JPS5935940A - Extra-high molecular weight polyethylene laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (1) Field of the Invention The present invention relates to a laminate obtained by melt-bonding ultra-high molecular weight polyethylene (hereinafter referred to as UHP E) and a thermoplastic resin other than UHP E. , the laminate is characterized by a small thickness.

(2) Background of the technology UHPE has the highest Ii (abrasion resistance) of all plastics, and also has excellent physical properties such as low-temperature impact resistance, sliding properties, and sound deadening properties, so it is used in bobbers, shooters, etc. It is used in a wide range of applications such as liners, conveyors, scree, pickers, etc. Demand is expected to increase significantly in the future.

(3) Prior art The present inventors focused on the excellent physical properties of UHPE, and improved the heat resistance and rigid ring physical properties, which are disadvantages of UHPE, without impairing those physical properties, and further reduced costs. C Patent Application 1983-348 for inventing a basic bonding technology for UHPE and other laminates made of thermoplastic resins other than UHPE.
76, 57-38753.

57-45328).

However, due to these prior inventions, the first fetus was UH.
When obtaining a wide and thin laminate in which the PE However, the disadvantage of causing warping was destroyed. Therefore, we conducted research to obtain a flat laminate with no warpage using a similar bonding method, and found that the second layer is a thermoplastic resin or elastomer with a mold shrinkage rate close to that of UHPE. It has been found that a laminate with small warpage can be obtained only in certain cases. Furthermore, as a result of research to ensure that warpage-free laminates can be obtained even when using a wide range of other thermoplastic resins, we found that the first layer is made of UHPE and the third layer is made of UHP.
In a laminate made of a thermoplastic resin other than E, the second layer interposed between the first layer and the third layer has low creep, a mold shrinkage rate lower than both layers, and a high rigidity. It was discovered that by providing layers, a laminate with low creep and low stiffness can be obtained.
Following the above application, a patent application was filed.

However, in this prior application, the second layer is made of a thermoplastic resin filled in a layered body having pores or pores, a thermoplastic resin containing a mixture of powder and granules, or a thermosetting resin. Therefore, when using a mixture, it is complicated to mix them, and when using a crushed thermosetting resin, it is difficult to melt thermoplastic resins other than U)]' PE for the first layer and UHPE for the third layer. At the same time, the thermosetting resin composition must be cured, which is very complicated.

(4) Purpose of the invention The purpose of the present invention is that the first layer is UHPE and the third layer is UHP.
E J ivy) thermoplastic resin, between these,
As a second layer, mixing powder with a thermoplastic resin;
Another object of the present invention is to provide a small UHPE laminate with a layer that does not require curing of a thermosetting resin at the same time as melting of a thermoplastic resin.

(5) Structure of the Invention The above-mentioned object of the present invention is to provide a laminate including a UHPE layer and a thermoplastic resin layer other than UHPE, which is heated at a temperature of at least the crystal melting point of UHPE and at most 300°C, and at a temperature of 5 to 97 m2. The first layer is UHPE and the third layer is UHP, obtained by molding at a pressure of above and 500 kg/crn2 or less.
Oak is made of thermoplastic resin other than E, and as a second layer between these, the bending elastic modulus is 5,000 gamma theory 2''.
This can be achieved by a UHPE thin layered body characterized by interposing a thermoplastic resin having a molding shrinkage rate smaller than that of the third layer thermoplastic resin.

Here, the molding shrinkage rate means that the polymer is placed in a compression mold,
20 kg/crn pressure from room temperature in 15 minutes
After raising the temperature to 0°C, hold at the same temperature and pressure for 20 minutes, then cool to room temperature for 15 minutes under the same pressure. After molding, mold the obtained molded product (150 x 150 x 5 mm) at a temperature of 20°C and a relative humidity of 65%. It is the average shrinkage rate in the vertical and horizontal directions measured after being left in a room for 24 hours.

In the present invention, the UHPE of the first layer refers to a polyethylene composition containing as a main component a viscosity average molecular weight of 500,000 or more, preferably 1,000,000 or more. The crystal melting point and molding shrinkage rate of UHPE are 125-145°C, respectively.
and 10-30.

Additives to IJHPE2 include aliphatic hydrocarbons such as paraffin wax and low molecular weight polyethylene wax;
Plasticizers, lubricants, and interfaces such as alicyclic hydrocarbons such as cyclointene and cyclopentadiene, higher alcohols such as cetyl alcohol and stearyl alcohol, aliphatic esters such as butyl oleate, and higher fatty acid metal salts such as zinc stearate. Activators and, if necessary, silica powder, calcium carbonate, alumina, aluminum hydroxide, carpin black fillers, coloring agents, etc., and products containing these additives alone or in mixtures may also be used. Can be done. Further, the shape of UHPE when used may be either a powder or a molded body.

In the present invention, the thermoplastic resin of the third layer has a molding shrinkage rate of 10% to 30%, preferably 12% to 25%.
Less crystalline resin and higher.

Polyolefins such as medium or low density ethylene, polypropylene, polybentenamer, nylon 6, nylon 11, nylon 12, nylon 6.6, nylon 6.1
Examples include homopolyamide or coryamide such as No. 0, saturated polyester such as polyethylene terephthalate and polybutylene terephthalate, and polyacetal.

Furthermore, these resins may contain fillers such as glass fiber, carbon fiber, calcium carbonate, silica powder, alumina, aluminum hydroxide, etc., or additives such as plasticizers, stabilizers, lubricants, colorants, and antistatic agents. , can be used as long as the molding shrinkage rate is within the above range.

When used in a trench, the shape may be powder, granule, or molded body.

In the present invention, the second N thermoplastic resin is the UH of the first layer.
The thermoplastic resin other than PE and UHPE in the third layer suppresses the shrinkage force after molding, so the laminate is slightly warped. Such a thermoplastic resin must have a lower molding shrinkage rate and greater rigidity than the resins of the first and third layers. What if the second layer is styrene elastomer or 7J? If the material is soft at room temperature and has low rigidity, such as liptadiene, the laminate will warp even though the molding shrinkage rate is lower than that of the third layer thermoplastic resin.

In the present invention, the thermoplastic resin of the second layer has a flexural modulus of 9//crn2 or more of 5,000, preferably 10
,000 kg/cm2 or more in rigidity, and a molding shrinkage rate of 10 times smaller, preferably less than 0.8%, and is a non-quality resin that is acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, etc. Suitable examples include polymers, polycarbonate, polystyrene, polymethyl methacrylate, polyenylene oxide, polyvinyl chloride, or chlorinated polyvinyl chloride.

Furthermore, fillers such as glass fiber, carbon fiber, calcium carbonate, silica powder, alumina, aluminum hydroxide, plasticizers, stabilizers, etc. are added to these resins.
Those containing small amounts of additives such as lubricants, colorants, and antistatic agents can also be used. The shape at the time of single use may be any one of powder, granule, and molded body.

The thickness of the second layer thermoplastic resin is preferably 5% or more and 95 inches or less, more preferably 10% or more and 50 inches or less of the thickness of the entire laminate. If the ratio of the thickness of the second layer is less than 5 inches, the effect of the second layer will not be fully exhibited and warping will occur easily, and if it is more than 95%, the thickness of UHPE in the entire laminate will increase. Thin Kupp, UH
It is difficult to create a laminate that takes full advantage of the characteristics of PE.

As a method for obtaining the laminate of the present invention, a compression molding method, a transfer molding method, an injection molding method, an extrusion molding method, etc. can be used, and the compression molding method will be explained as an example.

First, a first layer of UHP E powder is placed in a compression mold, then a second layer of thermoplastic resin powder, and then a third layer of thermoplastic resin powder. This three-layer composition was heated at a molding temperature of higher than the crystalline melting point of UHPE and the melting point of the thermoplastic resin and lower than 300°C, and at a molding temperature of 5 kg/crn2 or higher, and
The laminate of the present invention is obtained by heating and pressurizing for 5 to 60 minutes at a pressure of 0 kg 7 cm" W and then cooling to room temperature for 5 to 60 minutes. Here, the laminate of the present invention is obtained when the molding temperature is the same as the crystal melting point and thermoplasticity of IJHPE. When the temperature is lower than the melting point of the resin, sufficient bonding force cannot be obtained, and at temperatures as high as 300℃, the U
HPE is thermally decomposed, its molecular weight decreases, and physical properties deteriorate, so it is difficult to clean. Further, when the molding pressure is lower than 5 kg7cm2, the time required for molding is extremely long and the bonding force is weak, which is not preferable. 500kg/cT
Even if it is higher than n2, the molding time will not be shortened, so it is preferable. Furthermore, if the heating and pressurizing time is shorter than 5 minutes, the UHPE may not be sufficiently sintered or the thermoplastic resin may not be sufficiently melted.
If the length is too long, the thermoplastic resin will be easily thermally decomposed and the cost will increase, which is not preferable.

(6) Examples and Comparative Examples Next, the present invention will be explained in more detail by Examples, and the effects of the present invention will be shown in comparison with Comparative Examples.

Example 1 UHP for compression molding mold (between 1,50 x 150 x 50)
E powder (Hizex Million 2 manufactured by Mitsui Petrochemical Industries, Ltd.)
40M) 4:l, smooth it evenly, add 33g of polyvinyl chloride powder as a second layer on top of it, and smooth it evenly, then add polypropylene as a third layer on top of it. 41 g of powder was added and leveled uniformly in the same manner. This composition was heated from room temperature to 190°C over 15 minutes under a pressure of 100 kvcIn2, and then held as such for 20 minutes. Thereafter, the mixture was cooled to room temperature in 15 minutes under a pressure of 100 kg 7 cm 2 using a cooling press to obtain a laminate having a thickness of 5 sheets. The thickness of the obtained laminate was 0.3 mm.

The warpage measurement method is to mold a laminate (150 x 150 The height t (Figure 1) was measured.

Examples 2 to 4 The same method as in Example 1 except that the thermoplastic resin shown in Table 1 was used instead of the polyvinyl chloride powder of the second layer in Example 1, and molding was performed at the molding temperature shown in Table 1. Each laminate was obtained.

(ll) Examples 5 to 6 Same as Example 1 except that the thermoplastic resin shown in Table 1 was used instead of the polypropylene powder of the third layer in Example 1, and the molding was performed at the molding temperature shown in Table 1. Each laminate was obtained using the method described above.

The measurement results of the thickness of the laminates obtained in Examples 2 to 6 are shown in Table-
The rules were as shown in 1.

Comparative Example 1 The second layer of Example 1 except that the polyvinyl chloride powder was not used and the amount of polyzolopyrine powder was 61 g.
Molding was carried out under the same molding conditions as in Example 1 to obtain a laminate having a thickness of 5 mm.

Comparative Examples 2 and 3 Table 1 was used instead of polypropylene powder in Comparative Example 1.
A laminate was obtained in the same manner as in Comparative Example 1, except that the thermoplastic resin shown in Table 1 was used and molded at the molding temperature shown in Table 1.

The measurement results of the thickness of the laminates obtained in Comparative Examples 1 to 3 are shown in Table-
The rules were as shown in 1.

(12) Table-1 υYohiteU) MXF (7) Effects of the invention Since the UHPB laminate obtained by the present invention has small warpage, it has the same effect as the conventional molded product of UH and PE alone. The workability of storage and lining is improved, and the lining can be made flat. In addition, it is only necessary to use UHPE in areas that require wear resistance, sliding properties, low-temperature impact resistance, sound dampening properties, etc., and therefore UHPE can be used only in areas that require wear resistance, sliding properties, low-temperature impact resistance, and sound damping properties. A laminate having the same wall thickness as the molded product can be molded in a short molding cycle, and the amount of expensive UHPE used can be significantly reduced, so costs can be reduced. Furthermore, the second and third layers can be selected depending on the application and purpose, so heat resistance,
It is also possible to improve physical properties such as dimensional stability, creep resistance, and rigidity. Another advantage of the present invention is that when lining is performed, the resin can be selected depending on the material of the lining surface, making the process easy. Since the laminate obtained by the present invention has the above effects,
VC can be used for the lining of cement, coal, ore, sand, grain, tobacco, salt, sugar, etc., silos, bunkers, sheets, etc., and the lining of truck beds, freezers, etc.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the locations where warpage was measured. a... Laminated body (150 x 1.50 x 5 stripes) b... Horizontal substrate C... Warp dimensions (throat) Patent applicant Asahi Organic Feather Industry Co., Ltd. Patent application representative Patent attorney Akira Aoki Patent attorney Kazu Nishidate Patent Attorney Tera 1) Yutaka Patent Attorney Akiyuki Yamaguchi

Claims (1)

[Scope of Claims] 1. A laminate comprising an ultra-high molecular weight polyethylene layer and a thermoplastic resin layer other than ultra-high molecular weight polyethylene, the temperature being above the crystal melting point of ultra-high molecular weight polyethylene and below 300°C; kli'/an2 or more and 500 kg
The first layer is made of ultra-high molecular weight polyethylene, the third layer is made of a thermoplastic resin other than ultra-high molecular weight polyethylene, and the second layer is made of a thermoplastic resin other than ultra-high molecular weight polyethylene, which is obtained by molding at a pressure of 7 cm2 or less. 1. An ultra-high molecular weight polyethylene laminate, characterized in that it has a shoulder plate weighing 5,000 kg, and has a thermoplastic resin interposed therein which has a smaller mold shrinkage rate than the thermoplastic resin of the third layer. 2. The laminate according to claim 1, wherein the thermoplastic resin of the third layer has a molding shrinkage rate of 10% or more and 3.0% or less. 3. The laminate according to claim 2, wherein the thermoplastic resin of the third layer has a molding shrinkage rate of 1.2 inches or more and 25% or less. 4. Third layer thermoplastic resin olefin. The laminate according to claim 1, which is a homopolyamide, a copolyamide, a saturated polyester, or a polyacetal, or a mixture thereof. 5. The laminate according to claim 1, wherein the thermoplastic resin of the second layer has a molding shrinkage rate of less than 10%. 6. The laminate according to claim 4, wherein the thermoplastic resin of the second layer has a molding shrinkage rate of less than 0.8%. 7 The thermoplastic resin of the second layer is acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polycarbonate,? The laminate according to claim 1, wherein the laminate is listyrene, polymethyl methacrylate, polyphenylene oxide, polyvinyl chloride, chlorinated polyvinyl chloride, or a mixture thereof.