JP2005138537A - Gas-barrier laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas-barrier film which is excellent in initial gas-barrier properties, especially in water vapor-barrier property, high in flexural resistance, and low in deterioration in barrier properties during printing. <P>SOLUTION: In the film, an inorganic barrier layer 50-300 Å in thickness is formed on at least one side of a plastic substrate, and a resin layer is laminated between the plastic substrate and the inorganic barrier layer. The inorganic barrier layer is made from Al, Si, oxygen, and nitrogen. The weight ratio of Al atoms to Si atoms is 15:85-40:60. The molar ratio of nitrogen to oxygen is 10-40%. The total number of moles of oxygen atoms and nitrogen atoms based on 100 g of a pure metal component meets a specified formula. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a protective layer for electronic materials such as foods that are excellent in gas barrier properties, particularly water vapor barrier properties, dislike moisture, pharmaceuticals that require high water vapor barrier properties, packaging materials for electronic materials, and organic EL and solar cells. .

  As packaging materials and packages having excellent gas barrier properties, those obtained by depositing aluminum on a PET film, those obtained by laminating aluminum foil, or transparent gas barrier films using aluminum oxide or silicon oxide are used. It was.

  Such conventional packaging materials and packages have the following problems. Aluminum foil or aluminum vapor deposition is excellent in gas barrier properties but is opaque and has a drawback that the contents during packaging cannot be seen. In addition, when aluminum is included in the packaging material and part of the packaging body, there is a problem that the plastic film cannot be collected and reused (recycled).

An aluminum oxide thin film is provided on a plastic film, and a high gas barrier film has been proposed (see, for example, Patent Document 1).
Japanese Patent Laid-Open No. 2001-6442

  However, although this method has a high barrier property against oxygen, the barrier property is not so high with respect to water vapor, and there is no particular mention about a sufficient water vapor barrier property depending on the contents.

In order to solve such a problem, an example using aluminum oxide / aluminum nitride and silicon has been reported (for example, see Patent Document 2).
JP 2002-361778 A

  However, although this method is described as having a high barrier property against oxygen, there is no description regarding the water vapor barrier property.

  In addition, these inorganic vapor-deposited films have low adhesion to the base material, and are inferior in flexibility compared to the base material film, so that cracks occur in the inorganic thin film during printing, laminating, and bag making. There was a problem such as remarkably reduced properties.

  The present invention is intended to provide a gas barrier film that is excellent in initial gas barrier properties, particularly water vapor barrier properties, has high flex resistance, and has little deterioration in barrier properties even during printing.

That is, the gas barrier film of the present invention is a film in which an inorganic barrier layer having a thickness of 50 to 300 mm is provided on at least one surface of a plastic substrate, and a resin layer is laminated between the plastic substrate and the inorganic barrier layer. And the inorganic barrier layer is made of Al, Si, oxygen, and nitrogen, the weight ratio of Al atoms to Si atoms is in the range of 15:85 to 40:60, and the molar ratio of nitrogen to oxygen is 10 The total number of moles of oxygen atoms and nitrogen atoms with respect to 100 g of the pure metal content satisfies the following formula.
Qc = _Ototal * (1-n) + _Ntotal * n
= (0.056a + (3.559-0.036a) * 2) (1-n)
+ (0.037a + 3.559-0.036a) × (4/3)
= (0.017n-0.016) a-2.375n + 7.119 (1)

0.9 × Qc <Q <1.0 × Qc (2)

a: Weight of Al in 100 g of metal content (15 <a <40)
n: molar ratio of N to O (0.1 <n <0.4)
Q: Actual acid / nitridation degree Qc of thin film Q: Complete acid / nitridation degree calculated from calculation O _total : Total amount of oxygen required for complete oxide (mol)
N _total : Total amount of nitrogen required for complete nitride (mol)

  In this case, the organic compound in which the resin layer contains an acid group-reactive functional group is a resin layer made of methylol melamine in which part or all of the methylol group is alkyletherified. It is preferable to be laminated between them.

  In this case, the organic resin in which the resin layer contains a hydroxyl group is preferably a polyvinyl alcohol polymer.

  Furthermore, in this case, the resin layer is laminated with a coating layer formed by mixing so that the weight ratio of the organic compound containing a hydroxyl-reactive functional group / the organic resin containing a hydroxyl group is larger than 20/80. Is preferred.

  Furthermore, in this case, the inorganic barrier layer is preferably formed by physical vapor deposition such as vacuum vapor deposition or DC magnetron sputtering.

  A coating layer containing an organic compound containing two or more hydroxyl-reactive functional groups and an organic resin containing a hydroxyl group as essential components is laminated on at least one surface of the plastic substrate, and a thickness of 50 to 50 is further formed thereon. By providing a barrier layer made of a mixed system of 300 ア ル ミ ニ ウ ム aluminum and silicon oxide and nitride, the barrier property, particularly the water vapor barrier property, is improved, the flexibility is high, and the barrier property is less lowered after printing. Thus, an extremely useful packaging material excellent in environmentally friendly practical characteristics can be obtained.

  The plastic substrate as used in the present invention is a film obtained by melt-extrusion of an organic polymer and stretching, cooling, and heat setting in the longitudinal direction and / or the width direction as necessary. , Polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2, 6-naphthalate, nylon 6, nylon 4, nylon 66, nylon 12, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, wholly aromatic polyamide, polyamideimide, polyimide, poly Examples include ether imide, polysulfone, polyphenylene sulfide, and polyphenylene oxide. These organic polymers may be copolymerized or blended with a small amount of other organic polymers.

  Furthermore, known additives such as UV absorbers, antistatic agents, plasticizers, lubricants, colorants and the like may be added to the organic polymer, and the transparency thereof is not particularly limited. When used as a transparent gas barrier film, a film having a transmittance of 50% or more, preferably 70% or more, more preferably 85% or more is preferable.

  The plastic substrate of the present invention may be subjected to corona discharge treatment, glow discharge treatment, or other surface roughening treatment prior to laminating the thin film layer as long as the object of the present invention is not impaired. In addition, anchor coat treatment, printing, and decoration may be applied. The plastic substrate of the present invention has a thickness of preferably 5 to 200 μm, more preferably 8 to 50 μm, and particularly preferably 10 to 30 μm.

The base material layer in the present invention may be a laminated film. There are no particular limitations on the type of laminate, the number of laminations, the lamination method, and the like in the case of a laminated film, and any one of known methods can be selected according to the purpose.
A specific coating layer is laminated on at least one surface of such a base material layer. As the coating layer, an organic compound containing two or more hydroxyl-reactive functional groups and an organic resin containing a hydroxyl group are essential components. The organic compound containing a hydroxyl-reactive functional group needs to contain two or more hydroxyl-reactive functional groups in order to crosslink the organic resin containing a hydroxyl group.

  Such organic compounds containing two or more hydroxyl-reactive functional groups include dialdehyde compounds such as glyoxal and glutaraldehyde, dicarboxylic acids such as succinic acid and adipic acid, and diisocyanate compounds such as diphenylmethane diisocyanate and hexamethylene diisocyanate. And methylol compounds such as epoxy compounds, methylol urea, and methylol melamine. Of these, methylol melamine, in which some or all of the methylol groups are alkyl etherified, is preferred from the standpoint of gas barrier properties.

  The methylol melamine, in which part or all of the methylol group is alkyl etherified, has at least a part of hydrogen atoms of three amino groups bonded to the triazine ring substituted with a methylol group, and the number of methylol groups Is generally 3 to 6, and some or all of the methylol groups are alkyl etherified. The alkyl moiety of the alkyl etherified methylol melamine is a linear or branched chain having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. For example, methyl, ethyl, n- or iso-propyl, n-, iso- or tert-butyl. Specific examples of methylol melamine used in the present invention include hexakismethoxymethyl melamine, hexamethylol melamine pentamethyl ether, hexamethylol melamine tetramethyl ether, pentamethylol melamine pentamethyl ether, pentamethylol melamine tetramethyl ether, penta Examples include methylol melamine trimethyl ether, tetramethylol melamine tetramethyl ether, tetramethylol melamine trimethyl ether, trimethylol melamine trimethyl ether, and trimethylol melamine dimethyl ether. From the point of compatibility with polyvinyl alcohol polymers, trimethylol melamine Trimethyl ether and trimethylol melamine dimethyl ether are preferably used. The methylol melamine may contain a part of a condensate such as a dimer.

  On the other hand, examples of the organic resin containing a hydroxyl group used in the present invention include a resin containing a hydroxyl group at a side chain or a terminal. Specifically, acrylic polymers, fluoroolefin polymers, vinyl ester polymers, aromatic vinyl polymers, polyolefin polymers, polyester polymers, alkyd polymers, polyurethane polymers, etc. Is mentioned. Examples thereof include polyester resins, polyurethane resins, acrylic resins, polyvinyl alcohol polymers, cellulose and its derivatives, and starch. Especially, it is preferable to use a polyvinyl alcohol-type polymer at the point of expression of the gas barrier property which is the objective of this invention.

  The polyvinyl alcohol polymer has a vinyl alcohol unit as a main component, and the polymerization degree and saponification degree of the polyvinyl alcohol polymer are determined from the target gas barrier properties and the viscosity of the aqueous coating solution. The degree of polymerization is preferably 2600 or less from the viewpoint of coating workability because the aqueous solution viscosity is high and gelation tends to be difficult. If the saponification degree is less than 90%, sufficient oxygen gas barrier properties under high humidity cannot be obtained, and if it exceeds 99.7%, it is difficult to prepare an aqueous solution, and gelation tends to occur, which is not suitable for industrial production. Therefore, the saponification degree is preferably 90 to 99.7%, more preferably 93 to 99%. Various copolymerized or modified polyvinyl alcohol polymers such as a polyvinyl alcohol polymer copolymerized with ethylene and a polyvinyl alcohol polymer modified with silanol can also be used.

  In the present invention, the weight ratio of the organic compound containing two or more hydroxyl-reactive functional groups and the organic resin containing a hydroxyl group can be arbitrarily selected. From the viewpoint of gas barrier properties, a methylolmelamine / polyvinyl alcohol polymer is used. The weight ratio is preferably 20/80 to 95/5, more preferably 50/50 to 90/10. If this ratio is 20/80 or less, or 95/5 or more, the target oxygen barrier property and water vapor barrier property will not be sufficiently exhibited.

  The coating layer containing, as essential components, an organic compound containing two or more hydroxyl-reactive functional groups and an organic resin containing a hydroxyl group used in the present invention is usually formed by coating using a solvent. As a solvent for the coating liquid, it is preferable to use 100% water or a water / lower alcohol mixed solvent from the viewpoint of solubility. The lower alcohol is an alcoholic compound having a linear or branched aliphatic group having 1 to 3 carbon atoms, and specific examples include methanol, ethanol, ethylene glycol, n- or iso-propyl alcohol. Iso-propyl alcohol is particularly preferable. The total solid concentration of the coating liquid of the present invention is preferably 2 to 35%, more preferably 5 to 30%. Further, the coating solution may contain a curing catalyst.

  Examples of the catalyst include acidic catalysts such as benzenesulfonic acid, its amine salt and its ammonium salt, naphthalenesulfonic acid derivative, its amine salt and its ammonium salt, phosphoric acid, its amine salt and its ammonium salt. Specifically, dodecylbenzenesulfonic acid and its amine salt, ammonium salt, dinonylnaphthalenesulfonic acid and its amine salt, ammonium salt, p-toluenesulfonic acid and its amine salt, ammonium salt, phosphoric acid, dihydrogen phosphate Examples thereof include ammonium, ammonium monohydrogen phosphate, catalyst 500 (manufactured by Mitsui Cyanamid), catalyst 600 (same), catalyst 4040 (same), and the like. A neutral catalyst such as magnesium chloride can also be used.

  Further, if necessary, it is optional to add various known inorganic and organic additives such as an antistatic agent, a lubricant and an antiblocking agent to the coating layer as long as the object of the present invention is not impaired.

In this manner, a coating layer containing an organic compound containing two or more hydroxyl-reactive functional groups and an organic resin containing a hydroxyl group as essential components is formed on the substrate. As a method for forming the coating layer on the substrate, a method of coating the substrate with an aqueous solution is usually employed as described above. The coating method is not limited, but an optimal method may be selected depending on the coating amount and viscosity of the coating liquid to be used. A reverse roll coating method, a roll knife coating method, a die coating method, or the like may be employed.
The drying and heat treatment conditions during coating depend on the coating thickness and equipment conditions, but immediately send them to the stretching process in the perpendicular direction without providing a drying process and dry them in the preheating zone or stretching zone of the stretching process. Is preferred. In such a case, it is normally performed at about 50 to 250 ° C. If necessary, the substrate film may be coated with a corona discharge treatment, other surface activation treatment or a known anchor treatment agent before coating. Although the thickness of the coating layer of the present invention varies depending on the base material layer, the minimum thickness for exhibiting the gas barrier property is good, and it is usually 1 μm or less in terms of transparency, handleability, and economical efficiency. Is preferable.

  The barrier layer is formed of an inorganic film. In general, an oxide of aluminum or silica has been used for the transparent vapor-deposited film, but it cannot be said to have a sufficient water vapor barrier property. In the past, silicon nitride has been studied to improve water vapor barrier properties, but the film causes strong curl due to the strong internal stress of the thin film layer, and the thin film itself breaks down due to the strong internal stress. There was a problem of being. In addition, in order to solve the above problems, a method such as converting silicon nitride into silicon oxynitride has been used. However, the target water vapor barrier property decreases with increasing degree of oxidation, and conversely, the degree of oxidation decreases. When it decreases, the coloring becomes harder, the flexibility of the film is lowered, the film is broken by an external force, and the barrier property is lowered. Therefore, in the present invention, by forming a thin film of aluminum and silicon complex acid / nitride, it has high water vapor barrier properties, less coloring problems, and high durability against external stress. A barrier film can be provided.

  In this case, the gas barrier film preferably has an oxygen: nitrogen ratio of 3: 1 to 1: 3. When the oxygen ratio increases, the transparency increases, but the water vapor barrier property decreases, and when the oxygen ratio decreases, the water vapor barrier property improves, but the coloring becomes tight, the internal stress becomes too strong, and the film curls. Or the film is destroyed.

The total molar amount (ON _total ) of oxygen and nitrogen with respect to 100 g of pure metal content is calculated as follows.
1) Pure metal content When the weight of metallic aluminum in 100 g is ag, the molar amounts of Al and Si are Al _mol = a / 26.98.
Si _mol = (100−a) /28.09
It is represented by
2) The amount of oxygen required for Al ₂ O ₃ is (a / 26.98) × 1.5
The amount of oxygen required for SiO ₂ is ((100−a) /28.09) × 2
It becomes.
Therefore, the total amount of oxygen required for the complete oxide is
O _total = (a / 26.98) × 1.5 + ((100−a) /28.09) × 2
3) Since the nitride of Al is represented by AlN and the nitride of Si is represented by Si ₃ N ₄ , the amount of nitrogen necessary for AlN is a / 26.98
The amount of nitrogen required for Si ₃ N ₄ is ((100−a) /28.09) × (4/3)
Therefore, the total amount of nitrogen required for complete nitride is
N _total = a / 26.98 + (100−a) /28.09) × (4/3)
4) Here, when the molar amount of nitrogen with respect to oxygen is n, the total molar amount of oxygen and nitrogen with respect to 100 g of pure metal is ON _total = Qc
= O _total × (1-n) + N _total × n
= (0.056a + (3.559-0.036a) * 2) (1-n)
+ (0.037a + 3.559-0.036a) × (4/3)
= (0.017n-0.016) a-2.375n + 7.119

  In the present invention, an inorganic thin film is produced by using metallic aluminum or metallic silicon as a raw material and introducing oxygen and nitrogen in the aforementioned proportions. In this case, the ratio of aluminum to silicon in the inorganic thin film is preferably 15:85 to 40:60. When the aluminum ratio is low, sufficient barrier properties cannot be obtained. Conversely, when the aluminum ratio is high, high initial barrier properties can be obtained, but the film is easily broken by external stress such as gelbo.

The thin film in the present invention contains Al, Si, O, and N as elements, and the ratios thereof vary depending on the production conditions. This component may contain a trace amount (up to 3% with respect to all components) of other components within a range where the characteristics are not impaired. The thickness of the thin film is not particularly limited, but is preferably 50 to 500 mm, more preferably 70 to 300 mm, from the viewpoint of gas barrier properties and flexibility.
The nitrogen content is preferably in the range of 10 to 40% of the total of oxygen and nitrogen, and more preferably in the range of 20 to 35%. When the nitrogen content is lower than 10%, a sufficient water vapor barrier cannot be obtained, and when the nitrogen content exceeds 40%, coloring becomes intense or weak against external forces such as gelbo.

For the production of the oxide thin film, a PVD method (physical vapor deposition method) such as a vacuum vapor deposition method, a sputtering method, or an ion plating method is appropriately used. For example, in the vacuum deposition method, it is preferable to use a mixture of Al ₂ O ₃ , Al, SiO, SiO 2, SiO, or the like as an evaporation material source in terms of material handling and safety.
Further, the size of each particle needs to be an appropriate size so that the pressure during vapor deposition does not change. If the particle size is too large, it takes time to evaporate after heat is applied, and the pressure fluctuation increases. If the particle size is too small, bumping occurs, causing splash.
As a heating method, resistance heating, high frequency induction heating, electron beam heating, laser heating, or the like can be used. Further, as the reactive gas, oxygen, nitrogen, water vapor or the like may be introduced, or reactive vapor deposition using means such as ozone addition or ion assist may be used.
The emission current is preferably between 0.3 A and 1.0 A, more preferably between 0.5 and 0.8 A. When the emission current is less than 0.3 A, a sufficient evaporation rate cannot be obtained, and productivity is lowered. Further, if the emission current becomes too large, the amount of evaporation becomes too large, the pressure rises and the decomposition of alumina becomes large, and it becomes difficult to control the pressure.

Further, as long as a bias or the like is not applied to the substrate or the object of the present invention is not impaired, the production conditions may be changed.
The product of the present invention may be used as it is, but may be used by laminating or coating another organic polymer film or thin layer.

  For example, when using the vapor-deposited film of the present invention for packaging, the contents to be packaged may be laminated using various films or paper according to the required characteristics. A film (on PET) / PE, a gas barrier film (on PET) / CPP, a NY / gas barrier film (on PET) / PE, a gas barrier film (on NY) / PE, and the like are conceivable. The laminating method is not particularly limited, but a dry laminating method, an extrusion laminating method or the like is desirable. Furthermore, it may be printed for decoration or explanation of contents, or may be bonded to a design film or a reinforcing material.

  Since the present invention has high gas barrier properties, the present invention is excellent in gas barrier properties, particularly water vapor barrier properties, foods that dislike moisture, pharmaceuticals that require high water vapor barrier properties, packaging materials for electronic materials, organic It is a protective layer for electronic materials such as EL and solar cells.

  Next, an Example is given and this invention is demonstrated.

(Measurement method)
1) Measuring method of oxygen permeability The oxygen permeability of the prepared gas barrier film was measured using an oxygen permeability measuring device (OX-TRAN100 manufactured by Modern Controls).

2) Water vapor transmission rate The prepared sample was 40 ° C., 100% R.D. H. The measurement was performed using a measuring device (PARMATRAN-W) manufactured by MOCON, USA.

3) Film thickness Measurement was performed using a fluorescent X-ray analyzer (Rigaku Denki System 3270). X-rays were generated using a rhodium bulb at 50 kV and 50 mA.

4) Calculation of oxygen / nitrogen ratio Measurement was performed using an X-ray photoelectron spectrometer (ESCA-850M manufactured by Shimadzu Corporation).

(Example 1)
[Preparation of coating solution]
While stirring 920 g of water, 80 g of polyvinyl alcohol resin having no modification and a saponification degree of 98.5 mol% was gradually added. It heated to 90 degreeC, the polyvinyl alcohol resin was melt | dissolved completely, and 8% aqueous solution of polyvinyl alcohol resin was prepared. Next, 1000 g of this polyvinyl alcohol resin aqueous solution, methylated melamine M-30W (104 g manufactured by Sumitomo Chemical Co., Ltd., 756 g water, and 140 g isopropyl alcohol were mixed to prepare a coating solution having a solid content concentration of 8%.
[Coating on film]
A PET having an intrinsic viscosity of 0.62 (30 ° C., phenol / tetrachloroethane = 60/40) is pre-crystallized, then dried, extruded at 280 ° C. using an extruder having a T die, and a drum having a surface temperature of 40 ° C. It was rapidly cooled and solidified to obtain an amorphous sheet. Next, the obtained sheet was stretched 4.0 times at 100 ° C. in the longitudinal direction between the heating roll and the cooling roll. And the said coating liquid was apply | coated to the single side | surface of the obtained uniaxially stretched film so that the resin solid content thickness before extending | stretching might be 0.2 micrometer by the fountain bar coat method. Dried to a tenter, preheated at 100 ° C, stretched 4.0 times transversely at 120 ° C, heat treated at 225 ° C with 6% transverse relaxation, and 12 µm thick biaxially stretched polyester A film was obtained.
An Al—Si mixed acid / nitride was deposited on the coated PET. Formation of a gas barrier layer for oxidation / nitridation of aluminum / silicon by electron beam evaporation using particulate aluminum (purity 99.5%) of about 3 mm to 5 mm and SiO ₂ of about 3 mm to 5 mm as a deposition source. Went. The mixing ratio of aluminum and SiO ₂ was 25:75 by weight. The output of the electron beam was 0.5 A, the film feed rate was 100 m / min, and a film having a thickness of 150 Å (angstrom) was formed. The vacuum layer contains an unwinding part, a coating part, and a winding part, and can be continuously deposited on the film. The pressure during the deposition was adjusted to 2.5 × 10 ⁻⁴ Torr by introducing nitrogen gas. At this time, the oxygen partial pressure was 0.1 × 10 ⁻⁴ Torr, and the nitrogen partial pressure was 1.9 × 10 ⁻⁴ Torr. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC.

(Examples 2 to 6)
A coating layer was prepared with the composition shown in Table 1, and a deposited film was prepared in the same manner as in Example 1.

(Example 7)
A coating film was prepared in the same manner as in Example 1. A deposited film having a mixing ratio of aluminum and SiO 2 of 40:60 was formed on the obtained coating film. The inorganic vapor deposition film is prepared by electron beam vapor deposition using aluminum particles having a particle size of about 3 mm to 5 mm (purity 99.5%) and SiO ₂ of about 3 mm to 5 mm as a vapor deposition source. -A gas barrier layer of silicon oxidation / nitridation was formed. The mixing ratio of aluminum and SiO ₂ was 40:60 by weight. The output of the electron beam was 0.5 A, the film feed rate was 100 m / min, and a film having a thickness of 150 mm was formed. The vacuum layer contains an unwinding part, a coating part, and a winding part, and can be continuously deposited on the film. The pressure during deposition was adjusted to 2.5 × 10 ⁻⁴ Torr by introducing nitrogen gas and oxygen gas. At this time, the oxygen partial pressure was 0.2 × 10 ⁻⁴ Torr, and the nitrogen partial pressure was 1.7 × 10 ⁻⁴ Torr. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC.

(Comparative Example 1)
A film without coating was prepared under the same conditions as in Example 1, and a vapor deposition layer was prepared under the same conditions as in Example 1.

(Comparative Example 2)
A coating film was prepared in the same manner as in Example 1. A deposited film was formed on the obtained coating film.
The inorganic vapor deposition film is prepared by electron beam vapor deposition using aluminum particles having a particle size of about 3 mm to 5 mm (purity 99.5%) and SiO ₂ of about 3 mm to 5 mm as a vapor deposition source. -A gas barrier layer of silicon oxidation / nitridation was formed. The mixing ratio of aluminum and SiO ₂ was 10:90 by weight. The output of the electron beam was 0.45 A, the film feed rate was 100 m / min, and a film having a thickness of 150 mm was formed. The vacuum layer contains an unwinding part, a coating part, and a winding part, and can be continuously deposited on the film. The pressure during deposition was adjusted to 2.5 × 10 ⁻⁴ Torr by introducing nitrogen gas and oxygen gas. At this time, the oxygen partial pressure was 0.1 × 10 ⁻⁴ Torr, and the nitrogen partial pressure was 1.9 × 10 ⁻⁴ Torr. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC.

(Comparative Example 3)
A coating film was prepared in the same manner as in Example 1. A deposited film was formed on the obtained coating film. The inorganic vapor deposition film is prepared by electron beam vapor deposition using aluminum particles having a particle size of about 3 mm to 5 mm (purity 99.5%) and SiO ₂ of about 3 mm to 5 mm as a vapor deposition source. -A gas barrier layer of silicon oxidation / nitridation was formed. The mixing ratio of aluminum and SiO ₂ was 90:10 by weight. The output of the electron beam was 0.55 A, and the film feed rate was 100 m / min. The vacuum layer contains an unwinding part, a coating part, and a winding part, and can be continuously deposited on the film. The pressure during deposition was adjusted to 2.5 × 10 ⁻⁴ Torr by introducing nitrogen gas and oxygen gas. At this time, the oxygen partial pressure was 0.9 × 10 ⁻⁴ Torr, and the nitrogen partial pressure was 1.0 × 10 ⁻⁴ Torr. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC.

(Comparative Examples 4 and 5)
It was created under the same conditions as in Example 1 except that the coating liquid shown in Table 1 was coated.

(Comparative Example 6)
A coating film was prepared in the same manner as in Example 1. A deposited film was formed on the obtained coating film.
Aluminum and SiO ₂ were mixed at a ratio of 25:75, and an electron beam output of 0.5 A, a film feed rate of 100 m / min, and a 150 mm thin film were produced. The test was performed under the same conditions as in Example 1 except that nitrogen was not introduced, only oxygen was introduced, and the pressure during vapor deposition was adjusted to 2.5 × 10 −4 Torr.

[Create laminate film]
Next, about 3 μm of a polyurethane adhesive (manufactured by Toyo Morton Co., Ltd., main agent / curing agent TM-590 / CAT56) was applied to the vapor deposition surfaces of the obtained Examples 1-7 and Comparative Examples 1-6, and 80 After heat treatment at 0 ° C., a low density polyethylene film (L6102 thickness 40 μm, manufactured by Toyobo Co., Ltd.) was dry laminated at a nip pressure of 490 kPa on a metal roll heated to 80 ° C. to obtain a laminate film. About the obtained laminate film, the oxygen permeation amount and the water vapor permeation amount before and after the gelbo were measured.

  White color was printed on the whole surface using the gravure coater on the vapor deposition surface of the film of obtained Examples 1-7 and Comparative Examples 1-6. After printing, about 3 μm of polyurethane adhesive (manufactured by Toyo Morton Co., Ltd., main agent / curing agent TM-590 / CAT56) is applied to the printed surface, heat-treated at 80 ° C., and then a low density polyethylene film (L6102 manufactured by Toyobo Co., Ltd.) 40 μm) was dry laminated at a nip pressure of 490 kPa on a metal roll heated to 80 ° C. to obtain a laminated film. About the obtained laminate film, the oxygen permeation amount and the water vapor permeation amount before and after the gelbo were measured.

  Tables 1 to 3 show the results of the above examples and comparative examples.

  The present invention relates to a protective layer for electronic materials such as foods that are excellent in gas barrier properties, particularly water vapor barrier properties, dislike moisture, pharmaceuticals that require high water vapor barrier properties, packaging materials for electronic materials, and organic EL and solar cells. .

Claims (5)

A film in which an inorganic barrier layer having a thickness of 50 to 300 mm is provided on at least one surface of a plastic substrate, wherein a resin layer is laminated between the plastic substrate and the inorganic barrier layer, and the inorganic barrier layer Consisting of Al, Si, oxygen and nitrogen, the weight ratio of Al atoms to Si atoms is in the range of 15:85 to 40:60, the molar ratio of nitrogen to oxygen is 10 to 40%, and the pure metal content A gas barrier film, wherein the total number of moles of oxygen atoms and nitrogen atoms per 100 g satisfies the following formula:

Qc = _Ototal * (1-n) + _Ntotal * n
= (0.056a + (3.559-0.036a) * 2) (1-n)
+ (0.037a + 3.559-0.036a) × (4/3)
= (0.017n-0.016) a-2.375n + 7.119 (1)

0.9 × Qc <Q <1.0 × Qc (2)

a: Weight of Al in 100 g of metal content (15 <a <40)
n: molar ratio of N to O (0.1 <n <0.4)
Q: Actual acid / nitridation degree Qc of thin film Q: Complete acid / nitridation degree calculated from calculation O _total : Total amount of oxygen required for complete oxide (mol)
N _total : Total amount of nitrogen required for complete nitride (mol)
  2. The gas barrier laminate film according to claim 1, wherein the organic compound containing an acid group-reactive functional group is made of methylol melamine in which a part or all of the methylol group is alkyletherified. A gas barrier laminate film, characterized in that is laminated between a plastic substrate and an inorganic barrier layer.   3. The gas barrier laminate film according to claim 1 or 2, wherein the organic resin in which the resin layer contains a hydroxyl group is a polyvinyl alcohol polymer.   4. The gas barrier laminate film according to claim 1, wherein the resin layer has a weight ratio of an organic compound containing a hydroxyl-reactive functional group / an organic resin containing a hydroxyl group larger than 20/80. A gas barrier laminate film, characterized in that a coating layer formed by mixing with is laminated.   The gas barrier film according to claim 1, 2, 3, or 4, wherein the inorganic barrier layer is formed by physical vapor deposition such as vacuum vapor deposition or DC magnetron sputtering.