inventor can define the concept of a term appropriately to describe its invention in its best possible way It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims and their equivalents. .

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are not to be construed as limiting of the invention, . ≪ / RTI >

It is to be understood, however, that these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art to which the present invention pertains, But only by the scope of the claims set forth. Therefore, the definition should be based on the contents throughout this specification.

Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise.

It is to be understood that throughout the specification, when a section such as a layer, film, region, plate, or the like is referred to as being "on" or "on" another part, .

BEST MODE FOR CARRYING OUT THE INVENTION The gas barrier resin composition and the packaging film using the same according to an embodiment of the present invention will now be described in more detail with reference to the accompanying drawings.

The gas barrier resin composition of the present invention is an ester compound produced by a polymerization reaction between an organic polymer and a silane compound; Inorganic nanoparticles; And a solvent; Finally, the ester compound is in a state in which inorganic nanoparticles separated and inserted between the inorganic nanoparticles are dispersed.

Here, the present invention is a state in which an ester compound is produced by subjecting an organic polymer and a silane compound to hydrolysis and a polycondensation reaction, and nano-sized inorganic nanoparticles are dispersed in the ester compound.

The reason why the organic polymer is polymerized through the silane compound is that the waterproofing property of the film further enhances the gas barrier property of the product and further enhances the dispersibility of the inorganic nanoparticles dispersed in the ester compound And, consequently, the gas barrier properties of the final product are enhanced.

The compounding ratio of the gas barrier resin composition according to the present invention is 5 to 100 parts by weight of the silane compound relative to 100 parts by weight of the organic polymer; 1 to 25 parts by weight of layered inorganic nanoparticles; . ≪ / RTI >

In the gas barrier resin composition according to the present invention, the organic polymer may be a modified polyvinyl alcohol (PVA), unmodified polyvinyl alcohol (PVA), polyacrylonitrile, cellulose, ethylene-vinyl alcohol copolymer, ethylene- (Meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid- (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid- (meth) acrylic acid metal salt copolymer, (Meth) acrylic acid grafted polyethylene, (meth) acrylic acid grafted polypropylene, and (meth) acrylic acid grafted ethylene- (meth) acrylate, and preferably the molding of the film It has excellent properties, high surface activity, mechanical properties and adhesive strength, and is particularly biodegradable and decomposed by the bacteria found in the soil To use a highly eco-friendly and recyclable polyvinyl alcohol (Polyvinylalcohol) is preferred.

The organic polymer of the present invention may have a degree of saponification of 70 to 100%, and preferably has a saponification degree of 80 to 100%. When the degree of saponification of the organic polymer is lowered to 70% or less, the gas barrier property is lowered. Therefore, it is preferable to observe the degree of saponification degree.

The silane compound in the gas barrier resin composition of the present invention can be a known silane compound used in the art, and specific examples thereof include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, Methyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Triethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane diethyldiethoxysilane can be used, but the present invention is not limited thereto.

Preferably, the silane compound may be at least one selected from the group consisting of an alkoxysilane having an amino group, a hydrolyzate of an alkoxysilane having an amino group, and a partial condensate of an alkoxysilane having an amino group. More preferably, Aminopropyltriethoxysilane (APTES) or 3-aminopropyltrimethoxysilane (APTMS) or mixtures thereof.

The silane compound is preferably contained in an amount of 5 to 100 parts by weight, more preferably 10 to 45 parts by weight, and still more preferably 15 to 25 parts by weight based on 100 parts by weight of the organic polymer.

If the content of the silane compound is less than 5 parts by weight, the esterification reaction with the organic polymer and the crosslinking reaction are not carried out, thereby deteriorating the adhesion and gas barrier properties of the final product. On the other hand, The transparency of the final product and the adhesiveness under high temperature / high humidity conditions are deteriorated.

Therefore, when the content ratio of the silane compound is observed, a product having excellent gas barrier properties, adhesion and transparency of the final product can be produced.

Further, when the silane compound is applied in accordance with the above-mentioned content ratio, the coating solution or film using the conventional gas barrier resin composition can be produced without adhesion, such as low temperature treatment, aging treatment (annealing process) , Transparency and gas barrier properties, and thus the manufacturing process is greatly reduced.

In addition, when a coating solution or a film is prepared by using an additive such as a conventionally used crosslinking agent (for example, butanetetracarboxylic acid), there is a problem that a specific acid smell is generated. A product which does not generate such odor can be produced.

In the gas barrier resin composition of the present invention, the inorganic nanoparticles may be selected from the group consisting of mica, synthetic mica, bentrite, montmorillonite, hexylite, lapolite, bitelite, sapphire, mica, fluoromica smectite, sodium montmorillonite, magnesium montmorillonite , Beadellite, nontronite, hectoronite, sodium hectoronite, saponite, synthetic saponite, saponite, pyrophyllite, gluconite, vermiculite, polygorskin, sepiolite, But are not limited to, emollient, emollient, emollient, emollient, emollient, emollient, glucoside, amylolytic, amylolytic, amylolytic, amylolytic, amylolytic, amylolytic, Montronite, silicate, haloisite, metahaloysite, Chlorite, laponite, calcium sulfate, calcium carbonate, calcium carbonate, calcium carbonate, calcium carbonate, calcium carbonate, calcium carbonate, calcium carbonate, , Calcium carbonate, magnesium carbonate, talc, kaolin, silica, diatomaceous earth, zeolite, titanium oxide and alumina.

The inorganic nanoparticles preferably include 1 to 25 parts by weight, preferably 2 to 15 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the organic polymer.

When the content of the inorganic nanoparticles is less than 1 part by weight, the gas barrier property is deteriorated. On the contrary, when the inorganic nanoparticle content is more than 25 parts by weight, the gas barrier property is improved, but the improvement degree of the gas barrier property is in the steady state And the gas barrier effect can not be seen against the cost, and transparency, which is an important physical property due to the nature of the packaging film, may be sharply lowered.

When the content ratio of the inorganic nanoparticles is 25 parts by weight or more, a large amount of bubbles are produced during the production of the resin or coating liquid, and the viscosity of the resin or coating liquid may increase, and the dispersion operation may not be smooth.

By observing the weight range of the inorganic nanoparticles, it becomes possible to produce products such as resins and films having high gas barrier properties and transparency.

The average particle size of the inorganic nanoparticles may be 100 nm to 20,000 nm, preferably 200 nm to 10,000 nm, and more preferably 280 nm to 5,000 nm.

If the particle size of the inorganic nanoparticles is less than 100 nm, the nanoparticles are dispersed too tightly on the resin to generate gaps, so that it is difficult to exhibit excellent gas barrier properties. On the contrary, if the inorganic nanoparticles have a particle size of more than 20,000 nm, Can not be achieved.

The inorganic nanoparticles are finally dispersed in the ester compound. The inorganic nanoparticles in the dispersed state may have a particle size of 0.1 to 15 μm Preferably from 3 탆 to 12 탆, and more preferably from 5 탆 to 10 탆.

If the particle size of the dispersed inorganic nanoparticles is less than 1 占 퐉, it is difficult to exhibit excellent gas barrier properties because the resin nanoparticles are dispersed too tightly on the resin to generate gaps. On the other hand, if the particle size is more than 15 占 퐉, Smooth manufacture may not be achieved.

Examples of the solvent used in the gas barrier resin composition of the present invention include water (H ₂ O), ethyl alcohol, methyl alcohol, Isopropyl alcohol, 2-methoxy ethanol, propyl alcohol, pentyl alcohol, hexyl alcohol, butyl alcohol, octyl alcohol octyl alcohol and the like and an alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, poly-ethylene glycol, propylene glycol, diethylene glycol, Dipropylene glycol, hexylene glycol, triethylene glycol monomethyl ether (TGME), propylene glycyl ether acetate (propylene glyc glycol ethers such as glycerine, acetone, formamide, methyl ethyl ketone, methane, ethane, propane, and the like, Such as butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, and the like, And cyclohexanone may be used. Preferably, a mixed solvent of water and a lower alcohol having 1 to 5 carbon atoms in a weight ratio of 1: 10 to 5: 5 can be used .

The method of dispersing the inorganic nanoparticles in the esterified compound of the present invention may be a conventional dispersion method used in the art, but the present invention is not limited thereto.

As a specific example of the dispersion method, a horizontal bead mill, a centrifugal bead mill, and an ultrasonic dispersion method may be used. Preferably, the bead mill method or the centrifugal bead mill dispersion method using beads is used for the esterification It is possible to effectively disperse inorganic nanoparticles in a layered structure on a nanoscale, thereby producing a product having excellent gas barrier properties.

Here, the beads used in the centrifugal bead mill dispersion method may be a zirconia or zirconia silicate having a diameter of 0.01 mm to 1.0 mm, either alone or in combination with a certain ratio to form the gas barrier resin composition Lt; RTI ID = 0.0 > nanoscale < / RTI >

The viscosity of the gas barrier resin composition according to the present invention may be 430 to 930 cps. If the viscosity does not fall within the above-mentioned range, it is difficult to smoothly carry out the dispersion operation of the resin composition, so it is preferable to observe the above range.

The gas barrier resin composition of the present invention may further contain various additives in accordance with the needs and purposes of the user within the range not deviating from the ultimate purpose of the present invention in addition to the additives mentioned in the above- It will be evident that various equivalents may exist.

The gas barrier resin composition of the present invention can be used to provide a barrier film excellent in gas barrier property and recyclability.

1, which schematically illustrates a gas barrier film according to one embodiment of the present invention, includes a support layer 100; And a gas barrier layer (200) coated on at least one surface of the support layer (100) with the gas barrier resin composition of the present invention described above; .

In the case of the gas barrier film of the present invention, the layer structure of the gas barrier film of the present invention is monotonous, but exhibits a high gas barrier property so that the product can be reduced in weight, and is monotonously recycled in an eco-friendly manner.

In addition, since direct printing can be performed differently from the case of a film in which aluminum or the like is evaporated, the manufacturing process can be reduced and the manufacturing cost can be effectively reduced.

The support layer of the gas barrier film of the present invention may be a film or a sheet made of a material well known in the art. Specific examples of the support include polyethylene terephthalate (PET), polyethylene (PE), low density polyethylene (LDPE ), High density polyethylene (HDPE), linear low density polyethylene (LLDPE), polyamide (PA), nylon, polypropylene (PP), biaxially oriented polypropylene May be used.

The thickness of the support layer 100 may vary depending on the purpose and use of the user, but it may preferably have a thickness of 7 to 250 탆.

The support layer 100 may be further provided with a primer layer on at least one surface thereof for improving the close adhesion with the gas barrier resin coating composition.

The gas barrier layer 200 may have a thickness of 0.1 to 30 μm.

The gas barrier resin composition and the film using the same of the present invention are suitable for food packaging materials that require appropriate mechanical properties, high gas barrier properties, high transparency, water barrier properties, and adhesion properties. It can be recycled without being discarded.

Conventionally, usually, interlaminar bonds are laminated by using a polyurethane adhesive or an acrylic adhesive having a small molecular weight. In this case, adhesion is advantageous. However, due to a heterogeneous material having a small molecular weight during recycling and different thermal properties such as melting point, The possibility of pyrolysis and yellowing during the process was high, and recycling was practically impossible.

The present invention eliminates the need for an additional adhesive between the gas barrier coating layer and the support (substrate) film by introducing a novel organic or inorganic hybrid gas barrier resin composition having excellent adhesion, It can be recycled.

The present invention will be explained in more detail with reference to the following examples, which should not be construed as limiting the invention, but rather should be considered from an illustrative point of view. The scope of the present invention is not limited to the following description, but is expressed in the claims and any differences within the scope of equivalents thereof should be construed as being included in the present invention.

< Example >

The materials used in the following examples are as follows.

Organic polymers: polyvinyl alcohol (PVA), POVAL 105 (saponification degree 99%) and POVAL 217 (70% saponification degree)

Inorganic nanoparticles: nano clay, Sudden clay company CLOSITE 10A +

Crosslinking agent: aminopropyltrimethoxysilane and aminopropyltriethoxysilane

Solvent: Mixed solvent of distilled water and isopropyl alcohol (IPA)

Beads: zirconia beads, zirconia silicate beads

Support layer: polyethylene terephthalate (PET) film

< Manufacturing example >

First, an aqueous solution having a solid content of 10% is prepared under the condition of PVA at 70 占 폚 for 3 hours.

Thereafter, an aqueous solution containing 10% sodium hydroxide for the crosslinking agent is prepared.

Next, the PVA solution and the solution of the crosslinking agent are polymerized to prepare an ester compound.

After the nano-clay was added to the ester compound thus prepared, the solution was added to a bead mill containing beads and uniformly nano-dispersed to prepare a gas barrier resin coating liquid. Then, the resin coating solution was applied to a base film The PET film was coated to a thickness of 1.5 탆 and dried at 120 캜 for 2 minutes using a dryer to prepare a film sample.

Hereinafter, various examples and modifications described in Test Example 1, Test Example 2, and Test Example 3 described below are set forth in the following tables in detail.

Test Example  1: (primary experiment) PVA  Crosslinking and Nano-clay  Gas according to inclusion Barrier property  evaluation

&Lt; Solution composition ratio (weight ratio) > POVAL  105 POVAL  217 butane Tetra Carboxylic acid Poly
Acrylic acid Nano
Clay menstruum
(water) Reference Example 1 7 30 0.5 63 Reference Example 2 7 30 0.5 63 Reference Example 3 7 30 0.5 63 Reference Example 4 7 30 1.5 63 Reference Example 5 10 0.5 90 Reference Example 6 7 30 63 Reference Example 7 9 10 0.5 81 Reference Example 8 5 50 0.5 45

Note: POVAL 105: PVA with 99% or more saponification degree

POVAL 217: Partial saponification of 70% degree of saponification PVA

Butanetetracarboxylic acid: number average molecular weight less than 1000

Polyacrylic acid: Molecular weight 5,000

<Processing Conditions> BASE Film Dry film  thickness Drying conditions Dispersion method Bead  material Bead  size Reference Example 1 PET 12 μm 1.5 m 120 ° C, 2 minutes Horizontal bead mill Zirconia silicate 1.5mm Reference Example 2 PET 12 μm 1.5 m 120 ° C, 2 minutes level
Bead mill Zirconia silicate 1.5mm Reference Example 3 PET 12 μm 1.5 m 120 ° C, 2 minutes level
Bead mill Zirconia silicate 1.5mm Reference Example 4 PET 12 μm 1.5 m 120 ° C, 2 minutes level
Bead mill Zirconia silicate 1.5mm Reference Example 5 PET 12 μm 1.5 m 120 ° C, 2 minutes level
Bead mill Zirconia silicate 1.5mm Reference Example 6 PET 12 μm 1.5 m 120 ° C, 2 minutes level
Bead mill Zirconia silicate 1.5mm Reference Example 7 PET 12 μm 1.5 m 120 ° C, 2 minutes level
Bead mill Zirconia silicate 1.5mm Reference Example 8 PET 12 μm 1.5 m 120 ° C, 2 minutes level
Bead mill Zirconia silicate 1.5mm

&Lt; Evaluation of physical properties & Reference Example 1 Reference Example 2 Reference Example 3 Reference Example 4 Reference Example 5 Reference Example 6 Reference Example 7 Reference Example 8 Transparency Extremely
Great Extremely
Great Extremely
Great Great Extremely
Great Extremely
Great Extremely
Great Extremely
Great Oxygen permeability
(CC / M ² Day) 4.6 18 15 3.9 45 17 26 18

Referring to Reference Example 1 and Reference Example 2, it was observed that the use of 99% or completely saponified POVAL 105 for PVA increased the gas barrier property,

Referring to Reference Examples 3 to 8, it was found that the compounding ratio of the PVA aqueous solution and the crosslinking agent solution was 70:30, and the crosslinking reaction was the best in the case of Reference Example 7 in which the crosslinking agent solution was added in an amount of 10% The result showed that the gas barrier properties were not completely achieved. On the other hand, Reference Example 8, which was added in an amount of 50% or more, was found to cause degradation of inherent barrier properties of PVA.

As a result of the experiment of Reference Example 4 in which 1.5 wt% of the nano-clay is added, when the amount of the nano-clay is increased, the oxygen permeability is increased but the transparency is lowered. In addition, And productivity problems were found to occur.

Test Example  2: (Secondary experiment) PVA Cross-linking agent  Adhesion and gas according to selection and heat treatment conditions Barrier property  evaluation.

&Lt; Solution composition ratio (weight ratio) > POVAL  105 APTMS APTES butane Tetra Carboxylic acid Nano
Clay menstruum
(IPA / water) Reference Example 9 10 2.5 0.5 90 (20:80) Reference Example 10 10 2.5 0.5 90 (20:80) Reference Example 11 7 30 0.5 90 (20:80) Reference Example 12 10 2.5 0.5 90 (20:80) Reference Example 13 10 30 0.5 90 (20:80) Reference Example 14 10 2.5 0.5 90 (20:80) Reference Example 15 10 5 0.5 90 (20:80) Reference Example 16 10 1.5 0.5 90 (20:80)

<Processing Conditions> BASE Film Dry film  thickness Heat treatment condition Dispersion method Bead  material Bead  size Spare
dry
(80 ° C,
1 minute) Ten
process
(120 DEG C, 2 minutes) ferment
(50 &lt; 0 &gt; C, 24 hours) Reference Example 9 PET 12 μm 1.5 m O O O Horizontal bead mill Zirconia silicate 1.5mm Reference Example 10 PET 12 μm 1.4μm O O O level
Bead mill Zirconia silicate 1.5mm Reference Example 11 PET 12 μm 1.5 m O O O level
Bead mill Zirconia silicate 1.5mm Reference Example 12 PET 12 μm 1.5 m O O X level
Bead mill Zirconia silicate 1.5mm Reference Example 13 PET 12 μm 1.5 m O O X level
Bead mill Zirconia silicate 1.5mm Reference Example 14 PET 12 μm 1.5 m O O X level
Bead mill Zirconia silicate 1.5mm Reference Example 15 PET 12 μm 1.5 m O O O level
Bead mill Zirconia silicate 1.5mm Reference Example 16 PET 12 μm 1.5 m O O O level
Bead mill Zirconia silicate 1.5mm

&Lt; Evaluation of physical properties & Reference example
9 Reference example  10 Reference example
11 Reference example
12 Reference example
13 Reference example
14 Reference example
15 Reference example
16 Transparency Extremely
Great Extremely
Great Extremely
Great Great Extremely
Great Extremely
Great usually Extremely
Great Adhesiveness Great Great Great Great Inadequate Great Great usually High temperature and high humidity  Adhesiveness Great Great usually Great Bad usually Bad Bad Oxygen permeability
(CC / M ² Day) 4.6 18 15 3.9 45 17 26 18

Test Example  3: (third experiment) Nanoscale  Dispersion type gas Barrier property  evaluation

&Lt; Solution composition ratio (weight ratio) > POVAL  105 APTES Nano
Clay menstruum
(IPA / water) Example 1 10 2.5 0.5 90 (20:80) Example 2 10 2.5 0.5 90 (20:80) Example 3 10 2.5 0.5 90 (20:80) Comparative Example 1 10 2.5 0.5 90 (20:80) Comparative Example 2 10 2.5 0.5 90 (20:80) Comparative Example 3 10 2.5 1.5 90 (20:80)

<Processing Conditions> BASE FILM Dry film
thickness Preliminary drying
(80 DEG C, 1 minute) Heat treatment
(120 DEG C, 2 minutes) Dispersion
system Bead
material Bead
size ROTOR
RPM Example  One PET 12 μm 1.5 m O X Centrifugal bead mill Zirconia silicate 1.0 mm 3000 Example  2 PET 12 μm 1.4μm O X Centrifugal bead mill Zirconia silicate 1.0 mm 2000 Example  3 PET 12 μm 1.5 m O X Horizontal bead mill Zirconia silicate 0.5 mm 3000 Comparative Example  One PET 12 μm 1.5 m O X Ultrasonic dispersion Zirconia silicate Comparative Example  2 PET 12 μm 1.5 m O X Horizontal bead mill Zirconia silicate 1.5 mm 3000 Comparative Example  3 PET 12 μm 1.5 m O X Centrifugal bead mill Zirconia silicate 1.0 mm 1000

&Lt; Evaluation of physical properties & Example  One Example  2 Example  3 Comparative Example  One Comparative Example  2 Comparative Example  3 Coating viscosity (CPS) 550 930 430 150 270 3500 Coating Appearance bubble
Small amount Slight bubble generation Air bubble generation Slight bubble generation Small amount of bubbles Large amount of bubbles Transparency Very good Very good Very good Very good Very good Bad Coating Roughness Smooth Smooth Smooth coarseness Slightly rough Bad Coating agent average particle size 90 nm 156 nm 280 nm 10-15 mm 5-9 mm Adhesiveness Great Great Great Great Great High temperature and high humidity  Low adhesion Great Great Great Great Great Oxygen permeability
(CC / M ² Day) 0.8 0.7 1.3 5.8 3.5

As a result of the third experiment, it was found that the addition of IPA or ethanol at a certain portion of the solvent rather than the water alone caused less bubbles and lowered the viscosity of the coating agent.

In addition, a large difference in oxygen barrier property occurred depending on the dispersing method. In this case, Examples 1 and 2 using the centrifugal bead mill were observed to have the highest oxygen barrier properties.

In addition, in Comparative Example 1 using an ultrasonic dispersion method, bubbles were less likely to be generated and viscosity was low, which was considered to be good for forming a film film, but physical properties were deteriorated in oxygen barrier property.

Particularly, in Comparative Example 3 in which the centrifugal bead mill was used and the nanoclay was added in an amount of 1.5, a large amount of bubbles were generated, and the viscosity was too high, and the dispersion operation was not smooth.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the exemplary embodiments, but, on the contrary, Therefore, the scope of the present invention is not limited to the embodiments and the accompanying drawings

100: Support layer
200: gas barrier layer

Claims (16)

A silane compound containing at least one member selected from the group consisting of an alkoxysilane having an amino group, a hydrolyzate of an alkoxysilane having an amino group and a partial condensate of an alkoxysilane having an amino group, and an ester compound ;
Inorganic nanoparticles dispersed in the ester compound; And
menstruum; / RTI &gt;
Wherein the inorganic nanoparticles are dispersed in a horizontal bead mill or a centrifugal bead mill method using at least one kind of beads selected from the group consisting of zirconia and zirconia silicate having a diameter of 0.01 to 1.0 mm. Composition.
The method according to claim 1,
Wherein the dispersed inorganic nanoparticles have a layered structure.
The method according to claim 1,
Wherein the organic polymer comprises at least one member selected from the group consisting of modified polyvinyl alcohol (PVA), unmodified polyvinyl alcohol (PVA), polyacrylonitrile, and cellulose.
The method according to claim 1,
Wherein the organic polymer has a degree of saponification of 70 to 100%.
The method according to claim 1,
Wherein the silane compound comprises at least one selected from the group consisting of an alkoxysilane having an amino group, a hydrolyzate of an alkoxysilane having an amino group, and a partial condensate of an alkoxysilane having an amino group.
The method according to claim 1,
Wherein the silane compound is 3-aminopropyltriethoxysilane (APTES) or 3-aminopropyltrimethoxysilane (APTMS) or a mixture thereof.
The method according to claim 1,
The inorganic nanoparticles may be selected from the group consisting of bentonite, hectorite, lapolite, montmorillonite, vitelite, sapphire, miica, fluorinated miica, calcium sulfate, calcium carbonate, magnesium carbonate, talc, kaolin, silica, diatomaceous earth, zeolite, And alumina. &Lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt;
The method according to claim 1,
Wherein the inorganic nanoparticles have an average particle size of 100 nm to 20,000 nm.
The method according to claim 1,
Wherein the solvent comprises a mixed solvent of water and a lower alcohol having 1 to 5 carbon atoms in a weight ratio of 1: 10 to 5: 5.
delete delete Supporting layer; And
A gas barrier layer formed by coating the gas barrier resin composition of any one of claims 1 to 9 on at least one surface of the support layer; And a gas barrier film.
13. The method of claim 12,
The support layer may be made of polyethylene terephthalate (PET), polyethylene (PE), low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polyamide (PA), nylon, polypropylene , Biaxially oriented polypropylene (BOPP), and non-oriented polypropylene (CPP).
13. The method of claim 12,
Wherein the support layer has a thickness of 7 to 250 占 퐉.
13. The method of claim 12,
Wherein the gas barrier layer has a thickness of 0.1 to 30 占 퐉.
13. The method of claim 12,
A primer layer disposed on at least one side of the support layer so as to face the gas barrier layer; Further comprising a gas barrier film.

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