JP2021151786A - Gas barrier laminate using solventless adhesive, and gas barrier packaging material and pillow packaging bag comprising laminate - Google Patents

Abstract

To provide a laminate excellent in gas barrier properties and also excellent in bending resistance, and a packaging material using the laminate.SOLUTION: The gas barrier laminate includes at least a substrate layer, a gas barrier organic adhesive layer, a gas barrier inorganic vapor deposition layer, and a sealant layer. The gas barrier organic adhesive layer and the gas barrier inorganic vapor deposition layer are in contact with each other. The gas barrier organic adhesive layer is a layer formed by applying a two-pack curable solventless adhesive and curing it. The gas barrier organic adhesive layer has a solvent content of zero or 6 mg/m2 or less. The gas barrier laminate further includes a gas barrier coating film layer and a printing layer. The packaging material uses the laminate.SELECTED DRAWING: Figure 1

Description

The present invention has at least a base material layer (A), a solvent-free gas barrier organic adhesive layer (B), a gas barrier inorganic vapor deposition layer (C), and a sealant layer (D), and has a gas barrier inorganic 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-component curable solvent-free adhesive and cured. It is a formed layer, and the solvent content of the solvent-free gas barrier organic adhesive layer (B) is zero or 6 mg / m ²
The following relates to a gas barrier laminate, a gas barrier laminate having a gas barrier coating film layer (E) and / or a printing layer (F), and a gas barrier packaging material and pillow packaging composed of the gas barrier laminate. In particular, the present invention relates to a laminate having excellent bending resistance, oxygen barrier property, and water vapor barrier property (with reduced permeability of oxygen and water vapor), and a packaging material and pillow package made of the laminate. Further, the packaging material of the present invention is most suitable for a packaging bag or a retort bag.

Generally, a packaging material having a gas barrier property is composed of a laminate having at least a base material layer, a gas barrier layer, an adhesive layer, and a sealant layer, and in particular, as a gas barrier layer for improving the oxygen barrier property, a metal foil, A vapor-deposited film of metal or metal oxide is used.

However, although the metal foil as the gas barrier layer can achieve high oxygen barrier properties, it is thicker than the vapor-deposited film and the like, and as a result, the packaging material using the metal foil is also thicker and inferior in bending resistance. It has been known.

On the other hand, if a thin-film film of metal or metal oxide is used, the film thickness can be reduced and the film thickness is excellent, but the surface of the thin-film film has irregularities, so that it has sufficient oxygen barrier properties. Had the problem that it was difficult to achieve.

Further, Patent Document 1 describes a thermosetting gas (oxygen) barrier polyurethane resin containing a cured resin obtained by reacting an active hydrogen-containing compound (A) and an organic polyisocyanate compound (B) as an oxygen barrier material. Have been described.

The cured resin product contains 20% or more of a skeletal structure derived from metaxylene diisocyanate, and the proportions of the trifunctional or higher compounds among the above (A) and (B) are (A) and ( Gas (oxygen) barrier composite film (base film layer and thermosetting gas barrier polyurethane resin) using a thermosetting oxygen barrier polyurethane resin, which is characterized by being 7% by mass or more based on the total amount of B). Has a layer containing) is described.

Furthermore, Patent Document 2 describes a transparent coating film having a thin film layer of silicon oxide or aluminum oxide formed on at least one surface of a polymer film base material, and a heat-sealing resin film. A barrier laminate characterized by being bonded by a dry laminating 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 Packaging materials using this are described.

However, in Patent Document 1, since the composition must use a solvent having high polarity, the workability is poor. For example, when a highly soluble solvent such as acetone is used, it has a low boiling point and easily takes in water from the outside air, so that there is a problem that the adjusted viscosity tends to increase due to the reaction between water and isocyanate.

Further, in Patent Document 2, since the inorganic compound contained in the adhesive has a nano-order spherical or amorphous inorganic compound, the adhesive itself has an oxygen barrier property, particularly a load of bending. There is a problem that the oxygen barrier property of the case is not high.

Patent No. 4054972 Japanese Patent No. 3829526

The present invention solves the above-mentioned problems, and provides a laminated body having a small total number of constituent layers, excellent workability during production of the laminated body, excellent gas barrier property and bending resistance, and a packaging material composed of the laminated body. The purpose is to provide pillow packaging bags.

As a result of various studies, the present inventor has provided at least a base material layer (A), a solvent-free gas barrier organic adhesive layer (B), a gas barrier inorganic vapor-deposited layer (C), and a sealant layer (D). The gas barrier inorganic vapor-deposited 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 a two-component curing type solvent-free. A layer formed by applying an adhesive and being cured, and the solvent content of the solvent-free gas barrier organic adhesive layer (B) is zero or 6 mg / m ² or less. A gas barrier packaging material composed of a gas barrier laminate having a coating film layer (E) and / or a printing layer (F), and the gas barrier laminate, the gas barrier inorganic vapor deposition layer (C) is bonded to a two-component curable solvent-free adhesive. It has been found that the above object is achieved by forming the adhesive in contact with the solvent-free gas barrier organic adhesive layer (B) using an agent.

The present invention is characterized by the following points.
1. 1. A gas barrier laminate having at least a base material layer (A), a solvent-free gas barrier organic adhesive layer (B), a gas barrier inorganic vapor deposition layer (C), and a sealant layer (D), which is a gas barrier inorganic vapor deposition. The layer (C) and the solvent-free gas barrier organic adhesive layer (B) are laminated adjacent to each other, and the solvent-free gas barrier organic adhesive layer (B) is coated with a two-component curable solvent-free adhesive. A gas barrier laminate having a solvent-free gas barrier organic adhesive layer (B) having a solvent content of zero or 6 mg / m ² or less, which is a layer formed by further curing.
2. Further, it is a gas barrier laminate having a gas barrier coating film layer (E) between the base material layer (A) and the solvent-free gas barrier organic adhesive layer (B), and the gas barrier coating film layer (E) is The gas barrier laminate according to 1 above, which contains a sol-gel hydrolyzed polycondensate of a mixture of a metal alkoxide and a water-soluble polymer.
3. 3. The gas barrier laminate according to 1 or 2 above, further comprising a printing layer (F) between the base material layer (A) and the solvent-free gas barrier organic adhesive layer (B).
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, according to any one of 1 to 3 above. Gas barrier laminate.
5. The gas barrier laminate according to any one of 1 to 3 above, wherein the gas barrier inorganic vapor deposition layer (C) is a layer having an aluminum vapor deposition layer.
6. The gas barrier laminate according to any one of 1 to 5 above, wherein the thickness of the gas barrier inorganic vapor deposition layer (C) is 1 to 100 nm.
7. The gas barrier laminate according to any one of 1 to 6 above, wherein the solvent-free gas barrier organic adhesive layer (B) has a thickness of 0.5 to 6.0 μm.
Oxygen permeability in 8.23 ° C. 90% RH environment is 0.05 to 2.0 cc / m ² / da
1 to 7 above for oxygen barrier and water vapor barrier, which is y / atm and has a water vapor transmission rate of 0.01 to 2.0 g / m ^{2 / day / atm in a 40 ° C. 90% RH environment.} The gas barrier laminate according to any one.
9. After applying the bending load 5 times with the Gelboflex tester, the increase value of oxygen permeability under the environment of 23 ° C. and 90% RH from before applying the bending load is zero or 20.0 cc / m ² /. The gas barrier laminate according to any one of 1 to 8 above, which is day / atm or less.
10. The gas barrier laminate according to any one of 1 to 9 above, wherein the total number of constituent layers is 6 or less.
11. A gas barrier packaging material using the gas barrier laminate according to any one of 1 to 10 above. 12. A pillow packaging bag using the gas barrier laminate according to any one of 1 to 10 above.

The gas barrier laminate of the present invention and the gas barrier packaging material composed of the gas barrier laminate include at least a base material layer (A), a solvent-free gas barrier organic adhesive layer (B), a gas barrier inorganic vapor-deposited layer (C), and a sealant layer. The gas barrier inorganic vapor-deposited layer (C) and the solvent-free gas barrier organic adhesive layer (B) are in contact with each other, and the solvent-free gas barrier organic adhesive layer (B) is 2 A gas barrier laminate in which a liquid-curable solvent-free adhesive is applied and cured to form a layer, and the solvent content of the solvent-free gas barrier organic adhesive layer (B) is zero or 6 mg / m ^{2 or less.} Alternatively, it further has a gas barrier coating film layer (E) and / or a printing layer (F), and the gas barrier inorganic vapor-deposited layer (C) and the solvent-free gas barrier organic adhesive layer (B) are adjacent to each other. By combining these, the uneven recesses formed on the surface of the gas barrier inorganic vapor-deposited layer (C) are filled with the solvent-free gas barrier organic adhesive layer (B) and flattened to make the gas barrier property in the plane direction uniform. , Gas barrier It is possible to exhibit high gas barrier properties that could not be achieved in the past, while maintaining bending resistance by reducing the layer thickness of the inorganic vapor-deposited layer. Further, since the solvent-free gas barrier organic adhesive layer (B) is solvent-free and the solvent content is zero or 6 mg / m ² or less, the gas barrier property is further improved and the solvent odor is transferred to the contents. Can be expressed.

It is the schematic sectional drawing which shows an example about the layer structure of the gas barrier laminated body of this invention. It is the schematic sectional drawing which shows another example about the layer structure of the gas barrier laminated body of this invention. It is a schematic cross-sectional view which shows still another example about the layer structure of the gas barrier laminated body of this invention.

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

In the present invention, the total number of constituent layers is a detailed number of layers such as a base material layer, a gas barrier layer, an adhesive layer, and a sealant layer constituting the laminate, and the vapor deposition layer, AC coat, etc. in each layer are used. It is the number of layers including the specially treated coat layer. For example, the PET film layer with an aluminum vapor deposition layer is counted as two layers.

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

As shown in FIG. 1, the gas barrier laminate of the present invention includes a base material layer (A), a solvent-free gas barrier organic adhesive layer (B), a gas barrier inorganic vapor deposition layer (C), and a sealant layer (D). The basic structure is a structure in which and is laminated.

As another aspect of the gas barrier laminate of the present invention, as shown in FIG. 2, a gas barrier inorganic vapor deposition layer (a gas barrier inorganic vapor deposition layer) is further formed between the base material layer (A) and the solvent-free gas barrier organic adhesive layer (B). A gas barrier inorganic vapor deposition layer separate from C) and a gas barrier coating film layer (E) may be laminated.

As still another aspect of the laminate of the present invention, as shown in FIG. 3, the print layer (F) is laminated between the base material layer (A) and the solvent-free gas barrier organic adhesive layer (B). It may have the same configuration.

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

Next, the material of the gas barrier laminate of the present invention, a method for producing the same, and the like will be described.
As the resin name used in the present invention, the one commonly used in the industry shall be used. Further, the present invention is not limited to the various specific examples listed below.

[Base material layer (A)]
The base material layer (A) is a metal that is excellent in chemical or physical strength, can withstand the conditions for forming an inorganic vapor-deposited film, and can be satisfactorily retained without impairing the characteristics of the inorganic-deposited film. Inorganic materials such as metal oxides and organic materials such as resins can be used, for example, as films and sheets.

As the base material layer (A), a single-layer film or a multilayer laminated film is used, but is not particularly limited, and any film used for various packaging materials can be used. From these, a suitable one is freely selected and used according to the usage conditions such as the type of contents to be packaged and the presence or absence of heat treatment after filling.

Specific examples of the film preferably used as the base material layer (A) include paper, aluminum foil, cellophane, polyamide resin film, polyester resin film, olefin resin film, acid-modified polyolefin resin film, and polystyrene resin. Films, polyurethane-based resin films, acetal-based 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 copolymer, acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), vinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), Resin film composed of polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, etc., K-coated stretched polypropylene film, K-coated stretched nylon film, composite film in which two or more of these films are laminated. And so on.

Among them, uniaxially or biaxially stretched polyester films such as polyethylene terephthalate and polyethylene naphthalate, uniaxially or biaxially stretched polyamide films such as nylon 6, nylon 66 and MXD6 (polymethoxylylen adipamide), and
A biaxially stretched polypropylene film (OPP) or the like can be preferably used. Further, transparent vapor-deposited PET such as silica-deposited PET and alumina-deposited PET, aluminum-deposited biaxially stretched polypropylene film (OPP) and the like are also suitable.

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

(surface treatment)
Further, the film or sheet constituting the base material layer (A) and the base material layer (A) may be an adhesive layer such as a solvent-free gas barrier organic adhesive layer (B) or a gas barrier inorganic vapor deposition layer (C). In order to improve the adhesion to each inorganic vapor deposition layer, the surface of the base material layer (A) and the film or sheet constituting the base material layer (A) to be adhered to the base material layer (A) and the surface to be adhered to the base material layer (A) before laminating or vapor deposition, if necessary, in advance. , 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-deposited anchor coating agent layer, or other treatments, and other treatments may be performed. A barrier coat layer such as the gas barrier coating film layer (E) described later may be provided.

(Film molding method)
As the resin film or sheet used for the base material layer (A), for example, one kind or two or more kinds of resins selected from the above-mentioned resin group are used, and an extrusion method, a cast molding method, a T-die method, and cutting are used. It can be produced by a conventionally used film-forming method such as a method or an inflation method, or by a multi-layer coextrusion film-forming method using two or more kinds of resins. Further, from the viewpoint of film strength, dimensional stability, and heat resistance, the film can be stretched in the uniaxial or biaxial directions by using, for example, a tenter method or a tubular method.

(Additive)
The resin film or sheet used for the base material layer (A) has workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant property, slipperiness, releasability, and flame retardancy, if necessary. Lubricants, cross-linking agents, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, etc. for the purpose of improving and modifying properties, antifungal properties, electrical properties, strength, etc. The plastic compounding agent, the additive, and the like can be added, and the amount of the addition can be arbitrarily added as long as it does not adversely affect other performance.

[Solvent-free gas barrier organic adhesive layer (B)]
The solvent-free gas barrier organic adhesive layer (B) in the gas barrier laminate of the present invention is formed without solvent and has gas barrier properties, particularly oxygen and water vapor barrier properties.
The solvent content in the solvent-free 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) needs to be a two-component curable solvent-free adhesive. The two-component curable solvent-free adhesive is used after being heated to reduce its viscosity while remaining solvent-free at the time of laminating.

When a highly polar solvent is used for the curable isocyanate resin composition, workability is poor. When a highly soluble solvent such as acetone is used, the boiling point is low and water from the outside air is taken in. Therefore, there arises a problem that the viscosity of the curable isocyanate resin composition tends to increase due to the reaction between water and isocyanate.

Further, if the solvent-free gas barrier organic adhesive layer (B) contains a large amount of solvent, there is a concern that the solvent may weaken the adhesion between the layers of the laminate, and further, the obtained laminate was used. In a package made of a packaging material, there is a concern that the solvent odor may be transferred to the contents. Furthermore, due to volume shrinkage during drying, the solvent-free gas barrier organic adhesive layer (B) embedded in the concave-convex recesses on the surface of the gas barrier inorganic vapor deposition layer (C) is peeled off, causing defects. As a result, the gas barrier property is likely to be deteriorated, and even when the laminated body is bent, the peeling from the recess is large, which tends to lead to deterioration of the gas barrier property.

The thickness of the solvent-free gas barrier organic adhesive layer (B) is 0.5 to 6.0 μm, preferably 0.8 to 5.0 μm, and more preferably 1.0 to 4.5 μm. If it is thinner than the above range, the gas barrier property tends 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 property after bending.

(Two-component curable solvent-free adhesive)
The two-component curable solvent-free adhesive that forms the gas barrier organic adhesive layer (B) is, for example, a polyol (J) having two or more hydroxyl groups in one molecule and two or more isocyanate groups in one molecule. Examples thereof include a two-component curable solvent-free adhesive containing an isocyanate compound (K) having 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 portion in the polyester structure or the polyester polyurethane structure. ~ 100% by mass is derived from ortho-oriented aromatic dicarboxylic acids.

The polyvalent carboxylic acid refers to a polyvalent carboxylic acid and its anhydride or ester-forming derivative, and the ortho-oriented aromatic dicarboxylic acid refers to an ortho-oriented aromatic dicarboxylic acid and its anhydride or ester-forming derivative. ..

Further, the two-component curable solvent-free 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. It may contain one or more of the group consisting of a polyvalent carboxylic acid-modified polyester polyol (N) having a carboxyl group of the above and two or more hydroxyl groups.

In particular, a two-component curable type containing a polyvalent carboxylic acid-modified polyester polyol (N) and an isocyanate compound (K) having two or more isocyanate groups in one molecule and having 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 curable solvent-free adhesive is preferably in the range of −30 ° C. to 80 ° C., more preferably 0 ° C. to 70 ° C., and even more preferably 25 ° C. to 70 ° C. When the glass transition temperature is higher than 80 ° C., the flexibility of the cured coating film near room temperature is lowered, so that the adhesion to the substrate is deteriorated and the adhesive strength may be lowered.

On the other hand, if the temperature is lower than -30 ° C, there is a risk that sufficient oxygen barrier properties will not be obtained due to the vigorous molecular motion of the cured coating film near room temperature, and there is a risk that the adhesive strength will be reduced due to insufficient cohesive force.

A specific example of the curable isocyanate resin composition for an adhesive layer having an oxygen barrier property, which is a type containing a solvent, is the oxygen barrier adhesive PASLIM sold by DIC Corporation. Series, PASLIM VM001 / VM102C
P and the like can be mentioned.

(Polyprethane (J))
The 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 portion in the polyester structure or the polyester polyurethane structure. ~ 100% by mass is derived from ortho-oriented aromatic dicarboxylic acids.

Here, the polyester portion of the main skeleton structure is obtained by polycondensing a polyvalent carboxylic acid and a polyhydric alcohol by a known and commonly used method.
Examples of polyvalent carboxylic acids include aliphatic polyvalent carboxylic acids and aromatic polyvalent carboxylic acids.
Specific examples of aliphatic polyvalent carboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

Specific aromatic polyvalent carboxylic 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 can be mentioned. ..

Specific ortho-oriented aromatic dicarboxylic acids include orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and the anhydride or ester-forming property of these dicarboxylic acids. Examples include derivatives.
As the polyvalent carboxylic acids, these can be used alone or in combination of two or more.
Examples of the polyhydric alcohol include an aliphatic polyhydric alcohol and an aromatic polyhydric phenol.

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

Specific examples of the aromatic polyhydric phenol include hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, ethylene oxide extenders thereof, and hydrogenated alicyclic group. Etc. can be exemplified.

(Isocyanate compound (K))
The isocyanate compound (K) has two or more isocyanate groups in the molecule and may be either aromatic or aliphatic, may be either a low molecular weight compound or a high molecular weight compound, and may be a diisocyanate compound having two isocyanate groups. Known compounds such as three or more polyisocyanate compounds can be used. The isocyanate compound (K) may be a blocked isocyanate compound obtained by subjecting it to an 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 preferable from the viewpoint of imparting oxygen barrier properties, and in particular, isocyanate compounds containing a metaxylene skeleton are urethane-based. It is preferable because the oxygen barrier property can be improved not only by hydrogen bonding but also by π-π stacking between aromatic rings.

Specific examples of the isocyanate compound (K) include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydride diphenylmethane diisocyanate, metaxylylene diisocyanate, hydride xylylene diisocyanate, isophorone diisocyanate, or these. Trimer 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, metaxylylene diamine and other low molecular weight active hydrogen compounds and their alkylene oxide adducts, various polyester resins, polyether polyols, polyamides Examples thereof include an adduct-form, a burette-form, and an allophanate-form obtained by reacting with a high-molecular-weight active hydrogen compound of the above.

(Phosphate-modified compound (L))
The phosphoric acid-modified compound (L) has an effect of improving the adhesive strength to the inorganic member, and known and commonly used compounds can be used.

Specifically, phosphate, pyrophosphate, triphosphate, 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 and the like can be mentioned, and one or more of these can be used.

(Multivalent carboxylic acid-modified polyester polyol (N))
The 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 the polyester polyol having three or more hydroxyl groups in one molecule. It is obtained by reacting a polyvalent carboxylic acid with a moiety.

(Plate-shaped inorganic compound (M))
The plate-like inorganic compound (M) has an effect of improving the lamination strength and oxygen barrier property of the solvent-free gas barrier organic adhesive layer (B).
Specific examples of the plate-like inorganic compound (M) include kaolinite-serpentine clay minerals (haloysite, kaolinite, enderite, deckite, nacrite, etc., antigolite, chrysotile, etc.), pyrophyllite-talc. (Pyrophyllite, talc, kaolin, etc.) and the like, and one or more of these can be used.

[Gas barrier inorganic vapor deposition layer (C)]
The gas barrier inorganic vapor deposition layer (C) is a barrier membrane having a gas barrier property that prevents permeation of oxygen gas, water vapor, and the like, and examples thereof include a vapor deposition film made of an inorganic substance or an inorganic oxide.
Generally, the surface of the inorganic thin-film vapor deposition layer has ultrafine irregularities, and at the ultrafine level, the thickness of the inorganic thin-film deposition layer is not uniform, and the thin portion has a weak gas barrier property in the surface direction.

However, 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, so that the super structure is formed on the surface of the gas barrier inorganic vapor deposition layer (C). By having a structure in which fine uneven recesses are filled with a solvent-type gas barrier organic adhesive layer (B) having a gas barrier property and flattened, the gas barrier property in the plane direction is made uniform, and the gas barrier inorganic vapor deposition layer (C). ) Can be thinned to maintain bending resistance while exhibiting higher gas barrier properties than 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 preferable.

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

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

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

In the case of a silicon oxide or alumina vapor-deposited film, it 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 vapor deposition layer (C) can be formed by a conventionally known method using a conventionally known inorganic substance or an inorganic oxide, and the composition and the forming method thereof are not particularly limited.

Examples of the forming method include a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, a thermochemical vapor deposition method, and the like. And a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a photochemical vapor deposition method can be mentioned.

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

At that time, the surface of the sealant layer (D) can be pretreated as needed. Specifically, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow, etc. Physical treatment such as electric discharge treatment or chemical treatment such as oxidation treatment using chemicals or the like may be performed.

In the gas barrier laminate of the present invention, in order to further enhance the gas barrier property against oxygen gas, water vapor, etc., a gas barrier inorganic vapor deposition layer similar to the gas barrier inorganic vapor deposition layer (C) is used as a solvent-free gas barrier of the base material layer (A). It can also be provided on the side in contact with the organic adhesive layer (B). The pretreatment, the vapor deposition type, the vapor deposition film forming method, and the like are the same as those of the gas barrier inorganic vapor deposition layer (C).

[Sealant layer (D) (heat seal layer)]
The sealant layer (D) imparts heat-sealability to the gas barrier laminate of the present invention and the packaging material composed of the gas barrier laminate, and further imparts functions such as bending resistance and impact resistance. In particular, it is desirable that the bending resistance is imparted so that the deterioration of the gas barrier property after bending can be suppressed.

In the present invention, any material satisfying the above conditions can be used.
In the present invention, it is desirable that the sealant layer (D) has a heat-sealing resin layer. The heat-sealing resin layer may be one that can be melted by heat and fused to each other.
Suitable resins for the sealant layer (D) include polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, and the like. Polyolefin resins such as ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene are used as acrylic acid, methacrylic acid and anhydrous. Polyolefin resins modified with unsaturated carboxylic acids such as maleic acid, fumaric acid and others, ternary copolymer resin of ethylene- (meth) acrylic acid ester-unsaturated carboxylic acid, cyclic polyolefin resin, cyclic olefin copolymer, polyethylene terephthalate A resin film or sheet composed of one or more of resins such as (PET), polyacrylonitrile (PAN), and others, or other coating films and the like can be used.

As the film or sheet forming the resin layer, any unstretched film or sheet, or a stretched film or sheet stretched in the uniaxial or biaxial direction can be used.

The stretched film stretched in the biaxial direction is vertically stretched 2 to 4 times by, for example, a roll stretching machine at 50 to 100 ° C., and further laterally stretched 3 to 5 times by a tenter stretching machine in an atmosphere of 90 to 150 ° C. Subsequently, it can be obtained by heat treatment with the same tenter in an atmosphere of 100 to 240 ° C. Further, the stretched film may be simultaneously biaxially stretched or sequentially biaxially stretched.

As the layer structure of the sealant layer (D), a polyethylene / polypropylene + polyethylene / polypropylene multilayer film is suitable. Further, a film obtained by vapor-depositing an aluminum film on unstretched polypropylene (CPP) capable of heat-sealing, low-density polyethylene, or linear low-density polyethylene can also be used.

If necessary, a known bending resistance improving agent, an inorganic or organic additive, or the like can be added to the above resin.

(Film thickness of sealant layer (D))
The thickness of the sealant layer (D) can be arbitrarily selected, but from the viewpoint of strength as a packaging material and the like, it can be selected and used in the range of about 5 to 500 μm, preferably 10 to 250 μm, and further. It is preferably in the range of 15 to 100 μm. If it is thinner than this, sufficient laminating strength cannot be obtained even if it is heat-sealed, it does not function as a packaging material, and piercing resistance and the like are impaired. On the other hand, if it is thicker than this, the cost will increase and the film will become hard and workability will deteriorate.

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

The gas barrier coating film layer (E) is a hydrolyzate of a metal alkoxide 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 method catalyst, water, an organic solvent, or the like. Alternatively, it is preferably a layer formed from a resin composition such as a hydrolyzed condensate of a metal alkoxide.

As the metal alkoxide, one kind or two or more kinds represented by the following general formula can be preferably used.
R ¹ _n M (OR ² ) _m
(However, 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 or the like can be used. Specific examples of the organic group represented by R ¹ and R ² include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and an i-butyl group. Can be mentioned. Within the same molecule, these alkyl groups may be the same or different.

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 has a functional group that binds to organic substances. Examples include silane coupling agents.

The metal alkoxide may be used alone or in admixture 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 preferable, and for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, or the like can be used.

The above-mentioned silane coupling agent may be used alone or in admixture of two or more. In the present invention, the above-mentioned silane coupling agent can be contained in the range of about 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the above-mentioned alkoxide.

As the water-soluble polymer, either or both of a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer can be preferably used. Commercially available resins may be used. For example, as the ethylene / vinyl alcohol copolymer, Kuraray Co., Ltd., EVAL EP-F101 (ethylene content; 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soanol D2908 (ethylene content; 29 mol%) or the like can be used.

As polyvinyl alcohol-based resins, RS-110 (Kuraray Co., Ltd.'s RS polymer, RS-110 (degree of polymerization = 99%, degree of polymerization = 1,000)) and Kuraray Poval LM-20SO (degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd. 40%, degree of polymerization = 2,000), Gosenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, degree of polymerization = 1,400) 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 it is less than 5 parts by mass, the film forming property of the gas barrier coating film layer (E) is inferior and the brittleness tends to increase, and the weather resistance and the like tend to decrease. If it exceeds 500 parts by mass, the effect of improving the gas barrier property becomes low. It becomes a tendency.

As the sol-gel method 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 preferable. Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used. In particular, N, N-dimethylbenzylamine is preferable, and it is preferable to contain, for example, 0.01 to 1.0 parts by mass, particularly 0.03 to 0.3 parts by mass, per 100 parts by mass of the metal alkoxide. If it is less than 0.01 part by mass, the catalytic effect is too small, and if it is more than 1.0 part by mass, the catalytic effect is too strong and the reaction rate becomes too fast, which tends to cause non-uniformity.

As the acid, for example, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid can be used. The acid content is preferably 0.001 to 0.05 mol, more preferably 0.01 to 0.03 mol, based on the total molar amount of the alkoxy group of 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, the catalytic effect is too strong and the reaction rate becomes too fast, which tends to cause non-uniformity.

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

In the gas barrier coating film layer (E), a coating liquid made of the resin composition is usually used for roll coating such as gravure roll coater, spray coating, spin coating, dipping, brush, bar code, applicator and the like. It is formed by applying once or multiple times by a known means.

A specific example of the method for forming the gas barrier coating film layer (E) will be described below.
First, a coating liquid composed of a resin composition is prepared by mixing a metal alkoxide, a water-soluble polymer, a sol-gel method catalyst, water, an organic solvent, and if necessary, a silane coupling agent and the like. The polycondensation reaction gradually proceeds in the coating liquid.

Next, the coating liquid is applied by a conventional method onto the gas barrier inorganic vapor deposition layer laminated on the base material layer (A) and dried. Upon drying, polycondensation of the alkoxide and the vinyl alcohol polymer (and the silane coupling agent) further proceeds to form a layer of the composite polymer. Preferably, the above operation can be repeated to laminate a plurality of 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. As a result, the gas barrier coating film layer (E) can be formed on the gas barrier inorganic vapor 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 property is too small, and if it is larger than 100 μm, cracks are likely to occur.

[Print layer (F)]
If necessary, the gas barrier laminate of the present invention is, for example, between the base material layer (A) and the solvent-free gas barrier organic adhesive layer (B), particularly, for example, FIG. As shown in the above, letters, figures, symbols, and other desired patterns are arbitrarily formed between the gas barrier coating film layer (E) and the solvent-free gas barrier organic adhesive layer (B) by a normal printing method. The printed layer (F) can be provided.
[Laminated body and packaging material composed of the laminated body]
The conventional easy-to-open gas barrier laminate has a total number of constituent layers of about 8 including the AC coat and the metal vapor deposition layer, which makes the manufacturing process long and complicated. However, the easy-to-open gas barrier laminate of the present invention has been complicated. The total number of constituent layers of the sex gas barrier laminate can be reduced as compared with the conventional one, and the total number of layers can be 6 or less.

It is also possible to have a configuration of 7 or more layers, and it is possible to exhibit gas barrier properties of equal or higher levels with a relatively smaller total number of constituent layers than the conventional material. In addition, since the total number of constituent layers is small and the inorganic vapor deposition layer can be made thin, the process can be shortened and simplified, the laminated body can be made thin, the flexibility of the laminated body is improved, and the bending resistance is improved. Is improved.

As shown in FIG. 1, the laminate of the present invention and the packaging material composed of the laminate have a base material layer (A) and a gas barrier inorganic vapor deposition layer (C) provided on one side of the sealant layer (D). Further, as shown in FIG. 2, the gas barrier coating film layer (E) surface and the sealant layer (D) of the base material layer (A) provided with the gas barrier inorganic vapor deposition layer and the gas barrier coating film layer (E) on one surface. The printed layer (F) surface of the base material layer (A) provided with the gas barrier inorganic vapor deposition layer (C) provided on one side and the printed layer (F) as needed, as shown in FIG. And the gas barrier inorganic vapor deposition layer (C) surface provided on one side of the sealant layer (D) can be laminated via the solvent-free gas barrier organic adhesive layer (B) described above, respectively.

The gas barrier laminate of the present invention and the packaging material composed of the laminate have excellent gas barrier properties, and preferably have an oxygen permeability of 0.05 to 2.0 cc / m ² / under a 90% RH environment at 23 ° C.
It is day / atm, and the water vapor transmission rate in a 40 ° C. 90% RH environment is 0.01 to 2.0 g / m ² / day / atm.

Furthermore, in general, when a packaging bag is made by bending, heating, and crimping using a packaging material and the contents are filled with a vertical pillow, the packaging bag is physically loaded by heat, friction, pressure, or the like. Although the gas barrier property of the packaging bag is reduced due to exposure to, the packaging bag produced by using the gas barrier packaging material of the present invention has less deterioration in gas barrier property, preferably 5 times with a gelboflex tester. The increase value of the oxygen permeability in the environment of 23 ° C. and 90% RH after the bending load is applied is zero or 20.0 cc / m ² / day / atm or less from before the bending load is applied.

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

[Preparation of two-component curable solvent-free adhesive A]
The following raw materials are put into a polyester reaction vessel equipped with a rectification tube and a water separator and gradually heated to carry out an esterification reaction in a nitrogen atmosphere while maintaining a liquid temperature of 220 ° C and a steam temperature of 100 ° C. The esterification reaction was terminated when the acid value of the reaction solution became 1 mgKOH / g or less, and the solution 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 were added to the reaction solution, and the polyvalent carboxylic acid modification reaction was carried out while maintaining the solution temperature at 120 ° C., and the acid value became approximately half of the acid value calculated from the amount of maleic anhydride charged. The esterification reaction was terminated at this point, 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,
Hydroxy group value: 216.6 mgKOH / g,
Acid value: 96.2 mgKOH / g
Number of hydroxyl groups per molecule: 2 (design value)
Number of carboxyl groups per molecule: 1 (design value)

Next, as isocyanate compounds, "Death Module 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 (methaxylylene diisocyanate. 1). Using (number of isocyanate groups per molecule: 2), the polyvalent carboxylic acid-modified polyester polyol A obtained above is heated to 80 ° C. at the following compounding ratio to be uniformly mixed, cooled, and cured in two liquids. A mold-free adhesive A was obtained.
Polycarboxylic acid-modified polyester polyol A 100 parts by mass Death module N3200 49.5 parts by mass Takenate 500 28.9 parts by mass

[Example 1]
A 20 μm OPP (biaxially stretched polypropylene) film (P-2171 manufactured by Toyobo Co., Ltd.) treated with a single-sided corona as a base material layer and a single-sided aluminum vapor deposition treatment as a sealant layer (40 nm thickness). The aluminum-deposited surface of the 25 μm CPP (unstretched polypropylene) film (manufactured by Toray Film Processing Co., Ltd., 2703) was non-solvent laminated via a two-component curable solvent-free adhesive A.

The amount of the adhesive applied at this time was such that the thickness of the adhesive layer after curing was 3 μm. After laminating, it was aged at 40 ° C. for 1 day to obtain a laminated body. The gas barrier property, laminate strength, and solvent content of the obtained laminate were evaluated. The results are shown in Table 1.

Layer structure: OPP (20 μm) / solvent-free gas barrier organic adhesive (3 μm) / aluminum vapor deposition (40 nm) / CPP (25 μm)

[Example 2]
As a sealant layer, instead of a 25 μm-thick CPP that has been subjected to single-sided aluminum vapor deposition, a 25 μm-thick CPP (P1128 manufactured by Toyobo Co., Ltd., which has been subjected to single-sided corona treatment) is subjected to single-sided alumina vapor deposition (20 nm thickness). A laminate was obtained in the same manner as in Example 1 except that it was used, and evaluated in the same manner. The conditions for single-sided alumina vapor deposition are as follows.

Layer structure: OPP (20 μm) / solvent-free gas barrier organic adhesive (3 μm) / alumina vapor deposition (20 nm) / CPP (25 μm)
<Evaporation conditions>
Deposited surface: Corona treated surface Vacuum chamber-Vacuum degree; 2-6 x 10 ^{-6 mBar}
Vacuum degree in vapor deposition chamber: 2-5 x 10 ^-3 mBar
Cooling / electrode drum supply power: 10kW
Line speed: 100m / min
Next, immediately after forming the alumina vapor-deposited film having a thickness of 200 Å (20 nm) above, a glow discharge plasma generator was used on the alumina vapor-deposited film surface, and the power was 9 kW, oxygen gas: argon gas = 7. Using a mixed gas consisting of 0: 2.5 (unit: s1 m) ^{, 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 alumina vapor-deposited film surface to 54 dyne /. A plasma-treated surface improved by cm or more was formed.

[Example 3]
As a sealant layer, instead of a 25 μm-thick CPP that has been thin-filmed with aluminum on one side, a CPP with a thickness of 25 μm (P1128 manufactured by Toyobo Co., Ltd., which has been corona-treated on one side) is subjected to silicon oxide vapor deposition (20 nm thickness) on one side. In the same manner as in Example 1, a laminated body was obtained and evaluated in the same manner. The conditions for single-sided silicon oxide vapor deposition are as follows.

Layer structure: OPP (20 μm) / solvent-free gas barrier organic adhesive (3 μm) / silicon oxide vapor deposition (20 nm) / CPP (25 μm)
<Evaporation conditions>
Deposited surface: Corona treated surface Introduced gas: Hexamethyldisiloxane / Oxygen gas / Helium = 1.0 / 3.0 / 3.0 (Unit: s1m)
Vacuum chamber-Vacuum degree in the chamber; 2-6 x 10 ^-6 mBar
Vacuum degree in vapor deposition chamber: 2-5 x 10 ^-3 mBar
Cooling / electrode drum supply power: 10kW
Line speed: 100m / min

Next, immediately after forming the vapor-deposited film of silicon oxide having a thickness of 200 Å (20 nm) above, a glow discharge plasma generator was used on the vapor-deposited film surface of the silicon oxide, and the power was 9 kW, oxygen gas: argon gas =. Using a mixed gas consisting of 7.0: 2.5 (unit: s1 m) ^{, oxygen / argon mixed gas plasma treatment was performed at a mixed gas pressure of 6 × 10 -3} Torr, and the surface tension of the vapor-deposited film surface of silicon oxide was performed. Was improved by 54 dyne / cm or more to form a plasma-treated surface.

[Comparative Example 1]
The two-component curable solvent-free adhesive A is replaced with a two-component curable urethane adhesive (Toyo Morton Co., Ltd., Tomoflex TM-340 / Toyo Morton Co., Ltd. CAT-29) under aging conditions. The temperature was 25 ° C. for 1 day, and the same procedure as in Example 1 was carried out to obtain a laminate and evaluated in the same manner.

Layer structure: OPP (20 μm) / two-component curable urethane adhesive (3 μm) / aluminum vapor deposition (40 nm) / CPP (25 μm)

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

^{Further, the obtained Easy Peel CPP film is subjected to aluminum vapor deposition treatment under 5 × 10 -4} Torr by inducing and heating aluminum by a retractable vacuum vapor deposition machine to obtain a gas barrier inorganic vapor deposition layer (C). An Easy Peel CPP (unstretched polypropylene) film A having a thickness of 25 μm and having a single-sided aluminum vapor-deposited layer having a thickness of 40 nm was obtained.

AC coat (PICG Co., Ltd. P-1000, coating coat, after drying) on the corona treated surface of a 20 μm OPP (biaxially stretched polypropylene) film (manufactured by Toyobo Co., Ltd., P-2171) treated with single-sided corona. A 12 μm PET film (manufactured by Toyobo Co., Ltd., biaxially stretched PET film, E-5100, 12 μm thick,) which had a thickness of 3 g / m ^{2) and was subjected to single-sided aluminum vapor deposition treatment on the AC coated surface under the following vapor deposition conditions.} The aluminum-deposited surface of (single-sided corona-treated) was laminated by extrusion lamination via low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., LC600A). The thickness of polyethylene was adjusted to 7 μm.

Next, AC coating was applied to the non-deposited surface of the laminated aluminum-deposited PET, and the AC-coated surface and 25 μm Easy Peel CPP film A having easy-opening property were formed into low-density polyethylene (Japan Polyethylene Corporation). Manufactured by LC600A.), Extruded and laminated. The thickness of polyethylene was adjusted to 7 μm. After laminating, aging treatment was performed at 25 ° C. for 1 day to obtain a laminated body, which was evaluated in the same manner.

Layer structure: OPP (20 μm) / AC coat / PE (7 μm) / Aluminum vapor deposition (40 nm) / PET (12 μm) / AC coat / PE (7 μm) / CPP (25 μm)
<Evaporation conditions>
Deposited surface: Corona treated surface Vacuum chamber-Vacuum degree; 2-6 x 10 ^{-6 mBar}
Vacuum degree in vapor deposition chamber: 2-5 x 10 ^-3 mBar
Cooling / electrode drum supply power: 10kW
Line speed: 100m / min

Next, immediately after forming the aluminum vapor deposition film having a thickness of 400 Å (40 nm) above, a glow discharge plasma generator was used on the aluminum vapor deposition film surface, and the power was 9 kW, oxygen gas: argon gas = 7. Using a mixed gas consisting of 0: 2.5 (unit: s1 m) ^{, oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 6 × 10 -3} Torr, and the surface tension of the aluminum vapor-deposited film surface is 54 dyne /. A plasma-treated surface improved by cm or more was formed.

[Comparative Example 3]
The solvent-free gas barrier organic adhesive was replaced with the solvent-containing gas barrier organic adhesive described below in the same manner as in Example 1, and a laminate was obtained and evaluated in the same manner.

Layer structure: OPP (20 μm) / solvent-containing gas barrier organic adhesive (3 μm) / aluminum vapor deposition (40 nm) / CPP (25 μm)

(Preparation of solvent-containing gas barrier organic adhesive)
The following adhesive and solvent were mixed to prepare a solvent-containing gas barrier organic adhesive.

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

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

[Gas barrier property]
^{(1) Oxygen permeability Oxygen permeability (cc / m 2} / day / atm) under the conditions of 23 ° C. and 90% RH using OXTRAN2 / 20 manufactured by MOCON in the United States after cutting each laminate into A4 size. ) Was measured.
(2) Moisture vapor transmission rate Each laminate is cut into A4 size, and using PERMATRAN 3/31 manufactured by MOCON in the United States, water vapor transmission rate (g / m ² / day / atm) under the conditions of 40 ° C. and 90% RH. ) Was measured.
(3) After bending load After applying bending load 5 times with a gelboflex tester, oxygen permeability was measured by the same method and conditions as described above.
[Amount of solvent contained]
^{The total amount (mg / m 2} ) of toluene, ethyl acetate, IPA, methanol, and MEK in the film was measured by the DNP method. Passes were those with a total amount of zero or 6 mg / m ² or less.

[Result Summary]
Examples 1 to 3 having the solvent-free gas barrier organic adhesive layer (B) have the same lamination strength as Comparative Example 1 using the conventional two-component curable urethane adhesive, and are higher than Comparative Examples 2 and 3. It was better and the gas barrier property after bending was higher than that of Comparative Examples 1 and 2 and Comparative Example 3 using the solvent-containing gas barrier adhesive.

Claims (12)

A gas barrier laminate having at least a base material layer (A), a solvent-free gas barrier organic adhesive layer (B), a gas barrier inorganic vapor deposition layer (C), and a sealant layer (D).
The gas barrier inorganic vapor deposition layer (C) and the solvent-free gas barrier organic adhesive layer (B) are laminated adjacent to each other.
The solvent-free gas barrier organic adhesive layer (B) is a layer formed by applying a two-component curable solvent-free adhesive and further curing.
The solvent content of the solvent-free gas barrier organic adhesive layer (B) is zero or 6 mg / m ² or less.
Gas barrier laminate. Further, it is a gas barrier laminate having a gas barrier coating film layer (E) between the base material layer (A) and the solvent-free gas barrier organic adhesive layer (B), and the gas barrier coating film layer (E) is The gas barrier laminate according to claim 1, which contains a sol-gel hydrolyzed polycondensate of a mixture of a metal alkoxide and a water-soluble polymer. The gas barrier laminate according to claim 1 or 2, further comprising a printing layer (F) between the base material layer (A) and the solvent-free gas barrier organic adhesive layer (B). 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, any one of claims 1 to 3. The gas barrier laminate according to. The gas barrier laminate according to any one of claims 1 to 3, wherein the gas barrier inorganic vapor deposition layer (C) is a layer having an aluminum vapor deposition layer. The gas barrier laminate according to any one of claims 1 to 5, wherein the thickness of the gas barrier inorganic vapor deposition layer (C) is 1 to 100 nm. The gas barrier laminate according to any one of claims 1 to 6, wherein the solvent-free gas barrier organic adhesive layer (B) has a thickness of 0.5 to 6.0 μm. Oxygen permeability in a 90% RH environment at 23 ° C is 0.05 to 2.0 cc / m ² / day.
/ Atm, and the water vapor transmission rate in a 40 ° C. 90% RH environment is 0.01 to 2.0 g / m ² / day / atm.
The gas barrier laminate according to any one of claims 1 to 7, which is used for an oxygen barrier and a water vapor barrier. After applying a bending load 5 times with a gelboflex tester,
The increase in oxygen permeability under a 90% RH environment at 23 ° C. from before the bending load is applied is zero or 20.0 cc / m ² / day / atm or less.
The gas barrier laminate according to any one of claims 1 to 8. The gas barrier laminate according to any one of claims 1 to 9, wherein the total number of constituent layers is 6 or less. A gas barrier packaging material using the gas barrier laminate according to any one of claims 1 to 10. A pillow packaging bag using the gas barrier laminate according to any one of claims 1 to 10.

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