JP2011161838A - Gas barrier laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent gas barrier film used suitably when a high gas barrier property is required. <P>SOLUTION: The gas barrier laminated film includes a gas barrier layer 2 and a gas barrier film layer 3 laminated on one side and a gas barrier layer 4 and a gas barrier film layer 5 laminated on the other side, of a substrate layer 1 and further satisfies following relations; 0.001≤XaYa, 0.001≤XbYb and (Xa+Xb)(Ya+Yb)≤0.5: provided that the gas barrier layers 2 and 4 consist of silicon oxide, the gas barrier film layers 3 and 5 are obtained by applying and drying a coating liquid containing a silicon compound of the formula: Si(OR<SP>1</SP>)<SB>4</SB>, a silicon compound of the formula: (R<SP>2</SP>Si(OR<SP>3</SP>)<SB>3</SB>)<SB>n</SB>and an ingredient e.g. PVA; wherein the film thicknesses (Xa) and (Xb) respectively of the gas barrier layers 2 and 4 are 0.005-0.5 μm and the film thicknesses (Ya) and (Yb) respectively of the gas barrier film layers 3 and 5 are 0.05-3 μm. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is a transparent gas barrier laminate that is suitably used when high gas barrier properties are required in the fields of packaging of foods, daily necessities, pharmaceuticals, etc., and fields such as solar cell related members and electronic device related members. Related to film.

  Packaging materials used for packaging of food, daily necessities, pharmaceuticals, etc., suppress the alteration of the contents, so that the functions and properties can be maintained even during packaging, oxygen, water vapor, etc. that permeate the packaging material, It is necessary to prevent the influence of the gas that alters the contents, and it is required to have a gas barrier property that blocks these gases.

  As packaging materials having ordinary gas barrier properties, vinylidene chloride resin films or films coated with vinylidene chloride resins that are relatively excellent in gas barrier properties have been often used. However, these packaging materials have high gas barrier properties. Cannot be used for packaging that requires Therefore, when a high gas barrier property is required, a packaging material in which a metal foil such as aluminum is laminated as a gas barrier layer has to be used. A packaging material in which a metal foil such as aluminum is laminated has almost no influence of temperature and humidity and has a high gas barrier property. However, these packaging materials have many disadvantages, such as being unable to see the contents through them, having to be disposed of as non-combustible materials after use, and being unable to use metal detectors to inspect the contents. Had.

  As a packaging material that overcomes these drawbacks, Patent Document 1 discloses that a gas barrier layer is formed by depositing a thin film layer of a transparent inorganic oxide such as silicon oxide, aluminum oxide, or magnesium oxide on a base layer made of a transparent plastic film. In addition, a laminated film obtained by laminating an appropriate gas barrier coating layer thereon is disclosed.

On the other hand, in recent years, the solar cell market has been rapidly expanding with increasing interest in global warming. As a solar cell structure, a single solar cell element is not used as it is, and generally several to several tens of elements are wired in series and in parallel, and packaged to protect the element for a long period of time. Is done and unitized. The unit built in this package is called a solar cell module. Generally, the surface that is exposed to sunlight is covered with glass, the gap is filled with a filler made of thermoplastic, and the back is made of a heat-resistant, weather-resistant plastic material, etc. The structure is protected by a sheet.
Since these solar cell modules are used outdoors, sufficient durability and weather resistance are required in the materials used and their configurations. In particular, the back protective sheet is required to have high gas barrier properties as well as weather resistance. This is because the filler in the unit is peeled off due to the permeation of moisture and the wiring is corroded, which adversely affects the module output itself.
Conventionally, as this back surface protection sheet for solar cells, a laminated structure in which an aluminum foil is sandwiched from both sides with a white fluorine-based film has been often used. However, this fluorine-based film has a weak mechanical strength, so that the solar cell element and the aluminum foil are short-circuited to adversely affect the battery performance. Further, since the price is high, it is necessary to reduce the price of the solar cell module. There are two obstacles. In order to improve these problems, there is an increasing demand for a gas barrier film having both weather resistance and high gas barrier properties without using an aluminum foil.
Also, development has been made to make this solar cell module flexible, and in order to achieve this, it is necessary to replace the glass substrate on the surface where the sunlight hits with a sheet made of a plastic material, etc. Similarly to the back protective sheet, weather resistance and high gas barrier properties are required.

In recent years, with the development of electronic paper and organic EL, which are expected as next-generation FPDs, in order to achieve flexibility in these FPDs, there is an increasing demand for replacing glass substrates with plastic films. The glass substrate has a gas barrier property required to suppress deterioration of internal elements due to oxygen and water vapor derived from the environment. However, the above-mentioned gas barrier film for packaging materials does not reach the barrier level, and in electronic paper, organic EL, etc. to which a plastic film can be applied, the gas barrier is 100 to 10,000 times that of a food packaging material barrier film. It is said that sex is necessary.
In order to realize such a plastic film having a high gas barrier property, it is formed by a dry coating method such as a reactive vapor deposition method using electron beam vapor deposition or induction heating vapor deposition, a sputtering method, or a plasma chemical vapor deposition (CVD) method. Inorganic oxide thin films have been studied as those that can be expected to exhibit high gas barrier properties.

  Among them, a silicon oxide thin film formed by a plasma CVD method using an organosilane compound has been studied as a barrier layer exhibiting high gas barrier properties, and has been put into practical use in the food packaging field. Patent Document 2 reports that adhesion and transparency are improved by controlling the carbon concentration and the composition of the silicon oxide thin film.

Japanese Patent Laid-Open No. 7-164591 Japanese Patent Laid-Open No. 11-322981

  However, the laminated film described in Patent Document 1 has deteriorated gas barrier properties such as oxygen permeability and water vapor permeability when subjected to normal processing as a packaging material such as printing, laminating, and bag making. It had the disadvantage that it would end up. Moreover, even if the dry coating method is used to obtain a plastic film having a high gas barrier property, a high-temperature process is necessary or dense if an attempt is made to obtain a dense film in order to aim at a high gas barrier property. For this reason, the stress in the film tends to increase. For this reason, it is difficult to obtain a dense film within the usable temperature range of the plastic film, or problems such as poor adhesion and cracking due to the large difference in thermal expansion coefficient between the plastic film and the inorganic oxide thin film. And high gas barrier properties are not easily developed. In addition, the transparent barrier film described in Patent Document 2 is described as being slightly inferior in water vapor barrier properties, and is not gas barrier properties for FPDs such as electronic paper and organic EL that require high gas barrier properties. It is enough.

  Therefore, the object of the present invention is to provide a particularly high gas barrier property, in which the gas barrier property is not deteriorated even when subjected to ordinary processing in the field of packaging of food, daily necessities, pharmaceuticals, etc., and in the field of solar cell related members and electronic device related members. It is an object of the present invention to provide a transparent gas barrier laminate film that can be suitably used when the is required. In particular, the object of the present invention is to solve the problem of insufficient gas barrier properties for FPDs such as the back surface protection sheet and surface protection sheet of the solar cell module described above, electronic paper and organic EL, and the oxygen barrier. The object is to provide a transparent gas barrier laminate film having excellent properties and water vapor barrier properties.

As means for solving the above-mentioned problems, the invention according to claim 1 is characterized in that the gas barrier layer 2, the gas barrier coating layer 3, and the other surface are formed on one surface of the base material layer 1 made of a transparent plastic film. In the gas barrier laminated film formed by sequentially laminating the gas barrier layer 4 and the gas barrier coating layer 5 on the top,
The gas barrier layer 2 and the gas barrier layer 4 are made of silicon oxide,
The gas barrier coating layer 3 and the gas barrier coating layer 5 are:
At least one of a silicon compound represented by the general formula Si (OR ¹ ) ₄ (1) and a hydrolyzate thereof,
At least one of a silicon compound represented by the general formula (R ² Si (OR ³ ) ₃ ) _n (2) and a hydrolyzate thereof,
(In the general formulas (1) and (2), R ¹ and R ³ represent CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ , R ² represents an organic functional group, and n represents 1 or more. And a coating solution containing a water-soluble polymer having a hydroxyl group is applied and dried.
And the film thickness (thickness Xa) of the gas barrier layer 2 and the film thickness (thickness Xb) of the gas barrier layer 4 are 0.005 μm or more and 0.5 μm or less,
The film thickness (thickness Ya) of the gas barrier coating layer 3 and the film thickness (thickness Yb) of the gas barrier coating layer 5 are 0.05 μm or more and 3 μm or less,
The gas barrier laminate film is characterized in that the relationship between Xa, Xb, Ya and Yb satisfies the following three formulas.
0.001 ≦ XaYa
0.001 ≦ XbYb
(Xa + Xb) (Ya + Yb) ≦ 0.5
(The unit of the thickness of Xa, Xb, Ya, Yb in the formula is μm)
The invention according to claim 2 is characterized in that the general formula (R ² Si (OR ³ ) ₃ ) _n (2) is represented by the formula (NCO-R ⁴ Si (OR ³ ) ₃ ) ₃ (wherein R ⁴ represents (CH ₂ ) _n and _n represents a number of 1 or more), and is a trimer 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate It is a gas-barrier laminated film of Claim 1.
The invention described in claim 3 is characterized in that the gas barrier layer 2 and the gas barrier layer 4 respectively laminated on the surface of the base material layer 1 are formed by a plasma chemical vapor deposition (CVD) method. Item 3. A gas barrier laminate film according to Item 1 or 2.
The invention according to claim 4 is characterized in that, in the general formula Si (OR ¹ ) ₄ (1), the hydrolyzable group (R ¹ ) is C ₂ H _5. The gas barrier laminate film according to any one of the above.
The invention according to claim 5 includes an acrylic polyol, an isocyanate, and a silane coupling agent between the base material layer 1 and the gas barrier layer 2 and between the base material layer 1 and the gas barrier layer 3. The gas barrier laminate film according to claim 1, further comprising a primer layer.
The invention according to claim 6 is that the general formula (R ² Si (OR ³ ) ₃ ) _n (2) is 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate. It is a gas-barrier laminated film in any one of Claims 1-5 characterized by the above-mentioned.

  According to the present invention, in the packaging field of foods, daily necessities, pharmaceuticals, etc., gas barrier properties are not deteriorated even if normal processing as a packaging material is performed, and the contents can be confirmed by seeing through the packaging material. Moreover, the transparent gas barrier laminated film which can be used suitably when especially high gas barrier property is required for solar cell modules and FPD can be provided.

It is sectional drawing of an example of the gas barrier laminated film of this invention.

Hereinafter, embodiments of the gas barrier laminate film of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view of an example of the gas barrier laminate film of the present invention. A gas barrier layer 2 made of silicon oxide and a gas barrier coating layer 3 are formed on one surface of the base material layer 1, and a gas barrier layer 4 made of silicon oxide and a gas barrier coating layer 5 are formed on the other surface in the thickness direction. The gas barrier coating layer 3 and the gas barrier coating layer 5 are sequentially laminated.
At least one of a silicon compound represented by the general formula Si (OR ¹ ) ₄ (1) and a hydrolyzate thereof,
At least one of a silicon compound represented by the general formula (R ² Si (OR ³ ) ₃ ) _n (2) and a hydrolyzate thereof,
(In the general formulas (1) and (2), R ¹ and R ³ represent CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ , R ² represents an organic functional group, and n represents Represents a number of 1 or more)
And a coating solution containing a water-soluble polymer having a hydroxyl group is applied, heated, and dried.

In the gas barrier laminate film of the present invention, the base material layer 1 is made of a transparent plastic film. Examples of transparent plastic films include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene and polypropylene, polyether sulfone (PES), polystyrene films, polyamide films, and polyvinyl chloride. Films, polycarbonate films, polyacrylonitrile films, polyimide films, biodegradable plastic films such as polylactic acid, and the like are used.
These transparent plastic films may be either stretched or unstretched, but those having excellent mechanical strength and dimensional stability are preferred. In particular, polyethylene terephthalate stretched in the biaxial direction is preferably used from the viewpoints of heat resistance and dimensional stability. Moreover, the transparent plastic film may contain additives such as an antistatic agent, an ultraviolet ray preventing agent, a plasticizer, and a lubricant. Further, in the transparent plastic film, the surface on the side where other layers are laminated may be subjected to corona treatment, low temperature plasma treatment, ion bombardment treatment, chemical treatment, solvent treatment, etc. in order to improve adhesion. .
The thickness of the base material layer 1 made of these transparent plastic films is not particularly limited. However, considering the suitability as a packaging material and the suitability for processing when other layers are laminated, it is practical. Is preferably in the range of 3 to 200 μm, particularly in the range of 6 to 30 μm.

  In the gas barrier laminate film of the present invention, the method for forming the gas barrier layer 2 and the gas barrier layer 4 is not particularly limited. However, the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide are vacuumed on the surface of the base material layer 1. In order to exhibit high gas barrier properties by forming a film inside, a plasma chemical vapor deposition (CVD) method is preferable at present, and the film can be formed on one or both sides of the base material layer made of the plastic film. Further, it is possible to perform continuous vapor deposition by taking advantage of the characteristics of the base material layer 1 made of a plastic film, and it is preferable to use a roll-up vacuum deposition apparatus. As the plasma generator, a low-temperature plasma generator such as direct current (DC) plasma, low-frequency plasma, high-frequency plasma, pulse wave plasma, tripolar plasma, or microwave plasma is used.

  The gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide, which are laminated by the plasma CVD method, can be formed using a silane compound having carbon in the molecule and oxygen gas as raw materials, and an inert gas is added to the raw materials. A film can also be formed. Examples of the silane compound having carbon in the molecule include tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetramethylsilane (TMS), hexamethyldisiloxane (HMDSO), and tetramethyldisiloxane. A relatively low molecular weight silane compound such as methyltrimethoxysilane may be selected, and one or more of these silane compounds may be selected. Among these silane compounds, TEOS, TMOS, TMS, HMDSO, tetramethylsilane and the like are preferable in view of the film forming pressure and the vapor pressure.

  In the film formation by the plasma CVD method, the silane compound vaporized and mixed with oxygen gas is introduced between the electrodes, and the plasma is formed by applying electric power with a low-temperature plasma generator, on the surface of the base material layer 1. Can be stacked. In the plasma CVD method, the film quality of the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide can be changed by various methods. For example, the silane compound and the gas species can be changed, and the silane compound and oxygen gas can be changed. The mixing ratio, increase / decrease in applied power, etc. can be considered.

  Further, as a method for forming the gas barrier layer 2 and the gas barrier layer 4 other than the plasma CVD method, a vacuum vapor deposition method is preferable. As with the plasma CVD method, the gas barrier layer 2 and the gas barrier layer 4 are formed on one side or both sides of the substrate layer made of the plastic film. Can do. In the current vacuum vapor deposition method, the electron source heating method, the resistance heating method, the induction heating method, or the like is preferable as the heating means for the evaporation source material in the vacuum vapor deposition apparatus. Moreover, in order to improve the adhesiveness with the base material layer 1, a plasma assist method, an ion beam assist method, etc. can also be used. Further, in order to increase the transparency of the deposited thin film layer, reactive deposition may be performed by blowing oxygen gas or the like.

  In the gas barrier laminate film of the present invention, the gas barrier layer 2 and the gas barrier layer 4 respectively laminated on the surface of the base material layer 1 are transparent and excellent in blocking a gas that alters the contents such as oxygen and water vapor. Has gas barrier properties. The thickness Xa [μm] of the gas barrier layer 2 and the thickness Xb [μm] of the gas barrier layer 4 are each 0.005 μm to 0.5 μm, more preferably 0.005 μm to 0.3 μm. Here, if the film thickness is less than 0.005 μm, a uniform vapor-deposited thin film layer may not be obtained, and the function as a gas barrier material cannot be sufficiently achieved. On the other hand, if the film thickness exceeds 0.5 μm, it is difficult to maintain the flexibility of the deposited thin film layer, and if an external stress such as bending or pulling is applied, the deposited thin film layer may be cracked.

In the gas barrier laminate film of the present invention, the gas barrier coating layer 3 and the gas barrier coating layer 5 are:
i) at least one of a silicon compound represented by the general formula Si (OR ¹ ) ₄ (1) and a hydrolyzate thereof,
ii) at least one of a silicon compound represented by the general formula (R ² Si (OR ³ ) ₃ ) _n (2) and a hydrolyzate thereof,
(In the general formulas (1) and (2), R ¹ and R ³ represent CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ , R ² represents an organic functional group, and n represents 1 (Represents the number above)
And iii) obtained by coating, heating and drying a coating solution containing a water-soluble polymer having a hydroxyl group.

According to the present invention, the gas barrier coating layer is sufficiently insolubilized by including these three components. Since R ² Si (OR ³ ) ₃ of the general formula (2) forms hydrogen bonds with the water-soluble polymer having Si (OR ¹ ) ₄ of the general formula (1) and a hydroxyl group by hydrolysis, the pores of the barrier On the other hand, the organic functional group forms a network, thereby preventing the water-soluble polymer having a hydroxyl group from swelling due to the addition of water to the hydrogen bond, thereby significantly improving the water resistance.
In addition, the hole of a barrier means the part which does not form the precise | minute network in a film | membrane but facilitates permeation | transmission of gas.

  Further, by providing the gas barrier coating layers 3 and 5 in combination with the gas barrier layers 2 and 4 on the base material layer 1, high gas barrier properties can be obtained. Furthermore, even if there is no adhesion coating layer so-called primer layer or special treatment layer between the base material layer 1 and the gas barrier layers 2, 4, oxygen permeability, and after boil sterilization treatment and retort sterilization treatment, and It is possible to provide an inexpensive and highly practical laminated film in which deterioration of the laminate strength or the like is not observed and the gas barrier layers 2 and 4 are hardly peeled off from the base material.

In general formula (1), R ¹ can be used as long as it can be represented by CH ₃ , C ₂ H ₅ , C ₂ H ₄ OCH ₃ , or the like. Among these, tetraethoxysilane in which R ¹ is C ₂ H ₅ is preferable because it is relatively stable in an aqueous solvent after hydrolysis.

The metal alkoxide condenses after hydrolysis to form a ceramic film. However, since the metal oxide is hard and cracks easily occur due to distortion due to volume reduction during condensation, it is very difficult to form a thin, transparent and uniform condensate film on the film. Therefore, by adding a polymer, flexibility can be imparted to the structure and cracks can be prevented to form a film. However, even if the addition of the polymer is visually uniform, it is often microscopically separated into silicon or a metal oxide and a polymer portion, which tends to be a barrier hole and gas barrier properties are likely to be lowered.
Therefore, by adding a water-soluble polymer having a hydroxyl group, a strong hydrogen bond between the hydroxyl group of the polymer and the hydroxyl group of the hydrolyzate of the metal alkoxide is utilized to cause the metal oxide to condense with the polymer during condensation. Disperses well and exhibits high gas barrier properties close to ceramics. Further, by depositing this film on the gas barrier layer made of silicon oxide, the gas barrier properties, water resistance, and moisture resistance, which are much higher than the effects obtained by each single layer, are exhibited. However, since the coating layer made of a mixture of a metal alkoxide or a hydrolyzate thereof and a water-soluble polymer having a hydroxyl group is composed of hydrogen bonds, it swells and dissolves with water. Even if there is a synergistic effect due to the laminated structure with the gas barrier layer, the gas barrier property is likely to deteriorate under severe conditions such as boiling and retorting.

On the other hand, in this invention, this swelling can be prevented by adding the compound of the said General formula (2).
In the general formula (2), the organic functional group (R ² ) is preferably a non-aqueous functional group such as vinyl, epoxy, methacryloxy, ureido, and isocyanate. The water resistance of the non-aqueous functional group is further improved because the functional group is hydrophobic.
When the compound represented by the general formula (2) is a multimer, a trimer is preferable, more preferably a general formula (NCO-R ⁴ Si (OR ³ ) ₃ ) ₃ (wherein R ⁴ is (CH ₂ ) _n , n is 1 or more) 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate. This is a condensate of 3-isocyanatoalkylalkoxysilane.

This 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate is known to exhibit the same performance as the reaction due to the polarity of the nurate part, although the isocyanurate part has no chemical reactivity. Yes. In general, it is added to an adhesive or the like in the same manner as 3-isocyanate alkylalkoxysilane, and is known as an adhesion improver. Therefore, by adding 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate to Si (OR ¹ ) and a water-soluble polymer having a hydroxyl group, the gas barrier laminate film based on hydrogen bonds is water-soluble. It is possible to prevent swelling due to water and improve water resistance. In addition, 3-isocyanatealkylalkoxysilane has high reactivity and low liquid stability, whereas the nurate part is not water-soluble due to its polarity, but is easily dispersed in an aqueous liquid and keeps the liquid viscosity stable. Its water resistance is equivalent to that of 3-isocyanatoalkylalkoxysilane. Furthermore, the nurate part is not only water-resistant, but Si (OR ¹ ) ₄ and a water-soluble polymer having a hydroxyl group are less likely to be pores of the barrier due to its polarity.

1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate may be produced by thermal polymerization of 3-isocyanatepropylalkoxysilane, and may include 3-isocyanatepropylalkoxysilane as a raw material. But there is no problem. More preferred is 1,3,5-tris (3-trialkoxysilylpropyl) isocyanurate, and still more preferred is 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate.
This methoxy group has a high hydrolysis rate, and those containing a propyl group can be obtained at a relatively low price.

In addition, as the organic functional group R ² of the general formula (2), a 3-glycidoxypropyl group or a 2- (3,4-epoxycyclohexyl) group can be preferably used. Since these organic functional groups form hydrogen bonds with Si (OR ¹ ) ₄ and the water-soluble polymer of the general formula (1) by hydrolysis, they do not easily become barrier pores and do not impair gas barrier properties. Water resistance can be improved.
However, some epoxy-based silane compounds as described above may have mutagenic properties. Further, when the organic functional group (R ² ) is vinyl or methacryloxy, irradiation with ultraviolet rays or an electron beam is required in the production process, and the cost tends to increase due to an increase in equipment and processes. In the case where the organic functional group (R ² ) is ureido, there is a specific odor, and in the case of an isocyanate, the reactivity is high and the pot life is short. For these reasons, it is considered that 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate is more preferable as the component ii) used in the present invention.

  As the water-soluble polymer having a hydroxyl group in the gas barrier coating layer in the gas barrier laminate film of the present invention, polyvinyl alcohol, starch, and celluloses are preferable. Particularly when polyvinyl alcohol (hereinafter referred to as PVA) is used for the coating agent of the present invention, the gas barrier property is most excellent. This is because PVA is a polymer containing the largest number of hydroxyl groups in the monomer unit, so that it can have a very strong hydrogen bond with the hydroxyl group of the metal alkoxide after hydrolysis. PVA as used herein is generally obtained by saponifying polyvinyl acetate, and saponification is complete saponification in which only several percent of acetic acid groups remain from so-called partially saponified PVA in which several tens of percent of acetic acid groups remain. Includes up to PVA. The molecular weight of PVA has various degrees of polymerization ranging from 300 to several thousand, but there is no problem in the effect even if any molecular weight is used. However, a high molecular weight PVA generally having a high saponification degree and a high polymerization degree is preferred because of its high water resistance.

As generally known, the hydrolysis method of Si (OR ¹ ) ₄ is performed using an acid or alkali catalyst, alcohol and water. Preferably, acid hydrolysis is easy to control. At this time, there is no problem even if a generally known catalyst such as tin chloride or acetylacetonate is added to further control the hydrolysis.

In the method of mixing the coating liquid, the effect is manifested by mixing hydrolyzed Si (OR ¹ ) ₄ , a water-soluble polymer having a hydroxyl group, and (R ² Si (OR ³ ) ₃ ) _n in any order. . When (R ² Si (OR ³ ) ₃ ) _n is mixed and present in the form of oil droplets without being dispersed in the coating solution, it can be hydrolyzed and finely dispersed as described above. preferable. In particular, if Si (OR ¹ ) ₄ and (R ² Si (OR ³ ) ₃ ) _n are separately hydrolyzed and then added to the water-soluble polymer, fine dispersion of SiO ₂ and addition of Si (OR ¹ ) ₄ It is desirable considering the decomposition efficiency.

Incidentally, i) the general formula _{^{Si (OR 1) 4 ... (}} 1) silicon is represented by the compounds and at least one of a hydrolyzate thereof, ii) the general formula _{^{(R 2 Si (OR 3)}} 3) n ... In the coating liquid containing at least one of the silicon compound represented by (2) and its hydrolyzate, and iii) a water-soluble polymer having a hydroxyl group, the mixing ratio is the solid content weight of i) Is preferably set to 3 to 30, and iii) to 5 to 50 (both solid weights).

  The coating liquid used to form the gas barrier coating layer is stabilized with clay minerals such as isocyanate compounds, colloidal silica and smectite, taking into account the adhesion to ink and adhesives, wettability, and prevention of cracking due to shrinkage. Known additives such as a colorant, a colorant, and a viscosity modifier can be added within a range that does not impair gas barrier properties and water resistance.

  As a method for forming the gas barrier coating layer 3 and the gas barrier coating layer 5, a normal coating method can be used. For example, dipping method, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing method, spray coating, gravure offset method and the like can be used. It coats on a gas barrier layer using these coating methods.

  Any of these methods can be used for drying the gas barrier coating layer 3 and the gas barrier coating layer 5 as long as it is a method of heating the coating layer such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, UV irradiation, etc. Further, two or more of these may be combined.

The role of the gas barrier coating layer 3 and the gas barrier coating layer 5 in the gas barrier laminate film of the present invention is to perform normal processing such as printing, laminating, bag making, etc. on the gas barrier layer 2 and the gas barrier layer 4 having excellent gas barrier properties. Protection function when applied, and protection function when external stress such as bending or pulling is applied,
Further, the gas barrier coating layer 3 and the gas barrier coating layer 5 described above exhibit high gas barrier properties,
Furthermore, the function of filling the defects of the gas barrier layer by forming on the surfaces of the gas barrier layer 3 and the gas barrier layer 5 to improve the gas barrier property,
Furthermore, it is a gas barrier property improving function that is manifested by tightening the gas barrier layer by internal stress due to curing shrinkage during the formation of the gas barrier coating layer.

  The thickness Ya of the gas barrier coating layer 3 and the thickness Yb of the gas barrier coating layer 5 are preferably 0.05 μm or more and 3 μm or less. When the film thickness is less than 0.05 μm, it is difficult to form a uniform coating layer, and sufficient protective functions and gas barrier properties are not exhibited, and also due to curing shrinkage when the gas barrier coating layer 3 and the gas barrier coating layer 5 are formed. The gas barrier layer 2 cannot be sufficiently tightened by the coating layer 3 and the gas barrier layer 4 cannot be sufficiently tightened by the coating layer 5 because the internal stress is slightly generated. I can't expect it. On the other hand, if the film thickness exceeds 3 μm, cracks are likely to occur when the gas barrier coating layer 3 and the gas barrier coating layer 5 are formed, and internal stress due to curing shrinkage acts excessively, and adhesion between the gas barrier layer 2 and the gas barrier layer 4 is improved. There is a high possibility of decline.

  Further, in order for the gas barrier coating layer 3 and the gas barrier coating layer 5 to exhibit the above-described function of improving gas barrier properties due to curing shrinkage and not to reduce the adhesion, the thicknesses of the gas barrier coating layer 3 and the gas barrier coating layer 5 are as follows. It is also necessary to consider the balance between the thickness of the gas barrier layer 2 and the thickness of the gas barrier layer 4 made of silicon oxide. That is, as described above, one of the roles of the gas barrier coating layer 3 and the gas barrier coating layer 5 is to provide gas barrier properties by tightening the gas barrier layer by internal stress due to curing shrinkage when the gas barrier coating layer 3 and the gas barrier coating layer 5 are formed. Although there is a function to improve, the internal stress acts on the gas barrier layer 2 and the gas barrier layer 4 as the thickness of the gas barrier coating layer 3 and the gas barrier coating layer 5 increases, and the gas barrier layer 2 and the gas barrier layer 4 against the internal stress. The resistance force of the gas barrier layer 2 and the gas barrier layer 4 decreases as the thickness of the gas barrier layer 2 and the gas barrier layer 4 increases. For example, even if the same internal stress acts on the gas barrier layer 2 and the gas barrier layer 4, As the thickness increases, it cannot withstand internal stress and adhesion decreases. There is a direction.

  The gas barrier coating layer 3 and the gas barrier coating layer 5 can be formed by curing by applying the above-described coating solution and drying by applying heat. At this time, the base material layer made of a plastic film is used. No. 1 tends to soften, and if the internal stress due to the above-described curing shrinkage is applied thereto, the adhesiveness is lowered. That is, when the gas barrier layer 2 and the gas barrier coating layer 3 are laminated on one surface of the substrate layer 1 and the gas barrier layer 4 and the gas barrier coating layer 5 are laminated on the other surface as in the present invention, the substrate layer Since the gas barrier coating layer 3 and the gas barrier coating layer 5 need to be cured by applying heat twice to dry, the base material layer 1 is softened by drying and is caused by curing shrinkage due to the above-described decrease in adhesion. The occurrence of internal stress occurs twice, and there is a higher possibility that the adhesion will be lower than when only the gas barrier layer 2 and the gas barrier coating layer 3 are laminated on the base material layer 1, for example, a gas barrier layer having the same thickness. A gas barrier coating layer having the same thickness as that of the gas barrier layer 2 and the gas barrier coating layer 3 on one surface of the base material layer 1, and a gas barrier layer 4 and a gas barrier coating layer 5. In the case of the layer, toward the latter adhesion is reduced.

  That is, in order to create a gas barrier laminated film with good adhesion, the upper limit value of the gas barrier layer thicknesses Xa [μm] and Xb [μm] and the gas barrier coating layer thicknesses Ya [μm] and Yb An inversely proportional relationship is established with the upper limit combined with [μm], and the thicknesses Xa, Xb, Ya, and Yb must satisfy the inequality (Xa + Xb) (Ya + Yb) ≦ α (positive number). The value of α varies depending on the formation method of the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide, the curing conditions of the gas barrier coating layer 3 and the gas barrier coating layer 5, and the like. The adhesion of the laminated film is generally good. Therefore, the thicknesses Xa, Xb, Ya and Yb preferably satisfy the inequality (Xa + Xb) (Ya + Yb) ≦ 0.5.

  Furthermore, as described above, the internal stress due to curing shrinkage during the formation of the gas barrier coating layer 3 increases as the thickness of the gas barrier coating layer 3 increases, and the resistance of the gas barrier layer 2 increases with the thickness of the gas barrier layer 2. The smaller the thickness, the smaller. That is, the thickness Xa [μm] of the gas barrier layer 2 described above is in the range of (0.005 ≦ Xa ≦ 0.5) and the thickness Ya [μm] (0.05 ≦ Ya ≦ 3) of the gas barrier coating layer 3. As the thickness Xa of the gas barrier layer 2 is increased, and the thickness Ya of the gas barrier coating layer 3 is further increased, the effect of the gas barrier property improving function expressed by tightening the gas barrier layer 2 is increased. However, in other words, when the thickness Xa of the gas barrier layer 2 is thin, the thickness Ya of the gas barrier coating layer 3 is thick, and when the thickness Ya of the gas barrier coating layer 3 is thin, the thickness Xa of the gas barrier layer 2 If the thickness is not increased, the gas barrier property improving function will not be sufficiently exhibited. That is, in order to fully exhibit the gas barrier property improving function, there is an inversely proportional relationship between the lower limit value of the thickness Xa of the gas barrier layer 2 made of silicon oxide and the lower limit value of the thickness Ya of the gas barrier coating layer 3. Thus, the thicknesses Xa and Ya must satisfy the inequality XaYa ≧ β1 (positive number).

  Furthermore, in the same manner as the relationship between the gas barrier layer 2 and the gas barrier coating layer 3 described above, the internal stress due to curing shrinkage when forming the gas barrier coating layer 5 increases as the thickness of the gas barrier coating layer 5 increases. The resistance force 4 decreases as the thickness of the gas barrier layer 4 increases. That is, the above-mentioned thickness Xb [μm] of the gas barrier layer 4 is (0.005 ≦ Xb ≦ 0.5) and the thickness Yb [μm] (0.05 ≦ Ya ≦ 3) of the coating layer 5 is As the thickness Xa of the gas barrier layer 4 is increased, and the thickness Ya of the gas barrier coating layer 5 is further increased, the effect of the above-described gas barrier property improving function that is manifested by tightening the gas barrier layer 4 increases. However, in other words, when the thickness Xb of the gas barrier layer 4 is thin, the thickness Yb of the gas barrier coating layer 5 is thick, and when the thickness Yb of the gas barrier coating layer 5 is thin, the thickness Xb of the gas barrier layer 4 is If the thickness is not increased, the gas barrier property improving function will not be sufficiently exhibited. That is, in order to fully exhibit the gas barrier property improving function, there is an inversely proportional relationship between the lower limit value of the thickness Xb of the gas barrier layer 4 made of silicon oxide and the lower limit value of the thickness Yb of the gas barrier coating layer 5. Therefore, the thicknesses Xb and Yb must satisfy the inequality XbYb ≧ β2 (positive number).

  Furthermore, the values of β1 and β2 vary depending on the method of forming the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide, the type of coating liquid for forming the gas barrier coating layer 3 and the gas barrier coating layer 5, the curing conditions, and the like. However, β1 and β2 are 0.001 or more, and the gas barrier property-improving function works sufficiently. Therefore, it is preferable that the thicknesses Xa and Ya satisfy the inequality XaYa ≧ 0.001, and the thicknesses Xb and Yb also satisfy the inequality XbYb ≧ 0.001.

That is, in order for the gas barrier coating layer 3 and the gas barrier coating layer 5 to exhibit the above-described gas barrier property-improving function and not deteriorate the adhesion, the thickness Xa [μm] of the gas barrier layer 2 made of silicon oxide and The thickness Xb [μm] (0.005 ≦ Xa (or Xb) ≦ 0.5) of the gas barrier layer 4, the thickness Ya [μm] of the gas barrier coating layer 3, and the thickness Yb [ μm] (0.05 ≦ Ya (or Yb) ≦ 3) preferably satisfies the following three inequalities.
0.001 ≦ XaYa
0.001 ≦ XbYb
(Xa + Xb) (Ya + Yb) ≦ 0.5
The unit of Xa, Xb, Ya, Yb in the formula is μm.

In the gas barrier laminate film of the present invention, the gas barrier coating layer 3 and the gas barrier coating layer 5 have at least one of a silicon compound represented by the general formula Si (OR ¹ ) ₄ and a hydrolyzate thereof, the general formula (R ² Si (OR ³ ) ₃ ) At least one of a silicon compound represented by _n and a hydrolyzate thereof (provided that R ¹ and R ³ represent CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃₎ . R ² represents an organic functional group, n represents a number of 1 or more), a water-soluble polymer having a hydroxyl group, and a coating solution obtained by coating, heating and drying, and Xa , Xb, Ya, Yb satisfy both the above specific inequalities, so that both adhesion and high barrier properties can be achieved. In particular, even in the case of having a two-layer structure of a gas barrier layer and a gas barrier coating layer on each of both surfaces of the base material layer 1 as in the gas barrier laminate film of the present invention, or when having a complicated laminate structure as described later. Further, it is possible to have a high barrier property while maintaining adhesion between the base material layer and the gas barrier layer and adhesion between the gas barrier layer and the gas barrier coating layer.

In the gas barrier laminated film of the present invention, a primer layer may be provided between the base material layer and the gas barrier layer in order to further improve the adhesion between the base material layer 1 and the gas barrier layer 2 or the gas barrier layer 3.
As the primer layer, for example, an organic polymer obtained by a two-component reaction of a polyol selected from acrylic polyol, polyvinyl acetal, poly-still polyol, polyurethane polyol and the like with an isocyanate compound, or a polyisocyanate compound and water Organic compounds having urea bonds, polyethyleneimine or derivatives thereof, polyolefin-based emulsions, polyimides, melamines, phenols, and organic silicas such as organically modified colloidal silica, silane coupling agents and hydrolysates thereof The thing which has a silane compound as a main ingredient is mentioned. In particular, a combination of an acrylic polyol, an isocyanate compound, and a silane coupling agent is preferable. When a primer layer composed of this combination is used, stable and higher adhesion can be obtained between the base material layer and the gas barrier layer.

  The thickness of the primer layer is generally a thickness after drying, desirably 0.005 μm or more and 1 μm or less, and more preferably 0.01 μm or more and 0.5 μm or less. When the thickness is less than 0.01 μm, it is difficult to obtain a uniform coating film from the viewpoint of coating technology. On the other hand, when the thickness is more than 0.5 μm, the cost is increased, which is economically disadvantageous.

The gas barrier laminate film of the present invention comprises a gas barrier layer 2 made of at least silicon oxide on one surface of the base material layer 1, a gas barrier coating layer 3 on the other surface, a gas barrier layer 4 made of silicon oxide on the other surface, and a gas barrier. The coating layer 5 is sequentially laminated in the thickness direction, and the gas barrier coating layer 3 and the gas barrier coating layer 5 are
At least one of a silicon compound represented by the general formula Si (OR ¹ ) ₄ (1) and a hydrolyzate thereof,
At least one of a silicon compound represented by the general formula (R ² Si (OR ³ ) ₃ ) _n (2) and a hydrolyzate thereof,
(However, R ¹ and R ³ are CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ , R ² is an organic functional group)
As long as it is obtained by coating, heating, and drying a coating solution containing a water-soluble polymer having a hydroxyl group, it may have a more complicated laminated structure.
For example, a laminate of a gas barrier layer and a gas barrier layer may be laminated on the gas barrier layer 3 or the gas barrier layer 5. Furthermore, a printing layer may be laminated on the surface of the gas barrier coating layer 3 or the gas barrier coating layer 5. In this case, a printing layer having a thickness of 0.1 to 2.0 μm can be laminated without any particular limitation by a known printing method or coating method using a conventional printing ink conventionally used.

The gas barrier laminate film of the present invention can be laminated with other films and used in the field of packaging of food, daily necessities, pharmaceuticals, etc., and the fields of solar cell related members and electronic equipment related members. For example, the gas barrier laminate film of the present invention may be used as the outermost layer, and an intermediate film layer or a heat seal layer may be laminated via an adhesive. Moreover, the gas barrier laminate film of the present invention is used as an intermediate layer, an outer film layer or the like is laminated on one side of the film via an adhesive, and a heat seal layer or the like is formed on the other side of the film via an adhesive. A stacked structure may be used.
A transparent film layer is used as the intermediate film layer or the outer film layer. Examples of such transparent film layers include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polyamide films, polycarbonate films, polyacrylonitrile films, and polyimide films. It is done. Examples of the heat seal layer include polyethylene, polypropylene, ethylene vinyl acetate copolymer, ethylene / methacrylic acid copolymer, ethylene / methacrylic acid ester copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester. Synthetic resins such as copolymers and cross-linked products of these metals are used. Although the thickness of an intermediate | middle film layer, an outer film layer, and a heat seal layer is decided according to the objective, generally it is the range of 15-200 micrometers. As the adhesive, a one-component curable type or two-component curable polyurethane adhesive or the like is used. In order to laminate these layers through an adhesive, a dry laminating method or the like can be used. In addition, as another method for laminating the heat seal layer, a method (extrusion lamination) in which the synthetic resin of the heat seal layer is hot melt extruded can be used.

  EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not restrict | limited to the following example. In the following Examples 1, 2, and 3, as shown in FIG. 1, the gas barrier layer 2 and the gas barrier coating layer 3 are formed on one surface of the base material layer 1, and the gas barrier layer 4 is formed on the other surface. A gas barrier laminate film in which the gas barrier coating layer 5 was sequentially laminated was produced.

A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 25 μm was prepared as the base material layer 1 and placed in a vacuum deposition apparatus. A mixed gas of 5 sccm of hexamethyldisiloxane (HMDSO) / 100 sccm of oxygen is introduced between the electrodes, a high frequency of 13.56 MHz is applied to form 0.5 kW to form plasma, and a thickness of 0.1 mm is formed on one surface of the base material layer 1. A gas barrier layer 2 made of 03 μm silicon oxide was laminated.
Next, it was re-installed in a vacuum deposition apparatus, a mixed gas of 5 sccm of hexamethyldisiloxane (HMDSO) / 100 sccm of oxygen was introduced between the electrodes, and a high frequency of 13.56 MHz was applied to form a plasma by applying 0.5 kW. A gas barrier layer 4 made of silicon oxide having a thickness of 0.03 μm was stacked on the other surface of the layer 1.
Next, the solutions (A) to (C) prepared by the following method were mixed at a ratio of A / B / C = 100/20/10 (solid content weight ratio), and this coating solution was mixed with the above bar coater. It apply | coated on the surface of the gas barrier layer 2, it was made to dry at 120 degreeC for 1 minute, and the 0.3-micrometer gas barrier coating layer 3 was formed.

≪Solution for gas barrier coating layer≫
(A): 17.9 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ , hereinafter referred to as TEOS) and 72.1 g of hydrochloric acid (0.1N) are added to 10 g of methanol, followed by stirring for 30 minutes and hydrolysis. Hydrolysis solution (B) having a solid content of 5% (weight ratio in terms of SiO ₂ ): 5% (weight ratio) of polyvinyl alcohol, water / methanol = 95/5 (weight ratio) aqueous solution (C): 1, 3 , 5-tris (3-trimethoxysilylpropyl) isocyanurate, water / IPA = 1/1 solution, solid content 5% (weight ratio R ² Si (OH) ₃ conversion)

  Next, the solutions (A) to (C) prepared by the above method are mixed at a ratio of A / B / C = 100/20/10 (solid content weight ratio), and this coating solution is mixed with a bar coater. It apply | coated on the surface of the gas barrier layer 4, it was made to dry at 120 degreeC for 1 minute, and the 0.3-micrometer gas barrier coating layer 5 was formed. Thus, the gas barrier laminate film of Example 1 was produced.

  In the gas barrier laminated film of Example 1, the thicknesses of the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide laminated on the surface of the base material layer 1 are both 0.3 μm, and the surface of the gas barrier layer 2 and the gas barrier layer 4 The thicknesses of the gas barrier coating layer 3 and the gas barrier coating layer 5 laminated on the surface of each were 0.3 μm. Other conditions were the same as in Example 1. Thus, a gas barrier laminate film of Example 2 was produced.

  In the gas barrier laminate film of Example 1, the gas barrier layer 2 and the gas barrier layer 4 laminated on the surface of the base material layer 1 were vaporized by an electron beam heating method to form a gas barrier layer having a thickness of 0.03 μm. . Other conditions were the same as in Example 1. Thus, the gas barrier laminate film of Example 3 was produced.

[Comparative Example 1]
In the gas barrier laminate film of Example 1, only the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide were laminated on both surfaces of the base material layer 1, and the gas barrier coating layer 3 and the gas barrier coating layer 5 were not laminated. . Thus, a gas barrier laminate film of Comparative Example 1 was produced.

[Comparative Example 2]
In the gas barrier laminate film of Example 1, the thicknesses of the gas barrier layer 2 and the gas barrier layer 4 made of silicon oxide laminated on the surface of the base material layer 1 are both 0.5 μm, and the surface of the gas barrier layer 2 and the gas barrier layer 4 The thicknesses of the gas barrier coating layer 3 and the gas barrier coating layer 5 laminated on the surface were both 0.5 μm. Other conditions were the same as in Example 1. Thus, a gas barrier laminate film of Comparative Example 2 was produced.

Hereinafter, each gas barrier laminated film of Examples 1, 2, 3 and Comparative Examples 1, 2 produced as described above is referred to as a single film.
Next, a printing layer having a thickness of 1.2 μm is laminated on the surface of the coating layer 3 of each of the single films of Examples 1, 2, 3 and Comparative Example 2 and the surface of the gas barrier layer 2 of the single film of Comparative Example 1. did. Hereinafter, these are called printing films.
Next, a heat-seal layer of polypropylene having a thickness of 50 μm is laminated on the surface of the printing layer of each of the printing films of Examples 1, 2, 3 and Comparative Examples 1 and 2 with a polyurethane adhesive of 5 g / m 2. did. Hereinafter, these are called laminated films.

<Comparison evaluation>
1. Oxygen permeability About the single-piece | unit film, printing film, and laminated | multilayer film of Examples 1, 2, and 3 and Comparative Examples 1 and 2, it was 30 degreeC- by the oxygen permeability meter (MOCON OX-TRAN 2/21) by Modern Control. The oxygen permeability (cc / m ² · 24 h · MPa) in a 70% RH atmosphere was measured.
2. Water Vapor Permeability For the single films of Examples 1, 2, and 3 and Comparative Examples 1 and 2, using a water vapor permeability meter (MOCON PERMATRAN-W 3/31) manufactured by Modern Control Co., under a 40 ° C.-90% RH atmosphere. The water vapor permeability (g / m ² · 24 h) of was measured.
3. Lamination strength The laminate strength (N / 15 mm) of the test pieces slit to a width of 15 mm from the laminated films of Examples 1, 2, 3 and Comparative Examples 1 and 2 was measured with an ordinary Tensilon universal testing machine.
These measurement results are shown in Table 1.

As can be seen from Table 1, the gas barrier laminate films (single film, print film and laminate film) of Examples 1, 2 and 3 have low oxygen permeability and water vapor permeability and high laminate strength. ing.
On the other hand, the printed film and laminated film made of the gas barrier laminated film of Comparative Example 1 in which the gas barrier coating layer is not laminated are oxygen permeable compared to the gas barrier laminated films of Example 1, Example 2 and Example 3. The degree was high and the gas barrier property was poor.
Further, the gas barrier layer 2 and the gas barrier layer 4 are formed by a plasma CVD method, the thickness Xa [μm] of the gas barrier layer 2, the thickness Xb [μm] of the gas barrier layer 4, and the thickness Ya [μm] of the gas barrier coating layer 3 The gas barrier laminate film of Example 2 in which the thickness Yb [μm] of the gas barrier coating layer 5 is (Xa + Xb) (Ya + Yb)> 0.5 is compared with the gas barrier laminate films of Example 1 and Example 3. In addition, the gas barrier property was at the same level, but the laminate strength of the laminated film was inferior.

  The gas barrier laminate film of the present invention is suitably used in the field of packaging of foods, daily necessities, pharmaceuticals, etc., and in the field of solar cell related members and electronic equipment related members, where particularly high gas barrier properties are required.

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... Gas barrier layer 3 ... Gas barrier coating layer 4 ... Gas barrier layer 5 ... Gas barrier coating layer

Claims (6)

A gas barrier laminate film in which a gas barrier layer 2, a gas barrier coating layer 3, and a gas barrier layer 4 and a gas barrier coating layer 5 are sequentially laminated on one surface of a base material layer 1 made of a transparent plastic film. In
The gas barrier layer 2 and the gas barrier layer 4 are made of silicon oxide,
The gas barrier coating layer 3 and the gas barrier coating layer 5 are:
At least one of a silicon compound represented by the general formula Si (OR ¹ ) ₄ (1) and a hydrolyzate thereof,
At least one of a silicon compound represented by the general formula (R ² Si (OR ³ ) ₃ ) _n (2) and a hydrolyzate thereof,
(In the general formulas (1) and (2), R ¹ and R ³ represent CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ , R ² represents an organic functional group, and n represents 1 or more. And a coating solution containing a water-soluble polymer having a hydroxyl group is applied and dried.
And the film thickness (thickness Xa) of the gas barrier layer 2 and the film thickness (thickness Xb) of the gas barrier layer 4 are 0.005 μm or more and 0.5 μm or less,
The film thickness (thickness Ya) of the gas barrier coating layer 3 and the film thickness (thickness Yb) of the gas barrier coating layer 5 are 0.05 μm or more and 3 μm or less,
A gas barrier laminate film, wherein the relationship between Xa, Xb, Ya and Yb satisfies the following three formulas.
0.001 ≦ XaYa
0.001 ≦ XbYb
(Xa + Xb) (Ya + Yb) ≦ 0.5
(The unit of the thickness of Xa, Xb, Ya, Yb in the formula is μm) The general formula (R ² Si (OR ³ ) ₃ ) _n (2) is represented by the formula (NCO-R ⁴ Si (OR ³ ) ₃ ) ₃ (wherein R ⁴ represents (CH ₂ ) _n . The gas barrier laminate according to claim 1, wherein n represents a number of 1 or more, and is a trimer 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate. the film.   The gas barrier property according to claim 1 or 2, wherein the gas barrier layer 2 and the gas barrier layer 4 respectively laminated on the surface of the base material layer 1 are formed by a plasma chemical vapor deposition (CVD) method. Laminated film. The gas barrier laminate according to claim 1, wherein the general formula Si (OR ¹ ) ₄ (1) has a hydrolyzable group (R ¹ ) of C ₂ H _5. the film.   A primer layer made of acrylic polyol, isocyanate, and silane coupling agent is further laminated between the base material layer 1 and the gas barrier layer 2 and between the base material layer 1 and the gas barrier layer 3. The gas barrier laminate film according to any one of claims 1 to 4, wherein The general formula (R ² Si (OR ³ ) ₃ ) _n (2) is 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate. The gas barrier laminate film according to any one of the above.

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