JPH1142744A - Multilayer laminate, molding and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminate having excellent heat resistance, flexibility, transparency and gas barrier properties, and excellent toughness by laminating two types or more layers each having specific thickness and component composition. SOLUTION: In the laminate obtained by laminating layers made of two or more types of materials, at least one type of the layer has a thickness of 0.001 to 1 μm or preferably 0.001 to 0.8 μm, and 0.001 to 25 wt.% of laminar silicate is contained in the layer. The silicate is dispersed so that a mean value of (long diameter + short diameter)/2 of the ten silicates selected at random becomes 0.001 to 0.9 μm on an electron microscope photograph of its section. As preferable combination, the one type of the layer is made of polyolefin having a glass transition temperature of -10 deg.C or lower, and at least other one type of the layer is made of a combination of polyamide, polyolefin, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer laminate in which different types of layers are laminated, and more particularly to a multilayer laminate in which different types of thin film layers made of a thermoplastic resin are laminated and integrated, a molded product comprising the same, and The present invention relates to a method for manufacturing a multilayer laminate.

[0002]

2. Description of the Related Art Conventionally, reflective polymer materials, especially mirrors, pearlescent mirrors, metallic glossy mirrors, half mirrors, polarizers, awning sheets, light transmission control sheets, etc. have been used as laminates in which a large number of organic polymer thin films are laminated. Known (JP-A-4-268505, JP-A-4-2
95804, JP-A-4-31370). Such a polymer laminate has a thickness of, for example, 0.009 to 0.045 μm.
It has a structure in which two or more kinds of polymer thin films are repeatedly superposed and extremely laminated.

[0003] As such a multilayer laminate, a laminate formed of various different materials is desired.
For example, a foam laminate in which a resin thin film containing a foaming agent and a resin thin film not containing a foaming agent are alternately laminated, or a resin layer having excellent gas barrier properties and a resin layer having excellent flexibility and toughness alternate. There is a demand for a composite laminate or the like laminated on a substrate.

[0004] Multiple extrusion molding or co-injection molding is known as a method for producing a laminate in which thermoplastic resins are laminated in multiple layers. In these molding methods, a multi-composite is formed by co-extrusion molding or co-injection molding of different layers, and a laminate having the properties of each layer can be obtained.

However, a multilayer laminate excellent in transparency, gas barrier properties and toughness has not been obtained so far. In the conventional multiple extrusion molding method or co-injection molding method, the thickness of each layer to be laminated is limited, so that it is not possible to obtain a thin-film laminate, and an ultra-multilayer film having several tens to about 1,000 layers. Complicated operations are required to mold the resin.

[0006] Japanese Patent Application Laid-Open No. Hei 8-302068 discloses that
A resin composition containing a layered compound composed of a fibrous inorganic filler having a small dispersion size is described. However, even if a film is formed from such a resin composition, various physical properties cannot be improved in a well-balanced manner because the film is a single-layer film.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a multilayer laminate in which layers made of various kinds of different materials are laminated in a multi-layer structure, and which has both properties of a material forming the layers and excellent toughness. It is an object of the present invention to provide a laminate, particularly a multilayer laminate excellent in heat resistance, flexibility, transparency and gas barrier properties and also excellent in toughness, and a molded article comprising the same. Another object of the present invention is a multilayer laminate in which layers composed of various dissimilar materials are laminated in a multilayer manner.The multilayer laminate having both the properties of the material forming the layer and excellent toughness, particularly heat resistance, An object of the present invention is to propose a method for producing a multilayer laminate that can easily produce a multilayer laminate having excellent flexibility, transparency, gas barrier properties, and excellent toughness.

[0008]

SUMMARY OF THE INVENTION The present invention relates to the following multilayer laminate, molded product and manufacturing method. (1) A multilayer laminate in which two or more layers are laminated,
The at least one layer has a thickness of 0.001 to 1 μm,
Further, the layered silicate is contained in this layer in an amount of 0.01 to 25% by weight, and the layered silicate is dispersed so that the average value of (major axis + minor axis) / 2 becomes 0.01 to 0.9 μm. A multilayer laminate characterized in that: (2) One layer is a layer made of a polyolefin having a glass transition temperature of -10 ° C or lower measured by a differential scanning calorimeter (DSC), and at least one other layer is a layer made of a polyamide or a polyolefin. (1)
The multilayer laminate according to the above. (3) The total number of layers in which different types of resin layers are alternately laminated is 20
The multilayer laminate according to the above (1) or (2), which has a thickness of from 1 to 100,000. (4) A film or sheet comprising the multilayer laminate according to any one of (1) to (3). (5) An injection molded article comprising the multilayer laminate according to any one of the above (1) to (3). (6) A rotary molded article obtained by rotationally molding the multilayer laminate according to any one of the above (1) to (3). (7) A hollow molded article obtained by hollow molding the multilayer laminate according to any one of the above (1) to (3). (8) a step of forming a laminar flow in which at least two types of layers are laminated, a step of dividing the laminar flow by a longitudinal division surface intersecting a lamination interface to form a divided laminar flow, A method of manufacturing a multilayer laminate including a step of twisting a flow with a longitudinal direction as a rotation axis, and a step of laminating and unifying the twisted divided laminar flows to form a laminated laminar flow. The seed layer contains 0.01 to 2 layered silicates.
5% by weight, and the thickness of this layer is finally 0.001 to
A method for producing a multilayer laminate, wherein the laminar flow or the laminar laminar flow is thinned so as to have a width of 1 μm to increase the width.

The material forming the layers constituting the multilayer laminate of the present invention is not particularly limited, and known organic polymers such as thermoplastic resins can be preferably used, but inorganic compounds such as polysiloxane can also be used. . Specific examples of the thermoplastic resin include, for example, linear low-density polyethylene (L
LDPE), high density polyethylene (HDPE), ethylene / propylene copolymer (EPR), ethylene / α-olefin copolymer, ethylene / cycloolefin copolymer, polypropylene (PP), propylene / α-olefin copolymer , Polyolefin such as propylene / ethylene block copolymer (bPP), polyamide (PA) such as nylon 6, polystyrene (PS), polycarbonate (PC), ethylene / vinyl alcohol copolymer, ionomer, polyethylene terephthalate (PET), etc. And other known degradable polymers, conductive polymers, piezoelectric polymers, and compositions containing two or more of these. These resins may be modified with functional groups such as carboxylic anhydride and hydroxyl group. Among these, polyolefins, especially polyolefins and polyamides having a glass transition temperature of -10C or less, preferably -125 to -11C, measured by a differential scanning calorimeter (DSC) are preferred.

The combination of the above materials is not particularly limited, and two or more different materials can be used in any combination. In a preferred combination, one layer has a glass transition temperature measured by DSC of -10 ° C or lower, preferably -12 ° C.
5 to -9C polyolefin, and at least one other
Combinations wherein the seed layer is a polyamide or polyolefin.

The multilayer laminate of the present invention is a laminate in which layers composed of two or more materials as described above are laminated, and at least one layer has a thickness of 0.001 to 1 μm, preferably 0 to 1 μm. 0.001 to 0.8 μm, more preferably 0.0
0.5 to 0.8 μm, and 0.001 to 25% by weight, preferably 0.001 to 2% by weight of a layered silicate in this layer.
0% by weight, more preferably 0.001 to 15% by weight.

The layered silicate in the layer has an average value of (major axis + minor axis) / 2 of 10 randomly selected layered silicates in an electron micrograph of a cross section (hereinafter referred to as an average dispersion size). 0.01 to 0.9 μm,
Preferably, the particles are dispersed so as to have a thickness of 0.01 to 0.8 μm, and more preferably 0.01 to 0.7 μm. The average dispersion size of the layered silicate in the conventional laminate is usually about 1 to 6 μm.

In the multilayer laminate of the present invention, one layer has a specific thickness as described above and contains a specific amount of a specific layered silicate (hereinafter referred to as a layered silicate-containing layer). However, another layer may have a specific thickness as described above, may be a layer containing a specific amount of a specific layered silicate, or may be a layer other than such a layer. It may be a layer.

The total number of layers of the multilayer laminate of the present invention is 20 to
It is desirably 100,000, preferably 50-100,000. If the number of layers is less than 20, transparency and toughness may not be sufficient, and if it exceeds 100,000, layers may be disturbed and the layers may not be uniform, resulting in poor appearance. The total thickness of the multilayer laminate of the present invention varies depending on each application, but is generally about 1 μm to 50 mm, preferably about 10 μm to 2 mm.

When the multilayer laminate of the present invention comprises two types of layers, the combination of materials is, for example, nylon 6 (NY).
6) / PE, NY6 / PP, NY6 / EPR, bPP /
EPR, PP / ethylene / α-olefin copolymer, P
ET / PP, PET / PE, PS / PP, PS / PE and the like. Among these, NY6 / PE, NY
6 / PP, NY6 / EPR and bPP / EPR are preferred.

In the case of a multilayer laminate comprising two types of layers, the ratio of the total thickness of one A layer to the other B layer is 1:99 to
It is desirably 99: 1, preferably 5:95 to 95: 5. When the layer A contains the layered silicate and the layer B does not contain the layered silicate, all of the layer A may not contain the layered silicate, and some of the layer A Only the layers may contain layered silicates.

The phyllosilicate used in the present invention is a compound in which a silicate layer and a metal cation layer, each of which is made of a swellable clay mineral, are in a layered form, and are formed into fine particles by pulverization or other means. Is a powder. Examples of the swellable clay mineral include smectite, vermiculite, mica, and chlorite. Specific examples of the smectite include saponinite, hectorite, montmorillonite, and saukonite. Specific examples of vermiculite include trioctohydralouver miculite and dioctohydraloulumiculite. Specific examples of the compound belonging to mica include muscobite, phylogopite, biotite, lepidrite, paragonite, tetrasilicic mica and the like.

In addition, swellable mica obtained by subjecting talc to a fluorine treatment, or one having the above structure obtained by hydrothermal synthesis can also be used as the layered silicate. Further, compounds in which metal cations present between the layers of these layered compounds are replaced with different same ions such as sodium, potassium, lithium and the like can be mentioned.

As the layered silicate used in the present invention, those obtained by ion-exchanging metal ions existing between layered silicates with organic ions are preferably used. By ion-exchanging the metal ions with organic ions, the layered silicate is made organophilic and the layered compound is easily crushed by increasing the interlayer distance. The organic ion is preferably an organic cation.

In the present invention, examples of the organic cation preferably used for ion exchange of metal ions include tetraalkylammonium salts such as hydrochlorides of amines or amino acids. When the organic cation is an amine, it is preferably a linear monoamine or diamine having 6 to 20 carbon atoms.

When the organic cation is an amino acid, it preferably has 4 to 30 carbon atoms. Specifically, lysine, arginine, γ-aminocyclohexylcarboxylic acid, glutamic acid, p-aminohydrocinnamic acid,
Histidine, tryptophan and the like can be mentioned.

The tetraalkylammonium salt desirably has at least one alkyl group having 4 to 50, preferably 6 to 20 carbon atoms. When the number of carbon atoms is less than 4, the interlayer expansion effect by ion exchange is not sufficient, and the layered silicate is hardly finely dispersed. On the other hand, if it is larger than 50, it becomes difficult for the exchange to the organic cation to proceed smoothly.

In the present invention, an alkyl ammonium salt halide can be used as the tetraalkyl ammonium salt. Specific examples of such an alkyl ammonium salt halide include distearyl dimethyl ammonium chloride and the like.

As a specific method for ion-exchanging a metal cation with an organic cation, for example, after sufficiently solvating the layered silicate with water or ketone, the organic cation is added thereto to sufficiently convert the layered silicate. Ion exchange of metal ions between layers with organic cations. The addition amount of the organic cation for ion exchange is suitably in the range of 1 to 10 equivalents of the cation exchange capacity. The interlayer distance of the layered silicate obtained by the above method is preferably 0.7 to 5 nm. In addition,
The interlayer distance can be determined by X-ray diffraction.

In the multilayer laminate of the present invention, in order to disperse the layered silicate so as to have the above-mentioned average dispersion size, the layer containing the layered silicate in an aggregated state must have a thickness on the order of submicron. A method of applying a shearing force to the layered silicate to make the layered silicate into a finely dispersed state from the agglomerated state can be adopted.

In addition to the layered silicate, dyes, pigments or foaming agents, other fillers, stabilizers and the like may be added. For example, an A layer containing a dye (or pigment),
A combination with a layer B containing no dye (or pigment),
Alternatively, a combination of a layer A and a layer B containing dyes (or pigments) of different colors, for example, is exemplified. Further, a combination of the layer A containing a foaming agent and the layer B containing no foaming agent is exemplified.

The multilayer laminate of the present invention can be produced by, for example, a co-extrusion method such as a multilayer T-die method, a multilayer inflation method, an extrusion lamination method, a wet or dry lamination method, a multilayer blow method, a two-color molding method, a sandwich molding method,
Although it can be manufactured by employing a general method of forming a multilayer laminate such as a stamping method, it is preferable to manufacture by a method capable of forming a multilayered thin film without disturbing the layer interface.
Preferred production methods include the following:

First, a laminar flow in which at least two kinds of different layers are laminated is formed. In this case, at least one of the layers forming the laminar flow contains 0.01 to 25% by weight of the layered silicate. Since the laminar flow is usually formed at relatively high temperature and high pressure by co-extrusion molding, the adhesion of each layer is high.
Next, the laminar flow is divided at a longitudinal division plane intersecting the lamination interface to form a plurality of divided laminar flows. The number of divided laminar flows is usually preferably about 2 to 6. Laminar flow splitting can be performed at once to form the desired number of split laminar flows,
It can be done in multiple stages. In the latter case, for example, two divisions are sequentially performed, and a desired number of divided laminar flows can be formed.

Next, the divided laminar flow is twisted with the longitudinal direction as a rotation axis. The torsion angle is usually preferably 10 to 90 °. The twisting direction may be any direction around the rotation axis.
Further, the divided laminar flows may be twisted in the same direction, or the adjacent laminar flows may be twisted in opposite directions. Preferably, the twisted laminar flows are spaced apart from one another and are maintained parallel to one another. Next, the twisted divided laminar flows are overlapped and laminated to form a laminated laminar flow.

In the above-mentioned process, when the first laminar flow or the laminar laminar flow is thinned at any time and the width is increased, each layer is thinned to have almost the same shape as the first laminar flow and the number of laminations is increased. A laminated laminar flow is obtained. Such a laminar flow can be further thinned and multilayered by repeating the same steps of division-twisting-lamination-thinning as in the previous case. Then, by repeating this operation, each layer is thinned, and the thin film layers are multilayered to produce a multilayer laminate having a uniform distribution. In this case, division-torsion-so that the thickness of the layer containing the layered silicate is finally 0.001 to 1 μm.
The steps of lamination and thinning are repeated. By forming a thin film in this manner, the layered silicate can be dispersed at the average dispersion size.

The laminar flow may be two layers or three or more layers.
The layer on the front side and the layer on the back side may be the same layer or different layers. Each layer is determined to have an initial thickness so that a layer to be finally laminated has a desired ratio.

In the above process, the number of laminations in the first laminar flow is preferably 2 to 10, preferably 2 to 4. The total thickness of the first laminar flow is usually about 100 μm to about 50 mm, and the thickness of each layer is usually about 50 μm to about 20 mm.
It is preferred that it is about. The number of repetitions of each process is 1 to
It is suitably 20 times, preferably 1 to 10 times.

In the above-mentioned production method, it is preferable to carry out the operations of the respective steps by passing a laminar flow formed by co-extrusion molding through a molding die in a heat-softened state. In this case, if one cycle of each step can be performed by one mold, each step can be repeated by connecting many molds having the same shape in series.

The multilayer laminate obtained as described above can be obtained as a molded article having an arbitrary shape such as a film, a sheet and a block. For example, a multilayer film having a thickness of about 100 μm to 3 mm, a multilayer sheet having a thickness of about 3 to 10 mm,
A block-like laminate having a thickness of about 10 to 50 mm can be obtained.

By selecting the material of each layer,
A unique characteristic is obtained by combining the respective characteristics. For example, by combining a layer having excellent gas barrier properties and a layer having excellent rigidity, a molded article having a composite property of both can be obtained. In this case, since at least one layer contains the layered silicate, it is excellent in toughness. As described above, the type, material, combination, number of layers, shape, and the like of each layer can be selected according to the characteristics of the target molded article, and can be used for the target application.

The method for manufacturing a multilayer laminate according to the present invention will be described with reference to the drawings. FIG. 1 is a perspective view showing a method for manufacturing a multilayer laminate according to the present invention. In FIG. 1, a laminar flow 1 is a flat laminar flow, in which different types of resin layers 2 and 3 are laminated in a molten state, and moves in the arrow X direction. The laminar flow 1 is obtained by co-extrusion molding or co-injection molding.

The laminar flow 1 is divided into four laminar flows 1 by the dividing surfaces 8a, 8b, 8c orthogonal to the lamination interface 4 of the resin layers 2, 3.
a, 1b, 1c, and 1d. This divided laminar flow 1
a, 1b, 1c and 1d are respectively twisted by 90 ° in the same direction. In this case, the twisted divided laminar flows 1a, 1b, 1
c and 1d are preferably kept parallel to each other. The twisted divided laminar flows 1a, 1b, 1c, 1d are laminated and integrated to form a laminated laminar flow 7 composed of eight layers of 2/3/2/3/2/3/2/3. In this case, each divided laminar flow 1
a, 1b, 1c, and 1d may be laminated and integrated at once, or may be laminated and integrated in multiple stages, for example, two stages.

The laminar flow 7 thus formed is
To repeat each step, it is sent to the next division step. At this time, it is preferable that the laminar flow 7 is made thinner to increase the width. This thinning and widening is performed by, for example, laminating the laminar flow 7.
It can be performed by moving in a flow path having a taper such that the thickness becomes smaller and the width becomes wider in the traveling direction. Further, it can be performed by rolling the laminated laminar flow 7 with a roll. When the laminar flow 7 is sent to the dividing step, it is preferable that the torsion of the laminar flow 7 is returned to the original angle as shown in FIG. By doing so, the continuously obtained laminated laminar flow 7 can be moved to the next dividing step on the roll.

By repeating each step in this manner, the resin layers 2 and 3 are further thinned and multilayered, and a multilayer laminate in which thin film layers are laminated is obtained. For example, in FIG. 1, by repeating each step once for the laminar flow 7, 3
A multilayer laminate of 2 layers, 128 layers by repeating twice, 2048 layers by repeating 4 times, and 2 × 4 ^{n + 1} layers by repeating n times is obtained. The number of repetitions can be arbitrarily selected. The thickness of each layer can be adjusted by selecting the thickness of the resin layers 2 and 3 of the first laminar flow 1 or the number of repetitions, and a thin film layer having a thickness of 0.001 to 1 μm is laminated. A multilayer laminate can be easily obtained.

In the above-mentioned multilayer laminate, unique characteristics in which the respective characteristics are combined can be obtained by arbitrarily combining the materials of the resin layers 2 and 3. For example, by combining a resin having excellent gas barrier properties and a resin having excellent rigidity, the combined properties of the two can be obtained and the toughness of the layered silicate can be obtained. Such a multilayer laminate can be used for containers, packaging materials, and other uses as it is, or further subjected to secondary processing such as stretching or rolling as necessary to further reduce the thickness of each layer.

Although FIG. 1 shows an example in which there are two laminar resin layers, three or more resin layers may be used. Further, the number of divided laminar flows can be arbitrarily selected, for example, two. In this case, each step is repeated n times for the laminated laminar flow 7 to obtain 2 × 2
^{An n + 1} multilayer laminate is obtained. Further, the direction and angle of the torsion can be arbitrarily selected. For example, divided laminar flows 1a, 1
c is twisted by + 90 °, and the divided laminar flows 1b and 1d are turned by -90 °
It may be twisted. In this case, 2 / (3.3) / (2 ·
A laminated laminar flow composed of five layers of 2) / (3.3) / 2 is formed. The torsion angle is usually 10 to 90 °. When the torsion angle is small, the interval between the divided laminar flows is too small, and it becomes difficult to secure a flow path for each divided laminar flow in the die. On the other hand, when the torsion angle is large, the flow path interval between the divided laminar flows can be sufficiently ensured, but a long flow path is required when returning the torsion to the original angle.

FIGS. 3 and 4 are schematic views showing a particularly preferred embodiment of the method for producing a multilayer laminate of the present invention. FIG. 3 is a schematic view of a heated multilayer resin flow moving through a flow path in a molding die. FIG. 4 is a plan view, and FIG. 4 is a schematic side view of FIG. 3 and FIG. 4, from the point, the step of forming a laminar flow 1 in which different types of layers are stacked, from the point, the step of forming the divided laminar flows 1a, 1b, 1c, 1d, and from the point, the divided laminar flow 1a , 1b, 1c, 1d, from the point, from the point, the divided laminar flow 1a, 1b,
1C shows a step of forming a laminated laminar flow 7 by laminating and integrating 1c and 1d.

The laminar flow 1 is expanded in the width direction from the point, and the point is thinner and wider than the point. The laminar flow 1 is divided into two at the point while expanding in the width direction from the point, then divided again at the point, and finally divided into four divided laminar flows 1a, 1b, 1c and 1d. Since the laminar flow 1 is evenly distributed by sequentially dividing in this way, the resin flow is prevented from being biased, and molding can be stably performed.

The divided laminar flows 1a, 1b, 1c and 1d are 90 °
Although it is twisted, since the distance from the point of each of the divided laminar flows 1a, 1b, 1c, and 1d is the same, it is possible to perform shaping without variation among the divided laminar flows 1a, 1b, 1c, and 1d. .

The divided laminar flows 1a, 1b, 1c, and 1d are laminated and integrated. The laminar flows are divided into two layers once at a point and then finally laminated and integrated at a point. By successively laminating and integrating in this way, it is possible to obtain a laminated laminar flow 7 in which interlayer adhesion is further strengthened and homogeneity is enhanced as compared with the case of laminating and integrating at one time. Such a laminar flow 7 can sufficiently exhibit mechanical strength and various desired performances. In addition, the resin flow path from the point has a smaller thickness in the traveling direction and has a wide taper, and a laminar flow 7 thinner and wider than the point is obtained at the point.

The multilayer laminate of the present invention utilizes properties such as heat resistance, flexibility, transparency, gas barrier properties and toughness,
It can be suitably used for contents storage such as food packaging containers, cosmetic containers, various medicine containers, and pharmaceutical packaging materials.

The film or sheet of the present invention is a film or sheet comprising the multilayer laminate of the present invention,
The multilayer laminate of the present invention as it is, or the multilayer laminate is further thinned or stretched as a stretched film or sheet, a protective film for protecting glass and the like, and a secondary file is processed for clear files, holders, etc. It can be suitably used for stationery applications, bent products such as clear cases for confectionery, dolls and the like.

The injection molded article of the present invention is an injection molded article obtained by injection molding the multilayer laminate of the present invention. Injection molding can be performed by cutting a sheet or film of the obtained multilayer laminate into a strip shape, and filling and injecting (for example, 180 to 280 ° C.) while supplying it to a hopper. The injection molded article thus obtained can be suitably used for housing of home electric appliances, automobile interior use, automobile exterior use such as fenders, bumpers, side moldings, mudguards, mirror covers, etc., and building material use.

The rotomolded article of the present invention is a rotomolded article obtained by spin-molding the multilayer laminate of the present invention. Rotational molding can be performed by supplying a sheet or film of a multilayer laminate to a heated mold and rotating and pressing it while melting. The rotomolded body thus obtained can be suitably used for applications such as large structural parts such as boats and bathtubs.

The hollow molded article of the present invention is a hollow molded article obtained by subjecting the multilayer laminate of the present invention to hollow molding. In the hollow molding, the sheet or film of the obtained multilayer laminate is cut into strips, melted while being supplied to an extruder, to form a hollow parison, and 1.5 to 5 times the parison by air blowing. This can be done by inflating to a degree. The hollow molded article thus obtained can be suitably used for applications such as cosmetic containers, various drug containers, and drinking water containers.

In the case of injection molding, rotational molding, and hollow molding, if the thickness of the laminate is 500 nm or less even when the multilayer laminate is melted, even if the laminate structure is broken, a finely dispersed structure is exhibited, so that good physical properties are exhibited. You.

[0052]

The multilayer laminate of the present invention has at least one layered silicate having a specific thickness and a specific thickness.
Since the seed layer is laminated with different kinds of layers, it has the characteristics of the material forming the layer and also has excellent toughness, especially excellent heat resistance, flexibility, transparency and gas barrier properties and also excellent toughness I have.

Since the molded article of the present invention is molded from the above-mentioned multilayer laminate, it has both properties of the material forming the layer and excellent toughness, and particularly excellent in heat resistance, flexibility, transparency and gas barrier properties. Also has excellent toughness.

In the method for producing a multilayer laminate according to the present invention, a laminar flow in which at least two types of layers are laminated is divided in a longitudinal direction intersecting a lamination interface, and the obtained divided laminar flow is twisted and then laminated and integrated. Thus, a multilayer laminar flow is formed, so that different types of thin film layers can be easily laminated in a multi-layer manner, whereby the above-mentioned multilayer laminate in which the layered silicate is finely dispersed can be easily produced.

[0055]

BEST MODE FOR CARRYING OUT THE INVENTION The method for measuring physical properties in an embodiment of the present invention is as follows. 1) Melt flow rate (MFR) Measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM C1238. 2) Layer Thickness A cross section of the sample was cut into thin slices with a microtome, and the polyamide resin layer was stained with phosphotungstic acid, and the polyolefin resin layer was stained with ruthenic acid, and observed and measured with an electron microscope. 3) Haze Using a film having a thickness of 500 μm, measurement was performed using a digital turbidimeter NDH-20D manufactured by Nippon Denshoku Industries Co., Ltd. 4) Film Impact Strength A film having a thickness of 500 μm was measured at 23 ° C. in accordance with ASTM D3420.

5) Oxygen Permeability Coefficient A film having a thickness of 500 μm was measured at 23 ° C. and 0% RH in accordance with the JIS K7126 B method. 6) Oil resistance Using a test piece having a thickness of 3 mm, a length of 8 cm, and a width of 8 cm, the sample was immersed in JIS No. 3 oil at 40 ° C. for 24 hours, and the weight change rate was measured. 7) Dispersion size The cross section of the sample was cut into thin slices with a microtome and observed and measured with a transmission electron microscope. At least three different parts were observed and averaged.

Example 1 Na-type montmorillonite, a fibrous layered silicate (Kunipia F, trade name, manufactured by Kunimine Sangyo Co., Ltd., major axis = 10 μm)
m, minor axis = 3 μm) was suspended in 1 liter of water, stirred at room temperature for 10 minutes, then added with 50 g of distearyldimethylammonium chloride, and further stirred for 30 minutes to obtain a suspension mixture. .

This was treated with nylon 6 (NY6) (CM10 manufactured by Toray).
07, trade name, MFR = 62 g / 10 min) added to 2.5 kg, and extruded from Extruder A 240
The mixture was extruded at 200C, and polyethylene (PE) (MFR = 20 g / 10 min, glass transition temperature = -120C) was extruded from the extruder B at 200C. At this time, the weight ratio between the discharge amount (Qa) of the extruder A and the discharge amount (Qb) of the extruder B was adjusted to be Qa / Qb = 30/70, and the layered silicate-containing NY layer and the PE layer were adjusted. And a two-layer laminar flow in a heated state was formed, and the laminar flow was divided into two by a division plane parallel to the longitudinal direction and perpendicular to the lamination interface.

After the obtained two-layer laminar flow is twisted by 90 ° with its longitudinal direction as the axis of rotation, the flat directions of the divided laminar flows are maintained parallel to each other, and the flat surfaces of the respective divided laminar flows are overlapped. By stacking and laminating together, a laminated laminar flow of four layers in a heated state is produced, and the above steps are repeated to obtain a total of 8
The number of layers was 1024, and a multilayer laminated film having a thickness of 500 μm was obtained. Table 1 shows the results. Average thickness of NY layer: 0.34 μm Average thickness of PE layer: 0.8 μm Average value of (major axis + minor axis) / 2 of dispersed montmorillonite:
0.2 μm

Example 2 Except that an ethylene-propylene copolymer (EPR) (MFR = 0.7 g / 10 min, ethylene content 80 mol%, glass transition temperature = -58 ° C.) was extruded from an extruder B at 200 ° C. As in Example 1, the number of layers was 1024.
A multilayer laminated film having a thickness of 500 μm was obtained. Table 1 shows the results. Average thickness of NY layer: 0.35 μm Average thickness of EPR layer: 0.78 μm Average value of (major axis + minor axis) / 2 of dispersed montmorillonite:
0.2 μm

Example 3 A suspension mixture obtained in the same manner as in Example 1 was mixed with a propylene / ethylene block copolymer (bPP) (MFR = 5).
7 g / 10 min, decane-soluble portion = 10.2 wt%,
The intrinsic viscosity of the decane-soluble part [η] = 6.5 dl / g, glass transition temperature = −58 ° C.). Extruded from the extruder B at 200 ° C.
= 0.7g / 10min, ethylene content 80mol%)
Extruded. At this time, the weight ratio between the discharge amount (Qa) of the extruder A and the discharge amount (Qb) of the extruder B is Qa / Qb = 70 /
The thickness was adjusted to 30 and a multilayer laminated film having 1024 layers and a thickness of 500 μm was obtained in the same manner as in Example 1. Table 1 shows the results. Average thickness of bPP layer: 0.8 μm Average thickness of EPR layer: 0.34 μm Average value of (major axis + minor axis) / 2 of dispersed montmorillonite:
0.5 μm

Comparative Example 1 The nylon 6 (CM1007 manufactured by Toray, trademark, MFR = 62 g)
/ 10 min) and a mixture of talc and nylon 6 / talc = 98/2 were extruded from extruder A at 240 ° C., and PE (MFR = 20 g /
10 min). At this time, the weight ratio between the discharge amount (Qa) of the extruder A and the discharge amount (Qb) of the extruder B is Qa /
Adjust so that Qb = 30/70, NY with talc
A laminated body in a heated state of two layers, a PE layer and a PE layer, was formed, and the number of layers was 1024 and the thickness was 500 μm in the same manner as in Example 1.
m was obtained. Table 2 shows the results. Average thickness of NY layer: 0.34 μm Average thickness of PE layer: 0.78 μm Average value of (major axis + minor axis) / 2 of dispersed talc: 1.2 μm

Comparative Example 2 The above-mentioned EPR (MFR = 0.7 g) was obtained at 200 ° C. from an extruder B.
/ 10 min, ethylene content 80 mol%), except that the number of layers was 1024,
A multilayer laminated film having a thickness of 500 μm was obtained. Table 2 shows the results. Average thickness of NY layer: 0.38 μm Average thickness of EPR layer: 0.89 μm Average value of (major axis + minor axis) / 2 of dispersed talc: 1.2 μm

Comparative Example 3 The above bPP (MFR = 57 g / 10 min, decane soluble part = 10.2% by weight, intrinsic viscosity of decane soluble part [η]
= 6.5 dl / g) and talc in a weight ratio of bPP / talc = 98/2 were extruded at 240 ° C. from extruder A, and extruded at 200 ° C. from extruder B at 200 ° C.
(0.7 g / 10 min, ethylene content: 80 mol%). At this time, the weight ratio between the discharge amount (Qa) of the extruder A and the discharge amount (Qb) of the extruder B is Qa / Qb = 70/3.
Except that it was adjusted to be 0, the same as in Comparative Example 1
A multilayer laminated film having 1024 layers and a thickness of 500 μm was obtained. Table 2 shows the results. Average thickness of bPP layer: 0.78 μm Average thickness of EPR layer: 0.33 μm Average value of (major axis + minor axis) / 2 of dispersed talc: 1.2 μm

Comparative Example 4 The suspension mixture obtained in Example 1 was mixed with the nylon 6 (CM1007 manufactured by Toray, trademark, MFR = 62 g / 10 min).
The mixture was extruded at 240 ° C. from an extruder while removing the solvent with a vent to obtain a T-die film having a thickness of 500 μm. Table 3 shows the results.

Comparative Example 5 The suspension mixture obtained in Example 1 was mixed with the nylon 6 (CM1007 manufactured by Toray, trademark, MFR = 62 g / 10 min).
5. 5 kg and the PE (MFR = 20 g / 10 min)
25 kg, and extruded the mixture at 240 ° C. from the extruder while removing the solvent by venting.
A T-die film having a thickness of 500 μm was obtained. Table 3 shows the results
Shown in

[0067]

[Table 1] * 1 Average value of (major axis + minor axis) / 2 of randomly selected fibrous silicate

[0068]

[Table 2] * 1 Average value of (major axis + minor axis) / 2 of randomly selected fibrous silicate

[0069]

[Table 3] * 1 Average value of (major axis + minor axis) / 2 of randomly selected fibrous silicate

From the results of Tables 1 to 3, it can be seen that all of the examples have a better balance of physical properties than the corresponding comparative examples.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a method for manufacturing a multilayer laminate according to the present invention, showing each step.

FIG. 2 is a perspective view showing a state in which the twist of the laminar flow is returned to the original angle.

FIG. 3 is a schematic plan view showing a preferred embodiment of each step shown in FIG.

FIG. 4 is a schematic side view showing a preferred embodiment of each step shown in FIG.

[Explanation of symbols]

 1 Laminar flow 1a, 1b, 1c, 1d Divided laminar flow 2, 3 Resin layer 4 Laminated interface 7 Laminated flow 8a, 8b, 8c Dividing surface

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // B29K 23:00 77:00 B29L 9:00 22:00

Claims (8)

[Claims] 1. A multilayer laminate in which two or more layers are laminated, wherein at least one layer has a thickness of 0.001 to 1
μm, and the layered silicate is 0.01 to 25 μm in this layer.
% Of the layered silicate (major axis + minor axis) /
2. A multilayer laminate characterized by being dispersed such that the average value of 2 is 0.01 to 0.9 μm. 2. One layer comprises a differential scanning calorimeter (DSC).
The multilayer laminate according to claim 1, wherein the layer is a layer composed of a polyolefin having a glass transition temperature of -10 ° C or lower, and at least one other layer is a layer composed of a polyamide or a polyolefin. 3. The multilayer laminate according to claim 1, wherein the total number of different resin layers alternately laminated is 20 to 100,000. 4. A film or sheet comprising the multilayer laminate according to claim 1. 5. An injection molded article comprising the multilayer laminate according to any one of claims 1 to 3. 6. A rotary molded article obtained by rotationally molding the multilayer laminate according to claim 1. 7. A hollow molded article obtained by hollow molding the multilayer laminate according to any one of claims 1 to 3. 8. A step of forming a laminar flow in which at least two kinds of layers are stacked, a step of forming the divided laminar flow by dividing the laminar flow at a longitudinal division surface intersecting a lamination interface, A step of twisting the divided laminar flow with the longitudinal direction as a rotation axis; and a step of laminating and unifying the twisted divided laminar flow to form a laminated laminar flow. The laminar or laminar flow is laminar so that at least one layer contains 0.01 to 25% by weight of the layered silicate and this layer has a final thickness of 0.001 to 1 μm. A method for producing a multilayer laminate, comprising: