JPH0769335A - Easy incineration multilayer plastic structure - Google Patents

Abstract

(57) [Summary] [Purpose] Burning calories are sufficiently lower than conventional containers for simple polyolefins, less odor and gas are generated during incineration, and they have excellent surface properties, surface gloss, and impact strength. Provide an easily incinerated multi-layer plastic structure. [Structure] A polyester resin layer is provided on the outer surface layer, and an impact resistance improver is added to the polyolefin resin layer containing an inorganic filler.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic structure having a multi-layer structure, more specifically, a multi-layer blow-molded container, a multi-layer sheet, formed from a polyester resin and an inorganic-filled polyolefin resin, A multi-layered plastic structure such as a multi-layered film, which has a lower calorific value than a conventional polyolefin simple structure and can be used for containers such as bottles and tubes having excellent surface gloss, and packaging materials .

[0002]

2. Description of the Related Art Conventionally, a single polyolefin container is
High burning calories (10,000 to 1 in the incineration process after use)
1000 kcal / kg), smoke generation, melt dripping, and other problems. Further, vinyl chloride resin is considered to have problems such as odor and gas generation during incineration.

As a method for solving these various problems, there is a method of filling a polyolefin resin with an inexpensive inorganic filler such as calcium carbonate to reduce burning calories and improve the incineration property. However, in this case, there are problems that the stain resistance is poor, the appearance is not good, and the strength is weak against an impact such as dropping.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems of the prior art.
The problem is an easily incinerated multi-layered plastic structure that has a sufficiently low calorific value compared to conventional polyolefin single containers, has less odor and gas during incineration, and has excellent surface properties, surface gloss, and impact strength. To provide things.

[0005]

The present invention reduces the burned calories of the entire structure to about 70% of that of the polyolefin resin alone, prevents the impact strength from dropping and the like from decreasing, and has excellent surface properties and Since it has surface gloss, it is characterized in that an impact resistance improver is added to the inorganic filler-containing polyolefin resin layer and at least one layer of the layer constitution is a polyester resin layer.

The easily incinerated multi-layer plastic structure of the present invention is a multi-layer plastic structure having at least a polyester resin layer, an adhesive resin layer, and an inorganic filler-containing polyolefin resin layer, wherein the outer surface layer is a polyester resin layer. And the impact-resistant improver is added to the inorganic filler-containing polyolefin resin layer.

Further, an embodiment of the present invention is a layer structure of a multilayer plastic structure, comprising a polyester resin layer,
Adhesive resin layer, inorganic filler-containing polyolefin resin, and polyolefin resin layer having at least four resin structures, polyester resin layer, adhesive resin layer, inorganic filler-containing polyolefin resin layer, adhesiveness At least 3 types of resin layer and polyester resin layer 5
For example, the resin structure of layers is sequentially laminated.

In addition, a material containing a recycled material for the multilayer plastic structure in an inorganic filler-containing polyolefin resin layer, and a recycled material for the multilayer plastic structure between the adhesive resin layer and the inorganic filler-containing polyolefin resin layer. Provided are those having a material layer, those having a recycled material layer of the multilayer plastic structure on one side surface or both side surfaces of the polyolefin resin layer, and the like.

The inorganic filler-containing polyolefin resin layer used in the present invention is a polypropylene resin such as a homopolymer, a block copolymer or a random copolymer, or a polyethylene resin having a low density, a medium density, a high density or the like. A polyolefin resin containing 60% by weight of an inorganic material can be used.

As the impact resistance improving component added to this layer, a glycidyl group-containing resin, a resin comprising an ethylene / α-olefin copolymer, a resin comprising a propylene / α-olefin copolymer and the like can be used.

As the polyester resin used in the present invention, a resin composed of a copolymer of a polybasic acid and a polyhydric alcohol can be used. Such polybasic acid preferably contains terephthalic acid as a main component, and polyhydric alcohol preferably contains ethylene glycol as a main component. The polybasic acid and polyhydric alcohol,
Other polybasic acids and other polyhydric alcohols can be included as comonomer components, respectively.

Other polybasic acids that can be contained as a comonomer component in the polybasic acid include isophthalic acid,
A polybasic acid such as naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid or diphenyl ether dicarboxylic acid can be used.

Other polyhydric alcohols which can be contained as a comonomer component in the polyhydric alcohol include trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentylene glycol, diethylene glycol, 1,
A polyhydric alcohol component such as 1-cyclohexanedimethylol can be used.

As the adhesive resin used as the adhesive layer,
An acid modified product of an ethylene / α-olefin copolymer resin, an acid modified product of a polypropylene copolymer resin, a glycidyl group-containing resin and the like can be used, and these resins may be used alone or in a blend with another resin. Ethylene / α-
In the acid-modified olefin copolymer resin, as the α-olefin, 1-butene, 1-pentene, 1-heptene, 1-octene or the like can be used alone or in combination. As an acid modification method, an ethylenically unsaturated carboxylic acid or the like can be obtained by graft-modifying the copolymer resin with an acid anhydride thereof to obtain an acid modification product.

The glycidyl group-containing resin may be a copolymer of a glycidyl group-containing composition and ethylene, or a copolymer of a glycidyl group-containing composition and another α-olefin. As the glycidyl-containing composition, an acrylic ester such as glycidyl methacrylate can be used. The content of the glycidyl group in the glycidyl group-containing copolymer resin is preferably about 8 to 20 mol%. If the glycidyl group content is too large, the thermoplastic resin lacks thermal stability, and if it is too small, the adhesiveness to the polyester resin becomes poor. Become.

As the inorganic filler in the inorganic filler-containing polyolefin resin layer, calcium carbonate, talc, mica, aluminum hydroxide, silica and the like are preferable, and when the adhesiveness with the polyolefin is poor, the surface treatment of the inorganic filler is carried out. Alternatively, a coupling agent may be used. The filling amount of the inorganic filler can be up to about 75% by weight, but about 10 to 65% is preferable. If the filling amount is too large, the workability and drop impact properties will be poor, and conversely, if the filling amount is too small, the effect of reducing burned calories will be small.

The polyolefin resin used in the present invention has a density of about 0.85 to 0.97, such as ultra low density polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, and the like. , Or a mixture thereof. Further, it may be a polypropylene resin, for example, a polypropylene homopolymer, a random copolymer or a block copolymer of propylene and ethylene or another α-olefin, or a mixture of these resins.

The impact resistance improving component added to the inorganic filler-containing polyolefin resin layer is a glycidyl group-containing resin, a resin comprising an ethylene / α-olefin copolymer, or a propylene / α-olefin copolymer. The resin may be a resin, and the resin used for the adhesive layer or the resin having a composition different from that of the resin can be used alone or as a mixture thereof.

As the polyolefin resin layer, a polyethylene resin having a density of about 0.85 to 0.97, for example, ultra low density polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, etc., or a mixture thereof Etc. can be used. Further, it may be a polypropylene resin, for example, a polypropylene homopolymer, a random copolymer or a block copolymer of propylene and ethylene or another α-olefin, or a mixture of these resins. As the other polyolefin resin, polybutene resin, polymethylpentene resin, or the like can be used. It may also be a mixture of these polyolefin resins.

The polyolefin resin layer containing an inorganic filler and the polyolefin resin layer may be the same polyolefin resin or a combination of different polyolefin resins, but a material having good adhesiveness between the two resins. Need to choose.

There is no particular restriction on the layer thickness ratio of each layer in the multilayer plastic structure, but if the ratio of the inorganic filler-containing polyolefin layer or the polyester resin layer to the total layer becomes small, the purpose is to reduce combustion calories. Since it cannot be achieved sufficiently, the total layer thickness of the inorganic filler-containing polyolefin layer and the polyester resin layer is preferably about 30% or more of the total layer thickness, but the range is not limited.

The easily incinerated multi-layer plastic structure in the present invention may be a sheet-like material, a film-like material or a molded product thereof. Alternatively, it may be a container obtained by stacking and extruding parisons having these layer configurations and performing hollow blow molding using compressed air.

[0023]

EFFECTS OF THE INVENTION The easily incinerated multilayer plastic structure of the present invention comprises a polyester resin having low combustion calories and less generation of harmful gas during combustion, and an inorganic filler-containing polyolefin resin having low combustion calories, which are components for improving impact resistance. Is added, the strength improvement as a plastic structure, stain resistance, surface property, surface glossiness, and low burning calories are realized.

[0024]

【Example】

<Example 1> Using a multi-layer blow molding machine having three screw extruders, a non-crystalline polyester resin is used for screw A and a carboxylic acid graft-modified product of ethylene / butene copolymer resin is used as an adhesive layer for screw B. , Screw C is made of high density polyethylene resin with calcium carbonate 6
15% by weight of resin composed of ethylene / α-olefin copolymer as impact resistance improving component in 0% by weight filled resin
The added resin composition is supplied and plasticized and extruded under the following conditions to form a laminated parison which becomes a polyester resin layer / adhesive layer / inorganic filled polyethylene layer in this order from the outer layer through a blow molding head. Was sandwiched in a blow molding die having an 800 ml cylindrical bottle-shaped cavity, the upper part of the parison was cut, and blow molding was performed using compressed air. The obtained bottle has a glossy appearance,
There were no problems in terms of physical properties. The processing conditions are shown below.

Screw diameter Barrel temperature Layer ratio Screw A 30 mm 200 ° C. 10% Screw B 30 mm 200 ° C. 10% Screw C 50 mm 200 ° C. 80%

Example 2 Using a multi-layer blow molding machine having four screw extruders, a non-crystalline polyester resin is used for screw A and a carboxylic acid of ethylene / butene copolymer resin is used for screw B as an adhesive layer. A graft-modified product, a resin composition obtained by adding 15% by weight of a resin composed of an ethylene / α-olefin copolymer as an impact resistance-improving component to a resin in which 60% by weight of calcium carbonate is filled in a high-density polyethylene resin for the screw C. A high-density polyethylene resin is supplied to the screw D as the innermost layer, plasticized and extruded under the following conditions, and then a polyester resin layer / adhesive layer / inorganic-filled polyethylene layer / high-density polyethylene in order from the outer layer through a blow molding head. A laminated parison consisting of layers is formed, and the parison has a cavity of 800 ml cylindrical bottle shape. That scissors blow molding molds, after cutting the parison top were blow molded using a compressed air. The obtained bottle had an appearance gloss and had no problem in physical properties. The processing conditions are shown below.

Screw diameter Barrel temperature Layer ratio Screw A 30 mm 200 ° C. 10% Screw B 30 mm 200 ° C. 10% Screw C 50 mm 200 ° C. 70% Screw D 30 mm 200 ° C. 10%

<Embodiment 3> A bottle container having a four-layer structure was molded by the same method as in Embodiment 2, and 50: ethylene / glycidyl methacrylate copolymer resin and ethylene / α-olefin copolymer resin were used as an adhesive layer. A resin composed of propylene / α-olefin copolymer as an impact resistance-improving component in a polypropylene block copolymer resin filled with 60% by weight of calcium carbonate as an inorganic filler-containing layer by supplying materials mixed in a weight ratio of 50 20
A resin composition added by weight% and a polypropylene block copolymer resin as the innermost layer were supplied and molded. The obtained bottle had an appearance gloss and had no problem in physical properties. The processing temperature conditions are shown below.

Screw diameter Barrel temperature Layer ratio Screw A 30 mm 200 ° C. 10% Screw B 30 mm 210 ° C. 10% Screw C 50 mm 210 ° C. 70% Screw D 30 mm 210 ° C. 10%

<Example 4> A bottle container having a four-layer structure was molded by the same method as in Example 2, and a carboxylic acid graft-modified product of ethylene / butene copolymer resin was supplied as an adhesive layer to contain an inorganic filler. As a layer, a resin obtained by filling high-density polyethylene resin with 60% by weight of calcium carbonate, a material obtained by crushing a scrap product of the multilayer plastic structure according to this example, and an ethylene / glycidyl methacrylate copolymer resin are in a weight ratio of 4: 4, respectively. A resin composition mixed in a ratio of 2 and a high-density polyethylene resin as the innermost layer were supplied and molded. The obtained bottle had an appearance gloss and had no problem in physical properties. The processing temperature conditions are shown below.

Screw diameter Barrel temperature Layer ratio Screw A 30 mm 200 ° C. 10% Screw B 30 mm 200 ° C. 10% Screw C 50 mm 200 ° C. 70% Screw D 30 mm 200 ° C. 10%

Example 5 Using a multi-layer blow molding machine having three screw extruders, a non-crystalline polyester resin was used for screw A and a carboxylic acid of ethylene-butene copolymer resin was used as an adhesive layer for screw B. The graft-modified product, screw C, is a high-density polyethylene resin filled with 60% by weight of calcium carbonate, a material obtained by pulverizing a scrap product of the multilayer plastic structure according to this example, and an ethylene-glycidyl methacrylate copolymer resin. The resin composition mixed at a ratio of 4: 4: 2 was supplied and plasticized and extruded under the following conditions. The molten resin of the screw A and the molten resin of the screw B were respectively discharged into two channels after flowing out from the screw. Branch and blow through the blow molding head in order from the outer layer to the polyester resin layer / adhesive layer / inorganic filled poly Styrene layer / adhesive layer / made polyester resin layer, 10% layer ratio than the outer layer / 5% / 70% /
Forming a 5% / 10% laminated parison, sandwiching the parison into a blow mold having a cylindrical bottle-shaped cavity while pre-flowing nitrogen gas into the parison,
After cutting the upper part of the parison, blow molding was performed using compressed air. The obtained bottle had an appearance gloss, had no problem in physical properties, and had sufficient resistance to oily contents. The processing conditions are shown below.

[0033]

Comparative Example 1 Using a multi-layer blow molding machine having three screw extruders, a screw A is made of a non-crystalline polyester resin, and a screw B is made of a carboxylic acid of an ethylene / butene copolymer resin as an adhesive layer. A high-density polyethylene resin filled with 60% by weight of calcium carbonate is supplied to the graft modified product and screw C, plasticized and extruded under the following conditions, and a polyester resin layer is sequentially provided from the outer layer through a blow molding head. / Adhesive layer / Inorganic-filled polyethylene layer is formed, and the parison is sandwiched in a blow molding die having a cavity of 800 ml cylindrical bottle shape, the upper part of the parison is cut, and blow molding is performed using compressed air. It was The processing conditions are shown below.

Screw diameter Barrel temperature Layer ratio Screw A 30 mm 200 ° C. 10% Screw B 30 mm 200 ° C. 10% Screw C 50 mm 200 ° C. 80%

Comparative Example 2 Using a multi-layer blow molding machine having four screw extruders, screw A is made of an amorphous polyester resin, and screw B is made of an ethylene / butene copolymer resin carboxylic acid as an adhesive layer. Graft-modified product, screw C is a high density polyethylene resin filled with 60% by weight of calcium carbonate, screw D is a high density polyethylene resin as the innermost layer, plasticized and extruded under the following conditions, and a blow molding head To form a laminated parison consisting of a polyester resin layer / adhesive layer / inorganic filling layer / high-density polyethylene resin layer in this order from the outer layer, and the parison is inserted into a blow molding die having a 800 ml cylindrical bottle-shaped cavity. After cutting the upper part of the parison, blow molding was performed using compressed air. The processing conditions are shown below.

Screw diameter Barrel temperature Layer ratio Screw A 30 mm 200 ° C. 10% Screw B 30 mm 200 ° C. 10% Screw C 50 mm 200 ° C. 70% Screw D 30 mm 200 ° C. 10%

Comparative Example 3 A bottle container having a four-layer structure was molded by the same method as in Comparative Example 2, and an ethylene-glycidyl methacrylate copolymer resin and an ethylene / α-olefin copolymer resin were used as an adhesive layer at 50:50. By supplying the materials mixed in a weight ratio, calcium carbonate is added to the polypropylene block copolymer resin as an inorganic filler-containing layer.
A resin filled with 0% by weight and a polypropylene block copolymer resin as the innermost layer were supplied and molded. The processing temperature conditions are shown below.

Screw diameter Barrel temperature Layer ratio Screw A 30 mm 200 ° C. 10% Screw B 30 mm 210 ° C. 10% Screw C 50 mm 210 ° C. 70% Screw D 30 mm 210 ° C. 10%

<Comparative Example 4> A bottle container having a four-layer structure was molded by the same method as in Comparative Example 2, and a carboxylic acid graft modified product of an ethylene / butene copolymer resin was supplied as an adhesive layer to contain an inorganic filler. A resin composition in which a resin obtained by filling 60% by weight of calcium carbonate in a high-density polyethylene resin as a layer and a material obtained by pulverizing a scrap product of the multilayer plastic structure according to the present example are mixed in a weight ratio of 5: 5, respectively. A high density polyethylene resin was supplied as the innermost layer and molded. The processing temperature conditions are shown below.

Screw diameter Barrel temperature Layer ratio Screw A 30 mm 200 ° C. 10% Screw B 30 mm 200 ° C. 10% Screw C 50 mm 200 ° C. 70% Screw D 30 mm 200 ° C. 10%

Comparative Example 5 Using a multi-layer blow molding machine having three screw extruders, a screw A is made of a non-crystalline polyester resin, and a screw B is made of an ethylene / butene copolymer resin carboxylic acid as an adhesive layer. The graft modified product, the screw C, a high density polyethylene resin filled with 60% by weight of calcium carbonate, and a material obtained by crushing a scrap product of the multilayer plastic structure according to the present example, in a weight ratio of 5: 5, respectively. The resin composition mixed in 1. is supplied and plasticized and extruded under the following conditions. The molten resin of the screw A and the molten resin of the screw B are branched into two passages after flowing out from the screw, and are branched outside through a blow molding head. Layer to layer: polyester resin layer / adhesive layer / inorganic filled polyethylene layer / adhesive layer / polyester resin layer More 10% / 5% / 70% / 5% /
A laminated parison of 10% was formed, and while the nitrogen gas was pre-flowed into the parison, the parison was sandwiched between blow molds having a cylindrical bottle-shaped cavity, the upper part of the parison was cut, and then blown using compressed air. Molded. The processing conditions are shown below.

[0043]

Comparative Example 6 Using a single layer blow molding machine,
A high density polyethylene resin filled with 60% by weight of calcium carbonate was supplied to the screw, plasticized and extruded under the following conditions to form a parison through a blow molding head, and the parison was formed into an 800 ml cylindrical bottle-shaped cavity. It was sandwiched in a blow molding die having, and the upper part of the parison was cut, and then blow molding was performed using compressed air. The processing conditions are shown below.

[0045]

<Physical Properties Table> Burned calories Surface glossiness Drop strength (cal / g) (%) (Number of cracks) Example 1 5810 96 No damage Example 2 6370 96 No damage Example 3 6560 96 No damage Example 4 7300 96 Not damaged Example 5 5410 96 Not damaged Comparative Example 1 5120 96 3.1 times Comparative Example 2 5740 96 3.6 times Comparative Example 3 5760 96 3.0 times Comparative Example 4 6250 96 2. 9 times Comparative Example 5 4640 96 2.7 times Comparative Example 6 4390 3 1.0 times Note) Gloss is JIS Z8741 60 ° Specular gloss Drop strength is 5 ° C, average number of breaks at 1.0 m drop, n =
10. Maximum of 5 times for each sample. Burned calories are measured by the fuel test automatic cylinder fuel meter method.

[0047]

As described above, according to the present invention,
An easily incinerated multi-layer plastic structure is obtained which has an impact resistance strength against drops and the like, gloss, and an appearance that is excellent in surface properties, has a low calorific value during combustion, and generates little harmful gas.

Claims (11)

[Claims] 1. An easily incinerated multi-layer plastic structure comprising at least three resin layers, a polyester resin layer, an adhesive resin layer, and an inorganic filler-containing polyolefin resin layer, wherein the inorganic filler-containing polyolefin resin layer is provided. A multi-layered plastic structure characterized by adding a component for improving impact resistance to. 2. An easily incinerated multi-layer plastic structure comprising a resin composition of at least four layers of a polyester resin layer, an adhesive resin layer, an inorganic filler-containing polyolefin resin layer, and a polyolefin resin layer, containing an inorganic filler. A multilayer plastic structure comprising a polyolefin resin layer and an impact resistance improving component added thereto. 3. A polyester resin layer, an adhesive resin layer, an inorganic filler-containing polyolefin resin layer, an adhesive resin layer, and a polyester resin layer, which are formed by sequentially laminating at least three kinds and five layers of resin composition. An easily incinerated multi-layer plastic structure, wherein an impact-resistance improving component is added to an inorganic filler-containing polyolefin resin layer. 4. The easily incinerated multilayer plastic structure according to claim 1, wherein the polyolefin resin layer containing an inorganic filler is a polyolefin resin containing 10 to 60% by weight of an inorganic material. 5. The incinerable multilayer plastic structure according to any one of claims 1 to 4, wherein the inorganic filler-containing polyolefin resin layer contains a recycled material of the multilayer plastic structure. 6. A recycled material layer for the multi-layer plastic structure is provided between the adhesive resin layer and the inorganic filler-containing polyolefin resin layer.
Easily incinerated multi-layer plastic structure as described. 7. The easily incinerated multi-layer plastic structure according to claim 2, wherein a recycled material layer of the multi-layer plastic structure is provided on one side surface or both side surfaces of the polyolefin resin layer. 8. The easily incinerated multi-layer plastic structure according to claim 1, wherein the structure is a multi-layer blow-molded product having a polyester resin layer on its outer surface. 9. The easily incinerated multi-layer plastic structure according to claim 1, wherein the impact resistance improving component added to the inorganic filler-containing polyolefin resin layer is a resin containing a glycidyl group. 10. The impact resistance improving component added to the polyolefin resin layer containing an inorganic filler is a resin comprising an ethylene / α-olefin copolymer, and the impact resistance improving component is a resin. Easy incineration multilayer plastic structure. 11. The incinerator according to claim 1, wherein the impact resistance improving component added to the inorganic filler-containing polyolefin resin layer is a resin composed of a propylene / α-olefin copolymer. Multi-layer plastic structure.