JPH07329263A - Reinforced laminate - Google Patents

Abstract

(57) [Summary] [Purpose] Heat resistance, rigidity, dimensional stability, creep characteristics,
(EN) Provided is a reinforced laminate excellent in easy incineration property and improved in heat sealability. [Issue] Containing (I) a high molecular weight component ethylene / α-olefin copolymer and (B) a low molecular weight component ethylene homopolymer or ethylene / α-olefin copolymer, each of which has a specific property (II) Specific properties are given to a layer made of a resin composition which is a mixture and which has a specific property and an ultrahigh molecular weight polyethylene as a main component and (C) an inorganic filler. A reinforced laminated body, comprising laminating layers made of an ethylene (co) polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reinforced laminate, and more specifically, it has excellent heat resistance, rigidity, dimensional stability, creep properties, mechanical properties, etc. as a molded product, and is semitransparent as a film, and incinerated. Sometimes it relates to reinforced laminates with low calorific value. As a result of having such advantages, the reinforced laminate can be produced by a molding method such as extrusion molding, blow molding, injection molding, and various films, sheets such as garbage bags, medical waste bags, and heavy packaging bags. It can be used as a wide range of molded products such as pipes, hollow containers, and various coating materials.

[0002]

2. Description of the Related Art Conventionally, a composition obtained by blending linear low-density polyethylene with calcium carbonate has excellent heat resistance, rigidity, dimensional stability, creep properties, etc., and is semi-transparent. Since it is incinerable, it is widely used in the fields of films, sheets, pipes, hollow containers, various coating materials, etc. by utilizing these characteristics. In general, these compositions have the drawback that the range of use is limited because the impact strength, mechanical strength, etc., when compared with the base resin, is greatly reduced as a result of incorporating calcium carbonate. It was In order to improve these drawbacks, by adding a specific calcium carbonate to a specific ethylene / α-olefin copolymer, ethylene
A technique for obtaining a composition having improved physical properties such as impact strength from an α-olefin copolymer is also disclosed (JP-A-59).
-122533). However, the conventional linear low-density polyethylene generally has a very narrow molecular weight distribution, and therefore has a low n-value and poor flow characteristics, and further has insufficient mechanical strength at low temperatures.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a resin component having excellent molding processability and excellent mechanical properties at low temperature with an inorganic filler to obtain heat resistance, rigidity,
The object of the present invention is to obtain a reinforced laminate having excellent dimensional stability, creep properties, easy incineration properties, etc. and improved heat sealability.

[0004]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in view of the above-mentioned objects, the inventors have found that a specific ethylene / α
-Ultra-high molecular weight polyethylene having excellent mechanical properties obtained by blending an olefin copolymer and a relatively low molecular weight ethylene resin, particularly mechanical properties and flow properties at low temperature, as a main component A layer made of a specific ethylene (co) polymer as an inner layer and / or an outer layer is provided for a layer made of a resin composition excellent in mechanical strength and moldability obtained by mixing a resin component and an inorganic filler. The present invention has been completed by finding that a reinforced laminate having flexibility which is a characteristic of an ethylene (co) polymer and excellent heat sealability can be obtained by laminating the layers.

That is, the present invention relates to (I) (A) ethylene which satisfies the intrinsic viscosity (η ₁ ) of 2.0 to 9.0 dl / g and the density (d ₁ ) of 0.88 to 0.94 g / cm ^3. Copolymer with C3-C18 α-olefin 20-80
% By weight and (B) intrinsic viscosity (η ₂ ) 0.2 to 2.0 dl / g
Less, the density (d ₂₎ 0.88~0.97g / ethylene homopolymer or ethylene and 3 to 18 carbon atoms cm ³ satisfying α
A mixture containing 80 to 20% by weight of a copolymer with an olefin and having an intrinsic viscosity (η) of 2.0 to 5.2 dl / g,
Density (d) is 0.88 to 0.94 g / cm ³ and n-value is 1.
50 to 90 parts by weight of a resin component mainly composed of ultra-high molecular weight polyethylene of 7 to 3.5 and (C) an inorganic filler 10 to
(II) an ethylene / α-olefin copolymer having a (D ₁ ) density of 0.86 to 0.94 g / cm ³ and a (D ₂ ) high pressure for a layer comprising a resin composition containing 50 parts by weight. What is provided is a reinforced laminate characterized by laminating, as an inner layer and / or an outer layer, a layer made of at least one ethylene (co) polymer selected from ethylene (co) polymers obtained by a radical polymerization method. Is. The present invention also has a density of 0.86 to 0.94 g / in the above inorganic filler.
It is intended to provide a reinforced laminate characterized by using a masterbatch composed of 10 to 50% by weight of an ethylene / α-olefin copolymer of cm ³ and 50 to 90% by weight of an inorganic filler.

The details of the present invention will be described below. Ethylene / α-used as the high molecular weight component (A) in the present invention
The olefin copolymer is ethylene and α having 3 to 18 carbon atoms.
-With olefin as a component, especially having 4 carbon atoms
Those using α-olefins of 10 to 10 are preferable from the viewpoint of mechanical properties. Specifically as the α-olefin, 1-
Butene, 1-pentene, 1-hexene, 4-methyl-1
-Pentene, 1-octene, 1-nonene, 1-decene and the like. It should be noted that the α-olefin may be used in combination of two or more kinds.

The above high molecular weight component (A) ethylene / α-
The olefin copolymer has an intrinsic viscosity (η ₁ ) of 2.0.
.About.9.0 dl / g, preferably 2.3 to 8.5 dl / g, and more preferably 2.5 to 8.0 dl / g.
When (η ₁ ) is less than 2.0 dl / g, the melt elasticity and mechanical properties of the obtained composition are low, and when it exceeds 9.0 dl / g, the moldability is deteriorated.

The density (d ₁ ) of the component (A) is 0.88.
In the range of up to 0.94 g / cm ³ , preferably 0.89 to 0.93 g /
cm ³ is used. Those having a (d ₁ ) of less than 0.88 g / cm ³ are not preferable because they are difficult to manufacture and cause stickiness of the obtained composition. On the other hand, (d ₁ ) is 0.9
When it exceeds 4 g / cm ³ , melt elasticity and mechanical properties are deteriorated, which is not preferable.

As the component (A) used in the present invention, ethylene / α particularly satisfying the following conditions (a) and (b):
-Olefin copolymers are preferable because they significantly improve the mechanical strength at low temperatures. (A) In the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method, the ratio S of the area Ib under the curve at the elution temperature of 25 to 90 ° C. to the area Ia under the curve at the elution temperature of 90 ° C. or higher
(Ib / Ia) is S ₁ or less calculated from the following equation, S ₁ = 20 η ₁ ⁻¹ exp [−50 (d ₁ −0.90)] (b) 25 ° C. o-dichlorobenzene soluble content W ( (% By weight) is W ₁ or more calculated from the following formula, W ₁ = 20 exp (−η ₁ ). As in (a) above, continuous temperature rise from L. Wild et al. Elution fractionation method (Temperature
Rising Elution Fractionation (TREF); Journal of Poly
mer Science: Polymer Physics Edition, Vol.20, 441-4
55 (1982)) in the elution temperature-elution amount curve (FIG. 1), between the area Ia under the curve at an elution temperature of 90 ° C. or more and the area Ib under the curve at an elution temperature of 25 to 90 ° C. It is necessary that a specific relationship be established. The value of S is S
_When it exceeds ₁ , the branching distribution becomes almost uniform, and as a result, the highly branched component extremely effective for melt elasticity and mechanical properties, particularly mechanical properties at low temperature, is relatively decreased, which is not preferable. In addition, the above (b) 25 ℃ o-
The dichlorobenzene-soluble component represents the amount of a component having an extremely large amount of branching such that the elution temperature is too low to be quantified by the continuous temperature-rising elution fractionation method described above. It is necessary to be above. When the value of W is less than W ₁ , there are few highly branched components that are extremely effective for melt elasticity and mechanical properties, particularly mechanical properties at low temperatures, and thus it is not preferable as described above.

The low molecular weight component (B) used in the present invention is an ethylene homopolymer or an ethylene / α-olefin copolymer. As the α-olefin, those having 3 to 18 carbon atoms are used as in the case of the component (A), and those having 4 to 10 carbon atoms are particularly preferable from the viewpoint of mechanical properties. Specifically, 1-butene, 1-pentene, 1-hexene, 4
-Methyl-1-pentene, 1-octene, 1-nonene,
1-decene etc. are mentioned. It should be noted that the α-olefin may be used in combination of two or more kinds.

The intrinsic viscosity (η ₂ ) of the above component (B) is 0.2.
A range of less than 2.0 dL / g is used, preferably 0.3.
˜1.8 dl / g, more preferably 0.4 to 1.6 dl / g. If (η ₂ ) is less than 0.2 dl / g, the mechanical properties of the obtained composition, particularly at low temperature, are deteriorated, while if it exceeds 2.0 dl / g, the flow properties of the composition are low. Both of them are not preferable because they decrease.

The density (d ₂ ) of the component (B) is 0.88.
The range is from 0.97 g / cm ³ , preferably 0.91 to 0.9.
96 g / cm ³ is used. Those having a (d ₂ ) of less than 0.88 g / cm ³ are not preferable because they are difficult to manufacture and cause stickiness of the obtained composition. On the other hand, when (d ₂ ) exceeds 0.97 g / cm ³ , melt elasticity and mechanical properties deteriorate, which is not preferable.

The blending ratio of the component (A) and the component (B) in the present invention is 20 to 80% by weight of the component (A) and 80 to 20% by weight of the component (B), and preferably 3 for each.
0 to 70% by weight and 70 to 30% by weight. When the amount of the component (A) is less than 20% by weight, melt elasticity and mechanical properties, especially at low temperature, are low, while 80% by weight.
When it exceeds, the flow characteristics deteriorate, so neither of them can be used.

The resin component of the ultrahigh molecular weight polyethylene layer of the present invention is obtained by blending both components (A) and (B) as described above, but the properties of the resin component after blending must be within the specified range. I won't. That is, the intrinsic viscosity (η) of the resin component is 2.0 to 5.2 dl / g, preferably 2.5 to
It is 4.0 dl / g. When (η) is less than 2.0 dl / g, melt viscosity and mechanical properties, especially at low temperature, are low,
When it exceeds 5.2 dl / g, the flow characteristics are deteriorated, so that both are not preferable. The density (d) of the resin component is 0.
88 to 0.94 g / cm ³ , preferably 0.89 to 0.9
It is 3 g / cm ³ . When (d) is less than 0.88 g / cm ^3, it is difficult to manufacture and causes stickiness of the resin component, and when it exceeds 0.94 g / cm ³ , mechanical properties such as dart impact value deteriorate. . Further, the n-value of the resin component is 1.7 to 3.
It is necessary to be 5, and preferably 2.0 to 3.0. When the n-value is less than 1.7, the high-speed moldability is poor and the value is 3.5.
When it exceeds, white powder and smoke are likely to be generated during molding due to an increase in low molecular weight components.

The method for producing the resin component of the (I) layer used in the present invention is not particularly limited. For example, the components (A) and (B) may be individually produced by one-step polymerization, and then the two may be mixed by a known method, or two-step or more multi-step polymerization may be performed by a known polymerization method. It may be manufactured. In the case of the former mixing, a known method such as a method of kneading with a single-screw or twin-screw extruder or a Banbury mixer, or a solution mixing method can be used. The latter method by multi-stage polymerization means, for example, using a plurality of reactors, for example, maintaining the reactor of the first stage under the polymerization conditions of the high molecular weight ethylene / α-olefin copolymer of the component (A), A method for producing a resin component by maintaining the second stage reactor under the polymerization conditions of the low molecular weight polymer of component (B) and continuously circulating the polymer produced in the first stage to the second stage. is there. However, (A) and (B)
Each component of may be produced in any reactor,
The manufacturing order and the number of stages are not particularly limited.

The component (C) inorganic filler used in the present invention may be in the form of powder, granule, plate, needle, sphere, fiber or the like. Specific examples include calcium carbonate and magnesium carbonate. , Calcium sulfate, calcium silicate, aluminum hydroxide, magnesium hydroxide, clay, diatomaceous earth, talc, alumina, silica sand, iron oxide, metal powder, antimony trioxide, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon Powdery filler such as black, mica, sericite, pyrophyllite, foil-like filler such as aluminum flake, flat or scale-like filler such as graphite, glass fiber, carbon fiber, graphite fiber, whiskers, metal fiber , Examples of mineral fibers such as silicone carbide fiber, asbestos and wollastonite Door can be. Among these inorganic fillers, calcium carbonate is the most preferable from the viewpoints of easy incineration and economical efficiency.

The calcium carbonate may be so-called heavy calcium carbonate obtained by mechanically crushing limestone, or so-called precipitated calcium carbonate obtained by a carbon dioxide gas compounding method. However, it is necessary that the average particle size obtained from the specific surface area is 4 μm or less. If calcium carbonate having an average particle size of more than 4 μm is used, a composition having excellent impact resistance cannot be obtained. The average particle size is preferably 3 μm or less.

In the present invention, the inorganic filler may be used as it is, but in order to further improve the dispersibility of the inorganic filler in the composition (thus improving the impact resistance etc.) and enhancing the moldability. In addition, it is preferable to coat the surface with a fatty acid such as stearic acid or oleic acid or a derivative thereof, or a surface treatment agent such as paraffin, wax, organic silane, organic titanate, or epoxy resin. When the above surface treatment is performed, the amount of the surface treatment agent is 0.2 with respect to the inorganic filler.
It is preferably about 2% by weight. If it is less than 0.2% by weight, the dispersibility or processability may not be improved in some cases, and even if a surface treatment agent in excess of 2% by weight is used, further improvement in properties is usually not expected and it is not economical.

(C) in 100 parts by weight of the resin composition
The amount of the inorganic filler compounded is 10 to 50 parts by weight, preferably 2
It is 0 to 40 parts by weight. If it is less than 10 parts by weight, the effect of easy incineration cannot be obtained, and if it exceeds 50 parts by weight, mechanical strength such as tensile fracture strength and dirt impact strength is inferior, so it is preferable to select from this range.

In the present invention, when the inorganic filler is blended with the resin component, it can be easily blended by a known method which is generally used as a blending method of the resin composition. As one example, the above components (A) to (C)
And, if desired, various additives are dry blended by using a mixer such as a tumbler, a ribbon blender or a Henschel type mixer, and then melt-mixed by a continuous melt kneader such as a single-screw extruder or a twin-screw extruder, and then extruded. The resin composition can be obtained by preparing pellets by

As another compounding method, the density is 0.8.
A resin composition having a high concentration of the inorganic filler (hereinafter referred to as “masterbatch”) is obtained by mixing 6 to 0.94 g / cm ³ of the ethylene / α-olefin copolymer and the total amount of the inorganic filler, and melt-kneading the mixture. It is also possible to obtain a resin composition by a so-called masterbatch method in which the masterbatch is mixed with the above components (A) and (B) and optionally various additives. According to the masterbatch method, 10 to 50% by weight of an ethylene / α-olefin copolymer having a density of 0.86 to 0.94 g / cm ³ and an inorganic filler of 50 to 50% by weight are used.
It is preferable to use a masterbatch consisting of 90% by weight. When the amount of the inorganic filler exceeds 90% by weight, the dispersibility of the inorganic filler is lowered and the mechanical strength of the laminate is lowered,
On the other hand, if the amount is less than 50% by weight, the compounding amount of the masterbatch increases, resulting in poor productivity and the effect of the masterbatch method cannot be obtained.

The components of the layer (II) in the present invention include
(D ₁ ) Ethylene / α-with a density of 0.86 to 0.94 g / cm ³
At least one selected from olefin copolymers and ethylene (co) polymers by (D ₂ ) high pressure radical polymerization method
Seed ethylene (co) polymers.

The above (D ₁ ) density is 0.86 to 0.94 g / cm ^3.
The ethylene / α-olefin copolymer of ethylene is an ethylene-α-olefin having 3 to 12 carbon atoms, which is obtained by a high, medium or low pressure method and other known polymerization methods using a Ziegler catalyst or the like.
It is a copolymer with olefin and has a density of 0.86 to 0.9.
Ultra low density polyethylene less than 1 g / cm ³ and density 0.9
It contains 1 to 0.94 g / cm ³ of linear low density polyethylene. Specific α-olefins include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-dodecene and the like. Among these, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable, and 1-butene is particularly preferable. Α- in ethylene copolymer
The olefin content is preferably 5 to 40 mol%.

As the ethylene (co) polymer (D ₂ ) produced by the high pressure radical polymerization method, an ethylene homopolymer having a density of 0.91 to 0.94 g / cm ³ produced by the high pressure radical polymerization method,
Examples thereof include an ethylene-vinyl ester copolymer and a copolymer of ethylene and an α, β-unsaturated carboxylic acid or its derivative.

Density of 0.9 by the high pressure radical polymerization method
The ethylene homopolymer of 1 to 0.94 g / cm ³ is a known high-pressure low-density polyethylene.

The above-mentioned ethylene-vinyl ester copolymer means ethylene as a main component produced by a high-pressure radical polymerization method, and vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, stearic acid. It is a copolymer of vinyl ester monomers such as vinyl and vinyl trifluoroacetate and other unsaturated monomers. Among these, ethylene-vinyl acetate copolymers can be mentioned as particularly preferable ones. That is, ethylene 50 to 99.5% by weight, vinyl acetate 0.5 to
Copolymers consisting of 50% by weight and 0 to 25% by weight of other unsaturated monomers are preferred.

The above-mentioned copolymer of ethylene with α, β-unsaturated carboxylic acid or its derivative is a copolymer of ethylene with α, β-unsaturated carboxylic acid or its derivative and other unsaturated monomers. Examples of the compound include metal salts, amides, and imides thereof, and preferably ethylene-ethyl acrylate copolymer produced by a high-pressure radical polymerization method. That is, ethylene 50
~ 99.5% by weight, acrylic acid ethyl ester 0.5-5
Copolymers consisting of 0% by weight and 0 to 25% by weight of other unsaturated monomers are preferred.

The other unsaturated monomer is propylene,
1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, olefins having 3 to 10 carbon atoms of 1 decene; vinyl esters of C ₂ -C ₃ alkanoic acid; methyl acrylate , Methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, glycidyl acrylate,
At least one selected from the group consisting of acrylic acid and methacrylic acid esters such as glycidyl methacrylate; ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and maleic anhydride, or anhydrides thereof. It is a seed.

The melt flow rate (MFR) of the ethylene (co) polymer used as the (II) layer in the present invention is
0.01-50g / 10min, preferably 0.1-30g / 10mi
n, more preferably 0.2 to 20 g / 10 min.

The method for producing the reinforced laminate of the present invention includes:
Various known methods such as a co-extrusion method, an extrusion lamination method and a combination thereof can be adopted.
In the case of producing a film of an easily incinerated reinforced laminate, a layer made of a resin composition in which an inorganic filler is mixed with a resin component containing ultra-high molecular weight polyethylene as a main component, and a raw material resin for an inner layer and / or an outer layer are respectively prepared. A method of extruding with a separate extruder, supplying to a die having a multilayer structure, and molding by a co-extrusion molding method of an in-die bonding type and / or an outside-die bonding type,
Alternatively, there may be mentioned a laminating method in which an inner layer and / or an outer layer is melt-extruded and laminated on a layer formed of a resin composition in which an inorganic filler is mixed with a resin component containing a preformed ultrahigh molecular weight polyethylene as a main component. When a layer made of a resin composition in which an inorganic filler is mixed with a resin component containing ultra-high molecular weight polyethylene as a main component and an inner layer and / or an outer layer are molded in advance, these layers are uniaxial or biaxial. It may be stretched in the direction.

The thickness of the reinforced laminate of the present invention varies depending on the use, but it is 10 to 50 μm for a dust bag and 50 to 250 μm for a heavy packaging bag. Among these layer configurations, the layer made of a resin composition in which an inorganic filler is mixed with a resin component containing ultra-high molecular weight polyethylene as a main component has a thickness of 5 to 200 μm.
Is preferred. If it is less than 5 μm, the mechanical strength is weak, and if it exceeds 200 μm, the film bag lacks flexibility and is difficult to handle. The thickness of the inner layer and / or the outer layer is preferably 5 to 50 μm. If it is less than 5 μm, the heat-sealing strength is not sufficient, and if it exceeds 50 μm, the ratio to the ultra high molecular weight polyethylene layer becomes large,
It is not preferable because sufficient mechanical strength characteristics cannot be obtained.

In the present invention, when preparing the resin components of the (I) and (II) layers, if necessary, an antistatic agent, an antifogging agent, an organic filler, an antioxidant, a lubricant, an organic or inorganic type Known additives such as a pigment, an ultraviolet absorber, a dispersant, a nucleating agent, a foaming agent, a flame retardant, and a cross-linking agent can be added to the extent that the characteristics of the invention are not essentially impaired.

[0033]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention. First, the test method used in the present invention will be described. <Test Method> (1) Intrinsic Viscosity The intrinsic viscosity [η] measured with a 135 ° C. decalin solution is shown. (2) Density Density gradient tube method (23
The density measured in (° C) is shown. (3) Continuous heating elution fractionation method L. Wild et al. (J. Polymer Sci, PPE, Vol. 20, 44)
1-455 (1982)). [Measurement method] In a stainless steel column having a capacity of 8.5 liter packed with Celite 545, the sample was put into o-dichlorobenzene so that the concentration was 0.05% by weight, and 135 ° C.
After injecting 5 ml of the solution that has been heated and dissolved in 2., the sample is deposited on the surface of Celite by cooling to 25 ° C. at a cooling rate of 4 ° C./min. Next, while flowing o-dichlorobenzene through this column at a constant rate of 1 ml / min, the temperature is raised at a constant rate of 50 ° C./hr, and the samples are sequentially eluted. At this time, the relationship between the elution temperature and the elution amount, that is, the composition distribution is obtained by measuring the absorption of the asymmetric stretching vibration of methylene for the wave number of 2950 cm ^-1 in the sample eluted in the solvent using an infrared spectrophotometer. . (4) Area ratio S by continuous temperature rising elution fractionation method In the graph (Fig. 1) showing the composition distribution by the relationship between the elution temperature and the elution amount by continuous temperature rising elution fractionation method, the area under the curve at an elution temperature of 90 ° C or higher Is defined as Ia, and the elution temperature is 25 to
When the area under the curve at 90 ° C is Ib, the area ratio S
Is represented by S = Ib / Ia. (5) 25 ° C. o-dichlorobenzene soluble component W 0.5 g of a sample was heated in 20 ml of o-dichlorobenzene at 135 ° C. for 2 hours to completely dissolve the sample and then cooled to 25 ° C. in 2 hours. To do. This solution at room temperature 25
After standing overnight at ℃, filtered through a Teflon filter to collect the filtrate, measure the absorption of methylene asymmetric stretching vibration at a wave number of 2950 cm ^-1 with an infrared spectrophotometer, and use the calibration curve prepared in advance to collect the filtrate. Quantify the sample concentration of. (6) n-value Using a Koka type flow tester manufactured by Shimadzu Corporation, extruded from a die of 2 mmφ × 40 mm at a resin temperature of 170 ° C., a low test pressure of 20 kg / cm ² and a high test pressure of 150
The apparent shear rate in kg / cm ² is calculated and calculated by the following equation 1.

[Equation 1] (7) Melt flow rate (MFR) Measured according to JIS K6760. (Measurement temperature 1
(90 ° C., load 2.16 kg) (8) Tensile breaking strength and tensile breaking elongation of film Measured in accordance with ASTM D882. (Pulling speed 5
00 mm / min) (9) Dirt impact strength Measured according to ASTM D1709. (10) Tensile Impact Value Measured according to ASTM D1822. (-10
(° C) (11) Heat seal temperature Using a heat sealer manufactured by Tester Sangyo Co., Ltd., width 15
mm, heat seal time 1 second, heat seal pressure 1.5k
Seal the sample under the condition that only gf / cm ² and the upper bar are heated up, and use it as a sample. The heat seal strength of this sample is measured by T peeling at a pulling speed of 300 mm / min, and the temperature at which the heat seal strength reaches 1 kgf / 15 mm width is taken as the heat seal temperature. (12) Film moldability Extrusion conditions such as a decrease in the extrusion amount, a rise in the extrusion pressure, an increase in the power consumption, a decrease in the high-speed moldability, the film stability, and the appearance of the film when the film is formed alone or in the coextrusion molding process. Etc., and evaluate based on the following three-stage criteria. ◯: Extrusion status, film stability, film appearance, etc. were all good Δ: Extrusion status, film stability, film appearance, etc. were poor ×: Extrusion status, film stability, film appearance, etc. Also bad

The inorganic filler, masterbatch resin and inner / outer layer resin used in Examples and Comparative Examples are shown below. <Inorganic filler> Calcium carbonate [Average particle size = 1.7 µm; trade name: BSK-5, Dowa Calfine Co., Ltd.] <Resin for masterbatch> (1) Ultra low density polyethylene (VLDPE) [Density = 0.905g / cm ³ , MFR = 1.0g / 10min; Trade name: Nisseki Softlex D9510, Nippon Petrochemical
Ltd.] (2) linear low density polyethylene (LLDPE-1) [Density ^{= 0.925g / cm 3, MFR =} 2.0g / 10min; trade name: Nippon Rinirekkusu BF3310, Nippon Oil of
Co., Ltd. <Resin for Inner and Outer Layers> (1) Ultra Low Density Polyethylene (VLDPE) [Density = 0.905 g / cm ³ , MFR = 1.0 g / 10 min; Trade Name: Nisseki Softlex D9510, Nippon Oil Co., Ltd. Chemistry
Ltd.] (2) linear low density polyethylene (LLDPE-1) [Density ^{= 0.925g / cm 3, MFR =} 2.0g / 10min; trade name: Nippon Rinirekkusu BF3310, Nippon Petrochemicals
(3) Ethylene-vinyl acetate copolymer (EVA) [VA content = 3% by weight, MFR = 0.3 g / 10 min; trade name: Nisseki Lexron V152, manufactured by Nippon Petrochemical Co., Ltd. ] (4) Ethylene-ethyl acrylate copolymer (EEA) [EA content = 5% by weight, MFR = 1.0 g / 10 min; trade name: Nisseki Lexlon A2050, manufactured by Nippon Petrochemical Co., Ltd.]

<Example 1> Intrinsic viscosity (η ₁ ) 4.3 dl / g and density (d ₁ ) 0 as component (A) obtained by a two-stage polymerization process according to Japanese Patent Laid-Open No. 4-249562. 47% by weight of ethylene / 1-butene copolymer of 0.916 g / cm ³ and intrinsic viscosity (η ₂ ) as component (B)
A mixture J ₁ consisting of 0.83 dl / g and 53% by weight of an ethylene / α-olefin copolymer having a density (d ₂ ) of 0.917 g / cm ³ was prepared. The physical properties thereof are shown in Table 1. To 70 parts by weight of this mixture, 30 parts by weight of calcium carbonate as a component (C) having a mean particle size of 1.7 μm obtained by surface treatment with a saturated fatty acid was mixed with a tumbler mixer, and then the screw diameter was 65 mmφ. , L / D
Extrusion temperature of 200 ° C using the same direction twin-screw extruder of = 30
(Cylinder temperature 200 ° C., die temperature 200 ° C.) were melt mixed, and pellets were prepared through a pelletizer.
The resin composition thus obtained is used as the resin for the core layer,
The linear low density polyethylene (LLDPE-1) was used as the resin for the inner and outer layers to form a laminated film using a 2-kind 3-layer coextrusion inflation film molding machine. The blown film molding machine has a screw diameter of 65 mmφ and 4
It was equipped with two single-screw extruders of 0 mmφ and L / D = 25, and was molded under the conditions of an extrusion temperature of 200 ° C. and a blow-up ratio of 2.0. The laminated film has a thickness of 1 core layer.
The thickness was 50 μm, and the inner and outer layers were each 15 μm. The results of measuring the physical properties of the obtained laminated film are shown in Table 2. From the results in the table, it is understood that the film has good moldability, and the laminated film has excellent tensile breaking strength, tensile breaking elongation, and dart impact strength.

<Examples 2 to 5> Component (A) of resin for core layer
And (B) and the resin for the inner and outer layers was changed, and the masterbatch method in which the resin for the masterbatch was added when calcium carbonate was further compounded was adopted, and the same procedure as in Example 1 was carried out. Table 1 shows the compositions and physical properties of the components (A) and (B) of the resin for core layer and the mixtures J _{2 to} J ₅ thereof. Tables 2 and 3 show the constitution and physical properties of the laminated film.

<Example 6> The same procedure as in Example 1 was carried out except that a resin component with W <W ₁ was used as the component (A). The results are shown in Tables 1 and 3.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

<Comparative Example 1> The compounding amount of calcium carbonate was 6
The same procedure as in Example 1 was carried out except that 0 part by weight was used.
That is, as the polyethylene composition of the resin for the core layer, J ₁ was used as in Example 1 (Table 4). Table 5 shows the constitution and physical properties of the laminated film. As can be seen from the table, the moldability of the film is poor, and the tensile breaking strength, tensile breaking elongation, and dart impact strength of the laminated film are poor, which is not preferable.

Comparative Example 2 A polyethylene composition H ₁ was used in which the component (A) was W <W ₁ and the intrinsic viscosity of the mixture of the components (A) and (B) was 1.45 dl / g. Others were the same as in Example 1. Table 4 shows the composition and physical properties of H ₁ , and Table 5 shows the constitution and physical properties of the laminated film. As can be seen from the table, the moldability of the film is poor, and the tensile breaking strength, tensile breaking elongation, and dart impact strength of the laminated film are poor, which is not preferable.

<Comparative Example 3> Consists of 16% by weight of component (A) and 84% by weight of component (B), and the intrinsic viscosity of the mixture of both components is 1.33 dl / g, the density is 0.951 g / cm ³ and Besides n- value was used a resin component H ₂ is 1.60, was obtained in the same manner as in example 1. Table 4 shows the composition and physical properties of H _2.
Table 5 shows the constitution and physical properties of the laminated film.
As can be seen from the table, the moldability of the film is rather poor, and the tensile breaking strength, tensile breaking elongation, and dart impact strength of the laminated film are inferior.

Comparative Example 4 A resin component H ₃ comprising 85% by weight of component (A) and 15% by weight of component (B) and having a limiting viscosity of a mixture of both components of 1.81 dl / g was used. Was performed in the same manner as in Example 1. Table 4 shows the composition and physical properties of H ₃ , and Table 6 shows the constitution and physical properties of the laminated film. As can be seen from the table, the moldability of the film is poor, and the tensile breaking strength, tensile breaking elongation, and dart impact strength of the laminated film are poor, which is not preferable.

Comparative Example 5 As the resin component of the core layer, a commercially available linear low density polyethylene (LLDPE-2, trade name:
Nisseki Linirex BF0310, Nippon Petrochemical Co., Ltd.
The same method as in Example 1 was used, except that L
Table 4 shows the physical properties of LDPE-2, and Table 6 shows the constitution and physical properties of the laminated film. As can be seen from the table, the moldability of the film is rather poor, and the tensile breaking strength, tensile breaking elongation, and dart impact strength of the laminated film are inferior, which is not preferable.

Comparative Example 6 Same as Example 1 except that other commercially available linear low density polyethylene (LLDPE-3, trade name: # 10, manufactured by Phillips) was used as the resin component of the core layer. I went the same way. Table 4 shows the physical properties of LLDPE-3.
Table 6 shows the constitution and physical properties of the laminated film. As can be seen from the table, the moldability of the film is rather poor, and the tensile breaking strength, tensile breaking elongation, and dart impact strength of the laminated film are inferior, which is not preferable.

[0047]

[Table 4]

[0048]

[Table 5]

[0049]

[Table 6]

<Reference Examples 1 to 4> The heat sealing temperature of the reinforced laminate of the present invention was compared with the heat sealing temperature of only the resin composition layer used in the reinforced laminate. Using J ₁ and J ₂ as the core resin, 30 parts by weight of calcium carbonate was mixed with 70 parts by weight of each to form a resin composition,
The LLDPE-1 was used as the resin for the inner and outer layers.
The results are shown in Table 7. As can be seen from the table, when the inner and outer layers are not laminated, the heat seal temperature is high and the heat seal characteristics are poor.

[0051]

[Table 7]

[0052]

INDUSTRIAL APPLICABILITY The reinforced laminate of the present invention has excellent heat resistance, rigidity, dimensional stability, creep properties, mechanical properties and the like as a molded product, and is flexible as an ethylene (co) polymer property. It has excellent heat resistance and heat sealability, and has a low calorific value when incinerated. As a result of having these advantages, the reinforced laminate can be suitably used for molding methods such as extrusion molding, blow molding, and injection molding, and various films and sheets such as dust bags, medical waste bags, and heavy packaging bags. It can be used as a wide variety of molded products such as pipes, hollow containers, various coating materials, and foam materials.

[Brief description of drawings]

FIG. 1 is a schematic diagram of an area ratio S in an elution temperature-elution amount curve by a continuous temperature rising elution fractionation method.

Claims (3)

[Claims] 1. (I) (A) Intrinsic viscosity (η ₁ ) 2.0 to 9.
20 to 80% by weight of a copolymer of ethylene and an α-olefin having ³ to 18 carbon atoms, which satisfies 0 dl / g and a density (d ₁ ) of 0.88 to 0.94 g / cm ³ , and (B) an intrinsic viscosity ( η ₂ ) 0.2
To less than 2.0 dl / g, density (d ₂ ) 0.88 to 0.97 g / cm ³
A mixture containing 80 to 20% by weight of an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 18 carbon atoms, and having an intrinsic viscosity (η) of 2.0.
Resin component 50 to 90 based on ultra high molecular weight polyethylene having a density of (d) of 0.88 to 0.94 g / cm ³ and an n-value of 1.7 to 3.5. (II) (D ₁ ) ethylene / α having a density of 0.86 to 0.94 g / cm ³ with respect to a layer made of a resin composition containing 10 parts by weight and (C) 10 to 50 parts by weight of an inorganic filler. -A layer composed of an olefin copolymer and at least one ethylene (co) polymer selected from ethylene (co) polymers by (D ₂ ) high-pressure radical polymerization is laminated as an inner layer and / or an outer layer. A reinforced laminated body characterized by. 2. The reinforced laminate according to claim 1, wherein the ethylene / α-olefin copolymer as the component (A) satisfies the following (a) and (b): In the elution temperature-elution amount curve by the continuous temperature elution fractionation method, the ratio S (Ib / Ib / of the area Ib under the curve of the elution temperature of 25 to 90 ° C. to the area Ia under the curve of the elution temperature of 90 ° C. or more
Ia) is not more than S ₁ calculated from the following equation, S ₁ = 20η ₁ ⁻¹ exp [−50 (d ₁ −0.90)] (b) 25 ° C. o-dichlorobenzene soluble content W (% by weight) Is W ₁ or more calculated from the following equation, W ₁ = 20 exp (−η ₁ ). 3. When blending the inorganic filler, 10 to 50% by weight of an ethylene / α-olefin copolymer having a density of 0.86 to 0.94 g / cm ³ and 50 to 90% by weight of an inorganic filler. A reinforced laminate according to claim 1 or 2, wherein a masterbatch consisting of is used.