JPH0344104B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel compositions of 1-butene polymers and their uses. It is already widely known that 1-butene polymers are polymers that can contain large amounts of organic or inorganic fillers, and 1-butene polymers containing large amounts of fillers
- Various uses of butene polymer compositions have also been proposed. For example, a paper-like sheet made by adding a filler to a 1-butene polymer having certain properties to a maximum content of about 80% and stretching it (Japanese Patent Application Laid-Open No. 48-42069);
There is a sound insulating material made by rolling a 1-butene polymer with a maximum of about 70% by weight of metal or metal oxide powder (Japanese Unexamined Patent Publication No. 1983-6651). However, in the 1-butene polymer used for these, the amount of filler that can be included is at most 80% by weight.
Its use was also limited. The present inventors have conducted various studies in order to further improve the multifilling properties of 1-butene polymers while maintaining the excellent properties of 1-butene polymers. - exhibits a multifilling property not found in butene polymers, and that the filled composition has a
-Completed the present invention by discovering that a butene polymer exhibits various unique properties while retaining its characteristic physical properties, and that various unique materials can be obtained by subjecting the filled composition to a specific processing method. We were able to. That is, the present invention provides () a 1-butene polymer having the following properties (a) to (c) (a) an average molecular weight of 100,000 to 1,000,000 (b) α other than 1-butene in the 1-butene polymer
- an olefin content of 0 to 50 mol%, (c) a crystallinity of 10 to 55%, and () a filler that does not dissolve in the copolymer () and is solid at room temperature; The proportion is 3 to 25% by weight,
The proportion of () is 75 to 97% by weight (() and ()
(total of 100% by weight). The average molecular weight is calculated using the intrinsic viscosity [η] measured in a decalin solution at 115°C, and is calculated as [η] = 9.49×
10 ^-5 Mw ^0.73 formula [SSStwala, RJValles, and
DWheui, J. Appl. Polymer Sci., 97, 7.
(1963)]. Further, the crystallinity was determined by X-ray diffraction method. The present invention will be explained in detail below. The 1-butene polymer used in the present invention is a 1-butene homopolymer or a copolymer of 1-butene and another α-olefin. α used here
-Olefins include, for example, ethylene, propylene, 1-pentene, 1-octene, 1-decene,
Examples include 1-dodecene and 4-methyl-1-pentene. These α-olefins can be used alone or in combination. Further, the 1-butene polymer used in the present invention has an average molecular weight of about 100,000 to about 1,000,000, and an α-olefin content of about 0 to about 50 mol% in the polymer.
and the degree of crystallinity must be about 10 to about 55%. If these requirements are not met, multi-filling properties will be poor, and even if multi-filling is possible, the shape retention of the filled composition will be poor and the effects of the present invention, which will be described later, will not be sufficiently achieved, so the above requirements are necessary for the present invention. . Next, the filler used in the present invention must be insoluble in the above copolymer and must be solid at room temperature. These fillers include inorganic and organic fillers. Examples of inorganic fillers include magnesium carbonate, calcium carbonate, clay, kaolin, bentonite, talc, silica, mica,
Diatomaceous earth, silica sand, pumice powder, slate powder, asbestos, alumina white, barium sulfate, lithopone, calcium sulfate, molybdenum disulfide, graphite, glass fiber, glass bulb, foamed glass bulb,
fly ash, volcanic glass hollow body, synthetic inorganic hollow body, single crystal potassium titanate, carbon black,
carbon fiber, carbon hollow sphere, anthracite powder,
Various natural and artificial fibers such as artificial quartzite, hydroxides such as magnesium and calcium, sulfates such as barium and calcium, mica vermiculite, graphite, metals or metal oxides such as iron, alcohol, and zinc, and ferrite. or flake-like. Organic fillers include cellulose powder, wood powder, paper and cloth strips, cotton linters, polyvinyl alcohol fibers, polyethylene,
Examples of the present invention include various types of plastics such as polypropylene and ultra-high molecular weight polyethylene in the form of fibers, powders, or flakes. Among these, magnesium hydroxide, carbon black, carbon fiber, ferrite,
It is preferable to use inorganic fillers such as mica, talc, and calcium carbonate in order to achieve various effects of the present invention. The loading of these fillers should be from about 75 to about 97% by weight, preferably from about 80 to about 97% by weight, based on the total amount of 1-butene polymer and filler.
95% by weight, more preferably about 80 to about 93% by weight
It is. If it is less than about 75% by weight, the specific effects of the present invention described below will not be achieved, and if it exceeds about 97% by weight, the shape retention of the product obtained from the composition will deteriorate, so it is necessary to be within the above range. It is. The composition of the present invention may contain general additives such as weathering stabilizers, antioxidants, antistatic agents, lubricants, slip agents, antiblocking agents, antifogging agents, dyes, and pigments. It doesn't matter. The polymer composition according to the invention has various characteristics. One of them is good shape retention despite the high filler content. This depends on the polymer used, but this is because even in a composition containing a large amount of filler, a certain degree of crystallinity of the polymer is maintained. This can be confirmed by the development of the melting point of the polymer in the composition and the development of the yield value in a tensile test of a test piece molded from the composition. Due to its good shape retention,
It is possible to produce filler master batch pellets, and it is also possible to produce various molded products. In addition, since the polymer composition of the present invention has good multi-filling properties and good shape retention, depending on the type of filler, the use of the polymer composition of the present invention can significantly reduce the manufacturing cost of molded products, as well as It is possible to take advantage of various characteristics such as imparting flammability and conductivity, lowering combustion heat, and having less molding shrinkage and atto shrinkage of molded products. The compositions of the present invention can be prepared by known mixing methods, usually using equipment such as a two roll, Banbury mixer, twin screw extruder or shell blender. The composition is molded and processed into the desired object using various commonly used molding machines. Next, a wear-resistant magnetic tape will be explained as a first use of the 1-butene polymer of the present invention. Magnetic tape is usually made of a plastic film base made of polyester or acetate, on which fine magnetic metal powder mixed with adhesive is thinly and evenly applied. This magnetic tape generally does not have sufficient wear resistance, and has the disadvantage that magnetic metal powder tends to fall off when used for a long period of time. As a filler for the 1-butene polymer according to the present invention, the fine magnetic metal powder described above is used in the form of a stretched tape or stretched on a base of plastic film such as polyester or acetate. It is a magnetic tape with excellent properties. That is, due to the excellent wear resistance and multi-filling property of the 1-butene polymer, the magnetic metal powder kneaded into the polymer does not easily fall off.
The tape also has excellent surface smoothness. Conventional poly-1-butene resin has excellent abrasion resistance but lacks multi-filling properties, so it is not always possible to firmly fill the required amount of magnetic metal powder, and it also has poor filling properties. The surface smoothness was also insufficient. When the 1-butene polymer composition of the present invention is used in a magnetic tape, the amount of magnetic metal powder in the composition is preferably about 80 to about 95% by weight, although it depends on the conditions, and the stretching ratio of the tape is is about to about 50
The thickness of the tape is about 0.5 to about 100μ. For example, a magnetic tape using the 1-butene polymer composition of the present invention contains 10 mol% of propylene.
85% by weight of Mn-based ferrite powder was added to 15% by weight of the 1-butene polymer No. 20, and the mixture was kneaded at 190°C for 10 minutes using a Banbury mixer, then formed into a sheet with a thickness of 200μ, which was further rolled to form a 10μ thick sheet. It can be obtained by making a film with a certain thickness, laminating it with a 60μ thick polyester film, and then slitting it to the required width. In this application, it is preferable to use maleic anhydride grafted poly-1-butene in an amount of 0.5 to 5% by weight in the 1-butene polymer composition of the present invention. As the maleic anhydride grafted poly-1-butene, for example, those described in JP-A-60-31512 filed by the applicant of the present application can be used. Next, a plastic magnet will be explained as a second use of the 1-butene polymer composition according to the present invention. In general, oxide magnets such as ferrite magnets and compound magnets such as rare earth cobalt magnets have the disadvantage of being brittle because they are sintered materials. As a means to overcome these drawbacks and improve the dimensional accuracy of products, so-called plastic magnets and rubber magnets, in which magnet powder is hardened with a synthetic resin or rubber binder, have been put into practical use. However, since the saturation magnetization or residual magnetic flux density is reduced by the amount occupied by the binder, the magnetic properties generally deteriorate. Therefore, there has been a need for a plastic material that can be highly filled with magnetic powder and has excellent mechanical properties and processability (moldability) of the filling material. The present inventors have discovered that the composition used in the present invention, in which the 1-butene polymer is filled with a large amount of ferrite powder, solves the above problems and provides a plastic magnet with excellent performance. As the magnet powder used for this purpose, powders of ferrites such as barium ferrite, strontium ferrite, zinc ferrite, manganese ferrite, and magnesium ferrite, and rare earth cobalt magnets are used. Among these, ferrites are preferred. The blending ratio in the composition when blending these powders with the above-mentioned 1-butene polymer is as follows:
The amount is preferably about 80 to 95% by weight, and the blend is molded into the desired shape using various molding machines such as an extruder, press, and injection molding machine. The present invention has made it possible to obtain plastic magnets that have excellent magnetic properties such as coercive force and residual magnetic density (maximum energy product), as well as excellent mechanical properties and workability. Furthermore, as a third use of the 1-butene polymer composition according to the present invention, construction materials such as flooring or wall materials that have excellent flame retardancy and/or conductivity, wear resistance, and excellent workability will be explained. do. Plastic materials are generally easily combustible and have poor electrical conductivity, so when used as building materials such as flooring and wall materials, they must be imparted with flame retardancy and electrical conductivity to prevent dust from adhering to them. Among these, magnesium hydroxide, which does not generate toxic gas when burned, has recently come to be preferred as a flame retardant. However, in order to obtain satisfactory flame retardancy by incorporating magnesium hydroxide, a considerably large amount is required. Therefore, when applied to ordinary polymers, they have poor fillability, but when blended in sufficient amounts to provide sufficient flame retardance, they have good processability required for the production of flooring, wall materials, etc. The disadvantage was that the mechanical strength and abrasion resistance of the product were poor. The present inventors have found that when the 1-butene polymer composition of the present invention filled with magnesium hydroxide is used for flooring or wall materials, its multi-filling property not only provides sufficient flame retardancy but also conductivity. I discovered that you can also get sex. Moreover, it was discovered that it has excellent processability, which is necessary for manufacturing flooring and wall materials, as well as mechanical strength and abrasion resistance as a product. In this case, it is even more effective to use carbon black, carbon fiber, metal powder, or metal fiber together with magnesium hydroxide as a filler because the conductivity is further improved. When not used in combination with magnesium hydroxide, the flame retardant effect cannot be obtained, but other effects can be obtained as well. As for the composition for wall materials and floor materials, the blending ratio of magnesium hydroxide in the composition is preferably about 55%.
The amount of carbon black is about 10 to about 40% by weight. In addition, metal powder, fibers, and other conductive fillers are added to increase the total amount of fillers from 75 to 75%.
It is desirable that the content be 95% by weight. The unique properties of 1-butene polymers can be used to form wall materials and floor materials. That is, after the usual blending and kneading, it is sealed by extrusion molding, and while the 1-butene polymer of the seal molding is in the form of soft crystals, it is subjected to various molding processes such as stamping, bending, vacuum forming, etc. be able to. The present invention provides wall and flooring materials that have flame retardancy and conductivity, which have not been achieved satisfactorily with conventional plastics, by adding magnesium hydroxide, etc., and also have excellent abrasion resistance and workability. I started to be able to do it. Hereinafter, the present invention will be explained in more detail with reference to Examples. Examples 1 to 3, Comparative Examples 1 to 2 Table 1 shows examples of application to plastic magnets containing ferrite as a filler. A predetermined amount of manganese ferrite was added to polybutene-1 or polypropylene, mixed using a Banbury mixer at 200°C for 10 minutes, and then pulverized. The pulverized pellets were preheated at 200°C for 10 minutes, then cooled and pressed at 25°C and 50 kg/cm ² to produce a press-molded sheet. This sheet was magnetized to obtain the magnetic properties and tensile properties shown in Table 1.

【table】

[Table] Examples 4 to 7, Comparative Examples 3 to 5 Table 2 shows magnesium hydroxide as a filler,
An example of application of carbon black to flame-retardant conductive floor and wall materials was presented. A predetermined amount of magnesium hydroxide in polybutene-1 or polypropylene,
Carbon black was added and mixed using a Banbury mixer at 200°C for 10 minutes, followed by pulverization. Using an extruder, the crushed pellets are made into 20cm wide pellets.
A sheet with a thickness of 1 mm was made and its flame retardancy, conductivity, and abrasion resistance were measured. In addition, the sheet in the crystalline state immediately after cooling and solidification was subjected to stamping processing to examine post-processability. As a result, by using the polybutene-1 resin within the scope of the present invention, it is possible to reflect its excellent filler multi-filling property, and to have good flame retardancy, electrical conductivity, and abrasion resistance, as well as post-processing such as stamping. A resin composition with excellent properties can be obtained.

【table】

[Table] Examples 8 to 11, Comparative Examples 6 and 7 Table 3 shows an application example to a magnetic tape to which Mw-based ferrite powder was added as a filler. 2% by weight of maleic anhydride grafted polybutene-1 and a predetermined amount of manganese ferrite powder were added to polybutene-1 or polypropylene, and the mixture was kneaded at 190°C for 10 minutes using a Banbury mixer.
A 100μ thick sheet is coextruded with a 500μ thick polyester sheet using T-die molding at a molding temperature of 270°C, and this is rolled while applying tension in the longitudinal direction to create a 60μ thick film. did. The ferrite-containing surfaces of this film and general magnetic tape were rubbed with a jig covered with felt cloth, and the number of times of friction until the ferrite-containing portion disappeared due to wear was measured.

【table】

【table】

Claims (1)

[Scope of Claims] 1 () A 1-butene polymer having the following properties (a) to (c) (a) An average molecular weight of 100,000 to 1,000,000 (b) A polymer other than 1-butene in the 1-butene polymer α
- an olefin content of 0 to 50 mol%, (c) a crystallinity of 10 to 55%, and () a filler that does not dissolve in the copolymer () and is solid at room temperature; The proportion is 3 to 25% by weight,
The proportion of () is 75 to 97% by weight (() and ()
1-butene polymer composition having a total of 100% by weight). 2. The 1-butene polymer according to claim 1, wherein the filler in parentheses is at least one filler selected from the group of magnesium hydroxide, carbon black, carbon fiber, ferrite, mica, talc, and calcium carbonate. Coalescing composition.