JP2002052637A - Easily tearable gas barrier laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an easily tearable gas barrier laminated film with such advantages that a metal examination can be performed after heat sealing regarding the presence of an included foreign substance such as metallic powder and the film is suitable for a packaging bag which can be easily opened and also can be incinerated or reclaimed after use. SOLUTION: This easily tearable gas barrier laminated film is constituted of a laminate obtained by laminating a heat-sealable resin adhesive layer (III) on one of the sides of a polyolefin stretchable film base layer (I) with 150 gf or less tear strength, 80% or more non-transparency and 10 or more Clark rigidity (S value) and a gas barrier resin film layer (II) with an inorganic oxide thin film layer on the other side. The laminate has 200 gf or less tear strength and 90% or more surface glossiness.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to tea, coffee beans,
The present invention relates to an easily tearable gas barrier laminated film suitable for packaging powders such as bath salts, medicines, pesticides, fertilizers, candies (candy), and liquids such as mirin, liquor and fruit juice.

[0002]

2. Description of the Related Art Usually, tea, coffee beans, bath additives, medicines,
Pesticides, fertilizers, powders such as candy (candy), mirin,
Containers for packaging liquids such as sake and fruit juice are required to prevent the transmission of water vapor and oxygen and the transmission of visible light.
Therefore, in general, aluminum foil is printed on the back of wax-coated printing paper,
Ethylene acrylic acid copolymer, ethylene
Opaque gas barrier film consisting of a laminate provided with a heat-sealing resin layer such as vinyl acetate copolymer, and biaxially oriented polyethylene terephthalate film / polyethylene film adhesive layer / aluminum foil / biaxially oriented polypropylene film / polyethylene heat An opaque gas-barrier laminated film composed of a laminate of a sealing film has been used as a flexible packaging bag.

[0003]

In general, bags used for packaging the above-mentioned powders are filled with tea, coffee beans and pharmaceutical contents, and then foreign matter of metal powder is mixed in the bags. After inspecting the bag, heat seal the open mouth of the bag,
Shipping and storage. However, inspection with the bag open will provide an opportunity for dust and foreign matter to get into the bag.Therefore, after filling, heat-sealing the opening and checking whether metal powder has been mixed in. There is a demand from the market for providing a gas barrier film for forming a flexible packaging bag or the like that can be used. In addition, conventional packaging bags have the disadvantage that after incineration, the aluminum foil remains as burning waste and requires time and time for processing. Further, there is a need for a gas barrier film having excellent tearing properties, which does not spill when the packaging bag is opened and does not spill obliquely. The present invention provides a gas that can be easily inspected after filling and heat sealing of the open mouth, can be easily opened, and can be completely burned after use or suitable for recyclable packaging, etc. The purpose is to provide a barrier laminate film.

[0004]

According to a first aspect of the present invention, there is provided a stretched polyolefin-based film having a tear strength of 150 gf or less, an opacity of 80% or more, and a Clark stiffness (S value) of 10 or more. (I) A heat-sealing resin adhesive layer (III) is laminated on one side, and a gas barrier resin film layer (II) having an inorganic oxide thin film layer on the other side is laminated. An easily tearable gas barrier laminate film characterized in that the laminate has a tear strength of 200 gf or less and a surface gloss of 90% or more.

According to a second aspect of the present invention, the tear strength is 1
A gas barrier resin film layer (II) comprising an inorganic oxide thin film layer provided on a polyolefin-based stretched film base layer (I) having an opacity of 50 gf or less, an opacity of 80% or more, and a Clark stiffness (S value) of 10 or more. ), And a heat-sealing resin adhesive layer (III) is further laminated thereon, wherein the laminate has a tear strength of 200 gf or less and a surface glossiness of 90% or more, It is a gas barrier laminated film that can be easily torn.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The easily tearable gas barrier laminated film of the present invention will be described in detail below. [I] Structure of Gas Barrier Laminate Film The layer structure of the gas barrier laminate film that can be easily torn according to the present invention has a heat-sealable resin adhesive layer (III) /
With tear strength of 150 gf or less, opacity of 80% or more,
And a laminate comprising a polyolefin-based stretched film base layer (I) having a Clark stiffness (S value) of 10 or more / a gas barrier resin film layer (II) provided with an inorganic oxide thin film layer, or a tear strength of 150 gf or less. , Opacity 8
0% or more and Clark stiffness (S value) of 10 or more polyolefin-based stretched film base layer (I) / gas barrier resin film layer provided with inorganic oxide thin film layer (II) / heat sealing resin adhesive layer ( III). These laminates have a tear strength of 200 gf.
Hereinafter, the surface glossiness indicates physical properties of 90% or more. The printing P, if necessary, may be performed on the inorganic oxide surface side, on the surface of the polyolefin-based stretched film base layer (I), or on the gas gas barrier resin film surface side.

[II] Layer Structure of Gas Barrier Laminated Film (1) Polyolefin Stretched Film Base Layer (I) (a) Properties Polyolefin stretched film constituting the easily tearable gas barrier laminate film of the present invention The base layer (I) has a tear strength in either the MD direction or the TD direction (based on JIS P-8116) of 150 gf or less, preferably 120 gf or less, and opacity (JIS P
-8138) is 80% or more, preferably 85 to 100%
And either one of the MD direction (longitudinal stretching direction) and the TD direction (direction perpendicular to the longitudinal stretching direction) has a Clark stiffness (JIS P-8143) (S value) of 10 or more, preferably 10 to 300. Things are used. If the tear strength exceeds the above range, the tearing property at the time of opening is deteriorated. If the opacity is less than the above range, it is difficult to identify the print, and it is necessary to lower the light transmittance in order to prevent discoloration of the stored contents. Clark stiffness (S
If the value is less than the above range, it is too soft, and when used in a packaging bag, the stiffness is insufficient and it is difficult to use. Tear Strength The tear strength can be measured by measuring the tear strength of the polyolefin-based stretched film base layer (I) in either the MD direction or the TD direction according to JIS P-8116. Can be Clark stiffness The Clark stiffness was measured by measuring the Clark stiffness (JIS P-8143) in the MD direction or TD direction of the polyolefin-based stretched film base layer (I) using a measuring instrument (Kumaya Riki Kogyo Co., Ltd.) Made: Product name "OUTOMATI"
C CLARKSTIFFNESSTESTER ”) and the measurement method of JIS P-8143. Opacity The opacity can be measured by the method described in JIS P-8138.

(B) Types Examples of the material used for the polyolefin-based stretched film base layer (I) include the following. 3 to 65% by weight of inorganic fine powder or organic filler
And a film stretched by uniaxial or biaxial stretching. Void The polyolefin-based stretched film base layer (I) has fine voids inside the film, and the porosity calculated by the following formula (1) is 10 to 60%, preferably 15 to 45%. The opacity can be set to the opacity in the above range.

[0009]

(Equation 1)

In the above formula (1), ρ ₀ represents the true density of the stretched film, and ρ ₁ is the density (JIS) of the stretched film.
P-8118), but the true density is almost equal to the density before stretching, unless the material before stretching contains a large amount of air. This polyolefin-based stretched film base layer (I)
May be a single layer or a multilayer. In the case of a multilayer film, it may be produced by a co-extrusion molding method. For example, a film containing at least uniaxially stretched inorganic fine powder and / or an organic filler in an amount of 0 to 40% by weight is used as a core layer (A). A laminate as shown in FIG. 1 in which at least uniaxially stretched films containing 0 to 65% by weight of an inorganic fine powder and / or an organic filler are provided on both surfaces of the core layer as front and back layers (B, C). It may be a stretched film.

(C) Material Polyolefin Resin The polyolefin resin used for the polyolefin-based stretched film base layer (I) may be an ethylene-based resin such as high-density polyethylene, medium-density polyethylene, or low-density polyethylene, or a propylene-based resin. Polyolefin resin. These may be used in combination of two or more. Further, among these polyolefin resins, a propylene-based resin is preferable in terms of chemical resistance, cost, and the like. Examples of such a propylene-based resin include propylene homopolymers such as polypropylene exhibiting isotactic or syndiotactic and various degrees of stereoregularity, or ethylene and butene-1 having propylene as a main component and copolymerizable therewith. , Hexene-1, heptene-1, 4-methylpentene-1 and the like
-Copolymers with olefins. These copolymers may be binary, ternary, or quaternary, and may be random copolymers or block copolymers. When a propylene-based resin is used for the core layer, a thermoplastic resin having a melting point lower than that of a propylene-based resin such as polyethylene, polystyrene, or ethylene-vinyl acetate copolymer is used in order to improve stretchability. It is good to mix by weight%.

Inorganic fine powder Examples of the inorganic fine powder used for the above-mentioned polyolefin-based stretched film base layer (I) include calcium carbonate, calcined clay, silica, diatomaceous earth, talc, titanium oxide, barium sulfate and the like. These inorganic fine powders generally have a particle size of 0.03 to 7 μm.

Organic Filler As the organic filler used in the above-mentioned polyolefin-based stretched film base layer (I), polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polycarbonate,
Those having a melting point (eg, 120 to 300 ° C.) or a glass transition temperature (eg, 120 ° C. to 280 ° C.) or higher than the melting point of polyolefin resins such as nylon-6, nylon-6,6, and cyclic olefin polymer. used. These inorganic fine powders or organic fillers can be used alone or in combination.

(D) Stretching The stretching conditions for uniaxial or biaxial stretching are as follows:
Generally, the stretching ratio is preferably 4 to 10 times in both the longitudinal and transverse directions.
When using high-density polyethylene (melting point: 123-134 ° C), it is 110-120 ° C. The stretching speed is 10 to 3
50 m / min.

(E) Thickness The thickness of the polyolefin-based stretched film base layer (I) is generally 30 to 300 μm, preferably 40 to 200 μm.
μm, particularly preferably 50 to 150 μm.

(2) Heat-Sealable Resin Adhesive Layer (III) As the heat-sealable resin adhesive layer (III) constituting the easily tearable gas barrier laminate film of the present invention, an ethylene / acrylic acid copolymer Heat-sealing resins such as ethylene / vinyl acetate copolymer, low density polyethylene, metal salt of ethylene / (meth) acrylic acid copolymer (so-called Surlyn), chlorinated polyethylene and chlorinated polypropylene are used. The heat sealing resin generally has a melting point of 60 to 135 ° C., preferably 70 to 135 ° C.
One at 30 ° C. is used. This heat-sealable resin adhesive layer (III) can contribute to melting and bonding by heating when the easily tearable gas barrier film of the present invention is processed into a bag or the like.

Thickness The thickness of the heat-sealable resin adhesive layer (III) is generally 1
５０50 μm, preferably 2-40 μm.

The product layer These heat sealable resin adhesive layer (III) is also may be prepared by simultaneously melt-laminated in the production of the polyolefin oriented film base layer (I), the polyolefin oriented film base layer (I), or A heat-sealing resin may be extrusion-laminated on the gas barrier resin film layer (II), or a polyolefin-based stretched film base layer (I) or a gas barrier resin film layer (II)
Alternatively, a resin solution obtained by dissolving or dispersing the heat-sealable resin in an organic solvent such as toluene, xylene, or tetralin may be applied and dried. Further, gloss may be further contributed to the surface of the gas barrier laminated film which can be easily torn, or a heat sealing resin adhesive layer (III) may be formed on the surface of the inorganic oxide thin film layer (V).

(3) Gas barrier resin film layer (I
I) (a) Material gas barrier resin layer Gas barrier resin film layer (II) constituting the easily tearable gas barrier laminate film of the present invention
Is formed to greatly reduce the permeability of water vapor, oxygen and the like, and uses a gas barrier resin. Examples of the gas barrier resin include saturated polyesters such as polyethylene terephthalate and polyethylene-2,6-naphthalate, nylon 6, nylon 12, and nylon 6,6.
Polyamide etc., aromatic polycarbonates, polyvinylidene chloride, ethylene - moisture permeability and vinyl alcohol copolymer (JIS Z-0208) is 100g ^/ m 2 · 24
hr or less, preferably 50 g / m ² · 24 hr or less, and an oxygen permeability (JIS Z-1707) of 300 cc / m ²
・ 24 hr · atm or less, preferably 200 cc / m ²
・ Use the one with 24hr · atm or less.

Thickness The thickness of the gas barrier resin film layer (II) is from 6 to 40.
μm, preferably 8 to 20 μm.

(4) Inorganic Oxide Thin Film Layer (V) In order to improve the gas barrier property of the easily tearable gas barrier laminated film, an inorganic oxide thin film layer is formed on the surface of the gas barrier resin film layer (II). (V) is provided. This inorganic oxide thin film layer (V) is preferably provided on the surface of the gas barrier resin film layer (II) by a vapor deposition method.

As the material inorganic oxide thin film layer (V), amorphous Al
₂ O ₃ , SiOx, SnOx, ZnOx, IrOx (x
Is a number of 1 to 2) and the like. The inorganic oxide thin film layer (V) has a total light transmittance of 75% or more, preferably 80%.
The above transparent materials are preferred. The above total light transmittance is JI
It can be measured by SK-7105.

The thickness of the thick inorganic oxide thin film layer (V) is generally 5 to 600 n
m, preferably 20 to 500 nm.
When the thickness of the inorganic oxide thin film layer (V) is smaller than the above range,
Insufficient gas barrier properties. If the thickness of the inorganic oxide thin film layer (V) is larger than the above range, transparency is poor,
Cracks and peeling easily occur in the inorganic oxide thin film layer (V) itself. The thickness of the inorganic oxide thin film layer (V) is restricted by transparency, vapor deposition rate, gas barrier property, film winding property and the like.

Evaporation method As the above-mentioned evaporation method, a molded product is placed under vacuum (1 × 10 ⁻⁶ to 1 × 10 ⁻³ Torr) in a high frequency induction heating type evaporation machine.
Method of depositing an inorganic oxide by using a method (JP-B-53-12953)
Or an organic silicon compound which has been evacuated in advance and volatilized in a vapor deposition machine under vacuum,
A method in which plasma is generated from a gas flow containing oxygen and an inert gas by magnetron glow discharge to deposit SiOx on a molded article in the vapor deposition machine (JP-A-64-8777).
2, US Pat. No. 4,557,946, and US Pat. No. 4,599,678). Also, Industrial Materials, published in November 1990, Vol. 38, No. 1
No. 4, pp. 104-105, the principle of which is introduced, ion plating, high-frequency plasma CVD.
Method, an electron beam (EB) vapor deposition method, a method classified as a sputtering method, or the like can be employed. Among these inorganic oxides, silicon oxide and amorphous aluminum oxide are preferable in terms of transparency and workability, but silicon oxide is more preferable in terms of gas barrier properties. The determination of the crystallinity or the amorphousness of the aluminum oxide can be easily measured by an ordinary X-ray diffractometer using Cu Kα radiation. For example, when crystalline α-Al ₂ O ₃ is contained, a clear diffraction peak appears at a position where the diffraction angle 2θ is 43.39 degrees or 57.56 degrees. In the case of β-Al ₂ O ₃ , a position diffraction peak having a diffraction angle 2θ of 66.65 degrees or 33.43 degrees appears. The crystal particle size can also be measured from the half width of these diffraction peaks. In addition, γ-Al
Similar diffraction peaks can be similarly measured for other crystalline aluminum such as ₂ O ₃ and δ-Al ₂ O ₃ . In the case of amorphous aluminum oxide, a specific diffraction peak is not measured by an X-ray diffractometer. The non-crystalline aluminum oxide referred to here is one in which specific diffraction is not observed by X-ray diffraction.

(5) Primer (adhesive) (IV) Depending on the type of gas barrier resin film layer (II),
When the adhesion between the film layer (II) and the inorganic oxide thin film layer (V) is insufficient, a primer (between the gas barrier resin film layer (II) and the inorganic oxide thin film layer (V)) Adhesive) (IV) can be applied. Examples of such primers include, for example, polyester polyols / polyisocyanates and polyether polyols / polyisocyanates of polyurethane primers. The coating amount of the primer (adhesive) (IV) is generally 0.5 to 25 g / m ² (solid content). In addition, a gas barrier resin film layer (I) having a polyolefin-based stretched film base layer (I) and an inorganic oxide thin film layer (V)
The inorganic oxide thin film layer (V) may be covered with a heat-sealable resin adhesive layer (III) in order to increase the bonding workability with I).

In order to impart gloss to the surface on which the transparent plastic film is formed and to protect the printed surface, the surface of the polyolefin-based stretched film base layer (I) or
In order to form a transparent plastic film on the inorganic oxide thin film layer (V), various transparent plastic films are laminated or a transparent plastic coating film is formed. For the formation of transparent plastic films, vinyl chloride resins such as polyethylene and ethylene copolymers, polypropylene and propylene copolymers, ethylene / vinyl acetate copolymers, ionomers, polyvinyl chloride and their copolymers Transparent resins such as vinylidene chloride-based resins such as vinylidene chloride-vinyl chloride copolymer and polyester resins such as polyethylene terephthalate can be used.

The laminated product layer polyolefin stretched film base layer (I) and the gas barrier resin film layer (II) (adhesion), in producing a polyolefin stretched film base layer (I), a gas barrier resin film May be coextruded with a filler-containing resin film and stretched to produce a laminate of a polyolefin-based stretched film base layer (I) and a gas barrier resin film (II) at the same time, or the primer (adhesive And (4) the two may be adhered. As such a primer (adhesive) (IV), for example, a polyurethane-based primer is manufactured by Toyo Morton Co., Ltd.
150 (trade name) or BLS-2080A and BLS-
As a mixture of 2080B, a polyester primer is available as AD-503 (trade name) of the company. Such a primer is applied so that the basis weight is 0.5 to 25 g / m ² .

(6) Other Layers The easily tearable gas-barrier laminated film of the present invention is a polyolefin-based stretched film base layer (I), a heat-sealable resin film layer (III), a gas-barrier resin film. In addition to the layer (II), the inorganic oxide thin film layer (V) and the primer layer (adhesive) (IV), the rigidity, tear resistance and light opacity of the easily tearable gas barrier laminated film are improved. Woven, non-woven,
The light concealing layer, pulp paper, foamed resin layer, etc. may be formed between the heat-sealing resin adhesive layer (III) and the polyolefin-based stretched film base layer (I), or the gas barrier resinous film layer (II) and the polyolefin-based stretched layer. It may be provided between the film base layer (I).

[II] Physical Properties of Gas Barrier Laminate Film The gas barrier laminate film which can be easily torn according to the present invention must satisfy the following physical properties. Tear Strength The easily tearable gas barrier laminate film of the present invention has a tear strength in one of the MD and TD directions (based on JIS P-8116) of 200 gf or less, preferably 150 gf or less. When the tear strength of either the MD direction or the TD direction of the laminate used satisfies the above range, the laminate can be easily opened when used in a packaging bag. If the tear strength is greater than 200 gf, tearing may be difficult.

Surface glossiness The easily tearable gas barrier laminate film of the present invention has a surface glossiness (according to JIS P-8142) of 9
0% or more, preferably 95% or more. If the surface gloss is less than 90%, problems such as poor appearance after printing occur. The easily tearable gas barrier laminated film of the present invention preferably satisfies the following physical properties.

[0031] The moisture permeability of moisture permeability (JIS Z-0208) is ^5g / m 2 · 24h
r or less, preferably 2 g / m ² · 24 hr or less, more preferably 1 g / m ² · 24 hr or less.

[0032]Oxygen permeability Oxygen permeability (JIS Z-1707) is 5cc / m²・
24 hr · atm or less, preferably 2 cc / m²・ 24
hr · atm or less, more preferably 1 cc / m ²・ 24
hr · atm or less. In addition, coffee beans, high-grade roast
Dislike light rays such as tea, true tea, fruit juice, and shochu
Use an easily tearable gas for packaging the contents.
Total light transmittance of barrier film (JIS K-71
05) must be 0%. Thin thickness of each layer
When the opacity of light rays is insufficient, use polyolefin-based
The back surface of the stretched film base layer (I)
Perform black solid printing with a thickness of 1 to 5 μm by gravure printing
To form a concealing layer,
Stretched film base layer (I) and gas barrier resin film layer
In the primer layer for bonding (II), titanium oxide foil
Large amounts of white filler such as scars and titanium oxide fine particles (5
~ 75% by weight), and the primer adhesive is
10g / m²Form a concealing layer by applying
All light of easily tearable gas barrier laminated film
The line transmittance is set to 0%.

[III] Thickness of Gas Barrier Laminate Film The thickness of the easily tearable gas barrier laminate film of the present invention is generally from 40 to 350 for use in packaging bags.
μm, preferably 50 to 250 μm, particularly preferably 6 μm.
Flexibility is provided by setting the thickness to 0 to 200 μm.

[0034]

EXAMPLES The method of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[I] Production of Polyolefin Stretched Film Base Layer (I) (Production Example 1) (1) Melt flow rate (MFR: 230 ° C., 2.
A composition (A) in which 3% by weight of high-density polyethylene and 16% by weight of calcium carbonate having an average particle size of 1.5 μm are mixed with 81% by weight of polypropylene (melting point: about 164 to 167 ° C.) of 0.8 g / 10 min. Was kneaded with an extruder set at a temperature of 270 ° C., extruded into a sheet, and further cooled by a cooling device to obtain a non-stretched sheet. After the sheet was heated again to a temperature of 150 ° C., it was stretched 5 times in the machine direction to obtain a 5 times machine-stretched film. 54% by weight of polypropylene (melting point: about 164 to 167 ° C.) having a melt flow rate (MFR) of 4 g / 10 minutes and 46% by weight of calcium carbonate having an average particle size of 1.5 μm
Is kneaded at 210 ° C. in another extruder, and extruded into a sheet by a die.
This was laminated on both sides of the five-fold longitudinally stretched film obtained in the above step to obtain a laminated film having a three-layer structure. Next, after cooling the laminated film having the three-layer structure to a temperature of 60 ° C., it is heated again to a temperature of about 155 ° C., stretched 7.5 times in the transverse direction using a tenter, and stretched at a temperature of 165 ° C. Annealing treatment, cooling to a temperature of 60 ° C., slitting of the ears, and a three-layer structure (uniaxial stretching / biaxial stretching / uniaxial stretching) having a thickness of 60 μm (B / A / B = 10 μm / 40 μm / 10
μm) with a opacity of 87% and a porosity of 31
%, Density 0.79 g / cm ³ , surface glossiness 16%, Clark stiffness (S value) MD direction 13, TD direction 24, tear strength 20 gf (MD direction), 11 gf (TD direction) polyolefin stretched film base layer ( I) was obtained.

(Production Example 2) Melt flow rate (MF
R: 230 ° C., 2.16 kg load) 65% by weight of polypropylene (melting point: about 164 to 167 ° C.) 0.8 g / 10 min, 10% by weight of high-density polyethylene, and average particle size of 1.
A composition (A) mixed with 25% by weight of 5 μm calcium carbonate and a melt flow rate (MFR: 230 ° C.,
2. A composition (B) containing 99% by weight of polypropylene (melting point: about 164 to 167 ° C.) having a weight of 4 g / 10 min. And 1% by weight of rutile-type titanium dioxide having an average particle diameter of 0.2 μm; Rate (MFR: 230
And 100% by weight (C) of polypropylene (melting point: about 164 to 167 ° C.) having a weight of 4 g / 10 minutes (250 ° C., 2.16 kg load) were melt-kneaded at 250 ° C. using three separate extruders. Then, after supplying to one co-pressing die and laminating | stacking in a die (B / A / C), it extruded in sheet shape and cooled to about 60 degreeC with the cooling roll, and obtained the laminated film. After the laminated film is reheated to 145 ° C., it is stretched 5 times in the machine direction by utilizing the peripheral speed difference of a number of roll groups, reheated to about 150 ° C. again, and 8.5 times in the transverse direction with a tenter. Stretched. Then, after annealing at 160 ° C., it was cooled to 60 ° C.
Thickness 100 of layer structure (biaxial stretching / biaxial stretching / biaxial stretching)
μm (B / A / C = 3 μm / 94 μm / 3 μm), 90% opacity, 40% porosity, 0.66 g / cm ³ density, 96% surface gloss, Clark stiffness (S value) MD direction 25, TD direction 38, tear strength 25g
f (MD direction) and 18 gf (TD direction) of a polyolefin-based stretched film base layer (I) were obtained.

(Production Example 3) Melt flow rate (MF
R: 230 ° C., 2.16 kg load) 0.8 g / 10 min of polypropylene (melting point: about 164 to 167 ° C.) 60% by weight, low-density polyethylene 20% by weight (melting point: 111 ° C.)
And a composition (A) obtained by mixing 20% by weight of calcium carbonate having an average particle size of 1.5 μm, and a melt flow rate (MFR:
50% by weight of polypropylene (melting point: about 164 to 167 ° C.) having a weight of 230 g and a load of 2.16 kg) of 50% by weight, 45% by weight of calcium carbonate having an average particle size of 1.5 μm, and rutile dioxide having an average particle size of 0.2 μm. The composition (B) mixed with 5% by weight of titanium was melt-kneaded at 250 ° C. using three separate extruders. After that, it was supplied to one co-pressing die, laminated in the die, extruded into a sheet, and cooled to about 60 ° C. with a cooling roll to obtain a laminated film. After reheating this laminated film to 135 ° C., it is stretched 5 times in the longitudinal direction by utilizing the peripheral speed difference of a number of roll groups,
After an annealing treatment at 150 ° C., the temperature was cooled to 60 ° C., and the ears were slit to form a three-layer structure (uniaxial stretching / uniaxial stretching / uniaxial stretching) with a thickness of 80 μm (B / A / B = 5 μm / 7).
0 μm / 5 μm) with a opacity of 86%,
Porosity 28%, density 0.80 g / cm ³ , surface gloss 4
0%, Clark stiffness (S value) MD direction 33, TD direction 1
8. Tear strength 25 gf (MD direction), 250 gf
(TD direction) polyolefin-based stretched film base layer (I) was obtained.

(Production Example 4) Melt flow rate (MF)
R: 230 ° C., 2.16 kg load) 95% by weight of polypropylene (melting point: about 164 to 167 ° C.) of 4 g / 10 min.
Then, a composition obtained by mixing 5% by weight of calcium carbonate having an average particle size of 1.5 μm was melt-kneaded at 250 ° C. using an extruder. Thereafter, the sheet was extruded from an extrusion die into a sheet, and cooled to about 60 ° C. with a cooling roll to obtain a 100 μm-thick unstretched polypropylene film. This film has an opacity of 20%, a porosity of 0%, and a density of 0.9.
9 g / cm ³ , surface glossiness 40%, Clark stiffness (S
Value) vertical direction 12, horizontal direction 10, tear strength 160 gf
(MD direction), 180 gf (TD direction) of a polypropylene film was obtained.

(Production Example 5) An isocyanate compound (Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd.) and saturated polyester were applied to one side of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm (drawing ratio of 3 times in the longitudinal direction and 3 times in the transverse direction). (Byron 300 manufactured by Toyobo Co., Ltd.) was applied in a ratio of 50:50, followed by drying to form a resin layer having a thickness of about 0.1 μm. Next, on the resin layer, SiO ₂ having a purity of 99.9% was heated and evaporated under a vacuum of 8 × 10 ⁻⁵ Torr by a high-frequency induction heating method to form a SiO ₂ evaporated film having a thickness of 100 nm. Water vapor permeability of this product 1.0g ^/ m 2 · 24hr, oxygen permeability ^{0.8cc / m 2 · 24hr · atm} , the total light transmittance was 84%.

(Production Example 6) An isocyanate compound (Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd.) and a saturated polyester were coated on one side of a biaxially stretched polyethylene terephthalate film (three times in the machine direction and three times in the transverse direction) having a thickness of 12 μm. (Byron 300 manufactured by Toyobo Co., Ltd.) was applied in a ratio of 50:50, followed by drying to form a resin layer having a thickness of about 0.1 μm. Next, on the resin layer, Al ₂ O ₃ having a purity of 99.9% is heated and evaporated under a vacuum of 8 × 10 ⁻⁵ Torr by a high-frequency induction heating method to form an amorphous aluminum oxide film having a thickness of 100 nm. Was formed.
The biaxially stretched Al ₂ O ₃ deposited polyethylene terephthalate film had a water vapor transmission rate of 3 g / m ² · 24 hr, an oxygen transmission rate of 3 cc / m ² · 24 hr · atm, and a total light transmittance of 86%.

[II] Production of Gas Barrier Laminate Film Example 1 A 60 μm thick polyolefin stretched film base layer (I) obtained in Production Example 1 was coated on one side with a polyurethane primer (BLS, manufactured by Toyo Morton Co., Ltd.). -2080A and BLS
-2080B) was applied in an amount of 0.5 g / m ² (solid content). Next, gravure printing was performed on the SiO ₂ deposition side of the gas barrier resin film layer (II) obtained in Production Example 5, and the printed surface was bonded to the base layer (I) coated with the primer. On the other side (back side) of the base layer (I) coated with the primer, a polyurethane-based primer BL
An adhesive obtained by mixing 15 parts by weight of titanium oxide with 85 parts by weight of a mixture of S-2080A and BLS-2080B was 5 g /
m ² (solid content) is applied, and a low-density polyethylene film having a thickness of 40 μm is adhered and a thickness of approximately 115 μm (gas barrier resin film layer / SiO ₂ deposition / printing / polyolefin-based stretched film / low-density polyethylene film configuration), a water vapor permeability of 0.7g ^/ m 2 · 24hr, oxygen permeability ^{0.6cc / m 2 · 24hr · atm} , opacity 1
A laminate having 00%, total light transmittance of 0%, surface gloss of 98%, Clark stiffness (S value) of MD direction 15, TD direction 28, tear strength of 95 gf (MD direction), and 65 gf (TD direction) was obtained. Evaluation of the obtained laminated body, the following "freshness measurement"
And "openability". Table 1 shows the results. Freshness measurement This laminate was superimposed on two low-density polyethylene films so that the sides face each other, and the three sides were 190 mm wide and 10 mm wide.
180m vertical with heat impulse seal at 30 ° C for 30 seconds
After forming a bag having a width of 120 mm and a width of 120 mm, the bag was filled with 50 g of high-grade green tea, and the opening was heat-sealed. Next, it was confirmed by a metal detector from outside the bag that metal powder was not mixed. A bag filled with this high-grade green tea is placed at a relative humidity of 7
After being left in a constant temperature room at 5% and a temperature of 25 ° C. for 3 months, the bag was opened and the presence or absence of discoloration of the green tea and the flavor were examined. ：: The discoloration and flavor of the sencha were not inferior to those of the fresh tea before packaging. Δ: Discoloration was observed as compared to fresh tea before packaging. ×: Discoloration and change in flavor were observed as compared to fresh tea before packaging. Openability A notch was provided at the top of the side surface of the heat-sealed laminate to evaluate the ease of opening. ：: The film can be easily torn in a straight line from the notch, and the contents do not spill. Δ: Although tearing can be performed relatively easily from the notch portion, tearing may occur obliquely and contents may be spilled. X: Even if tearing was difficult or tearing could occur from the notch, the contents were spilled due to diagonal tearing.

Example 2 Instead of the polyolefin-based stretched film base layer (I) having a thickness of 60 μm of Production Example 1 used in Example 1, the thickness of 100 μm (B / A / C = 3 μm / B) obtained in Production Example 2 was used. 94 μm /
155 μm, opacity 100%, total light transmittance 0%, water vapor permeability 0,0 in the same manner as in Example 1 except that a polyolefin stretched film base layer (I) of 3 μm) was used.
7g ^/ m 2 · 24hr, oxygen permeability 0.6 cc / ^{m 2} ·
A laminate of 24 hr · atm was obtained. The obtained laminate was evaluated in the same manner as in Example 1, and the resulting freshness measurement was performed.
Table 1 shows the openability.

Example 3 Instead of the polyolefin-based stretched film base layer (I) having a thickness of 60 μm of Production Example 1 used in Example 1, the thickness of 80 μm obtained in Production Example 3 (B / A / B = 5 μm / 70 μm / 5
μm) except that the Al ₂ O ₃ vapor-deposited film obtained in Production Example 6 is used in place of the gas barrier resin layer (II) used in Example 1 using the polyolefin-based stretched film base layer (I). thickness 135 .mu.m, 100% opacity, total light transmittance of 0%, a water vapor permeability of ^2g / m ² · 24hr,
A laminate having an oxygen permeability of ² cc / m2 · 24 hr · atm was obtained. The obtained laminate was evaluated in the same manner as in Example 1, and the resulting freshness measurement and openability are shown in Table 1. In addition,
At the time of making the bag, the bag was manufactured such that the direction (MD) where the tear strength of the used base layer (I) was small was parallel to the opening direction at the time of opening.

Example 4 After the offset printing was performed on the surface of the polyolefin-based stretched film base layer (I) having a thickness of 100 μm obtained in Production Example 2, the polyurethane primer “BLS-” manufactured by Toyo Morton Co., Ltd. 2080A "and" BLS-208
An adhesive obtained by mixing 15 parts by weight of titanium oxide with 85 parts by weight of the mixture of “0B” was applied at 4 g / m ² (solid content), and the film side of the gas barrier resin film layer (II) obtained in Production Example 5 was coated on the film side. The polyurethane primer was applied to the SiO ₂ deposition side at 0.5 g / m ² (solid content). Then, a low-density polyethylene film having a thickness of 40 μm is bonded as a heat-sealable resin adhesive layer, and the thickness is approximately 116 μm.
m (Printing / configuration of the polyolefin oriented film / gas barrier resin film layer / SiO ₂ deposition / low-density polyethylene film), water vapor permeability of 0.7 g ^{/ m} 2 · 2
4hr, oxygen permeability 0.6cc ^/ m 2 · 24hr · at
m, opacity 100%, total light transmittance 0%, surface gloss 94%, Clark stiffness (S value) MD direction 25, TD direction 38, tear strength 100gf (MD direction), 72gf (T
(D direction) was obtained. The obtained laminate was evaluated in the same manner as in Example 1, and the resulting freshness measurement and openability are shown in Table 1.

Comparative Example 1 In place of the 60 μm-thick polyolefin stretched film base layer (I) used in Example 1, the thickness 1 obtained in Production Example 4 was used.
A film thickness of about 155 μm and an opacity of 1 were obtained in the same manner as in Example 1 except that a non-stretched polypropylene film of 00 μm was used.
00%, total light transmittance 0%, water vapor permeability 0.8 g / m
² · 24 hr or, oxygen permeability 0.7cc ^/ m 2 · 24hr
-A laminate of atm was obtained. The obtained laminate was evaluated in the same manner as in Example 1, and the resulting freshness measurement and openability are shown in Table 1.

[0046]

[Table 1]

[0047]

According to the gas barrier laminate film of the present invention which can be easily torn, the content is filled into a bag, and after heat sealing the opening, whether foreign matter such as metal powder is mixed or not is determined. An object of the present invention is to provide a gas barrier laminated film which can be easily inspected and which can be easily opened, and which is suitable for packaging bags which can be incinerated or recycled after use, and which can be easily torn. It is to be.

[Brief description of the drawings]

FIG. 1 is an enlarged cross-sectional view of an easily tearable gas barrier laminate film of an embodiment of the present invention.

FIG. 2 is an enlarged cross-sectional view of an easily tearable gas barrier laminate film of another embodiment of the present invention.

FIG. 3 is a perspective view of a green tea bag prepared by processing the easily tearable gas barrier laminated film of FIG. 1;

[Explanation of symbols]

 I: Polyolefin-based stretched film base layer (I) II: Gas barrier resin film layer (II) III: Heat seal resin adhesive layer (III) IV: Primer (adhesive) (IV) V: Inorganic oxide thin film layer A : Core layer B: Surface layer C: Back layer P: Printing 1: Sencha bag 2: Heat seal part 3: Notch part

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C23C 16/40 C23C 16/40 F term (Reference) 4F006 AA12 AA16 AA19 AA35 AA36 AA38 AB37 AB74 AB76 BA01 BA05 CA07 DA01 DA04 4F071 AA15X AA16 AA17 AA18 AA20 AA20X AA21 AA21X AA44 AA50 AA54 AA76 AA84 AA86 AB18 AB20 AB21 AB24 AB26 AF08 AF13Y AF16Y AF20Y AF30Y AF32Y AH04 BB06 BB07 BB08 BC01 BC12 BC13 4F100 AA01A AA01B AA01C AA17C AA19C AA20C AH00A AH00B AH00C AK01B AK01D AK03A AK06 AK07A AK51G BA03 BA04 BA07 BA10A BA10B BA10C BA10D BA13 BA44 CA23A CA23B CA23C CB03B DE01A DE01B DE01C DJ00A EH46 EJ37A EJ37B EJ37C EJ65G GB15 GB17 GB23 GB66 HB31A HB31C HB31D JA12C JD02 JD02D JK01A JK03 JK03A JL12B JL14 JL16 JN02A JN21 YY00 YY00A YY00B YY00C 4K030 BA43 BA44 BB12 CA07 CA12 FA04 LA11

Claims (12)

[Claims] 1. A tear strength of 150 gf or less and an opacity of 8
A heat-sealing resin adhesive layer (III) is laminated on one surface of a polyolefin-based stretched film base layer (I) having 0% or more and a Clark stiffness (S value) of 10 or more, and an inorganic oxide film is formed on the other surface. A laminate comprising a gas barrier resin film layer (II) provided with an object thin film layer, wherein the laminate has a tear strength of 200 gf or less and a surface glossiness of 90% or more. A tearable gas barrier laminated film. 2. A tear strength of 150 gf or less and an opacity of 8
A gas barrier resin film layer (II) provided with an inorganic oxide thin film layer on a polyolefin-based stretched film base layer (I) having 0% or more and a Clark stiffness (S value) of 10 or more; An easily tearable gas comprising a laminate having a heat-sealable resin adhesive layer (III) laminated thereon, wherein the laminate has a tear strength of 200 gf or less and a surface glossiness of 90% or more. Barrier laminated film. 3. A polyolefin-based stretched film base layer (I).
The easily tearable gas barrier laminated film according to claim 1 or 2, wherein the gas barrier resin film layer (II) is formed between the inorganic oxide thin film layer and the inorganic oxide thin film layer. 4. Polyolefin-based stretched film base layer (I)
The easily tearable gas barrier laminated film according to claim 1 or 2, wherein an inorganic oxide thin film layer is formed between the gas barrier resin film layer (II) and the gas barrier resin film layer (II). 5. A polyolefin-based stretched film base layer (I).
The easily tearable gas-barrier laminated film according to any one of claims 1 to 4, wherein one of the surfaces is printed (P). 6. A polyolefin-based stretched film base layer (I).
6. The easily tearable gas barrier according to claim 5, wherein the surface on which the printing (P) is applied is a surface opposite to the surface on which the gas barrier resin film layer (II) is formed. Laminated film. 7. A gas barrier resin film layer (II) comprising:
The print (P) has been applied to one side of the print medium.
The easily tearable gas-barrier laminated film according to any one of the above-mentioned items. 8. The easily tearable gas-barrier laminated film according to claim 1, wherein the inorganic oxide thin film layer has one surface printed (P). 9. The inorganic oxide thin film layer is a silicon oxide thin film layer or an amorphous aluminum oxide thin film layer.
A gas-barrier laminated film which can be easily torn as described in any one of the above. 10. The polyolefin-based stretched film base layer (I) comprises an inorganic fine powder and / or an organic filler in an amount of from 0 to 4%.
A stretched film stretched in at least uniaxial direction containing 0% by weight is used as a core layer (A), and on both sides of this core layer is stretched in at least uniaxial direction containing 0 to 65% by weight of an inorganic fine powder and / or an organic filler. The easily tearable gas barrier laminated film according to any one of claims 1 to 9, wherein the stretched film is a laminated stretched film provided as front and back layers (B, C). 11. The easily tearable gas barrier laminated film according to claim 10, wherein the polyolefin-based stretched film base layer (I) has a porosity of 10 to 60%. 12. The easily tearable gas barrier laminated film according to claim 1, wherein the polyolefin-based stretched film base layer (I) is a polypropylene-based stretched film.