JP7248052B2 - Easy-open gas barrier laminate using solvent-free adhesive, easy-open gas barrier packaging material and easy-open pillow packaging bag comprising the laminate - Google Patents

Description

The present invention has at least a substrate layer (A), a solventless gas barrier organic adhesive layer (B), a gas barrier inorganic deposition layer (C), and an easy-open sealant layer (D), and comprises a gas barrier inorganic adhesive layer (B). The vapor deposition layer (C) and the solvent-free gas barrier organic adhesive layer (B) are adjacent to each other, and the solvent-free gas barrier organic adhesive layer (B) is coated with a two-liquid curable solvent-free adhesive. is a layer formed by curing, and the solvent content of the non-solvent gas barrier organic adhesive layer (B) is zero or 6 mg/m ² or less, an easy-open gas barrier laminate, furthermore, a gas barrier coating Membrane layer (E
) and/or an easy-open gas barrier laminate having a printed layer (F), and a gas-barrier packaging material and a pillow packaging bag comprising the easy-open gas-barrier laminate. The present invention relates to a laminate having excellent water vapor barrier properties (having reduced permeability to oxygen and water vapor), a packaging material comprising the laminate, and a pillow packaging bag. Moreover, the packaging material of the present invention is most suitable for packaging bags and retort pouches.

In general, a packaging material having gas barrier properties comprises at least a laminate having a substrate layer, a gas barrier layer, an adhesive layer, and a sealant layer. Vapor-deposited films of metals or metal oxides are used.

However, although a metal foil as a gas barrier layer can achieve high oxygen barrier properties, it is thicker than vapor deposition films, etc. As a result, packaging materials using metal foil also become thicker and are inferior in bending resistance. It has been known.

On the other hand, if a vapor deposition film of metal or metal oxide is used, the film thickness can be reduced and the bending property is excellent. had the problem that it is difficult to achieve

Furthermore, in Patent Document 1, a thermosetting gas (oxygen) barrier polyurethane resin containing a resin cured product obtained by reacting an active hydrogen-containing compound (A) and an organic polyisocyanate compound (B) is disclosed as an oxygen barrier material. Are listed.

The resin cured product contains 20% by mass or more of a skeleton structure derived from meta-xylene diisocyanate, and among the above (A) and (B), the ratio of trifunctional or higher compounds is equal to (A) and ( A gas (oxygen) barrier composite film (base film layer and thermosetting gas barrier polyurethane resin) using a thermosetting oxygen barrier polyurethane resin, which is 7% by mass or more relative to the total amount of B) ) is described.

Furthermore, in Patent Document 2, a coating film having a transparency in which a thin film layer of silicon oxide or aluminum oxide is formed on at least one side of a polymer film substrate and the thin film layer surface of the coating film, and a heat-sealable resin film, A barrier laminate characterized by being adhered by a dry lamination method via a barrier adhesive containing one or more particles selected from inorganic silicon oxide and aluminum oxide materials, a polyester polyol, and an isocyanate compound, and A packaging material using this is described.

However, in Patent Document 1, the composition requires the use of a highly polar solvent, resulting in poor workability. For example, when a highly soluble solvent such as acetone is used, it has a low boiling point and easily absorbs water from the outside air, so there is a problem that the adjusted viscosity tends to increase due to the reaction between water and isocyanate. In 2, since the particle size of the inorganic compound contained in the adhesive is a nano-order spherical or amorphous inorganic compound, the oxygen barrier property of the adhesive itself, especially when a bending load is applied, is poor. There is a problem that it is not highly flexible.

Patent No. 4054972 specification Patent No. 3829526

The present invention solves the above problems and provides a laminate having a small total number of constituent layers, excellent workability during laminate production, and excellent easy-openability, gas barrier properties, and bending resistance, and the laminate. To provide a packaging material and a pillow packaging bag consisting of

As a result of various studies, the present inventors have found at least a substrate layer (A), a solventless gas barrier organic adhesive layer (B), a gas barrier inorganic deposition layer (C), and an easy-open sealant layer ( D), and has a structure in which the gas barrier inorganic vapor deposition layer (C) and the solventless gas barrier organic adhesive layer (B) are adjacent to each other, and the solventless gas barrier organic adhesive layer (B) is a two-liquid An easy-open gas barrier which is a layer formed by applying and curing a curable solventless adhesive, wherein the solvent content of the solventless organic gas barrier organic adhesive layer (B) is zero or 6 mg/m ² or less. Laminate, furthermore,
An easy-open gas barrier laminate having a gas barrier coating film layer (E) and/or a printed layer (F), and an easy-open gas barrier packaging material comprising the easy-open gas barrier laminate, comprising a gas barrier inorganic deposition layer The inventors have found that the above object can be achieved by forming (C) in contact with the solventless gas barrier organic adhesive layer (B) using a two-component curable solventless adhesive.
The present invention is characterized by the following points.

1. An easily peelable gas barrier laminate having at least a substrate layer (A), a solventless gas barrier organic adhesive layer (B), a gas barrier inorganic deposition layer (C), and an easily peelable sealant layer (D). The gas barrier inorganic deposition layer (C) and the solventless gas barrier organic adhesive layer (B) are laminated adjacent to each other, and the solventless gas barrier organic adhesive layer (B) is a two-component curing type It is a layer formed by applying a solventless adhesive and further curing it. The thickness of the solventless gas barrier organic adhesive layer (B) is 0.5 to 6 μm, and the solventless gas barrier organic adhesive layer. The easy-open gas barrier laminate, wherein the solvent content of (B) is zero or 6 mg/m ² or less.
2. Furthermore, an easy-open gas barrier laminate having a gas barrier coating layer (E) between the substrate layer (A) and the solvent-free gas barrier organic adhesive layer (B), the gas barrier coating layer 2. The easily openable gas barrier laminate according to 1 above, wherein (E) contains a sol-gel hydrolysis polycondensate of a mixture of a metal alkoxide and a water-soluble polymer.
3. 3. The easily openable gas barrier laminate according to 1 or 2 above, further comprising a printed layer (F) between the substrate layer (A) and the solventless gas barrier organic adhesive layer (B).
4. 4. Any one of 1 to 3 above, wherein the gas barrier inorganic vapor deposition layer (C) is a layer having one or more selected from the group consisting of an aluminum vapor deposition layer, an alumina vapor deposition layer, and a silica vapor deposition layer. Easy-to-open gas barrier laminate.
5. 4. The easily openable gas barrier laminate according to any one of 1 to 3 above, wherein the vapor-deposited inorganic gas barrier layer (C) is a layer having a vapor-deposited aluminum layer.
6. 6. The easy-open gas barrier laminate according to any one of 1 to 5 above, wherein the vapor-deposited gas barrier layer (C) has a thickness of 1 to 100 nm.
7. Oxygen permeability in an environment of 23°C and 90% RH is 0.05 to 2.0 cc/m ² /da
y/atm, and a water vapor permeability of 0.01 to 2.0 g/m ² /day/atm in an environment of 40° C. and 90% RH. The easily openable gas barrier laminate according to any one of the above.
8. The increase in oxygen permeability in an environment of 23° C. and 90% RH after applying a bending load five times with a gelbo flex tester from before applying the bending load is zero or 10.0 cc/m ² / day/atm or less, and the increase in water vapor permeability in an environment of 40° C. and 90% RH from before applying the bending load is zero or 2.0 g/m ² /day/atm.
8. The easily openable gas barrier laminate according to any one of 1 to 7 above, wherein:
9. 9. The easily openable gas barrier laminate according to any one of 1 to 8 above, wherein the total number of constituent layers is 6 or less.
10. An easy-open gas barrier packaging material using the easy-open gas barrier laminate according to any one of 1 to 9 above.
11. An easy-open pillow packaging bag using the easy-open gas barrier laminate according to any one of 1 to 9 above.

The easily-openable gas barrier laminate of the present invention and the easily-openable gas-barrier packaging material comprising the easily-openable gas-barrier laminate comprise at least a substrate layer (A), a non-solvent-type gas-barrier organic adhesive layer (B), and an inorganic gas-barrier layer. It has a vapor deposition layer (C) and an easy-open sealant layer (D), and has a structure in which the gas barrier inorganic vapor deposition layer (C) and the solvent-free gas barrier organic adhesive layer (B) are in contact with each other. The solvent-type gas barrier organic adhesive layer (B) is a layer formed by applying and curing a two-component curable solventless adhesive, has a thickness of 0.5 to 6 mm, and has a solvent content of zero or An easily openable gas barrier laminate having a weight of 6 mg/m ² or less, preferably further comprising a gas barrier coating film layer (E) and/or a printed layer (F), and a gas barrier inorganic deposition layer (C) By combining the non-solvent type gas barrier organic adhesive layer (B) adjacently, the uneven recesses occurring on the surface of the gas barrier inorganic deposition layer (C) are filled with the non-solvent type gas barrier organic adhesive layer (B). It is flattened and the gas barrier properties in the surface direction are uniformed, and the gas barrier inorganic vapor deposition layer is thinned to maintain bending resistance, while the total number of constituent layers is small, and the gas barrier properties are as high as or better than conventional ones. can be expressed. In addition, the solvent-free gas barrier organic adhesive layer (B) is solvent-free and has a solvent content of zero or 6 mg/m ² or less. reduction can be expressed. Moreover, since it has an easy-open sealant layer (D), the package can express easy-openability.

1 is a schematic cross-sectional view showing an example of the layer structure of a gas barrier laminate of the present invention; FIG. FIG. 4 is a schematic cross-sectional view showing another example of the layer structure of the gas barrier laminate of the present invention. FIG. 4 is a schematic cross-sectional view showing still another example of the layer structure of the gas barrier laminate of the present invention.

The easily-openable gas barrier laminate of the present invention, the easily-openable gas barrier packaging material and the easily-openable pillow packaging bag comprising the easily-openable gas-barrier laminate will be described in detail below with reference to the drawings.

In the present invention, the total number of constituent layers refers to the detailed number of layers such as the base material layer, the gas barrier layer, the adhesive layer, and the sealant layer, which constitute the laminate. It is the number of layers including special treatment coating layers. For example, a PET film layer with an aluminum deposition layer counts as two layers.

1 to 3 are schematic cross-sectional views showing an example of the layer structure of the easy-open gas barrier laminate of the present invention.

As shown in FIG. 1, the easy-open gas barrier laminate of the present invention comprises a substrate layer (A), a solventless gas barrier organic adhesive layer (B), a gas barrier inorganic deposition layer (C), and an easy-open layer. The basic structure is a structure in which a flexible sealant layer (D) is laminated.

As another embodiment of the easy-open gas barrier laminate of the present invention, as shown in FIG. 2, an inorganic gas barrier layer is further added between the substrate layer (A) and the non-solvent type gas barrier organic adhesive layer (B). A gas barrier inorganic vapor deposition layer separate from the vapor deposition layer (C) and a gas barrier coating film layer (E) may be laminated.

As still another embodiment of the easy-open gas barrier laminate of the present invention, as shown in FIG. 3, a printed layer ( F) may be laminated.

The above example is an example of the easily openable gas barrier laminate of the present invention, and the present invention is not limited thereto.

Next, the materials for the easily openable gas barrier laminate of the present invention, the method for producing the same, and the like will be described.
The name of the resin used in the present invention shall be that commonly used in the industry. Also, the present invention is not limited to the specific examples listed below.

[Base layer (A)]
As the substrate layer (A), a metal that has excellent chemical or physical strength, can withstand the conditions for forming an inorganic vapor deposition film, and can be well maintained without impairing the properties of the inorganic vapor deposition film, etc. Inorganic materials such as metal oxides and organic materials such as resins can be used, for example, as films and sheets.

As the substrate layer (A), a single layer film or a multilayer laminated film is used, but there is no particular limitation, and any film used for various packaging materials can be used. From among these, a suitable one is freely selected and used according to usage conditions such as the type of contents to be packaged and the presence or absence of heat treatment after filling.

Specific examples of films preferably used as the substrate layer (A) include paper, aluminum foil, cellophane, polyamide-based resin film, polyester-based resin film, olefin-based resin film, acid-modified polyolefin-based resin film, and polystyrene-based resin. Films, polyurethane resin films, acetal resin films, uniaxially or biaxially stretched films, K-coated films such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polybutene, Polyvinyl alcohol, ethylene-vinyl acetate copolymer, ionomer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-propylene copolymer, methylpentene, polyacrylonitrile, acrylonitrile - styrene copolymers, acrylonitrile-butadiene-styrene copolymers, polycarbonates, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymers (ETFE), Resin films made of polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, etc., K-coated oriented polypropylene films, K-coated oriented nylon films, composite films in which two or more of these films are laminated etc.
Among others, uniaxially or biaxially oriented polyester films such as polyethylene terephthalate and polyethylene naphthalate, uniaxially or biaxially oriented polyamide films such as nylon 6, nylon 66, MXD6 (polymetaxylylene adipamide), and biaxially An oriented polypropylene film (OPP) or the like can be preferably used. Transparent vapor-deposited PET such as silica vapor-deposited PET and alumina vapor-deposited PET, and aluminum vapor-deposited biaxially oriented polypropylene film (OPP) are also suitable.

(thickness)
The thickness of the substrate layer (A) can be arbitrarily selected, but from the viewpoint of moldability and transparency, it can be used by selecting it from the range of 1 μm to 300 μm, preferably from 1 to 100 μm. is. If it is thinner than this, the strength will be insufficient, and if it is thicker than this, the rigidity will be too high and processing may be difficult.

(surface treatment)
In addition, the substrate layer (A) and the film or sheet constituting the substrate layer (A) are each adhesive layer such as the solventless gas barrier organic adhesive layer (B) or the gas barrier inorganic deposition layer (C). In order to improve the adhesion with each inorganic vapor deposition layer, if necessary, in advance on the surface to be adhered of the base layer (A) and the film or sheet constituting the base layer (A) before lamination or vapor deposition. , corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, physical treatment such as glow discharge treatment, chemical treatment such as oxidation treatment using chemicals, adhesive layer , a treatment for forming a primer coating agent layer, an undercoat layer, a vapor deposition anchor coating agent layer, etc., and other treatments may be performed, an inorganic vapor deposition layer is provided after the surface treatment, and further, on the inorganic vapor deposition layer, A barrier coating layer such as a gas barrier coating layer (E) described later may be provided.

(Film forming method)
As the resin film or sheet used for the substrate layer (A), for example, one or more resins selected from the group of resins described above are used, and extrusion method, cast molding method, T-die method, cutting It can be produced by conventionally used film-forming methods such as method, inflation method, etc., or by multilayer co-extrusion film-forming method using two or more resins. Furthermore, from the viewpoints of film strength, dimensional stability and heat resistance, the film can be stretched uniaxially or biaxially using, for example, a tenter system or a tubular system.

(Additive)
The resin film or sheet used for the base material layer (A) has processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, and flame retardancy, if necessary. Lubricants, cross-linking agents, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, etc. can be added, and the amount of addition can be arbitrarily added according to the purpose within a range that does not adversely affect other performances.

[Solvent-free gas barrier organic adhesive layer (B)]
The solventless type gas barrier organic adhesive layer (B) in the easy-open gas barrier laminate of the present invention is formed without a solvent and has gas barrier properties, particularly oxygen and water vapor barrier properties.
The solvent content in the solventless gas barrier organic adhesive layer (B) is zero or 6 mg/m ² or less. In order to keep the solvent content low, the curable isocyanate resin composition forming the solvent-free gas barrier organic adhesive layer (B) must be a two-liquid curable solvent-free adhesive. The two-liquid curable solventless adhesive is used in a solventless state at the time of lamination by heating to reduce its viscosity.
When a solvent with high polarity is used in the curable isocyanate resin composition, the workability is poor. Therefore, the reaction between water and isocyanate tends to increase the viscosity of the curable isocyanate resin composition.

In addition, if the solvent-free gas barrier organic adhesive layer (B) contains a large amount of solvent, there is concern that the solvent may weaken the adhesion between the layers of the laminate. There is a concern that a solvent odor may be transferred to the contents of a package made of a packaging material. Furthermore, due to volume shrinkage during drying, the non-solvent type gas barrier organic adhesive layer (B) embedded in the concave and convex portions formed on the surface of the gas barrier inorganic vapor deposition layer (C) is peeled off, resulting in defects. The gas barrier property tends to be deteriorated due to the formation thereof, and when the laminate is folded, the peeling from the concave portions becomes large, which easily leads to deterioration of the gas barrier property.

The thickness of the solventless gas barrier organic adhesive layer (B) is 0.5 to 6.0 μm, preferably 0.8 to 5.0 μm, more preferably 1.0 to 4.5 μm. If it is thinner than the above range, the gas barrier properties tend to be insufficient, and if it is thicker than the above range, the bending resistance tends to be inferior, which tends to lead to a decrease in the gas barrier properties after bending.

(2-liquid curable solventless adhesive)
The two-component curable solventless adhesive that forms the gas barrier organic adhesive layer (B) includes, for example, a polyol (J) having two or more hydroxyl groups in one molecule and two or more isocyanate groups in one molecule. and a two-part curable solventless adhesive containing an isocyanate compound (K) and a phosphoric acid-modified compound (L). Here, the main skeleton of the polyol (J) having two or more hydroxyl groups in one molecule is a polyester structure or a polyester polyurethane structure, and 70 of the polyvalent carboxylic acid-derived structural moieties in the polyester structure or the polyester polyurethane structure ~100% by weight is derived from ortho-oriented aromatic dicarboxylic acids.

Polyvalent carboxylic acids refer to polyvalent carboxylic acids and their anhydrides and ester-forming derivatives, and the ortho-oriented aromatic dicarboxylic acids refer to ortho-oriented aromatic dicarboxylic acids and their anhydrides and ester-forming derivatives. .

In addition, the two-component curable solventless adhesive further comprises a plate-like inorganic compound (M), a polyester polyol (P) having two or more hydroxyl groups in one molecule, and one or two or more in one molecule. may contain one or more of the group consisting of polyvalent carboxylic acid-modified polyester polyols (N) having a carboxyl group and two or more hydroxyl groups.

In particular, it contains a polyvalent carboxylic acid-modified polyester polyol (N) and an isocyanate compound (K) having two or more isocyanate groups in one molecule, and has an acid value of 20 mgKOH/g or more. Solvent adhesives are preferred.

The glass transition temperature of the cured coating film of the two-component curing type solventless adhesive is preferably in the range of -30°C to 80°C, more preferably 0°C to 70°C, and still more preferably 25°C to 70°C. If the glass transition temperature is higher than 80° C., the flexibility of the cured coating film at around room temperature will be low, which may lead to poor adhesion to the substrate and reduced adhesive strength. On the other hand, when the temperature is lower than −30° C., there is a risk that sufficient oxygen barrier properties may not be obtained due to vigorous molecular movement of the cured coating film near room temperature, and that adhesive strength may be reduced due to insufficient cohesive strength.

As a specific example of the curable isocyanate resin composition for the adhesive layer, which is of the solvent-containing type and has oxygen barrier properties, there is an oxygen barrier adhesive PASLIM (PASLIM) sold by DIC Corporation. Series, PASLIMVM001/VM102C
P etc. are mentioned.

(Polyol (J))
Polyol (J) has two or more hydroxyl groups in one molecule, the main skeleton has a polyester structure or a polyester polyurethane structure, and 70 of the polyvalent carboxylic acid-derived structural moieties in the polyester structure or the polyester polyurethane structure ~100% by weight is derived from ortho-oriented aromatic dicarboxylic acids.

Here, the polyester portion of the main skeleton structure is obtained by subjecting polyhydric carboxylic acids and polyhydric alcohols to a polycondensation reaction by a known and commonly used method.

Polyvalent carboxylic acids include aliphatic polyvalent carboxylic acids and aromatic polyvalent carboxylic acids.

Specific aliphatic polycarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like.

Specific aromatic polycarboxylic acids include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalene. Dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; polybasic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids; .

Specific ortho-oriented aromatic dicarboxylic acids include orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and anhydride or ester-forming properties of these dicarboxylic acids. derivatives and the like.
These polyvalent carboxylic acids may be used alone or in combination of two or more.
Polyhydric alcohols include aliphatic polyhydric alcohols and aromatic polyhydric phenols.

Specific examples of aliphatic polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1, Examples include 6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and tripropylene glycol.

Specific examples of aromatic polyhydric phenols include hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, ethylene oxide extension products thereof, and hydrogenated alicyclic etc. can be exemplified.

(Isocyanate compound (K))
The isocyanate compound (K) has two or more isocyanate groups in the molecule, may be either aromatic or aliphatic, may be either a low-molecular compound or a high-molecular compound, and may be a diisocyanate compound having two isocyanate groups or , three or more polyisocyanate compounds, and other known compounds can be used. The isocyanate compound (K) may be a blocked isocyanate compound obtained by addition reaction using a known isocyanate blocking agent by a known and commonly used appropriate method.

Among them, polyisocyanate compounds are preferred from the viewpoint of adhesiveness and retort resistance, and those having an aromatic ring are preferred from the viewpoint of imparting oxygen barrier properties. It is preferable because oxygen barrier properties can be improved not only by hydrogen bonding but also by π-π stacking between aromatic rings.

Specific compounds of the isocyanate compound (K) include, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, meta-xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, or these Trimers of isocyanate compounds, and excess amounts of these isocyanate compounds, such as ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol , pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, metaxylylenediamine and other low-molecular-weight active hydrogen compounds and their alkylene oxide adducts, various polyester resins, polyether polyols, polyamides adducts, burettes, allophanates, etc. obtained by reacting with high molecular weight active hydrogen compounds.

(Phosphate-modified compound (L))
The phosphoric acid-modified compound (L) has the effect of improving the adhesive strength to inorganic members, and known and commonly used compounds can be used.
Specifically, phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphoric acid, etc., and one or more of these can be used.

(Polyvalent carboxylic acid-modified polyester polyol (N))
Polyvalent carboxylic acid-modified polyester polyol (N) having one or more carboxyl groups and two or more hydroxyl groups in one molecule is one of the hydroxyl groups of polyester polyols having three or more hydroxyl groups in one molecule. It is obtained by reacting polyvalent carboxylic acids with part.

(Plate-like inorganic compound (M))
The plate-like inorganic compound (M) has the effect of improving the lamination strength and oxygen barrier properties of the solvent-free gas barrier organic adhesive layer (B).
Specific examples of the plate-like inorganic compound (M) include kaolinite-serpentine clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, etc., antigorite, chrysotile, etc.), pyrophyllite-talc group (pyrophyllite, talc, kerorai, etc.), etc., and one or more of these can be used.

[Gas barrier inorganic deposition layer (C)]
The gas barrier inorganic deposition layer (C) is a barrier film having a gas barrier property that prevents the permeation of oxygen gas, water vapor, and the like, and includes a deposition film made of an inorganic material or an inorganic oxide.
In general, the surface of the inorganic vapor deposition layer has ultra-fine irregularities, and at the ultra-fine level, the thickness of the inorganic vapor deposition layer is not uniform, and the thin portions have weak gas barrier properties in the plane direction.

However, since the laminate of the present invention has a structure in which the gas barrier inorganic vapor deposition layer (C) and the solvent-type gas barrier organic adhesive layer (B) are in contact with each other, the ultra-high temperature generated on the surface of the gas barrier inorganic vapor deposition layer (C) By having a flattened structure in which the recesses of fine unevenness are filled with the solvent-type gas barrier organic adhesive layer (B) having gas barrier properties, the gas barrier properties in the plane direction are made uniform, and the gas barrier inorganic deposition layer (C ) can be made thinner to maintain bending resistance while exhibiting higher gas barrier properties than ever before.

The gas barrier inorganic vapor deposition layer (C) is preferably a layer having one or more selected from the group consisting of an aluminum vapor deposition layer, an alumina vapor deposition layer, and a silica vapor deposition layer, and particularly has an aluminum vapor deposition layer. is preferred.

The gas barrier inorganic deposition layer (C) can be provided directly on the sealant layer (D) without interposing an adhesive layer such as a non-solvent type gas barrier organic adhesive (B).

Furthermore, if necessary, it is possible to impart a light-shielding property to prevent transmission of visible light, ultraviolet rays, and the like. Also, the gas barrier inorganic deposition layer (C) may be composed of one layer or two or more layers. When composed of two or more layers, they may have the same composition or may have different compositions.

The thickness of the vapor-deposited gas barrier inorganic layer (C) is preferably from 1 to 200 nm, and more preferably from 1 to 100 nm, more preferably from 1 to 100 nm, and even more preferably in the case of an aluminum vapor-deposited film, although the more preferable thickness varies depending on the type of vapor deposition. is 15 to 60 nm, particularly preferably 10 to 40 nm.

In the case of a silicon oxide or alumina deposition film, the thickness is more preferably 1 to 100 nm, still more preferably 10 to 50 nm, and particularly preferably 20 to 30 nm.

The gas barrier inorganic deposition layer (C) can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and the composition and formation method are not particularly limited.

Formation methods include, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, and a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a photochemical vapor deposition method.

In the present invention, the gas barrier inorganic deposition layer (C) can be provided on the surface of the sealant layer (D) on the solventless type gas barrier organic adhesive layer (B) side.

At that time, the surface of the sealant layer (D) can be pretreated as necessary, specifically, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow A physical treatment such as discharge treatment or a chemical treatment such as oxidation treatment using a chemical agent may be performed.

In the easy-open gas barrier laminate of the present invention, in order to further enhance gas barrier properties against oxygen gas, water vapor, etc., a gas barrier inorganic vapor deposition layer similar to the gas barrier inorganic vapor deposition layer (C) is added to the substrate layer (A). It can also be provided on the side in contact with the solvent-type gas barrier organic adhesive layer (B). The pretreatment, vapor deposition species, vapor deposition film forming method, etc. are the same as those for the gas barrier inorganic vapor deposition layer (C).

[Sealant layer (D) (heat seal layer)]
The sealant layer (D) provides the easy-open gas barrier laminate of the present invention and the easy-open gas-barrier packaging material comprising the easy-open gas-barrier laminate with heat sealability and easy-openability, as well as flex resistance and resistance. It imparts functions such as impact resistance, and an easy peel film is used. In particular, it is desirable to impart flex resistance so that deterioration of the gas barrier property after flexing can be suppressed.

Any of an interfacial peeling type, a cohesive peeling type, and an interlaminar peeling type can be applied as the easy peel film, and can be appropriately selected and used according to the type of package and required properties.

As an indicator of easy-openability, the seal strength of the package is preferably in the range of 2 to 20 N/15 mm, and an easy-peel film capable of imparting seal strength within this range is used.
In the present invention, any material that satisfies the above conditions can be used.
In the present invention, the sealant layer (D) desirably has a heat-sealable resin layer. The heat-sealable resin layer may be one that can be melted and fused together by heat.

Suitable resins for the sealant layer (D) include polyethylene, low-density polyethylene, linear low-density polyethylene, metallocene polyethylene, non-stretched polypropylene, and the like, and a resin film composed of one or more of these resins. Alternatively, a sheet or other coating film or the like can be used.
As the layer structure of the sealant layer (D), a multilayer film of polyethylene/polypropylene+polyethylene/polypropylene is suitable. In addition, a film obtained by vapor-depositing an aluminum film on heat-sealable unstretched polypropylene (CPP), low-density polyethylene, or linear low-density polyethylene can also be used.
Known flex resistance improvers, inorganic or organic additives, and the like can be blended with the above resins, if necessary.

(Film thickness of sealant layer (D))
The thickness of the sealant layer (D) can be arbitrarily selected. It is preferably in the range of 15-100 μm. If the thickness is smaller than this, sufficient lamination strength cannot be obtained even if heat-sealed, the packaging material does not function, and the puncture resistance deteriorates. On the other hand, if it is thicker than this, the cost will rise and the film will become hard and workability will deteriorate.

[Gas barrier coating film layer (E)]
In the present invention, a gas barrier coating film layer is further provided between the substrate layer (A) and the solvent-type gas barrier organic adhesive layer (B) in order to enhance the barrier properties against gases such as oxygen gas and water vapor. (E) can be provided. The gas barrier coating film layer (E) may be provided on the gas barrier inorganic deposition layer laminated on the substrate layer (A).

The gas barrier coating film layer (E) is obtained by polycondensing a mixture of a metal alkoxide and a water-soluble polymer by a sol-gel method in the presence of a sol-gel catalyst, water, an organic solvent, etc. and hydrolyzing the metal alkoxide. It is preferably a layer formed from a resin composition such as a hydrolyzed condensate of a compound or a metal alkoxide.

As the metal alkoxide, one or more of the metal alkoxides represented by the following general formula can be preferably used.
^R1nM ₍ ^OR2 ) _m
(In the formula, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n+m represents the valence of M.)
Here, as the metal atom M, silicon, zirconium, titanium, aluminum and others can be used. Specific examples of organic groups represented by R ¹ and R ² include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl and i-butyl. can be mentioned. These alkyl groups may be the same or different in the same molecule.

Examples of such metal alkoxides include tetramethoxysilane Si(OCH ₃
) ₄ , tetraethoxysilane Si(OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si(OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si(OC ₄ H ₉ ) _{4 ,} etc., and a functional group that binds to an organic substance A silane coupling agent is mentioned.
The metal alkoxides may be used singly or in combination of two or more.

As the silane coupling agent, known organo-reactive group-containing organoalkoxysilanes can be used, but organoalkoxysilanes having an epoxy group are particularly preferred, such as γ-glycidoxypropyltrimethoxysilane, γ-Glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or the like can be used.

The above silane coupling agents may be used singly or in combination of two or more. In the present invention, the silane coupling agent as described above can be contained within a range of about 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the above alkoxides.

As the water-soluble polymer, either polyvinyl alcohol-based resin or ethylene-vinyl alcohol copolymer, or both of them can be preferably used. These resins may be commercially available. For example, ethylene-vinyl alcohol copolymers include EVAL EP-F101 (ethylene content: 32 mol%) manufactured by Kuraray Co., Ltd., and Soarnol manufactured by Nippon Synthetic Chemical Industry Co., Ltd. D2908 (ethylene content: 29 mol %) or the like can be used.

In addition, as the polyvinyl alcohol resin, RS-110 (degree of saponification = 99%, degree of polymerization = 1,000), RS polymer manufactured by Kuraray Co., Ltd., Kuraray Poval LM-20SO (degree of saponification = 40%, degree of polymerization = 2,000), Gohsenol NM-14 (degree of saponification = 99%, degree of polymerization = 1,400) manufactured by Nippon Synthetic Chemical Industry Co., Ltd., and the like can be used.

The content of the water-soluble polymer is preferably in the range of 5 to 500 parts by mass with respect to 100 parts by mass of the metal alkoxide. If the amount is less than 5 parts by mass, the gas barrier coating layer (E) will be inferior in film-forming properties, will become more brittle, and will tend to have lower weather resistance. tend to become.

As the sol-gel process catalyst, an acid or amine compound is suitable.

As the amine compound, a tertiary amine which is substantially insoluble in water and soluble in an organic solvent is suitable. Specifically, for example, N,N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used. N,N-dimethylbenzylamine is particularly preferred, and it is preferably contained in an amount of, for example, 0.01 to 1.0 parts by weight, particularly 0.03 to 0.3 parts by weight, per 100 parts by weight of the metal alkoxide. If the amount is less than 0.01 parts by mass, the catalytic effect is too small, and if it is more than 1.0 parts by mass, the catalytic effect is too strong, the reaction rate becomes too fast, and the reaction tends to be uneven.

Examples of acids that can be used include mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid. The acid content is preferably 0.001 to 0.05 mol, more preferably 0.01 to 0.03 mol, relative to the total molar amount of alkoxy groups in the metal alkoxide. If it is less than 0.001 mol, the catalytic effect is too small, and if it is more than 0.05 mol part, the catalytic effect is too strong and the reaction rate becomes too fast, tending to be non-uniform.

Methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used as the organic solvent.

The gas-barrier coating film layer (E) is coated with a coating liquid comprising the resin composition by a roll coating method such as a gravure roll coater, a spray coating method, a spin coating method, a dipping method, a brush method, a bar code method, an applicator method, and the like. It is formed by coating once or multiple times by conventionally known means.
A specific example of the method for forming the gas barrier coating film layer (E) will be described below.
First, a metal alkoxide, a water-soluble polymer, a sol-gel process catalyst, water, an organic solvent, and, if necessary, a silane coupling agent and the like are mixed to prepare a coating liquid composed of a resin composition. A polycondensation reaction proceeds gradually in the coating liquid.

Then, the coating solution is applied on the gas barrier inorganic deposition layer laminated on the substrate layer (A) by a conventional method and dried. Drying further promotes polycondensation of the alkoxide and vinyl alcohol polymer (and silane coupling agent) to form a composite polymer layer. Suitably, the above operations can be repeated to laminate multiple composite polymer layers.

Finally, the laminate coated with the coating liquid is heated at a temperature of 20 to 250° C., preferably 50 to 220° C., for 1 second to 10 minutes. Thereby, the gas barrier coating film layer (E) can be formed on the gas barrier inorganic deposition layer.

The gas barrier coating layer (E) may be a composite polymer layer in which one layer or two or more layers are laminated. The thickness of the gas barrier coating film layer (E) after drying is preferably in the range of 0.01 to 100 μm, more preferably 0.1 to 50 μm. If the thickness after drying is less than 0.01 μm, the improvement in gas barrier properties is too small, and if it is more than 100 μm, cracks tend to occur.

[Print layer (F)]
The easily-openable gas barrier laminate of the present invention may optionally be provided, as shown in FIG. As shown in FIG. 3, characters, figures, symbols, and other desired patterns are printed between the gas barrier coating film layer (E) and the non-solvent type gas barrier organic adhesive layer (B) by a normal printing method. An optional printed layer (F) can be provided.

[Laminate and packaging material comprising the laminate]
A conventional easy-open gas barrier laminate has a total number of constituent layers of about eight, including an AC coat, a metal vapor deposition layer, etc., and therefore the manufacturing process is long and complicated. The total number of constituent layers of the gas barrier laminate can be made smaller than before, and can be six layers or less. It is also possible to have a structure of 7 or more layers, and it is possible to exhibit equivalent or better gas barrier properties with a total number of structural layers that is relatively smaller than that of conventional materials. In addition, since the total number of constituent layers is small and the inorganic deposition layer can be made thin, the process can be shortened and simplified, the laminate can be made thinner, the flexibility of the laminate is improved, and the flexibility is improved. improves.

The laminate of the present invention and the packaging material comprising the laminate comprise, as shown in FIG. Further, as shown in FIG. 2, the gas barrier coating film layer (E) surface of the substrate layer (A) provided with the gas barrier inorganic vapor deposition layer and the gas barrier coating film layer (E) on one side, and the sealant layer (D) The gas barrier inorganic vapor deposition layer (C) surface provided on one side of the substrate layer (A) and the printed layer (F) of the base layer (A) provided with the printed layer (F) as necessary, as shown in FIG. It can be manufactured by laminating the surface and the gas barrier inorganic deposition layer (C) surface provided on one side of the sealant layer (D) with the solventless type gas barrier organic adhesive layer (B) interposed therebetween.

The easy-open gas barrier laminate of the present invention and the packaging material comprising the laminate are excellent in gas barrier properties, and preferably have an oxygen permeability of 0.05 to 2.0 cc/m ² / in an environment of 23°C and 90% RH. day/atm, and the water vapor transmission rate in an environment of 40° C. and 90% RH is 0.
01 to 2.0 g/m ² /day/atm.

Furthermore, in general, packaging materials are folded, heated, and crimped to produce a packaging bag, and when the contents are vertically pillow-filled, the packaging bag is subjected to physical load due to heat, friction, pressure, etc. Although the gas barrier property of the packaging bag is reduced due to exposure to the , the packaging bag produced using the gas barrier packaging material of the present invention has less deterioration in gas barrier property, preferably 5 times with a gelboflex tester After the bending load is applied, the oxygen permeability in an environment of 23° C. and 90% RH increases from the value before the bending load is applied to zero or 10.0 cc/m ² /day/atm or less.

[Package]
The pillow packaging bag of the present invention is a package obtained by pillow packaging the laminate obtained above, and is excellent in gas barrier properties and flex resistance.
The present invention will be specifically described with reference to examples.

[Preparation of two-liquid curing type solventless adhesive A]
The following raw materials are put into a polyester reaction vessel equipped with a rectifying tube and a water separator and gradually heated to carry out an esterification reaction while maintaining the liquid temperature of the reaction solution at 220°C and the vapor temperature of 100°C under a nitrogen atmosphere. The esterification reaction was terminated when the acid value of the reaction liquid became 1 mgKOH/g or less, and the liquid temperature was cooled to 120°C.
Phthalic anhydride 241.9 parts by mass Ethylene glycol 105.4 parts by mass Glycerin 75.2 parts by mass Titanium tetraisopropoxide 0.042 parts by mass

Next, the following raw materials are added to the reaction liquid, and the polyvalent carboxylic acid modification reaction is allowed to proceed while the liquid temperature is maintained at 120° C., and the acid value becomes approximately half of the acid value calculated from the charged amount of maleic anhydride. At this point, the esterification reaction was terminated and the mixture was cooled to obtain a polyvalent carboxylic acid-modified polyester polyol A.
Maleic anhydride 77.5 parts by mass The characteristics of the obtained polyvalent carboxylic acid-modified polyester polyol A are as follows.
Number average molecular weight: about 520,
hydroxyl value: 216.6 mgKOH/g,
Acid value: 96.2mgKOH/g
Number of hydroxyl groups per molecule: 2 (design value)
Number of carboxyl groups per molecule: 1 (design value)

Next, as isocyanate compounds, "Desmodur N3200" manufactured by Sumika Bayer Urethane (biuret form of hexamethylene diisocyanate. Number of isocyanate groups per molecule: 2 ) and "Takenate 500" manufactured by Mitsui Chemicals (meta-xylylene diisocyanate. 1 Number of isocyanate groups per molecule: 2), and the polyvalent carboxylic acid-modified polyester polyol A obtained above is heated to 80 ° C. and uniformly mixed at the following compounding ratio, cooled, and two-liquid curing. A mold solvent-free adhesive A was obtained.
Polyvalent carboxylic acid-modified polyester polyol A 100 parts by mass Desmodur N3200 49.5 parts by mass Takenate 500 28.9 parts by mass

[Example 1]
A 20 μm OPP (biaxially oriented polypropylene) film (manufactured by Toyobo Co., Ltd., P-2171) with a corona treatment of 20 μm as a substrate layer and a single-sided aluminum vapor deposition treatment (40 nm thickness) as a sealant layer. A 25 μm CPP (unstretched polypropylene) film (manufactured by Toray Advanced Film Co., Ltd., 2703) was non-solvent laminated via a two-liquid curable solvent-free adhesive A. At this time, the amount of the adhesive applied was such that the thickness of the adhesive layer after curing was 3 μm. After lamination, aging treatment was performed at 40° C. for 3 days to obtain a laminate. The obtained laminate was evaluated for gas barrier properties, laminate strength, and solvent content. Table 1 shows the results.
Layer structure: OPP (20 μm) / non-solvent type gas barrier organic adhesive (3 μm) / aluminum vapor deposition (40 nm) / CPP (25 μm)

[Example 2]
As the sealant layer, a 25 μm-thick CPP (manufactured by Toyobo Co., Ltd., P1128, one side corona-treated) was applied to one side with an alumina vapor deposition treatment (20 nm thick) instead of a 25 μm-thick CPP that was one-sided aluminum vapor deposition treated. A laminate was obtained in the same manner as in Example 1 except that it was used, and was evaluated in the same manner. The single-sided alumina deposition treatment conditions are as follows.
Layer structure: OPP (20 μm) / non-solvent type gas barrier organic adhesive (3 μm) / alumina vapor deposition (20 nm) / CPP (25 μm)
<Vapor deposition conditions>
Evaporation surface: Corona-treated surface Degree of vacuum in vacuum chamber: 2 to 6×10 ⁻⁶ mBar
Degree of vacuum in vapor deposition chamber: 2 to 5×10 ^-3 mBar
Power supplied to cooling/electrode drum: 10 kW
Line speed: 100m/min
Next, immediately after forming an alumina vapor deposition film having a thickness of 200 Å (20 nm), a glow discharge plasma generator was used on the surface of the alumina vapor deposition film, power was 9 kw, oxygen gas: argon gas=7. Using a mixed gas of 0:2.5 (unit: s1m), an oxygen/argon mixed gas plasma treatment was performed at a mixed gas pressure of 6×10 ⁻³ Torr to reduce the surface tension of the deposited alumina film surface to 54 dyne/. A plasma-treated surface was formed which was improved by 1 cm or more.

[Example 3]
As the sealant layer, a 25 μm thick CPP (manufactured by Toyobo Co., Ltd., P1128, one side corona treated) was applied to one side silicon oxide vapor deposition (20 nm thick) in place of the 25 μm thick CPP that was one side aluminum vapor deposited. A laminate was obtained and evaluated in the same manner as in Example 1 except that it was used in the same manner as in Example 1. The single-sided silicon oxide vapor deposition treatment conditions are as follows.
Layer structure: OPP (20 μm) / non-solvent type gas barrier organic adhesive (3 μm) / silicon oxide deposition (20 nm) / CPP (25 μm)
<Vapor deposition conditions>
Evaporation surface: Corona-treated surface Introduced gas: Hexamethyldisiloxane/oxygen gas/helium = 1.0/3.0/3.0 (unit: s1m)
Degree of vacuum in vacuum chamber: 2 to 6×10 ⁻⁶ mBar
Degree of vacuum in vapor deposition chamber: 2 to 5×10 ^-3 mBar
Power supplied to cooling/electrode drum: 10 kW
Line speed: 100m/min
Next, immediately after the deposition film of silicon oxide having a thickness of 200 Å (20 nm) was formed as described above, a glow discharge plasma generator was used on the surface of the deposition film of silicon oxide, power was 9 kw, oxygen gas: argon gas = Using a mixed gas of 7.0:2.5 (unit: s1m), an oxygen/argon mixed gas plasma treatment was performed at a mixed gas pressure of 6 × 10 ^-3 Torr to increase the surface tension of the deposited silicon oxide film surface. was improved by 54 dyne/cm or more.

[Comparative Example 1]
Two-component curable solvent-free adhesive A was replaced with a two-component curable urethane adhesive (Tomoflex TM-340 manufactured by Toyo-Morton Co., Ltd. / CAT-29 manufactured by Toyo-Morton Co., Ltd.), and the aging conditions were changed. A laminate was obtained in the same manner as in Example 1 except that the temperature was changed to 25° C. for 1 day, and the evaluation was performed in the same manner.
Layer structure: OPP (20 μm) / two-liquid curing urethane adhesive (3 μm) / aluminum vapor deposition (40 nm) / CPP (25 μm)

[Comparative Example 2]
A multilayer film of polyethylene/polypropylene+polyethylene/polypropylene was formed to obtain an easy peel CPP film with a thickness of 25 μm.

Furthermore, the obtained easy-peel CPP film was subjected to aluminum vapor deposition treatment under 5×10 ^-4 Torr by induction heating aluminum with a winding-type vacuum vapor deposition machine to form a gas barrier inorganic vapor deposition layer (C). A 25 μm thick easy peel CPP (unstretched polypropylene) film A having a 40 nm thick single-sided aluminum deposition layer was obtained.

A 20 μm OPP (biaxially oriented polypropylene) film (P-2171, manufactured by Toyobo Co., Ltd.) that was corona-treated on one side was AC-coated (P-1000, manufactured by DICG Co., Ltd., after drying). The AC coated surface and a 12 μm PET film (Biaxially stretched PET film E-5100 manufactured by Toyobo Co. ^, Ltd., one side aluminum vapor-deposited under the following vapor deposition conditions. Thickness 12 μm, One side was subjected to corona treatment.) was laminated by extrusion lamination via low-density polyethylene (LC600A, manufactured by Nippon Polyethylene Co., Ltd.). The thickness of polyethylene was adjusted to 7 μm.

Next, the non-deposited surface of the laminated aluminum-deposited PET is AC-coated, and the AC-coated surface and a 25 μm easy-peel CPP film A having easy peelability are coated with low-density polyethylene (Japan Polyethylene Co., Ltd.). LC600A.).
The thickness of polyethylene was adjusted to 7 μm. After lamination, aging treatment was performed at 25° C. for 1 day to obtain a laminate, which was similarly evaluated.
Layer structure: OPP (20 μm)/AC coat/PE (7 μm)/aluminum deposition (40 nm)/PET (12 μm)/AC coat/PE (7 μm)/CPP (25 μm)
<Vapor deposition conditions>
Evaporation surface: Corona-treated surface Degree of vacuum in vacuum chamber: 2 to 6×10 ⁻⁶ mBar
Degree of vacuum in vapor deposition chamber: 2 to 5×10 ^-3 mBar
Power supplied to cooling/electrode drum: 10 kW
Line speed: 100m/min
Next, immediately after forming an aluminum vapor deposition film having a thickness of 400 Å (40 nm) as described above, a glow discharge plasma generator was used on the surface of the aluminum vapor deposition film, power was 9 kw, oxygen gas:argon gas=7. Using a mixed gas of 0:2.5 (unit: s1m), an oxygen/argon mixed gas plasma treatment was performed at a mixed gas pressure of 6×10 ⁻³ Torr to reduce the surface tension of the deposited aluminum film surface to 54 dyne/. A plasma-treated surface was formed which was improved by 1 cm or more.

[Comparative Example 3]
A laminate was obtained and evaluated in the same manner as in Example 1 except that the solvent-free organic gas barrier adhesive was replaced with the following solvent-containing gas barrier organic adhesive.
Layer structure: OPP (20 μm)/solvent-containing gas barrier organic adhesive (3 μm)/aluminum deposition (40 nm)/CPP (25 μm)
(Preparation of solvent-containing gas barrier organic adhesive)
A solvent-containing gas barrier organic adhesive was prepared by mixing the following adhesive and solvent.

Adhesive: PASLIM VM001/VM102CP (manufactured by DIC Corporation) 19 parts by mass Solvent: Ethyl acetate 15 parts by mass

<Evaluation>
[Laminate]
Each laminate obtained in each example and each comparative example was cut into strips with a width of 15 mm, and a Tensilon tensile tester (RTC-1310A manufactured by Orientec Co., Ltd.) was used to test the laminate at 25 ° C. atmosphere. Below, the maximum load when the base material layer and the sealant layer were separated was measured by a T-shaped peeling method (tensile speed of 50 mm/min), and was defined as the laminate strength (N/15 mm). Furthermore, the peeling interface site was confirmed. The notations in Table 1 have the following meanings.
VM/CPP: Peeling at the interface between vapor deposition layer and CPP layer PE/VM: Peeling at the interface between polyethylene layer and vapor deposition layer Bond/VM: Peeling at the interface between adhesive layer and vapor deposition layer

[Gas barrier property]
(1) Oxygen Permeability Each laminate was cut into A4 size, and oxygen permeability (cc/m ² /day/atm ) was measured.
(2) Water vapor permeability Each laminate was cut into A4 size, and using PERMATRAN 3/31 manufactured by MOCON in the United States, water vapor permeability (g/m ² /day/atm ) was measured.
(3) After bending load After applying bending load five times with a gelbo flex tester, oxygen permeability and water vapor permeability were measured under the same method and under the same conditions as above.

[Solvent content]
The total amount (mg/m ² ) of toluene, ethyl acetate, IPA, methanol and MEK in the film was measured by the DNP method. A total amount of zero or 6 mg/m ² or less was considered acceptable.

[Result Summary]
Examples 1 to 6 exhibited gas barrier properties equal to or greater than those of Comparative Example 3, which is a conventional gas barrier laminate having a total number of constituent layers of 8, although the total number of constituent layers was 4.

Solvent-free gas barrier organic adhesive layer (B) formed using two-liquid curing solvent-free adhesive A
with a thickness of 0.5 to 6 μm, and having an easy-open sealant layer (D) are superior to Comparative Examples 1 to 3 using a conventional two-component curable urethane adhesive. The solvent content of the non-solvent type gas barrier organic adhesive layer (B) was low, and good packaging material seal strength was exhibited. However, Comparative Example 4, in which the non-solvent type gas barrier organic adhesive layer (B) had a thickness of only 0.1 μm, exhibited insufficient gas barrier properties.

Moreover, in Comparative Examples 1 and 2 using a normal two-liquid curing urethane adhesive containing a solvent, the solvent content of the adhesive layer was large.

Claims (10)

At least a substrate layer (A), a gas barrier inorganic deposition layer (G), a gas barrier coating layer (E), a solventless gas barrier organic adhesive layer (B), and a gas barrier inorganic deposition layer (C). , and an easy-open sealant layer (D) in this order,
The substrate layer (A), the gas barrier inorganic deposition layer (G), and the gas barrier coating layer (E) are laminated adjacent to each other,
The solvent-free gas barrier organic adhesive layer (B), the gas barrier inorganic deposition layer (C) and the easy-open sealant layer (D) are laminated adjacent to each other,
The gas barrier coating film layer (E) contains a sol-gel hydrolysis polycondensate of a mixture of a metal alkoxide and a water-soluble polymer,
The gas barrier inorganic deposition layer (G) is provided directly on the surface-treated surface of the substrate layer (A),
The easily peelable sealant layer (D) is an easy peel film having a layer structure consisting of polyethylene/polypropylene and polyethylene/polypropylene,
The solventless gas barrier organic adhesive layer (B) is a cured layer made of a two-component curable solventless adhesive,
The two-component curable solventless adhesive contains a polyvalent carboxylic acid-modified polyester polyol and an isocyanate compound,
The polyvalent carboxylic acid-modified polyester polyol has an ortho-oriented aromatic dicarboxylic acid-derived structure in the main skeleton,
The thickness of the solventless gas barrier organic adhesive layer (B) is 0.5 to 6 μm,
The solvent content of the solventless gas barrier organic adhesive layer (B) is zero or 6 mg/ ^m2 or less.
Easy-to-open gas barrier laminate. 2. The easy-open gas barrier laminate according to claim 1, further comprising a printed layer (F) between the substrate layer (A) and the solventless type gas barrier organic adhesive layer (B). The easy-to-open package according to claim 1 or 2, wherein the gas barrier inorganic deposition layer (C) is a layer having one or more selected from the group consisting of an aluminum deposition layer, an alumina deposition layer, and a silica deposition layer. gas barrier laminate. The easily openable gas barrier laminate according to claim 1 or 2, wherein the gas barrier inorganic deposition layer (C) is a layer having an aluminum deposition layer. The easily openable gas barrier laminate according to any one of claims 1 to 4, wherein the gas barrier inorganic deposition layer (C) has a thickness of 1 to 100 nm. The oxygen permeability under the environment of 23° C. and 90% RH is 0.05 to 2.0 cc/m ² /day/atm, and the water vapor permeability under the environment of 40° C. and 90% RH is 0.01 to 2.0 g. /m ² /day/atm,
The easily openable gas barrier laminate according to any one of claims 1 to 5, for use as an oxygen barrier and for a water vapor barrier. After giving 5 bending loads with the gelbo flex tester,
The increase in oxygen permeability in an environment of 23° C. and 90% RH from before applying the bending load is zero or 10.0 cc/m ² /day/atm or less.
The easily openable gas barrier laminate according to any one of claims 1 to 6. The easily openable gas barrier laminate according to any one of claims 1 to 7 , wherein the total number of constituent layers is 7 or less. An easy-open gas barrier packaging material using the easy-open gas barrier laminate according to any one of claims 1 to 8. An easy-open pillow packaging bag using the easy-open gas barrier laminate according to any one of claims 1 to 8.

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