JPH07268608A - Barrier laminate - Google Patents

Abstract

PURPOSE:To provide a highly practical barriering laminate excellent in adhesion between a resin film and a vapor-deposited thin film and in adhesion to an ink or adhesive added through post-processing and without the gas barrier property being deteriorated. CONSTITUTION:A coating film layer 3 consisting of an organosilicon compd. shown by the chemical formula R-Si-(OR')3 (wherein R is an org. functional group, and R' is a hydrolyzable group), a vapor-deposited thin film layer 4 consisting of a metal or a metallic compd. and a coating film layer 5 consisting of the organosilicon compd. are laminated on a polymer resin film substrate 2 to constitute the barrier laminate 1. The adhesion between the coating film layer consisting of the organosilicon compd. and the vapor-deposited thin film layer is excellent. The vapor-deposited thin film layer is protected by interposing it between the coating film layers consisting of the organosilicon compd., hence the vapor-deposited thin film is hardly deteriorated, and an excellent barrier property is maintained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas barrier laminate which can be effectively blocked from permeation of gases such as oxygen and water vapor, which is used in the field of packaging foods, pharmaceuticals and the like.

[0002]

2. Description of the Related Art In recent years, packaging materials used for packaging foods, pharmaceuticals, etc. are used to suppress deterioration of contents, particularly oxidation and deterioration of proteins, fats and oils in foods, and to maintain taste and freshness. In addition, in the case of pharmaceuticals that require aseptic handling, the effects of oxygen, water vapor and other gases that permeate the packaging material are prevented in order to prevent deterioration of the active ingredient and maintain efficacy. Therefore, it is required to have a gas barrier property of blocking these gases.

For this reason, a polyvinyl alcohol film (P
VA), ethylene vinyl alcohol copolymer film (EVOH), acrylonitrile film, etc.,
Further, polypropylene films, polyethylene films, etc. are used as packaging materials as gas barrier laminates as barrier films for blocking water vapor, and packaging films made of these packaging materials have been generally used. However, these films alone do not have gas barrier properties against both oxygen and water vapor, and are generally laminated or coated by laminating other types of polymer resin compositions having different properties which are said to have relatively high gas barrier properties. Although it has been used as a film for packaging materials, it is affected by temperature and humidity in storage and use environments,
In some cases, sufficient gas barrier properties cannot be exhibited.

Further, there is a resin film having a gas barrier property against both oxygen and water vapor, and a polyvinylidene chloride film (PVDC), a polyester film, a polypropylene film, and a coated film obtained by coating polyvinylidene chloride on a nylon film are available. is there. When such a resin film is discarded after use and incinerated, a toxic gas is generated, which may cause an environmental problem.

On the other hand, as a packaging material which requires a high gas barrier property, a conventional resin film (even a resin which does not have a high gas barrier property by itself with a suitable polymer resin composition) is used as a packaging material. Metal foils made of metals or metal compounds have been used. Such metal foils have excellent barrier properties against gases such as oxygen and water vapor, but when they are incinerated as waste after use, the metal remains as a residue and is difficult to reuse. The environmental impact is unavoidable.

As a solution to the above problems, recently, silicon oxide (SiO _x ) such as silicon monoxide (SiO), aluminum oxide (Al _x O _y ), metal such as aluminum (Al), Vapor-deposited films in which a metal oxide is formed on a resin film by a forming means such as vapor-deposition have been developed, and these have gas barrier properties superior to those of gas barrier materials composed of a polymer resin composition, There is little deterioration, and it is beginning to be used for packaging materials.

The packaging material made of these vapor-deposited films is rarely used as a vapor-deposited film alone, and is processed into a packaging container, a packaging bag or the like as post-processing after vapor deposition. For example, a packaging bag is processed into a bag shape by a bag-making process by further adhering a vapor deposition film to another base material.

[0008]

However, in the vapor-deposited film in which the above-mentioned metal or metal oxide is formed as a thin film on the resin film, the resin film is an organic compound, but an inorganic compound is formed on the resin film. , The physical properties such as mechanical properties, chemical properties, and thermal properties are very different. When these are laminated, mechanical stress and thermal stress are added to the vapor deposition thin film depending on the post-processing such as printing, bag making, container processing, laminating, etc. Distortion occurs in the thin film, cracks and pinholes are generated, and the chemical bonding state of the substance in contact with the vapor-deposited thin film is different, such as delamination between resin film, ink, adhesive, etc.
Furthermore, cohesive failure of the vapor-deposited thin film occurs, causing damage to the vapor-deposited thin film such as generation of cracks and pinholes. There is a problem that a high barrier property originally possessed by the gas such as air and water vapor permeates from the damaged portion, which is deteriorated.

In order to solve such problems, a method for improving the adhesion between the resin film as the vapor deposition base material and the vapor deposition film is, for example, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment or flame treatment of the surface of the resin film. The metal or metal oxide is vapor-deposited after the surface is activated by the above method. However, although improvement in adhesiveness can be expected due to an increase in secondary bonding force due to wetting of the vapor-deposited thin film, there is a problem that its activation ability decreases with time, and even this treatment does not always provide satisfactory adhesive strength. And it's not enough.

As another method, surface treatment with a chemical agent such as acid or alkali, or a copolymerized resin film obtained by copolymerizing a resin film with other resin components, or another resin is coextruded during film formation. However, it cannot be said to be sufficient.

Further, there is a method of applying an ethyleneimine-based, amine-based, epoxy-based, urethane-based or polyester-based coating agent on the surface of the resin film as the vapor deposition base material off-line or in-line. Although the adhesion is improved, the thermal dimensional stability of the coating layer is poor, so
The vapor-deposited thin film was subjected to mechanical stress when the resin film was thermally loaded, and as a result, the vapor-deposited thin film was cracked, pinholes, etc., and the barrier property was deteriorated.

Further, the adhesion between the vapor-deposited thin film formed on the resin film and the ink, adhesive, etc. added by the above-mentioned post-processing has been improved. Ethyleneimine-based, amine-based, epoxy-based There is a method of applying a coating agent such as urethane type or polyester type. Depending on the resin component of the coating agent, the adhesiveness is deteriorated or the barrier property is deteriorated, and both the adhesiveness and the barrier property are not satisfied. According to this, since the thermal dimensional stability of the coating layer is poor, the vapor-deposited thin film is mechanically stressed due to volume expansion or volume contraction due to the heat load applied with the passage of time or bag making or molding, and the vapor deposition thin film is cracked. , The occurrence of pinholes, etc., and delamination from ink, adhesive, etc. occurred, and the barrier properties deteriorated.

Therefore, according to the present invention, the adhesiveness between the resin film and the vapor-deposited thin film and the adhesiveness with the ink or adhesive added by the post-processing are excellent, and the barrier property against gases such as oxygen and water vapor is not deteriorated. It is intended to provide a barrier laminate having high practicality.

[0014]

The invention according to claim 1 provides a polymer resin film having the following chemical formula (I), R-Si- (OR ') ₃ (I) (wherein R is an organic compound). Which is a functional group and R'is a hydrolyzable group.), A coating layer made of an organosilicon compound represented by the formula (1), a vapor deposited thin film layer made of a metal or a metal compound, and a coating layer made of the organosilicon compound. It is a barrier laminated body characterized by being laminated in order.

The invention as defined in claim 2 is as set forth in claim 1.
Based on the invention of
The functional group (R) is -CH = CH₂-, -CH₂-CH₂−
CH ₂-NH₂-, -CH₂-NH₂-, -CH₂-N
HCONH₂, -CH₂-NH-CH₂-CH₂-NH
₂-, -CH₂-O-CH₂-(C₂H₃O) etc.
And the hydrolyzable group (R ′) is —Cl, —CH₃ , -CH₂
-CH₃ , -CH₂-CH₂-O-CH₃ Be equal
Is a barrier laminate.

According to a third aspect of the present invention, based on the first aspect of the present invention, a heat-adhesive resin layer is laminated on an outermost layer of a coating layer made of an organosilicon compound via an adhesive layer. It is a barrier laminated body characterized by the following.

[0017]

According to the present invention, the coating layer made of the organosilicon compound formed on the resin film has a strong binding force of the organic functional group in the organosilicon compound to the resin of the resin film,
High adhesion. When the organosilicon compound is dissolved in water or a mixed solution of water and alcohol during coating of the organosilicon compound, the hydrolyzable group of the organosilicon compound is hydrolyzed,
Active by producing a hydroxyl group (-OH) -Si-
An OH bond is formed, and this active -Si-OH bond forms a strong -O-Si-O-Si- bond of the coating layer made of an organosilicon compound by the thermal decomposition reaction in the drying step.

Since this active --Si--OH bond forms a strong bond --OMM--O--M-- in the presence of the metal element (M), the metal element (M ') and --Si-- of the vapor-deposited thin film are formed. O-
A strong bond of M ′ − is formed, and the adhesion between the coating layer made of an organosilicon compound and the vapor deposited thin film layer is improved.

The coating layer made of an organic silicon compound is excellent in heat resistance, thermal dimensional stability and hardness, and the vapor deposition thin film layer can be protected by the structure sandwiching the vapor deposition thin film layer.

[0020]

Embodiments will be described in detail based on embodiments of the present invention. FIG. 1 is a sectional view for explaining the constitution of the barrier laminate of the present invention, and FIG. 2 is a sectional view for explaining another constitution of the barrier laminate of the present invention.

In FIG. 1, reference numeral 1 denotes a barrier laminate, which is a resin film substrate 2, a coating layer 3 made of an organosilicon compound, a vapor-deposited thin film layer 4, and a coating layer 5 made of an organosilicon compound. The resin film substrate 2 is in the form of a sheet or a film, and is made of polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polyethylene 2,4-naphthalate, etc.), polyamide (nylon-6, nylon-12).
Etc.), polyvinyl chloride, polyvinyl alcohol, aromatic polyamide, polyamideimide, polyetherimide polysulfone, polyether sulfone, polyether ketone, polyarylate, polyphenylene sulfide, polyphenylene oxide, tetrafluoroethylene, trifluoroethylene monochloride. , A fluorinated ethylene-propylene copolymer, polyimide, etc. which are usually used as a packaging material can be used. These resin film base materials 2
Is appropriately selected from the above materials according to the application. A biaxially stretched resin film can be used if necessary. Known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, and a lubricant ₃ colorant can be added to these resin film base materials 2, and they are appropriately added as necessary.

Further, the surface of the resin film substrate 2 on which the coating layer 3 made of an organosilicon compound is formed is a known surface such as corona discharge treatment, plasma activation treatment, glow discharge treatment, reverse sputtering treatment, or roughening treatment. It is also possible to improve the adhesion of the vapor-deposited thin film by performing an activation treatment or by applying an ethyleneimine-based, amine-based, epoxy-based, urethane-based or polyester-based coating agent off-line or in-line.

The thickness of the resin film substrate 2 is not particularly limited, but considering the processability in the vapor deposition process, etc.
The range of 2 to 400 μm is preferable.

Coating layers 3, 5 made of an organosilicon compound
Is the following chemical formula (I), R-Si- (OR ')₃ (I) (where R is an organic functional group and R ′ is a hydrolyzable group
Is. ) Consisting of an organosilicon compound represented by
Functional group (R) is -CH = CH₂-, -CH₂-CH₂−
CH₂-NH₂-, -CH₂-NH₂-, -CH₂-N
HCONH₂, -CH₂-NH-CH₂-CH₂-NH
₂-, -CH₂-O-CH₂-(C₂H₃O) etc.
Of these, an epoxy group, an amino group and a urea group are preferable. Well
The hydrolyzable group (R ') is -Cl, -CH₃ , -CH₂−
CH₃ , -CH₂-CH ₂-O-CH₃ Etc. the above
Organosilicon compound of water or a mixture of water and alcohol
Apply an aqueous solution dissolved in the liquid. In this aqueous solution
Known isocyanate compound, silane coupling agent,
Common dispersants, stabilizers, viscosity modifiers, colorants, interfaces
Accompanied by significant chemical reaction with organosilicon compounds such as activators
If not, it can be added as needed
It

There are two methods for forming the coating film layer 3 made of an organosilicon compound, an in-line method of applying the resin film at the time of manufacturing the resin film and an off-line method of applying the resin film in a step different from the step of manufacturing the resin film. Compared to the off-line method, the number of steps is small and the amount of dust mixed in the manufacturing process is small, and the adhesion between the interface between the resin film and the coating layer made of an organosilicon compound is large. It can be said to be the preferred method.

In the in-line method, an unstretched resin obtained by heat-melting a polymer of a resin film and extruding the resin as it is, or a resin in a state where it is stretched in either the longitudinal direction or the uniaxial direction before crystal orientation is completed An aqueous solution of the above-mentioned organosilicon compound (including an aqueous solution, a mixed solution of water and alcohol, a hydrolyzate and a pyrolyzate of the organosilicon compound) is applied to the film surface. Before coating, surface treatment such as corona discharge treatment and plasma activation treatment may be performed. The applied resin film is biaxially stretched and heat set to complete the crystal orientation. The drying of the coating layer made of the organosilicon compound utilizes the step of heat-setting the resin film, but it is preferable to provide a drying step immediately before that.

As the off-line method, a known coating method can be used. Examples include roll coating, roll brushing, spray coating, air knife coating, gravure coating, impregnation and curtain coating.

The layer thickness of the coating layers 3 and 5 made of an organosilicon compound is not particularly limited, but the dry layer thickness may be in the range of 0.01 to 50 μm, and the reaction rate and the drying rate may be adjusted. In order to shorten the length, the range of 0.05 to 5 μm is preferable.

The deposited thin film layer 4 is made of Al, Si, Ti, Z.
Metals such as n, Zr, Mg, Sn, Cu and Fe and oxides, nitrides, sulfides and fluorides of these metals such as Al ₂ O ₃ , SiO, SiO ₂ , TiO ₂ and Zr.
O ₂ , MgO, SnO ₂ , ZnS, and MgF ₂ are used. As a forming method, an evaporation method such as vacuum evaporation, ion plating, or sputtering can be used, but vacuum evaporation and ion plating are preferable from the viewpoint of production efficiency. Resistance heating, electron beam (EB) heating, high frequency induction heating, or the like is used as a heating method for the vapor deposition apparatus.

The inside of the vapor deposition apparatus is 2 × 10 ⁻⁶ to 8 × 10 ^−3.
After evacuation to Torr, preferably 8 × 10 ⁻⁶ to 8 × 10 ⁻⁵ , a vapor deposition process is performed. The vapor-deposited metal thin film has a barrier property against oxygen and water vapor, but the barrier property varies depending on the material and film thickness of the thin film. Particularly, aluminum, silicon oxide, aluminum oxide and the like have excellent barrier properties.

The film thickness of the vapor-deposited thin film layer 4 may be in the range of 50 to 5000Å, preferably in the range of 300 to 1500Å. This is because when the film thickness is less than 50Å, the vapor-deposited thin film is likely to come off and the barrier property tends to vary.
If it exceeds 0 Å, the flexibility of the vapor-deposited thin film is impaired, cracks and pinholes are easily generated, and the barrier properties are deteriorated in both cases. In addition, vapor deposition thin film. The vapor deposition thin film is not limited to a single layer of a single component, and may be a vapor deposition thin film made of a mixture of the above vapor deposition materials, or may be a multilayer having two or more layers.

The coating layer 5 made of an organosilicon compound is the same as the coating layer 3 made of the above organosilicon compound,
The forming method is an off-line method.

Further, a thermoadhesive resin layer 8 is laminated via an adhesive layer 7 on the coating film layer 5 made of an organic silicon compound located at the outermost layer of the barrier laminate 10 of the present invention shown in FIG. The heat-adhesive resin layer 8 is used to process packaging containers such as bags and containers.

The heat-adhesive resin layer 8 is a resin layer which is easily heat-bonded by heating and pressing, and is made of, for example, polyolefin such as polyethylene, polypropylene, ethylene-propylene copolymer, polyester, polyamide, ionomer, ethylene-vinyl acetate copolymer. Examples thereof include acrylic resins such as acrylic acid esters and methacrylic acid esters, polyvinyl acetals, phenol resins, modified epoxy resins and copolymers and mixtures thereof, but are not limited to these as long as the above conditions are satisfied. Not a thing. In particular, polyolefin, polyester, polyamide, ethylene vinyl acetate copolymer and the like are preferable.

The layer thickness of the heat-adhesive resin layer 8 varies depending on the use, but is in the range of 1 to 200 μm, preferably 10
˜100 μm. As a forming method, a general processing method such as a dry laminating method, a solventless laminating method or an extrusion laminating method can be used.
The heat-adhesive resin layer 8 has a fusion temperature of 200 ° C. or lower, preferably 80 to 180 ° C., considering the heat resistance of the coating layer made of an organosilicon compound.

Hereinafter, specific examples of the present invention will be described in detail. <Example 1> Polyethylene terephthalate having a heat of crystal fusion of 9.7 cal / g was extruded from a die with an extrusion device,
While electrostatically applying on a drum cooled to 40 ° C, the film thickness is 15
A 3 μm unstretched resin film was produced. This film was placed on a metal roll heated to 95 ° C. in a flow direction of 3.65.
After being double-stretched, an aqueous solution of N- (β-aminoethyl) -γ-amino-propylmethoxysilane having a solid content of 2 wt% as an organosilicon compound was applied to one surface of the film by a gravure coating method, and then the film was subjected to a preheating zone of 95 ° C. , 102 ℃
Was stretched in the width direction by 3.85 times. Further 200-230
Heat treatment was performed at 4.0 ° C. for 4.0 seconds to give a film thickness of 0.
A 12 μm biaxially stretched ethylene terephthalate film having a coating layer made of a 2 μm organosilicon compound was prepared.

This biaxially stretched ethylene terephthalate film was wound up, loaded into an EB heating vacuum vapor deposition apparatus, and the degree of vacuum was set to 1.5 × 10 ^-5 Torr. (Purity 99.9
EB-Power of 30 kV-2A and winding speed of 1.5 m / sec. The pressure was 2 × 10 ⁻⁴ mbar and the film was vapor-deposited to a film thickness of 1000Å to form an aluminum vapor deposition layer.

A winding speed of 40 on the vapor-deposited aluminum layer.
m / min. N- (β-aminoethyl) -at a drying condition of 95 to 110 ° C and a coating amount of 0.15 g / m ^2.
An aqueous solution of γ-amino-propylmethoxysilane (organosilicon compound) having a solid content of 2 wt% is applied by a gravure coating method and dried to produce a barrier laminate of the present invention in which a coating layer made of an organosilicon compound is formed. did.

Furthermore, an unstretched polypropylene film having a thickness of 30 μm was bonded as a heat-adhesive resin layer to the coating layer surface of the outermost layer of the produced barrier laminate, which was made of an organosilicon compound, by a dry laminating method.
A barrier laminate of was prepared.

Example 2 γ-as an organosilicon compound
A barrier laminate was prepared in the same manner as in Example 1 except that an aqueous solution of aminopropyltriethoxysilane with a solid content of 2 wt% was used.

Example 3 Silicon monoxide (purity 99.99%) was used as the vapor deposition material, and EB-Power was 30 as the vapor deposition conditions.
A barrier laminate was produced in the same manner as in Example 1 except that kV-0.75A was used.

Example 4 A barrier laminate was prepared in the same manner as in Example 1 except that the vapor deposition material was aluminum oxide (purity 99.99%) and the vapor deposition conditions were EB-Power of 30 kV-0.75A. It was made.

<Comparative Example 1> A barrier laminate was prepared in the same manner as in Example 1 except that a polyurethane coating agent having a solid content of 20% was used instead of the organic silicon compound aqueous solution.

<Comparative Example 2> A barrier laminate was prepared in the same manner as in Example 1 except that a solution of a nitrocellulose-based coating agent having a solid content of 20% was used instead of the aqueous solution of the organic silicon compound.

Comparative Example 3 The vapor deposition material was silicon monoxide (purity 99.99%), and the vapor deposition conditions were EB-Power 30.
A barrier laminate was produced in the same manner as in Comparative Example 1 except that kV-0.75A was used.

Comparative Example 4 Aluminum was directly vapor-deposited on one side of a plain biaxially stretched polyethylene terephthalate film having a film thickness of 12 μm by a take-up EB heating vacuum vapor deposition apparatus, and the heat-adhesive resin layer was formed in the same manner as in Example 1. As a result, an unstretched polypropylene film having a film thickness of 30 μm was laminated to prepare a barrier laminate.

Examples 1 to 4 and Comparative Examples 1 to 4
The barrier laminates of were compared and evaluated as follows. The oxygen transmission rate and moisture vapor transmission rate, which show barrier properties, and the peeling strength, which shows the adhesion between the vapor-deposited thin film layer and the adjacent layer, were measured, and the results are shown in Table 1. The measurement conditions are as follows: oxygen permeability: Mocon method (MOCON-OXTRAN-
10 / 50A) Setting 25 degrees-100% RH Moisture vapor transmission rate: MOCON-PERMATRAN
-W6) 40 degree-100% RH peeling strength: Instron type tensile tester sample 15 mm width, peeling angle 90 degrees, peeling speed 300 mm
/ Min.

[0048]

[Table 1]

Table 1 shows that the barrier properties against oxygen and water vapor were good in Example 1, Example 2, Example 3, Example 4 and Comparative Example 4, but Comparative Example 1 and Comparative Example Example 2 and Comparative Example 3 were defective. As for the peel strength indicating the adhesion between the vapor-deposited thin film layer and the adjacent layer, good results were obtained in Example 1, Example 2, Example 3, Example 4 and Comparative Example 1, Comparative Example 2 and Comparative Example 3. However, Comparative Example 4 was somewhat defective.

[0050]

As described above, according to the present invention, by providing a coating layer made of an organic silicon compound on a resin film, the resin film has a strong binding force with the resin.
The adhesiveness is high, and a strong bond is formed with the coating layer made of an organic silicon compound, and the adhesiveness between the coating layer made of an organic silicon compound and the vapor deposition thin film layer is improved. Further, since the coating layer made of an organosilicon compound is excellent in heat resistance, thermal dimensional stability and hardness, the vapor deposition thin film layer is protected by forming the vapor deposition thin film layer between the coating layers made of an organosilicon compound. be able to. Due to this, when manufacturing the laminated body,
During post-processing, stress is not applied to the laminate during use, cracks in the vapor-deposited thin film due to deterioration over time, pinholes, and other deterioration do not occur easily, and the original excellent barrier properties against gases such as oxygen and water vapor are retained. be able to.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a barrier laminate of the present invention.

FIG. 2 is a cross-sectional view showing another embodiment of the barrier laminate of the present invention.

[Explanation of symbols]

1, 9, 10, 11 Barrier Laminate 2 Resin Film Substrate 3 Organosilicon Compound Coating Layer 4 Vapor Deposition Thin Film Layer 5 Organosilicon Compound Coating Layer 7 Adhesive Layer 8 Thermal Adhesive Resin Layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location // C08J 7/00 307 7/04 P

Claims (3)

[Claims] 1. A polymer resin film having the following chemical formula (I) and R—Si— (OR ′) ₃ (I) (wherein R is an organic functional group and R ′ is a hydrolyzable group). A barrier layer characterized by being formed by sequentially laminating a coating layer made of an organosilicon compound represented by the following formula, a vapor-deposited thin film layer made of a metal or a metal compound, and a coating layer made of the organosilicon compound. Laminate. Wherein said organic silicon compound an organic functional group constituting (R) is _{-CH = CH 2 -, - CH} 2 -CH 2 -CH
_{2 -NH 2 -, - CH 2} -NH 2 -, - CH 2 -NHC
_{ONH 2, -CH 2 -NH-CH} 2 -CH 2 -NH
_{2 -, - CH 2 -O-} CH 2 - is (C ₂ H ₃ O), etc., hydrolyzable group (R ') is -Cl, -CH _3, -CH ₂
-CH _3, barrier laminate according to claim 1, wherein it is a -CH ₂ -CH ₂ -O-CH ₃ and the like. 3. The barrier laminate according to claim 1, wherein a heat-adhesive resin layer is laminated on the coating layer made of the organosilicon compound provided on the outermost layer via an adhesive layer.