JP2000355075A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate enhanced in the close adhesiveness between the materials thereof, prevented from the ply separation (delamination) caused by the peneration of components in content and excellent in lamination strength. SOLUTION: A laminate A consists of at least a base material layer 1 and a heat sealable resin layer 2 and an adhesive layer 3 comprising an adhesive containing a polycarbodiimide resin having a carbodiimide group, a compd. having an active hydrogen group and a compd. having an isocyanate group is interposed between the base material layer 1 and the heat sealable resin layer 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate, and more particularly, to a laminate having excellent close-adhesion between layers and having extremely high laminating properties.
High strength, solid, liquid, powder, has the suitability of filling and packaging for various articles such as, for example, soft packaging bags,
The present invention relates to a laminate useful for producing packaging containers having various forms such as a laminating tube container, a paper container, and the like.

[0002]

2. Description of the Related Art Hitherto, in order to fill and package various articles such as food and drink, daily necessities, pharmaceuticals, industrial or chemical products, etc., laminates as packaging materials in various forms have been developed. ,Proposed. These laminates are usually made of various plastic films, paper substrates, aluminum foil or its vapor-deposited film, inorganic oxide-deposited film, etc. as a material, for example, contents to be filled and packed,
The distribution form, transaction form, storage and preservation form, the packaging material is designed in consideration of the conditions such as other, the material which met it from the above materials is selected, and they are combined, for example, It is manufactured by laminating by a dry laminating method or a melt extrusion laminating method or the like via a laminating adhesive or an adhesion aid. In the production of the laminate as described above, the laminating adhesive or the bonding aid used for bonding between the layers is usually, for example, a polyurethane-based, polyester-based or polyamide-based adhesive. , (Meth) acrylic, vinyl-based, polyolefin-based, etc., as a main component of the vehicle, a one-part or two-part curing type, or
Solvent-based or aqueous, solvent-free, solution-based or dispersion-based,
Various types of laminating adhesives in the form of a hot-melt type or the like, or adhesion aids such as an organic titanium type, an isocyanate (urethane) type, a polyethyleneimine type, a polybutadiene type, etc. are used. ing.

[0003]

However, in a laminate obtained by laminating using the above-mentioned adhesive for laminating or an adhesion auxiliary agent, the adhesive strength between each layer and the tight adhesion In fact, it is not something that can be fully satisfied. For example, in the case of using an adhesive for a polyurethane-based laminate comprising a polyester polyol, a polyether polyol, or a polyester urethane polyol and an isocyanate compound, the low content contained in the adhesive is used. There is a problem that delamination occurs due to a molecular weight volatile component and the laminate strength is inferior, and a decrease in adhesive strength due to hot water and the like also occur. In the case of using an isocyanate (urethane) adhesive aid,
There is a problem that it requires moisture and lacks stability in adhesion strength, close adhesion, and the like. Further, those using an adhesion aid such as an organic titanium-based, polyethyleneimine-based, or polybutadiene-based adhesive have the problems of poor water resistance and low adhesive strength. Therefore, the present invention improves the tight adhesion between the materials constituting the laminate, prevents the occurrence of delamination (delamination) or the like due to the penetration of components and the like contained in the contents, and provides excellent laminate strength. It is to provide a laminate.

[0004]

As a result of various studies to solve the above problems, the present inventor has found that at least a base film and a heat-sealing resin film are laminated to form a laminate. In producing, the substrate film and heat
Between the resin resin film and a polycarbodiimide resin having a carbodiimide group, a compound having an active hydrogen group, and an adhesive layer containing an adhesive having a compound having an isocyanate group. A laminated product was manufactured, and thus, the laminated product was used to produce a soft packaging bag, and a liquid product such as a detergent was filled and packaged in the soft packaging bag to produce a packaged product. , Base film and heat
Extremely high lamination strength between layers with the toseal resin film, for example, no phenomenon such as delamination due to penetration of components contained in the contents is observed, and extremely excellent contents resistance, etc. The present invention has been completed by finding that no leakage of contents and the like is observed, that the storage stability is excellent, and that a very good packaged product can be manufactured.

That is, the present invention comprises at least a base layer and a heat-sealing resin layer, and further comprises a carbodiimide group between the base layer and the heat-sealing resin layer. And a compound having an active hydrogen group and a compound having an isocyanate group and an adhesive layer containing an adhesive containing the compound having an isocyanate group.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned present invention will be described below in more detail with reference to the drawings and the like. First, FIGS. 1 and 2
FIG. 3 is a schematic cross-sectional view illustrating one example of the layer configuration of the laminate according to the present invention, and FIG. 3 is a diagram illustrating a packaging structure manufactured using the laminate according to the present invention shown in FIG. FIG. 4 is a schematic perspective view illustrating an example of the configuration of a container, and FIG. 4 is a schematic perspective view illustrating an example of the configuration of a packaged product in which contents are packed in the packaging container illustrated in FIG. FIG.

As shown in FIG. 1, a laminate A according to the present invention comprises at least a base material layer 1 and a heat-sealing resin layer 2.
And a polycarbodiimide resin having a carbodiimide group, a compound having an active hydrogen group, and an isocyanate group between the base material layer 1 and the heat-sealing resin layer 2. The basic structure is a structure in which an adhesive layer 3 made of an adhesive containing a compound is interposed. As another example of the laminate according to the present invention, as shown in FIG. 2, as shown in FIG. 2, the laminate comprises at least a substrate layer 1, an intermediate substrate layer 4, and a heat-sealing resin layer 2, A polycarbodiimide-based resin having a carbodiimide group and an active hydrogen group are provided between the base layer 1 and the intermediate base layer 4 or between the intermediate base layer 4 and the heat-sealing resin layer 2. compounds having, and isocyanate - can be exemplified a laminate a ₁ having the configuration in which the adhesive layer 3,3a interposed with an adhesive containing a compound having bets group. The above exemplifications illustrate one or two examples of the laminate according to the present invention, and the present invention is not limited thereto. For example, although not shown,
Depending on the packaging purpose and the like, further, a base material such as another plastic film can be arbitrarily laminated, and as an adhesive layer for bonding between the layers, the material constituting the laminate is used. It is not necessary to interpose an adhesive layer containing an adhesive containing a polycarbodiimide-based resin having a carbodiimide group, a compound having an active hydrogen group, and a compound having an isocyanate group between all the layers. Can be interposed at least between the innermost layer of the material in contact with the contents and the next material, and the other layers can be bonded by interposing an adhesive layer of another laminating adhesive. Good thing.

Next, in the present invention, as an example of a packaging container manufactured by using the above-described laminate, as shown in FIG. 3, the laminate shown in FIG. 1 is used. To explain by way of example, the pair of laminates A, A shown in FIG. 1 described above are overlapped with their heat-sealing resin layers 2 and 2 facing each other. Using a heating plate or a heating roll, heat-sealing is performed to form heat-sealing portions 11, 11, 11 and the laminate according to the present invention having an opening 12 at the upper end thereof. Can be used to produce a three-sided seal-type soft packaging bag B. Thus, in the present invention, as shown in FIG. 4, the opening 12 of the three-way seal type soft packaging bag B manufactured as described above.
Then, for example, the contents 13 such as a detergent are filled and packaged, and then the opening 12 is heat-sealed in the same manner as described above.
By forming the upper heat seal portion 14, a packaged product C using the three-sided seal type flexible packaging bag B using the laminate according to the present invention can be manufactured. The above examples illustrate one example of a packaging container manufactured using the laminate according to the present invention, and it is a matter of course that the present invention is not limited thereto. For example, although not shown, instead of using a pair of laminates as described above, one of the laminates is used, and
Half-fold and overlap with the sealable resin layer surface inside,
Thereafter, the two peripheral edges are heat-sealed to produce a two-way seal type soft packaging bag. Although not shown, the laminated body according to the present invention is used, for example, by changing the heat seal form and the like, for example, various forms such as a self-supporting bag, a gusset type bag, a laminating tube, and the like. Can be manufactured.

Next, in the present invention, the material constituting the laminate according to the present invention, the manufacturing method and the like will be described. First, as the material forming the base material layer constituting the laminate according to the present invention, Since it is a basic material constituting a laminate according to the present invention and a packaging container and the like using the same, a tough resin film or sheet having excellent properties in mechanical, physical, chemical, etc. -Can be used. Specifically, for example, polyester resin, polyamide resin, polyaramid resin, polyethylene resin, polypropylene resin, polystyrene resin, poly (meth) acrylic resin, polyvinyl chloride resin, polycarbonate Resin,
A tough resin film or sheet such as a styrene-acrylonitrile copolymer, a polyacetal resin, a fluorine resin, or the like can be used. Thus, as the resin film or sheet, any one of an unstretched film and a stretched film stretched in a uniaxial or biaxial direction can be used. Further, in the present invention, the thickness of the resin film or sheet may be any thickness that can be held to the minimum necessary for strength, rigidity, and the like. On the contrary, if it is too thin, the strength, rigidity, etc. decrease, which is not preferable. In the present invention, for the reasons described above, about 10 μm to 100 μm
The m position, preferably about 12 μm to 50 μm, is most desirable. Further, in the present invention, a desired printed pattern such as a character, a figure, a symbol, a picture, a pattern, etc. is printed on a front print or back print by a normal printing method on the resin film or sheet as described above. Printing or the like may be performed.

In the present invention, as a material for forming the above-mentioned base material layer, for example, various paper base materials constituting a paper layer can be used. The base material has moldability, bending resistance, rigidity, etc., for example, strong size bleached or unbleached paper base material, or pure white roll paper, kraft paper, paperboard, processed paper And other paper substrates, etc. can be used. In the above, the paper base constituting the paper layer has a basis weight of about 80
~ 600 g / m ² , preferably about 100 basis weight
It is desirable to use those of about 450 g / m ² .
Needless to say, in the present invention, a paper base constituting the paper layer and various resin films or sheets as the base films mentioned above can be used in combination.

Next, in the present invention, as a material for forming the heat-sealing resin layer constituting the laminate according to the present invention, any material can be used as long as it can be melted by heat and fused to each other. For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene- Acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer,
Polyolefin resins such as methylpentene polymer, acid-modified polyolefin resins obtained by modifying a polyolefin resin such as polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc., A resin film or sheet made of one or more other resins can be used. The resin film or sheet described above can be used in a single layer or a multilayer, and the resin film or sheet includes a barrier material against oxygen, water vapor and the like, for example, aluminum, A metal film such as silicon oxide or aluminum oxide, or a vapor-deposited film of an inorganic oxide or the like can be provided. The thickness of the resin film or sheet is preferably about 5 μm to 300 μm, and more preferably about 10 μm to 100 μm.

In the present invention, among the above resin films or sheets, it is particularly preferable to use linear low-density polyethylene. In other words, the linear low-density polyethylene has the advantage of improving the impact resistance with less propagation of breakage due to its tackiness, and also because the inner layer is in constant contact with the contents. It is also effective for preventing deterioration of environmental stress cracking resistance.
In the present invention, the linear low-density polyethylene,
Other resins can be blended, for example, by blending ethylene-butene copolymer or the like,
Although heat resistance is poor and seal stability tends to deteriorate in a high temperature environment, there is an advantage that tearability is improved and contributes to easy opening.

Furthermore, in the present invention, the above-described
Specific examples of the linear low-density polyethylene as a film or sheet of a resin having a sealing property include a film or sheet of an ethylene-α-olefin copolymer polymerized using a metallocene catalyst. Can be used. Ethylene polymerized using the above metallocene catalyst
As the α-olefin copolymer film or sheet, for example, a catalyst formed by a combination of a metallocene complex and an alumoxane such as a catalyst formed by a combination of zirconocene dichloride and methylalumoxane, that is, polymerized using a metallocene catalyst. An ethylene-α-olefin copolymer film or sheet can be used. The metallocene catalyst has a non-uniform active site and is called a multi-site catalyst, whereas the existing catalyst is called a single-site catalyst because the active site is uniform. To be more specific, the brand name “Kernel” manufactured by Mitsubishi Chemical Corporation, the brand name “Evolu” manufactured by Mitsui Petrochemical Industry Co., Ltd., Exxon Chemical (USA)
N Chemical Co., Ltd. product name "Exact (E
XACT) ", DOW CHEMICAL, USA
Product name “Affinity- (AFFI)
NITY), and a film of an ethylene-α-olefin copolymer polymerized using a metallocene catalyst such as “ENGAGE”. The film or sheet can be used in a single layer or a multilayer, and the thickness is 5 μm to 3 μm.
It is desirably about 00 μm, preferably about 10 μm to 100 μm. In the present invention, the heat seed as described above is used.
When a film or sheet of an ethylene-α-olefin copolymer polymerized by using a metallocene catalyst is used as the resin film having a property of being low-temperature, a low-temperature heat sheet is used when the bag is manufactured. This has the advantage that flexibility is possible.

Next, in the present invention, as an adhesive for forming an adhesive layer constituting the laminate according to the present invention, a polycarbodiimide resin having a carbodiimide group, a compound having an active hydrogen group, and an isocyanate A compound having a thiol group, and further, if necessary,
For example, fillers, stabilizers, plasticizers, antioxidants, light stabilizers such as ultraviolet absorbers, dispersants, thickeners, drying agents, lubricants,
An antistatic agent, a crosslinking agent, a solvent type optionally adjusted by adding and kneading thoroughly with a solvent such as toluene, ethyl acetate, methyl ethyl ketone, water and other diluents, and other additives, An aqueous adhesive or an emulsion adhesive can be used. Next, in the present invention, the adhesive prepared above is used, for example, a roll coat method, a gravure roll coat method, a kiss roll coat method, a squeeze roll coat method, By a coating method such as a reverse roll coating method, a curtain flow coating method, or the like, a coating amount, for example, 0.1 g / m ² to
About 10 g / m ² (dry state), preferably 0.5 g / m ²
m ^{2 to} 7 g / m ² (dry state), and then subjected to heat drying, aging treatment and the like to form an adhesive layer constituting the laminate according to the present invention. Can be formed.

In the above, the polycarbodiimide resin having a carbodiimide group is synthesized, for example, by a condensation reaction of an organic diisocyanate compound, which is a compound containing an isocyanate group, with the removal of carbon dioxide in the presence of a catalyst. Polymers having carbodiimide groups (-N = C = N-) can be used. The above polymer
May have an isocyanate group at the terminal. Thus, the carbodiimide group (-N = C
= N-) has an extremely high reactivity, easily forms a chemical bond with a functional group such as an active hydrogen group or the like, and can form an extremely strong adhesive layer.

In the above, examples of the compound having an active hydrogen group include a hydroxy group, an amino group,
A compound having a hydrogen atom bonded to oxygen, sulfur, nitrogen or the like such as a carboxyl group can be used. Specifically, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1.4-butanediol, 1.6-hexanediol, neopentyl glycol, trimethylol −
Diols such as lupropane and 3-methylpentaneddiol, polyethylene glycol, polyoxypropylene polyol, copolymers of ethylene oxide and propylene oxide, polyoxytetramethylene ether glycol
Polyether-based polyols, such as polyesters, polyadipate polyols, polycaprolactone diols, polycarbonates
Hydrocarbon-based polyols such as polyester-based polyols such as topolol, polybutadiene-polyol and polyacrylate-polyol, and polyurethane-based polyols
, Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and other aliphatic saturated dicarboxylic acids, maleic acid, fumaric acid and other aliphatic unsaturated carboxylic acids, phthalic acid, isophthalic acid, terephthalic acid, etc. Aromatic dicarboxylic acid, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1.8-diaminooctane, 1.9-
Aliphatic diamines such as diaminononane, 1.10-diaminodecane, aromatic amines such as o-phenylenediamine, m-phenylenediamine and p-phenylenediamine;
Others can be used.

Further, in the above, as the compound having an isocyanate group, for example, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, dicyclohexylmethane diisocyanate Aliphatic polyisocyanates such as hydrogenated xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine diisocyanate
And aromatic polyisocyanates such as naphthalene diisocyanate.

Next, in the present invention, a polycarbodiimide resin having a carbodiimide group, a compound having an active hydrogen group, an isocyanate, The compounding ratio of the compound having a group is such that the total equivalent of the carbodiimide group and the isocyanate group is in the range of the ratio of total equivalent / active hydrogen group equivalent = 1.0 to 2.0. Further, it is preferred that the ratio of carbodiimide group equivalent / isocyanate group equivalent = 0.1 to 20. In the above, if the total equivalent weight / equivalent weight of the active hydrogen group is less than 1.0, it is not preferable because crosslinking is not sufficiently performed and the adhesiveness tends to be insufficient in the tight adhesion, the content resistance, and the like. Total equivalents /
If the equivalent of the active hydrogen group exceeds 2.0, the crosslinking becomes excessive and the coating constituting the adhesive layer is apt to become brittle, which is not preferable. Further, in the above, if the equivalent of the carbodiimide group / the equivalent of the isocyanate group is less than 0.1, the content resistance, water resistance and the like are liable to be insufficient. If the equivalent weight / equivalent weight of the isocyanate group exceeds 20, it is not preferable because the tight adhesion tends to be insufficient.

Next, in the present invention, as the intermediate base material forming the intermediate base material layer constituting the laminate according to the present invention, for example, a property of blocking light such as sunlight, or
Water vapor gas, a material having a gas barrier property for preventing the permeation of oxygen gas, etc., can be used.
A single substrate may be used, or a composite substrate obtained by combining two or more types of substrates may be used. Specifically, for example, a resin film having an aluminum foil or a vapor-deposited film of aluminum or the like having a light-shielding property and a gas barrier property against water vapor gas, oxygen gas, or the like, a silicon oxide having a gas barrier property against water vapor gas, oxygen gas, or the like; A resin film having a deposited film of an inorganic oxide such as aluminum, a low-density polyethylene, a medium-density polyethylene, a high-density polyethylene, a linear low-density polyethylene, a polypropylene, and an ethylene-propylene having a barrier property against water vapor, water, etc. Resins such as films or sheets of resins such as polymers, polyvinylidene chloride, polyacrylonitrile, polyvinyl alcohol, and resins such as saponified ethylene-vinyl acetate copolymer having gas barrier properties against water vapor gas, oxygen gas, etc. Film or sheet, resin Can be used bets like - a colorant such as pigments, film or sheet of various colored resins having a light shielding property obtained by a film and kneaded by adding the desired additives. These materials can be used alone or in combination of two or more. The thickness of the above-mentioned film or sheet is arbitrary, but usually 5 μm to 3 μm.
It is preferably about 00 μm, more preferably about 10 μm to 100 μm. Further, in the above, the aluminum foil has a thickness of about 5 μm to 30 μm, and the aluminum or inorganic oxide deposited film has a thickness of about 1 μm to 30 μm.
Thousands of about $ 2000 to $ 2000 can be used. Examples of the resin film that supports the above-mentioned vapor-deposited film include polyester films, polyamide films, polyethylene films, polypropylene films, polyvinyl chloride films, polycarbonate films, polyvinylidene chloride films, and polyvinyl alcohol films. , An ethylene-vinyl acetate copolymer saponified film, etc. can be used.

Further, in the above, the inorganic oxide constituting the above-mentioned inorganic oxide vapor-deposited film is, for example, an inorganic oxide such as silicon oxide (SiO _x ), aluminum oxide, indium oxide, tin oxide, zirconium oxide or the like. Things can be used. Further, in the present invention, as the inorganic oxide, a mixture of silicon monoxide and silicon dioxide,
Alternatively, it may be a mixture of silicon oxide and aluminum oxide. In the present invention, as a method of forming a deposited film of an inorganic oxide, a vacuum deposition method such as an ion beam method and an electron beam method, a sputtering method, and a low-temperature plasma chemical vapor deposition method are used. It can be formed by forming a film. In the above description, the thickness of the deposited film of the inorganic oxide is usually preferably about 100 to 2000 ° in order to obtain a sufficient barrier property, and in particular, in the present invention, it is 200 to 1500 °.
Position is desirable. In the above, when the thickness of the inorganic oxide vapor deposition film exceeds 1500 °, especially when it exceeds 2000 °, cracks and the like are apt to be formed in the inorganic oxide vapor deposition film, and the risk of warpage deteriorating the barrier property. It is not preferable because of the problems of high material cost and high material cost.
If it is less than Å, it is difficult to see the effect,
Not preferred.

By the way, since packaging containers are usually subjected to severe physical and chemical conditions, strict packaging suitability is required for a laminate constituting the packaging container.
Various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing property, quality maintenance, workability, hygiene, etc. are required. In addition to such materials, other materials that satisfy the above conditions can be used arbitrarily. Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear Low density polyethylene,
Polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, Polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer Coalesce (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol
Resin, saponified ethylene-vinyl acetate copolymer,
Fluorine resin, diene resin, polyacetal resin,
Any known resin film or sheet such as polyurethane resin, nitrocellulose, etc. can be used. In addition, for example, synthetic paper can be used. In the present invention, the above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but is from several μm to 300 μm.
It can be used by selecting from a range of positions. Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film or a coating film.

Next, a method of manufacturing a laminate using the above-mentioned materials in the present invention will be described. The method includes a laminating method used when manufacturing a normal packaging material. Method, for example, wet lamination, dry lamination, solvent-free lamination
It can be carried out by an extrusion method, an extrusion lamination method, a co-extrusion lamination method, or other methods. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, for example, the surface of the base film or the like can be subjected to a pretreatment such as a corona treatment, an ozone treatment, and a frame treatment. . In the above, when extrusion lamination is performed, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin , Ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-
Methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic acid,
Extrusion laminating resins such as acid-modified polyolefin resins modified with unsaturated carboxylic acids such as methacrylic acid, maleic anhydride, fumaric acid and others can be used. In the present invention, for example, anchors such as polyester-based, isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, and organic titanium-based anchors are used.
Known coating agents and various adhesives for laminating such as polyurethane, poly (meth) acrylic, polyester, polyamide, epoxy, polyvinyl acetate, cellulose, etc. An anchor coating agent, an adhesive for laminating and the like can be used.

Next, in the present invention, a packaging container manufactured by using the above-mentioned laminated body will be described. Such a packaging container uses the above-mentioned laminated body,
The surfaces of the sealable resin layer are superposed on each other, and then the peripheral edge portion is heat-sealed to form a seal portion, which is used for packaging using the laminate according to the present invention. Containers can be manufactured. In the present invention, it is also possible to manufacture a packaging container having a structure in which a chuck tape that can be repeatedly fitted is provided on the inner surface of the packaging container and below the opening. Things. Thus, as a bag making method, the above-mentioned laminate is folded or overlapped so that the inner layer faces each other, and the peripheral end thereof is, for example, a side seal type. One-way seal type, three-way seal type, four-way seal type, envelope-attached seal type,
Heat seals such as gasoline-sealed seal type (pyro-seale type), pleated seal type, flat bottom seal type, square bottom seal type, etc. Thus, packaging containers having various forms using the laminate according to the present invention can be manufactured. In addition, for example, a self-supporting packaging bag (standing pouch), a tube container, and the like can be manufactured. In the above, as a method of the heat seal, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, or the like is used. Can be performed in the following manner. In the present invention,
For example, a one-piece type, a two-piece type, a spout, or a zipper for opening and closing can be attached to the packaging container as described above.

Next, in the present invention, in the case of a liquid-filled paper container containing a paper substrate as a packaging container using the laminate according to the present invention, for example, a paper substrate is laminated as a laminate. The laminated body is manufactured, and a blank plate for manufacturing a desired paper container is manufactured from the laminated body, and thereafter, the trunk portion, the bottom portion, the head portion, etc. are manufactured using the blank plate. Type or gable-top type liquid paper container or the like can be manufactured. Moreover, the shape can be manufactured by any of a rectangular container, a circular or other cylindrical paper can, and the like.

In the present invention, the packaging container produced as described above has an extremely high laminate strength between the base material layer and the heat-sealing resin layer, and is included in the contents, for example. Phenomena such as delamination due to penetration of components and the like are not observed, and extremely excellent in content resistance and the like. Also, no leakage of the contents and the like is observed, and the storage and storage stability is excellent and extremely excellent. A packaged product can be manufactured. Thus, packaging containers manufactured as described above include, for example, various articles such as foods and drinks, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, adhesives, and other chemicals or cosmetics, and others. It is excellent in suitability for packaging and storage, suitability for storage and the like.

[0026]

Next, the present invention will be described in more detail with reference to examples. Example An adhesive A and an adhesive B were prepared according to the following formulation. (Adhesive A) 100 parts by weight of a polyester having a weight average molecular weight of 15,000 condensed at a blending ratio of adipic acid / terephthalic acid = 5/1 and ethylene glycol / 1.6-hexanediol = 2/1 On the other hand, 10 parts by weight of hexamethylene diisocyanate buret and 3 parts by weight of a polycarbodiimide resin composed of a hexamer of hexamethylene diisocyanate are added, and thereafter, ethyl acetate / toluene = 4/1. Knead well with a solvent to obtain a solid content of 30
An adhesive A consisting of% by weight was prepared. (Adhesive B) 100 parts by weight of a polyester having a weight-average molecular weight of 15,000 condensed at a blending ratio of adipic acid / terephthalic acid = 5/1 and ethylene glycol / 1.6-hexanediol = 2/1 On the other hand, 10 parts by weight of a tolylene diisocyanate adduct of trimethylolpropane and 3 parts by weight of a polycarbodiimide resin consisting of a 10-mer of tolylene diisocyanate were added.
The mixture was sufficiently kneaded with a solvent consisting of toluene = 4/1 to prepare an adhesive B having a solid content of 30% by weight.

Example 1 The above adhesive A was used between the layers of a laminate comprising a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm / aluminum foil having a thickness of 9 μm / a non-oriented polypropylene film having a thickness of 60 μm. Then, dry lamination was performed through an adhesive layer having a thickness of 3.5 g / m ² (dry state) to produce a laminate according to the present invention having the following layer constitution. Biaxially stretched polyethylene terephthalate film having a thickness of 12 μm / adhesive layer / aluminum foil having a thickness of 9 μm / adhesive layer / unstretched polypropylene film having a thickness of 60 μm Then, the above-prepared pair of laminates was used. The unstretched polypropylene films are superposed on each other so that they face each other, and then the three sides are heat-sealed to form a three-sided heat seal.
A sealable soft packaging bag was produced. Next, into the soft packaging bag produced above, a seasoning composed of 4% acetic acid water / salad oil / commercial meat sauce = 1/1/1 was filled from the opening thereof, Heat-sealing the opening to form a top heat-sealed portion to produce a filled and packaged product;
Thereafter, the filled packaged product was retorted at 135 ° C. for 30 minutes to produce a packaged product. The above packaged product has excellent close-adhesion between the layers, does not show any phenomenon such as delamination (delamination), and does not show any phenomenon such as bag breakage. did it. In particular, the interlayer between the 9 μm aluminum foil on the content side and the unstretched polypropylene film having a thickness of 60 μm was excellent in tight adhesion, and no phenomenon such as delamination was observed.

Example 2 The above-mentioned adhesive B was used between the layers of a laminate consisting of an aluminum foil having a thickness of 9 μm / a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm / a linear low-density polyethylene film having a thickness of 60 μm. And a film thickness of 3.5 g / m
Dry lamination was carried out through an adhesive layer consisting of ² (dry state) to produce a laminate having the following layer constitution. 9 μm thick aluminum foil / adhesive layer / biaxially oriented polyethylene terephthalate film of 12 μm thickness / adhesive layer / linear low density polyethylene film of 60 μm thickness Next, the thickness of the laminate produced above A laminate comprising a low-density polyethylene layer having a thickness of 30 μm (extruded), a paper substrate having a basis weight of 400 g / m ² , and an ethylene-methacrylic acid copolymer layer having a thickness of 30 μm (extruded) on a surface of a 9 μm aluminum foil. Of the ethylene-methacrylic acid copolymer layer having a thickness of 30 μm and extruding and laminating both, to produce a laminate according to the present invention having the following layer constitution. Low-density polyethylene layer with a thickness of 30 μm / basis weight 40
Paper substrate of 0 g / m ² / ethylene-methacrylic acid copolymer layer of 30 μm thickness / aluminum foil of 9 μm thickness / adhesive layer / biaxially oriented polyethylene terephthalate film of 12 μm thickness / adhesive layer / A linear low-density polyethylene film having a thickness of 60 μm. Next, using the laminated body produced as described above, a 2-liter capacity gabelle top type carton having a size of 85 mm square was produced by a conventional method. Next, the car produced above
The ton is filled with a detergent liquid consisting of 30% by weight of a surfactant / 5% by weight of isopropyl alcohol / 5% by weight of ethanolamine / 60% by weight of water from the opening, and then the opening is filled. Heat sealed to produce a packaged product. When the above packaged product was left at 40 ° C. for one month, a biaxially stretched polyethylene terephthalate having a thickness of 12 μm on the contents side was obtained.
Excellent adhesion between the film and the linear low-density polyethylene film having a thickness of 60 μm, and delamination
No phenomenon such as breakage of the bag was observed, and the packaged product could be produced very well.

COMPARATIVE EXAMPLE 1 In the above adhesive A, 3 parts by weight of a polycarbodiimide resin consisting of a hexamer of hexamethylene diisocyanate was removed from the composition of the adhesive A. In the same manner as in A, the adhesive C was prepared. Next, in Example 1 above, instead of using the adhesive A, the above-mentioned adhesive C was used, and the other conditions were exactly the same as those in Example 1 to produce a laminate. Manufactured flexible packaging bags and packaging products. However, the packaged product produced as described above was inferior in the tight adhesion between the respective layers, and exhibited phenomena such as delamination (delamination) and phenomena such as bag breakage. In particular, the interlayer between the content-side 9 μm aluminum foil and the 60 μm-thick unstretched polypropylene film,
Poor adhesion was observed and phenomena such as delamination were observed.

Comparative Example 2 In the adhesive B, 3 parts by weight of a polycarbodiimide resin consisting of a 10-mer of tolylene diisocyanate was removed from the composition of the adhesive B.
In the same manner as in the above, the adhesive D was prepared. Next, in the above-mentioned Example 2, instead of using the adhesive B, the above-mentioned adhesive D was used, and the others were exactly the same as in the above-mentioned Example 2, to produce a laminate. Carton and packaging products were manufactured. However, when the above-mentioned packaged product was left at 40 ° C. for one month, the content-side 12 μm-thick 2 μm
Axial stretched polyethylene terephthalate film and thickness 60
The adhesiveness between layers with a linear low-density polyethylene film of μm is poor, and phenomena such as delamination are observed.
In addition, phenomena such as bag breaking were also observed.

The above Examples 1 and 2 and Comparative Examples 1 and 2
With respect to the laminate manufactured in 2, the adhesive strength between the layers was measured. The above adhesive strength was measured by cutting the laminate into a rectangle having a width of 15 mm, peeling the interlayer to be measured, and pulling the laminate at a speed of 50 mm / min with a tensile tester. The results measured above are shown in Table 1 below.

[0032]

As is clear from the above results, Example 1
The samples of Nos. 2 and 3 were far superior in laminating strength to those of Comparative Examples 1 and 2.

[0034]

As is apparent from the above description, the present invention provides a method for manufacturing a laminate by laminating at least a base film and a heat-sealing resin film. -An adhesive layer containing an adhesive containing a polycarbodiimide-based resin having a carbodiimide group, a compound having an active hydrogen group, and a compound having an isocyanate group is interposed between the layers of the toseal resin film. Laminate to produce a laminate, and then use the laminate to produce a soft packaging bag, and fill the soft packaging bag with a liquid content such as a detergent to form a packaged product. When manufactured, the laminate strength between the base film and the heat-sealing resin film is extremely high. For example, phenomena such as delamination due to penetration of components contained in the contents are recognized. Not very resistant Excellent capacity physical properties, also not observed leakage or the like of the contents or the like, excellent in its storage storage stability,
Very good packaging products can be produced.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view illustrating an example of a layer configuration of a laminate according to the present invention.

FIG. 2 is a schematic cross-sectional view illustrating an example of a layer configuration of a laminate according to the present invention.

FIG. 3 is a schematic perspective view illustrating an example of the configuration of a packaging container manufactured using the laminate according to the present invention shown in FIG. 1 described above.

FIG. 4 is a schematic perspective view illustrating an example of the configuration of a packaged product in which contents are filled and packed in the packaging container shown in FIG.

[Explanation of symbols]

A Laminated Body A ₁ Laminated Body B Three-Way Seal Type Soft Packaging Bag C Packaging Product 1 Base Layer 2 Heat-Sealable Resin Layer 3 Adhesive Layer 3a Adhesive Layer 4 Intermediate Base Layer 11 Heat Seal part 12 Opening part 13 Contents 14 Upper heat seal part

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AB10 AB33 AH00C AK01B AK07 AK42 AK49C AK51C AT00A AT00D BA03 BA04 BA07 BA10A BA10B EJ38 GB15 JK06 JL12B YY00C 4J034 CA04 CA05 CA15 CA24 CB03 CC04 DB03 CC03 CC04 DB07 DF02 DF12 DF16 DF20 DG03 DG04 DG06 DG08 DG09 DP03 DP18 FA02 FB04 FC03 FD01 GA05 GA33 HA01 HA06 HA07 HB06 HC03 HC12 HC13 HC17 HC22 HC46 HC52 HC61 HC63 HC64 HC67 HC71 HC73 QA01 QC03 RA05 EF1 EF EF EF EF 001 001 EF EF EF EF122 EF131 EF132 EF181 EF182 EF251 EF252 EH001 LA06 MA10 MA11 NA08

Claims (4)

[Claims] 1. A polycarbodiimide comprising at least a base material layer and a heat-sealing resin layer, and further having a carbodiimide group between the base material layer and the heat-sealing resin layer. A laminate characterized by interposing an adhesive layer of an adhesive containing a resin, a compound having an active hydrogen group, and a compound having an isocyanate group. 2. The total equivalent of the carbodiimide group and the isocyanate group is the total equivalent / the equivalent of the active hydrogen group =
The laminate according to claim 1, wherein the ratio is in the range of 1.0 to 2.0. 3. Equivalent of carbodiimide group / isocyanate
3. The laminate according to claim 1, wherein the equivalent weight of the group is in a range of 0.1 to 20. 4. 4. The laminate according to claim 1, further comprising an intermediate base material layer.