JP7275729B2 - Low-solvent odor easy-open gas barrier laminate using solventless adhesive, and low-solvent odor gas barrier packaging material and packaging bag comprising the laminate - Google Patents

Description

The present invention has at least a substrate layer (A), a low solvent content gas barrier organic adhesive layer (B), a gas barrier inorganic deposition layer (C), and an easy-open sealant layer (D). A low-solvent odor easy-open gas barrier laminate, a low-solvent odor easy-open gas barrier laminate further having a gas barrier coating layer (E) and/or a printed layer (F), and a packaging material comprising the laminate, The present invention relates to a packaging bag, particularly a pillow packaging bag, which uses the packaging material and is excellent in easy-openability, gas-barrier properties, bending resistance, and low solvent odor.
Moreover, the packaging material of the present invention is most suitable for various 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 ) 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 tends to take in 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 addition, in Patent Document 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, in particular, a bending load was applied. In this case, there is a problem that the oxygen barrier property is not high.

Japanese Patent No. 4054972 Japanese 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, bending resistance, and low solvent odor. and to provide a packaging material and a pillow packaging bag comprising the laminate.

As a result of various studies, the present inventors have found that at least a substrate layer (A), a gas-barrier organic adhesive layer (B), a gas-barrier inorganic deposition layer (C), and an easy-open sealant layer (D) A low-solvent odor, easy-to-open gas barrier laminate having , A layer formed by applying and curing a solvent-free adhesive resin composition, and the solvent content of the gas barrier organic adhesive layer (B) is zero or 6 mg/m ² or less, low solvent odor An easy-open gas barrier laminate, further comprising a low-solvent odor easy-open gas barrier laminate having a gas barrier coating layer (E) and/or a printed layer (F), and the low-solvent odor easy-open gas barrier laminate We have found that a low solvent odor gas barrier packaging material achieves the above objectives.

The present invention is characterized by the following points.
1. Low-solvent odor easy-open gas barrier laminate comprising at least a substrate layer (A), a gas-barrier organic adhesive layer (B), a gas-barrier inorganic deposition layer (C), and an easy-open sealant layer (D). and
The thickness of the base material layer (A) is 5 to 50 μm,
The gas barrier inorganic deposition layer (C) and the gas barrier organic adhesive layer (B) are laminated adjacent to each other,
The gas-barrier organic adhesive layer (B) is a layer formed by applying a solventless adhesive composition and further curing, and has a thickness of 0.6 to 6.0 μm.
The solvent content of the gas barrier organic adhesive layer (B) is zero or 6 mg/m ² or less.
Easy-to-open gas barrier laminate with low solvent odor.
2. The base material layer (A) is made of a biaxially stretched film containing a polypropylene resin,
The thickness of the base layer (A) is 18 to 40 μm.
2. The low-solvent odor easily openable gas barrier laminate according to 1 above.
3. The substrate layer (A) is made of a biaxially stretched film containing a polyethylene terephthalate resin,
The thickness of the base layer (A) is 5 to 40 μm.
2. The low-solvent odor easily openable gas barrier laminate according to 1 above.
4. Furthermore, a low-solvent odor easy-open gas barrier laminate having a gas barrier coating layer (E) between the base material layer (A) and the gas barrier organic adhesive layer (B),
The gas barrier coating film layer (E) contains a sol-gel hydrolysis polycondensate produced from a resin composition containing a metal alkoxide and a water-soluble polymer.
4. The easy-open gas barrier laminate with low solvent odor according to any one of 1 to 3 above.
5. Furthermore, between the substrate layer (A) and the gas barrier organic adhesive layer (B), it has a printed layer (F),
5. The easy-open gas barrier laminate with low solvent odor according to any one of 1 to 4 above.
6. 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.
6. The easy-open gas barrier laminate with low solvent odor according to any one of 1 to 5 above.
7. The gas barrier inorganic deposition layer (C) is a layer having an aluminum deposition layer,
6. The easy-open gas barrier laminate with low solvent odor according to any one of 1 to 5 above.
8. The gas barrier inorganic deposition layer (C) has a thickness of 1 to 100 nm.
8. The easy-open gas barrier laminate with low solvent odor according to any one of 1 to 7 above.
9. 9. The low-solvent odor easy-open gas barrier laminate according to any one of 1 to 8 above, wherein the solvent-free adhesive composition is a two-part curing type solvent-free adhesive composition.
Oxygen permeability in an environment of 10.23° C. and 90% RH is 0.05 to 2 cc/m ² /day/atm,
Water vapor permeability in an environment of 40° C. and 90% RH is 0.01 to 2 g/m ² /day.
for oxygen barrier and water vapor barrier,
10. The easy-open gas barrier laminate with low solvent odor according to any one of 1 to 9 above.
11. 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 20 cc/m ² /day/ atm or less;
11. The easy-open gas barrier laminate with low solvent odor according to any one of 1 to 10 above.
12. 12. The low-solvent odor easy-open gas barrier laminate according to any one of 1 to 11 above, wherein the total number of constituent layers is 6 or less.
13. A low-solvent odor gas barrier packaging material using the low-solvent odor easy-open gas barrier laminate according to any one of 1 to 12 above.
14. 14. A low solvent odor gas barrier packaging bag using the low solvent odor gas barrier packaging material according to 13 above.
15. 14. A low solvent odor gas barrier pillow packaging bag using the low solvent odor gas barrier packaging material according to 13 above.

The laminate and the packaging material comprising the laminate according to the present invention are obtained by combining the gas barrier inorganic vapor deposition layer (C) and the gas barrier organic adhesive layer (B) adjacently, so that the gas barrier inorganic vapor deposition layer (C) surface The recesses of the unevenness occurring in the surface are filled with the gas barrier organic adhesive layer (B) and flattened, the gas barrier properties in the surface direction are made uniform, and the thickness of the gas barrier inorganic vapor deposition layer (C) is reduced. While maintaining flex resistance, it is possible to exhibit gas barrier properties equal to or greater than conventional ones with a small total number of constituent layers.
In addition, since the solvent content of the gas-barrier organic adhesive layer (B) is low, the gas-barrier properties can be further improved, and the transfer of the solvent odor to the contents can be reduced.

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

A laminate, a packaging material comprising the laminate, and a pillow packaging bag according to the present invention will be described in detail below with reference to the drawings.

In the present invention, the total number of constituent layers is 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, and the vapor deposition layer, AC coating, etc. in each layer. 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 low-solvent odor easy-open gas barrier laminate of the present invention.

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

As another embodiment of the low-solvent odor easy-open gas barrier laminate of the present invention, as shown in FIG. A gas barrier inorganic deposition layer separate from the inorganic deposition layer (C) and a gas barrier coating film layer (E) may be laminated.

As another embodiment, as shown in FIG. 3, a printed layer (F) may be laminated between the substrate layer (A) and the gas-barrier organic adhesive layer (B).

The above example is an example of the low-solvent odor easy-open gas barrier laminate of the present invention, and the present invention is not limited thereto.
Next, the laminate according to the present invention, the packaging material comprising the laminate, the material for the pillow packaging bag, and the manufacturing method thereof 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) is 5 μm or more and 50 μm or less, preferably 15 μm or more and 40 μm or less, from the viewpoint of formability, transparency, and gas barrier property maintenance after bending. If the thickness is less than the above range, the rigidity of the laminate is too low, so that the layer that contributes to the gas barrier properties is likely to break when bent, and the strength of the laminate is likely to be insufficient. On the other hand, if the thickness is larger than this, the rigidity of the laminate becomes too high, so that the layer that contributes to the gas barrier property is likely to break when bent, and the processing of the laminate tends to be difficult.

The thickness of the base layer (A) is preferably 18 to 40 μm when the base layer (A) is made of a biaxially stretched film containing a polypropylene resin, and the base layer (A) contains a polyethylene terephthalate resin. In the case of a biaxially stretched film, the thickness is preferably 5 to 40 μm.

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

[Gas barrier organic adhesive layer (B)]
The gas-barrier organic adhesive layer (B) in the present invention is a layer formed by applying a solventless adhesive composition and further curing, and is adjacent to the gas-barrier inorganic deposition layer (C) in the laminate. It is laminated and has gas barrier properties, especially barrier properties against oxygen and water vapor.

The solvent content of the gas-barrier organic adhesive layer (B) in the laminate is zero or 6 mg/m ² or less. If the content is larger than the above range, the adhesion between the layers of the laminate may be weakened by the solvent. If the gas barrier organic adhesive layer (B) embedded in the layer peels off and causes defects, the gas barrier property tends to be deteriorated. prone to deterioration. Furthermore, in a package made of a packaging material using the obtained laminate, there is a possibility that the solvent odor may be transferred to the contents.

The thickness of the gas barrier organic adhesive layer (B) is preferably 0.6 to 6.0 μm, more preferably 0.8 to 5.0 μm, still 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.

The glass transition temperature of the gas-barrier organic adhesive layer (B) is preferably in the range of -30°C to 80°C, more preferably 0°C to 70°C, still more preferably 25°C to 70°C. If it is higher than the above range, the flexibility of the cured coating film at around room temperature may decrease, and the adhesion to the substrate may deteriorate, resulting in a decrease in adhesive strength. If it is lower than the above range, the molecular motion of the cured coating film may increase at around room temperature, which may make it difficult to exhibit sufficient oxygen barrier properties, or may reduce adhesive strength due to insufficient cohesion.

Examples of the adhesive resin composition for forming the gas barrier organic adhesive layer (B) include polyol (J) having two or more hydroxyl groups in one molecule and isocyanate having two or more isocyanate groups in one molecule. An adhesive resin composition containing a compound (K) and a phosphoric acid-modified compound (L) is mentioned.

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

In particular, it preferably 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.

The adhesive resin composition is preferably a two-component curable adhesive composition, more preferably a two-component curable solventless adhesive resin composition.
The adhesive resin composition is used, for example, in a solvent-free state by heating to reduce its viscosity during lamination.

Here, the term "solvent-free" as used in the present invention means that it does not actively contain a solvent. may be contained within the range where the solvent content of is zero or 6 mg/m ² or less.
Alternatively, it may contain a solvent capable of bringing the solvent content of the formed gas-barrier organic adhesive layer (B) into the above range.

(Polyol (J))
The polyol (J) has two or more hydroxyl groups in one molecule, and has one or more selected from the group consisting of a polyester structure, a polyester polyurethane structure, a polyether structure, and a polyether polyurethane structure. have. The polyester structure can be obtained, for example, by subjecting polyhydric carboxylic acids and polyhydric alcohols to a polycondensation reaction by a known and commonly used method, but the synthetic route is not limited thereto.

It is preferable that 70 to 100 mass % of the polyvalent carboxylic acid-derived structural moieties in the polyester structure or the polyester polyurethane structure are derived from ortho-oriented aromatic dicarboxylic acids. The ortho-oriented aromatic dicarboxylic acids refer to ortho-oriented aromatic dicarboxylic acids and their anhydrides and ester-forming derivatives.

Polyvalent carboxylic acids refer to polyvalent carboxylic acids and their anhydrides and ester-forming derivatives, and include, for example, 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 phosphate, etc., and one or more of these can be used.

(solvent)
The solvent dissolves the polyol (J) and the isocyanate compound (K), can uniformly disperse the phosphoric acid-modified compound (L) and the plate-like inorganic compound (M), and has an appropriate boiling point for the manufacturing process of the laminate. There is no particular limitation as long as it has volatility and the solvent content of the formed gas-barrier organic adhesive layer (B) can be zero or 6 mg/m ² or less.

If the adhesive resin composition contains, for example, a highly polar solvent, the workability tends to be poor. For example, when a highly soluble solvent such as acetone is used, the viscosity of the adhesive resin composition tends to increase due to the reaction between water and isocyanate due to its low boiling point and easy intake of water from the outside air. may occur.

In addition, if the 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 concern that the solvent odor may transfer to the contents of the package prepared in . Furthermore, due to volume shrinkage during drying, the gas barrier organic adhesive layer (B) embedded in the uneven recesses on the surface of the gas barrier inorganic vapor deposition layer (C) may peel off and cause defects. When the laminate is folded, the peeling from the concave portion is increased, which tends to lead to deterioration of the gas barrier property.
Therefore, it is preferable not to use a solvent in the present invention.

(Plate-like inorganic compound (M))
The plate-like inorganic compound (M) has the effect of improving the laminate strength and gas barrier properties of the 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.

(Polyvalent carboxylic acid-modified polyester polyol (N))
A polyvalent carboxylic acid-modified polyester polyol (N) is a compound having one or more carboxyl groups and two or more hydroxyl groups in one molecule.
The polyvalent carboxylic acid-modified polyester polyol (N) can be obtained, for example, by reacting a portion of the hydroxyl groups of a polyester polyol having 3 or more hydroxyl groups in one molecule with a polyvalent carboxylic acid.

[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, the laminate of the present invention has a structure in which the gas barrier inorganic vapor deposition layer (C) and the gas barrier organic adhesive layer (B) are in contact with each other. The gas barrier organic adhesive layer (B) having a gas barrier property fills the uneven recesses to form a flattened structure, so that the gas barrier property in the plane direction is made uniform, and the gas barrier inorganic deposition layer (C) is formed. It is possible to exhibit higher gas barrier properties than ever before while maintaining bending resistance by reducing the layer thickness.

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 an aluminum vapor deposition layer. It is preferable to have
The gas-barrier inorganic vapor-deposited layer (C) can be provided directly on the easy-open sealant layer (D) without an adhesive layer such as the gas-barrier organic adhesive layer (B) interposed therebetween.

Furthermore, if necessary, it is possible to impart a light-shielding property to block the 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 easy-open sealant layer (D) on the side of the gas barrier organic adhesive layer (B).

At that time, the surface of the easy-open sealant layer (D) can be pretreated as necessary. A treatment, a physical treatment such as a glow discharge treatment, or a chemical treatment such as an oxidation treatment using a chemical or the like may be performed.

Furthermore, 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 base material layer (A) as the gas barrier organic adhesive layer (B). It can also be provided on the side in contact with the 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).

[Easy-open sealant layer (D) (heat seal layer)]
The easy-open sealant layer (D) imparts functions such as heat sealability, flex resistance, and impact resistance to the laminate according to the present invention and the packaging material comprising the laminate. It is desirable to suppress the deterioration of the gas barrier property after bending by imparting
Furthermore, in the present invention, an easy-peel film is used for the easy-peelable sealant layer (D) in order to impart easy-peelability.
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, the easy-open sealant layer (D) preferably 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 easy-open sealant layer (D) include, for example, polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, metallocene polyethylene, polypropylene, and ethylene-acetic acid. Vinyl copolymer, ionomer resin, ethylene-ethyl(meth)acrylate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyolefin resin such as polyethylene or polypropylene modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc., terpolymer resins of ethylene-(meth)acrylic acid ester-unsaturated carboxylic acid, cyclic polyolefins Resins, cyclic olefin copolymers, polyethylene terephthalate (PET), polyacrylonitrile (PAN) and the like can be mentioned, and resin films or sheets or other coating films made of one or more of these resins can be used. .

As the film or sheet for forming the above resin layer, either an unstretched film or sheet or a uniaxially or biaxially stretched film or sheet can be used.

A biaxially stretched stretched film is longitudinally stretched 2 to 4 times with a roll stretching machine at 50 to 100° C., and further transversely stretched by 3 to 5 times with a tenter stretching machine in an atmosphere of 90 to 150° C., Subsequently, it can be obtained by heat treatment in an atmosphere of 100 to 240° C. using the same tenter. Moreover, the stretched film may be subjected to simultaneous biaxial stretching and sequential biaxial stretching.

As the layer structure of the easy-open sealant layer (D), a multilayer film of polyethylene/polypropylene and a mixture of 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.
In the present invention, any material that satisfies the above conditions can be used.

(Film thickness of easy-open sealant layer (D))
The thickness of the easy-open sealant layer (D) can be selected arbitrarily. 250 μm, more 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, and 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 layer (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) contains a sol-gel hydrolysis polycondensate produced from a resin composition containing a metal alkoxide and a water-soluble polymer in the presence of a sol-gel catalyst, water, an organic solvent, etc. It is preferably a layer that

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 the 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(OCH 3 ) 4 . ₄ H ₉ ) ₄ , etc., and silane coupling agents having functional groups that bond with organic substances.
The metal alkoxides may be used singly or in combination of two or more.

As the silane coupling agent, known organic 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. become a trend.

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 it 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 there is a tendency for unevenness to occur.

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 content of the acid 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 conventional method such as roll coating such as gravure roll coater, spray coating, spin coating, dipping, brush, bar code, applicator, etc. It is formed by applying one or more times by 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 film 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)]
In the laminate according to the present invention, if necessary, for example, between the substrate layer (A) and the gas barrier organic adhesive layer (B), in particular, for example, as shown in FIG. 3, a gas barrier coating layer Between (E) and the gas-barrier organic adhesive layer (B), a printed layer (F) can be provided in which characters, figures, symbols and other desired patterns are arbitrarily formed by a normal printing method. .

[Laminate and packaging material comprising the laminate]
In conventional laminates, in order to obtain sufficient gas barrier properties, the total number of constituent layers, including AC (anchor coat) and metal deposition layers, etc., must be about 8 or more. Although it was long and complicated, the laminate according to the present invention can reduce the total number of constituent layers compared to the conventional one, and can exhibit a gas barrier property equal to or higher than that of the conventional laminate with 6 layers or less. be.

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 according to the present invention and the packaging material comprising the laminate comprise, as shown in FIG. The gas barrier inorganic deposition layer (C) surface of (D) can be laminated via the gas barrier organic adhesive layer (B). Further, even when the substrate layer (A) has the gas barrier inorganic deposition layer and the gas barrier coating film layer (E) on one side as shown in FIG. 2, the gas barrier coating film of the substrate layer (A) The layer (E) surface and the gas barrier inorganic vapor deposition layer (C) surface of the adjacently laminated gas barrier inorganic vapor deposition layer (C) and the easy-open sealant layer (D) are bonded to the gas barrier organic adhesive layer (B ) may be laminated via. Furthermore, as shown in FIG. 3, even if the base material layer (A) optionally has a printed layer (F), the printed layer (F) is laminated adjacent to the surface. The gas barrier inorganic vapor deposition layer (C) and the gas barrier inorganic vapor deposition layer (C) surface of the easy-open sealant layer (D) may be laminated via the gas barrier organic adhesive layer (B).

The laminate according to the present invention may be aged by temperature and time depending on the structure of the laminate. The aging treatment can improve the adhesion of the layer interfaces of the laminate.
Aging is preferably at 30-50° C. for 1-3 days. If the temperature is lower than the above range or for a shorter time, the aging effect may not be sufficiently exhibited. It is difficult to improve more than this, and the productivity tends to deteriorate.

The laminate and the packaging material comprising the laminate according to the present invention have excellent gas barrier properties, and preferably have an oxygen permeability of 0.05 to 2 cc/m ² /day/atm in an environment of 23° C. and 90% RH. It has a water vapor permeability of 0.01 to 2 g/m ² /day in an environment of 40° C. and 90% RH.
Furthermore, when a packaging bag is made using a packaging material and the contents are vertically pillow-filled, the packaging bag is exposed to physical loads such as heat, friction, and pressure. The gas barrier property of the bag is lowered.

However, the packaging bag produced using the packaging material according to the present invention has little deterioration in gas barrier properties after filling with vertical pillows, and preferably, after applying a bending load 5 times with a gelbo flex tester, 23 The increase in oxygen permeability in an environment of 90° C. 90% RH from before the bending load is applied is zero or 20 cc/m ² /day/atm or less, and the water vapor permeability in an environment of 40° C. 90% RH is The increase from before applying the bending load may be zero or 20 g/m ² /day or less.

[Packaging bag]
The packaging bag according to the present invention is produced from the packaging material according to the present invention, and is excellent in easy-openability, gas barrier properties, low solvent odor, and bending resistance. Examples of packaging bags include pillow packaging bags.
The present invention will be specifically described with reference to examples.

<Preparation of raw materials>
PET film 1: T4100 PET film manufactured by Toyobo. One side corona treated. 10 μm thick.
PET film 2: PET film 1310 manufactured by Toray Advanced Film Co., Ltd.; Single-sided aluminum vapor deposition treatment (40 nm thick). 12 μm thick.
OPP films 1 to 6: OPP (biaxially oriented polypropylene) film, 2161, manufactured by Toyobo Co., Ltd.; One side corona treated. Thickness 18, 20, 25, 30, 40, 60 μm.
ONY film 1: ONY film N1100 manufactured by Toyobo. One side corona treated. 15 μm thick.
AC coating agent 1: Epomin P-1000 manufactured by Nippon Shokubai Co., Ltd.;
Solventless gas barrier organic adhesive composition 1: Prepared as follows.
Solvent-free gas barrier organic adhesive composition 2: Solvent-free PASLIM manufactured by DIC Corporation
Solvent-containing gas barrier organic adhesive composition 1: Prepared as follows.
Two-component curable urethane adhesive 1: Tomoflex TM-340 manufactured by Toyo-Morton Co., Ltd. / CAT-29 manufactured by Toyo-Morton Co., Ltd.
Low-density polyethylene 1: Low-density polyethylene manufactured by Japan Polyethylene Co., Ltd., LC600A. Easy Peel CPP Film 1: Made as follows.
Easy Peel CPP Film 2: Made as follows.
Easy Peel CPP Film 3: Made as follows.
Easy Peel CPP Film 4: Made as follows.
CPP film 1: CPP film 2703 manufactured by Toray Advanced Film Co., Ltd.; Single-sided aluminum vapor deposition treatment (40 nm). 25 μm thick.

[Preparation of resin composition 1 for gas barrier coating film]
The following raw materials were mixed to prepare a gas barrier coating film resin composition 1 for the gas barrier coating film layer (E).
Tetraethoxysilane 100 parts by mass EVAL EP-F101 20 parts by mass N,N-dimethylbenzylamine 0.2 parts by mass Isopropyl alcohol 300 parts by mass

[Preparation of non-solvent gas barrier organic adhesive composition 1]
A solvent-free gas-barrier organic adhesive composition 1 for the gas-barrier organic adhesive layer (B) was prepared by operating as follows.
First, the following raw materials are put into a polyester reaction vessel equipped with a rectifying tube and a water separator and gradually heated to esterify the reaction solution while maintaining the liquid temperature of 220 ° C. and the vapor temperature of 100 ° C. under a nitrogen atmosphere. The reaction was allowed to proceed, and when the acid value of the reaction liquid became 1 mgKOH/g or less, the esterification reaction was terminated 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 The 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 in the following compounding ratio, cooled, and a solvent-free gas barrier Organic adhesive composition 1 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

[Preparation of solvent-containing gas barrier organic adhesive composition 1]
A solvent-containing gas barrier organic adhesive composition 1 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

[Preparation of easy peel CPP film 1]
A three-layer film of polyethylene/polypropylene and a mixture of polyethylene/polypropylene was formed to obtain a film having a thickness of 25 μm.

Further, the obtained film was subjected to aluminum deposition treatment under 5×10 ⁻⁴ Torr by induction heating of aluminum using a winding-type vacuum deposition machine to form a gas barrier inorganic deposition layer (C) having a thickness of 40 nm. An easy-peel CPP (unstretched polypropylene) film 1 having a thickness of 25 μm and having an aluminum deposition layer on one side was obtained.

[Preparation of easy peel CPP film 2]
A three-layer film of polyethylene/polypropylene and a mixture of polyethylene/polypropylene was formed to obtain a film having a thickness of 25 μm.

Furthermore, an alumina deposition film (20 nm thick) was formed on the obtained film under the following conditions.
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 the alumina vapor deposition film, the surface of the alumina vapor deposition film is subjected to plasma treatment under the following conditions to form a plasma-treated surface in which the surface tension of the alumina vapor deposition film surface is increased by 54 dyne/cm or more, An easy peel CPP film 2 was obtained.
Plasma generator: Glow discharge plasma generator Power: 9kw
Mixed gas: oxygen gas/argon gas = 7.0/2.5 (unit: s1m)
Mixed gas pressure: 6×10 ⁻³ Torr

[Preparation of easy peel CPP film 3]
A three-layer film of polyethylene/polypropylene and a mixture of polyethylene/polypropylene was formed to obtain a film having a thickness of 25 μm.

Furthermore, a silicon oxide deposited film (20 nm thick) was formed on the obtained film under the following conditions.
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 deposited silicon oxide film is formed, the surface of the deposited silicon oxide film is subjected to plasma treatment under the following conditions to form a plasma-treated surface in which the surface tension of the deposited silicon oxide film surface is increased by 54 dyne/cm or more. As a result, an easy peel CPP film 3 was obtained.
Plasma generator: Glow discharge plasma generator Power: 9kw
Mixed gas: oxygen gas/argon gas = 7.0/2.5 (unit: s1m)
Mixed gas pressure: 6×10 ^-3 Torr

[Preparation of easy peel CPP film 4]
A three-layer film of polyethylene/polypropylene and a mixture of polyethylene/polypropylene was formed to obtain a film having a thickness of 25 μm.

[Example 1]
Using a PET film 1 as the base layer (A), a solventless gas barrier organic adhesive composition 1 as the gas barrier organic adhesive layer (B), and an easy peel CPP film 1 as the easy-open sealant layer (D), The corona-treated surface of the PET film 1 and the aluminum-deposited surface of the easy-peel CPP film 1 were laminated with the solvent-free gas-barrier organic adhesive composition 1 interposed therebetween, and then aged at 40° C. for 1 day to form a laminate. Obtained.
At this time, the amount of the solvent-free gas barrier organic adhesive composition 1 applied was such that the thickness after curing was 2 μm.
Various evaluations were carried out on the obtained laminate. Table 1 shows the results.
Layer structure: PET film 1 (10 μm)/solventless gas barrier organic adhesive resin composition 1 cured product (2 μm)/aluminum deposition (40 nm)/easy peel CPP film 1 (25 μm)

[Examples 2 to 7]
The same operation and evaluation as in Example 1 were performed except that the film for the substrate layer (A) was changed to the film shown in Tables 1 and 2. Tables 1 and 2 show the results.

[Example 8]
OPP film 5 as base layer (A), solventless gas barrier organic adhesive composition 1 as gas barrier organic adhesive layer (B), easy peel CPP film 1 as easy-open sealant layer (D), gas barrier coating film Layer (E) Resin composition 1 for gas barrier coating film was used.

The corona-treated surface of the PET film 1 is coated with the resin composition 1 for gas barrier coating film, and after drying, the dried surface of the resin composition 1 for gas barrier coating film and the aluminum-deposited surface of the easy peel CPP film 1 are separated. , and the solvent-free gas barrier organic adhesive composition 1, followed by aging treatment at 40° C. for 1 day to obtain a laminate.
At this time, the coating amount of the solvent-free gas barrier coating film resin composition 1 was such that the thickness after drying was 2 μm, and the coating amount of the gas barrier organic adhesive composition 1 was such that the thickness after curing was 2 μm. The amount was set to 2 μm.
The obtained laminate was evaluated in the same manner as in Example 1. Table 2 shows the results.

[Examples 9 and 10]
The same operation and evaluation as in Example 3 were performed except that the film for the easy-open sealant layer (D) was changed to the film shown in Table 2. Table 2 shows the results.

[Examples 11 and 12]
The same operation and evaluation as in Example 3 were performed except that the thickness of the gas barrier organic adhesive layer (B) was changed to the value shown in Table 3. Table 3 shows the results.

[Example 13]
Except for using the solventless gas barrier organic adhesive composition 2 for the gas barrier organic adhesive layer (B), the same operation and evaluation as in Example 3 were performed. Table 3 shows the results.

[Examples 14 and 15]
The same operation as in Example 13 was performed except that the film for the substrate layer (A) was changed to the film shown in Table 3, and the evaluation was performed in the same manner. Table 3 shows the results.

[Comparative Example 1]
A laminate was obtained in the same manner as in Example 3, except that the solvent-free gas barrier organic adhesive composition 1 was changed to a two-component curable urethane adhesive composition 1 and the aging conditions were changed to 25° C. for one day. , was similarly evaluated. Table 4 shows the results.

[Comparative Example 2]
The AC coating agent 1 is applied to the corona-treated surface of the OPP film 2 and dried, and the dried surface of the AC coating agent 1 and the aluminum-deposited surface of the PET film 2 are extruded through the melt-extruded low-density polyethylene 1. A laminate precursor was obtained by lamination. At this time, the thickness of one layer of low-density polyethylene was adjusted to 10 μm.

Next, the AC coating agent 1 is applied to the non-aluminum vapor-deposited surface of the PET film 2 of the laminate precursor and dried, and the AC coating agent 1 dry surface and the “easy peel CPP film 4 are combined with the melt-extruded low Extrusion lamination was carried out through density polyethylene 1. At this time, the thickness of one layer of low density polyethylene was adjusted to 10 μm, and aging treatment was performed at 25° C. for 1 day to obtain a laminate. The same evaluation was made and the results are shown in Table 4.

[Comparative Example 3]
A laminate was obtained and evaluated in the same manner as in Example 3 except that the solvent-free gas barrier organic adhesive composition 1 was changed to the solvent-containing gas barrier organic adhesive composition 1. Table 4 shows the results.

[Comparative Example 4]
A laminate was obtained in the same manner as in Example 3 except that the easy-peel CPP film 1 was changed to the CPP film 1, and evaluated in the same manner. Table 4 shows the results.

[Comparative Example 5]
The film for the substrate layer (A) was operated in the same manner as in Example 1, except that OPP film 6 was used, and evaluated in the same manner. Table 4 shows the results.

[Comparative Example 6]
The same operation and evaluation as in Example 3 were performed except that the thickness of the gas-barrier organic adhesive layer (B) was changed to 0.55 μm. Table 4 shows the results.

<Evaluation>
[Gas barrier property]
(1) Oxygen Permeability Each laminate was cut into A4 size, and oxygen permeability (cc/m ² /day/atm ) was measured. 2 cc/m ² /day/atm or less was regarded as acceptable.
(2) Water Vapor Permeability Each laminate was cut into A4 size, and the water vapor permeability (g/m ² /day) was measured under conditions of 40° C. and 90% RH using PERMATRAN 3/31 manufactured by MOCON in the United States. It was measured. 2 g/m ² /day or less was regarded as acceptable.
(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. The increase in oxygen permeability from before the bending load was 20 cc/m ² /day/atm or less, and the water vapor permeability was 20 g/m ² /day or less.

[Vertical pillow fillability]
Empty bags with no contents were evaluated for vertical pillow filling under the following conditions.
Filling machine: KBF-6100 (manufactured by Kawashima Seisakusho Co., Ltd.)
Packaging bag size: width 200 mm x height 240 mm
Sealing conditions: vertical sealing 140°C, horizontal sealing 150°C
Number of shots: 30/min

[Laminate strength]
A strip-shaped test piece with a width of 15 mm is cut out from the laminate, and a Tensilon tensile tester (RTC-1310A manufactured by Orientec Co., Ltd.) is used in an atmosphere of 25 ° C. in a T-shaped peeling method (tensile speed 50 mm / min). , the maximum load when the substrate layer and the sealant layer were separated was measured and taken as the laminate strength (N/15 mm). Furthermore, the peeling interface site was confirmed. The notations in Table 1 have the following meanings. A lamination strength of 1 N/15 mm or more was accepted.
Vapor/Steam: Peel off at the interface of gas barrier inorganic vapor deposition layer (C)/sealant layer (D) Contact/Vapor: Peel off at the interface of gas barrier organic adhesive layer (B)/gas barrier inorganic vapor deposition layer (C) Vapor deposition film = aluminum , alumina and silicon oxide.
Adhesives = solvent-free gas-barrier organic adhesive composition 1, solvent-free gas-barrier organic adhesive composition 2, solvent-containing gas-barrier organic adhesive composition 1, two-component curable urethane adhesive 1, low-density polyethylene 1.
Sealant part=CPP part of CPP films 1-4.

[Seal strength]
After heat-sealing the two laminates so that the sealant layers face each other, a test piece is cut into a strip with a width of 15 mm, and a Tensilon tensile tester (RTC-1310A manufactured by Orientec Co., Ltd.) is used. In an atmosphere of 25° C., the maximum load when the sealant layers were peeled was measured by a T-shaped peeling method (tensile speed of 50 mm/min), and the maximum load was taken as the seal strength (N/15 mm). A case of 2 to 20 N/15 mm was regarded as acceptable.

[Solvent Content of Gas Barrier Organic Adhesive Layer (B)]
The total amount (mg/m ² ) of toluene, ethyl acetate, IPA, methanol and MEK in the film was measured by gas chromatography. A total amount of zero or 6 mg/m ² or less was considered acceptable.

[Result Summary]
Examples 1 to 15 have good vertical pillow filling properties, oxygen permeability and water vapor permeability before and after bending load, lamination properties, and seal strength, even though the total number of constituent layers is 4 to 5 layers. and a gas barrier property equal to or greater than that of Comparative Example 2 in which the total number of constituent layers of the conventional gas barrier laminate is 8 layers.
However, in Comparative Examples 1 to 3, which did not have the gas barrier organic adhesive layer (B), the increase in oxygen permeability before bending load and/or oxygen permeability after bending load was high.
Comparative Example 4, which did not have the easy-open sealant layer (D), showed results of poor easy-openability due to too high sealing strength.
Comparative Example 5, in which the substrate layer (A) is too thick, showed high oxygen permeability and high water vapor permeability after bending load.
Comparative Example 6, in which the gas-barrier organic adhesive layer (B) was too thin, did not exhibit a sufficient oxygen permeability before the bending load, so the subsequent evaluation was discontinued.

1 Low solvent odor easy-open gas barrier laminate 2 Base layer (A)
3 Gas barrier organic adhesive layer (B)
4 gas barrier inorganic deposition layer (C)
5 Easy-open sealant layer (D)
6 gas barrier inorganic deposition layer 7 gas barrier coating film layer (E)
8 printed layer (F)

Claims (15)

Low-solvent odor easy-open gas barrier having at least a substrate layer (A), a gas-barrier organic adhesive layer (B), a gas-barrier inorganic deposition layer (C), and an easy-open sealant layer (D) in this order. A laminate,
The thickness of the base material layer (A) is 5 to 50 μm,
The gas barrier inorganic deposition layer (C) and the gas barrier organic adhesive layer (B) are laminated adjacent to each other,
The gas barrier inorganic deposition layer (C) is provided directly on the sealant layer (D) and has a thickness of 10 to 40 nm,
The gas barrier organic adhesive layer (B) is a layer formed by applying a solventless adhesive composition and further aging and curing , and has a thickness of 0.6 to 6.0 μm.
The adhesive resin composition for forming the gas barrier organic adhesive layer (B) contains a polyvalent carboxylic acid-modified polyester polyol (N) and an isocyanate compound (K),
The solvent content of the gas barrier organic adhesive layer (B) is zero or 6 mg/m ² or less.
Easy-to-open gas barrier laminate with low solvent odor. The base material layer (A) is made of a biaxially stretched film containing a polypropylene resin,
The thickness of the base layer (A) is 18 to 40 μm.
The low-solvent odor, easy-to-open gas barrier laminate according to claim 1. The substrate layer (A) is made of a biaxially stretched film containing a polyethylene terephthalate resin,
The thickness of the base layer (A) is 5 to 40 μm.
The low-solvent odor, easy-to-open gas barrier laminate according to claim 1. Furthermore, a low-solvent odor easy-open gas barrier laminate having a gas barrier coating layer (E) between the base material layer (A) and the gas barrier organic adhesive layer (B),
The gas barrier coating film layer (E) contains a sol-gel hydrolysis polycondensate produced from a resin composition containing a metal alkoxide and a water-soluble polymer.
The low-solvent odor and easy-open gas barrier laminate according to any one of claims 1 to 3. Furthermore, between the substrate layer (A) and the gas barrier organic adhesive layer (B), it has a printed layer (F),
The low-solvent odor easy-open gas barrier laminate according to any one of claims 1 to 4. 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.
The low-solvent odor easy-open gas barrier laminate according to any one of claims 1 to 5. The gas barrier inorganic deposition layer (C) is a layer having an aluminum deposition layer,
The low-solvent odor easy-open gas barrier laminate according to any one of claims 1 to 5. The gas barrier inorganic deposition layer (C) has a thickness of 1 to 100 nm.
The low-solvent odor easy-open gas barrier laminate according to any one of claims 1 to 7. The low-solvent odor easy-open gas barrier laminate according to any one of claims 1 to 8, wherein the solvent-free adhesive composition is a two-component curing type solvent-free adhesive composition. an oxygen permeability of 0.05 to 2 cc/m ² /day/atm under an environment of 23° C. and 90% RH;
Water vapor permeability in an environment of 40° C. and 90% RH is 0.01 to 2 g/m ² /day.
for oxygen barrier and water vapor barrier,
The low-solvent odor easy-open gas barrier laminate according to any one of claims 1 to 9. 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 20 cc/m ² /day/ atm or less;
The low-solvent odor easy-open gas barrier laminate according to any one of claims 1 to 10. 12. The low-solvent odor easy-open gas barrier laminate according to any one of claims 1 to 11, wherein the total number of constituent layers is 6 or less. A low-solvent odor gas barrier packaging material using the low-solvent odor easy-open gas barrier laminate according to any one of claims 1 to 12. A low solvent odor gas barrier packaging bag using the low solvent odor gas barrier packaging material according to claim 13. A low-solvent odor gas barrier pillow packaging bag using the low-solvent odor gas barrier packaging material according to claim 13.

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