JPS6366344B2 - - Google Patents

Description

[Detailed description of the invention]

[] Purpose of the invention The present invention relates to a composition comprising (A) chlorinated polyethylene, (B) low density polyethylene and (C) low molecular weight polyethylene, and an object thereof is to provide a composition with excellent flexibility. That is. [] Background of the Invention For some time now, crosslinking agents, vulcanizing agents, vulcanization accelerators, and vulcanization accelerators have been used in thermoplastic resin compositions and elastomers obtained by blending lubricants, plasticizers, etc. with thermoplastic resins. Rubber elastic compositions, such as plastic products and rubber products, obtained by vulcanization or crosslinking by heat treatment with the addition of additives such as antiaging agents and anti-aging agents, are used in a wide variety of fields. It is well known that it is used.
However, thermoplastic resin compositions with high rigidity contain large amounts of plasticizers, stabilizers, etc. in order to produce appropriate flexibility and stability against heat. As a result, plasticizers, stabilizers, etc. bleed out, creating safety problems. On the other hand, since the elastomer itself has double bonds in rubber elastic compositions, it is necessary to improve heat resistance and weather resistance. For this reason, anti-aging agents are added, but not only do anti-aging agents bleed out,
A process is required to create a cross-cured (cross-linked) product using a vulcanizing agent (cross-linking agent) or the like. Furthermore, if the product is used for a long period of time, there are drawbacks such as a decrease in rubber elasticity due to deterioration of the elastomer. For these reasons, both thermoplastic resin compositions and rubber elastomer compositions naturally have limitations in terms of use. [] Structure of the Invention Based on the above, the present inventors have conducted various searches in order to obtain a composition with excellent flexibility. or crystalline chlorinated polyethylene, (B) having a density of 0.900 to less than 0.930 g/ ^cm3 , a melting point of 106 to 130°C, and a melt index (temperature of 190°C and 100°C according to JIS K-6760); Measured under the condition of a load of 2.16 kg, hereinafter referred to as "MI") is 0.01 to 100 g/10 minutes, and the number of side chain alkyl groups having 1 to 10 carbon atoms is 3 per 1000 main chain carbon atoms. A composition consisting of low-density polyethylene with a molecular weight of ~35, and (C) low-molecular-weight polyethylene with a molecular weight of 300 to 10,000, and the proportion of the low-density polyethylene in the total amount of chlorinated polyethylene and low-density polyethylene. The proportion is 1 to 25% by weight,
We have discovered that a chlorinated polyethylene composition in which the blending ratio of low molecular weight polyethylene is 0.01 to 15 parts by weight based on 100 parts by weight of these is a composition with excellent flexibility.
We have arrived at the present invention. [] Effects of the Invention The chlorinated polyethylene composition obtained by the present invention not only has excellent flexibility, but also exhibits the following effects (characteristics). (1) Good heat resistance and flexibility. (2) Has weather resistance. (3) The dimensional accuracy of the molded product is excellent. (4) Not only does it have good moldability, but it also has a low shrinkage rate during molding. (5) By adding a nucleating agent and/or a stabilizer, a molded product with excellent transparency can be obtained. (6) There is almost no shrinkage even after heat treatment. (7) The elastic modulus of the molded product is low (elastomer-like). (8) Self-extinguishing. (9) It can reversibly change from transparent to opaque as the temperature changes, and light shielding can be easily adjusted. In other words, it is transparent at temperatures below 60℃, becomes opaque at temperatures above 60℃,
Demonstrates the effectiveness of so-called temperature-sensitive materials. The composition obtained by the present invention has the above-mentioned excellent effects and can be used in a wide variety of fields. In particular, it holds promise as a medical device. Its uses are shown below. (1) Medical equipment such as blood, infusions, blood transfusions, blood collection tubes, etc. (2) Conduits for blood, body fluids, drugs, blood transfusions, blood collection, infusions, etc. (3) Packing (4) Medical equipment such as blood, body fluids, drugs, blood transfusions, blood collection, infusions, etc. Medical equipment used (5) Bag for infusion, blood transfusion, etc. The composition of the present invention can be used as a temperature-sensitive material in a wide variety of fields. Representative examples of its uses are shown below. (1) Covering materials for roofs of warehouses, etc. to protect goods as temperatures rise (2) Sunshade tents, sunshade sheets (3) Window glass, room partition boards, blind boards (4) Agriculture, gardening (5) Corrugated panels for greenhouses, terraces, etc. [] Detailed description of the invention (A) Chlorinated polyethylene Does the chlorinated polyethylene used in the present invention chlorinate polyethylene powder or particles in an aqueous suspension? or by chlorinating polyethylene dissolved in an organic solvent (preferably by chlorinating it in an aqueous suspension). In general, it is amorphous or crystalline chlorinated polyethylene whose chlorine content is between 20 and 50% by weight, and especially when its chlorine content is 25% by weight.
~45% by weight amorphous and crystalline chlorinated polyethylene is preferred. The polyethylene is obtained by homopolymerizing ethylene or copolymerizing ethylene with at most 10% by weight of α-olefin (generally having at most 12 carbon atoms). Its density is generally between 0.910 and 0.970 g/cc. Moreover, its molecular weight is 50,000 to 700,000. (B) Low-density polyethylene The low-density polyethylene used in the present invention is obtained by copolymerizing ethylene and α-olefin. The density of the low density polyethylene is less than 0.900-0.940 g/ ^cm3 , and 0.905-0.940
Less than g/cm ³ is preferred, especially 0.905 to 0.930 g/cm ³
is suitable. The density of this low density polyethylene is 0.900g/ ^cm3
If it is less than that, the resulting composition will not have sufficient rigidity.
On the other hand, if it exceeds 0.940g/ ^cm3 , the rigidity is high, but
Unsuitable due to lack of flexibility. Further, the melting point is 106 to 130°C, preferably 106 to 125°C, and particularly preferably 110 to 125°C. If low density polyethylene with a melting point of less than 106° C. is used, the resulting composition will not have sufficient rigidity or heat resistance. On the other hand, if low-density polyethylene with a melting point exceeding 130° C. is used, the resulting composition will have high rigidity, but will lack flexibility, which is unsuitable. Furthermore, the MI of low density polyethylene is 0.01 to 100 g/10 min, and 0.1
-50 g/10 minutes is preferred, and 5-30 g/10 minutes is particularly preferred. MI of the low density polyethylene is 0.01
If it is less than g/10 minutes, moldability will be poor. On the other hand, 100
If it exceeds g/10 minutes, moldability is good, but a good product cannot be obtained due to lack of appropriate rigidity. α- used in the production of the low density polyethylene
Olefins are α-olefins having at most 12 carbon atoms, and typical examples include propylene, 1-butene, 1-hexene, 1-4-methylpentene, and 1-octene. The copolymerization ratio of the α-olefin in this low density polyethylene is usually 1.0 to 18% by weight. The short chain branch in this ethylene-based linear copolymer refers to a branch that is sufficiently short compared to the main chain, and has, for example, less than 10 carbon atoms. On the other hand, a long chain branch means a branch having a length sufficiently comparable to that of the main chain, and having, for example, 10 or more carbon atoms. The polyethylene used as a raw material in the production of the low-density polyethylene and the production of the chlorinated polyethylene is obtained by homopolymerizing ethylene alone or ethylene and the above-mentioned α-olefin in the presence of a so-called Ziegler catalyst or a Phillips catalyst. Obtained by copolymerization. Ziegler's catalyst is a transition metal compound (for example, a halogen-containing compound of titanium) or a carrier for the transition metal compound (for example, a magnesium-containing compound, a compound obtained by treating the magnesium-containing compound with an electron-donating organic compound). It is obtained from a so-called carrier-supported solid catalyst component obtained by supporting the catalyst component on a solid catalyst and an organoaluminum compound. Additionally, the Phillips catalyst is a carrier-supported catalyst obtained by supporting an oxide of chromium or molybdenum, or a compound of these oxides and zirconium on a carrier (for example, silica, silica-alumina), or a carrier-supported catalyst. It is obtained from organometallic compounds. The above catalysts are merely typical Ziegler catalysts and Phillips catalysts, and other known catalysts may also be used. The method for producing this copolymer is also a well-known method. (C) Low molecular weight polyethylene The molecular weight of the low molecular weight polyethylene used in the present invention is generally 300 to 10,000, particularly preferably 1,500 to 9,000. The low molecular weight polyethylene is a milky white, translucent powder, pellet or liquid. This low molecular weight polyethylene can be broadly classified into (1) a wax type with a softening point of 50 to 120°C and a specific gravity of 0.85 to 0.95, and (2) a wax type with a softening point of 100 to 140°C and a specific gravity of 0.90 to 0.95. A certain emulsion type (3) has a softening point of 60 to 110℃ and a specific gravity of 0.90 to
copolymer type whose softening point is 0.95 and (4)
There is an oxidized homopolymer type that has a temperature of 100 to 140°C and a specific gravity of 0.90 to 1.00. Regarding these low molecular weight polyethylenes, please refer to "Handbook: Rubber/Plastic Compounded Chemicals" edited by Rubber Digest Co., Ltd. (published by Rubber Digest Co., Ltd. in 1972).
Their manufacturing methods and physical properties are described in pages 303 to 325, as well as pages 96 to 102 of "Fine Polymers & Engineering Plastics" (Kagaku Kogyo Nippo Publishing Co., Ltd., published in 1978), and are well known. It is something that (D) Nucleating agent Although the composition of the present invention can be obtained by mixing chlorinated polyethylene, low density polyethylene and low molecular weight polyethylene, transparency can be imparted by further adding a nucleating agent. Is possible. The nucleating agent is generally used as a gelling accelerator for resins, and changes the spherulite structure of the resin. In other words, it is a compound that envelops resin crystals and imparts transparency so that a large number of small crystals are dispersed. Representative examples of this compound include organic carboxylic acids, aluminum salts of organic carboxylic acids, dibenzylidene sorbitol talc, unsaturated fatty acid amides, and metal salts of stearic acid and tobiloxystearic acid. (E) Stabilizer Generally, when chlorinated polyethylene is exposed to light, heat during melt-kneading, processing, and use for a long period of time, it undergoes dehydrochlorination, discoloration, and deterioration.To suppress this, chlorine-containing polymers are added. A stabilizer (dehydrochlorination inhibitor) known as a stabilizer is added to the solution. When the composition of the present invention is used as a medical device, the use of stabilizers harmful to the human body (eg, cadmium stearate, tin-containing compounds, lead-based compounds) should be avoided. For the above reasons, metal soaps (for example, calcium stearate), epoxy derivatives, and composite stabilizers (powder, paste, liquid) that are harmless to the human body are used. These stabilizers are well known from pages 266 to 297 of the aforementioned "Handbook of Chemicals Compounded with Rubber and Plastics." (F) Blending ratio In the composition of the present invention, the blending ratio of low-density polyethylene in the total amount of chlorinated polyethylene and low-density polyethylene is 1 to 25% by weight, and particularly preferably 2 to 25% by weight. The proportion of low density polyethylene in the total amount of chlorinated polyethylene and low density polyethylene is 1% by weight
If it is less than that, not only will it not be possible to obtain a composition or product with excellent processability, but also a suitable elastic body will not be obtained because it is soft. On the other hand, if it exceeds 25% by weight, not only will it be difficult to obtain a suitable elastic body due to poor flexibility, but
Poor heat resistance. In addition, the blending ratio of low molecular weight polyethylene to 100 parts by weight of the total amount of chlorinated polyethylene and low density polyethylene is 0.01 to 15 parts by weight, preferably 0.05 to 15 parts by weight, and especially
0.1 to 12 parts by weight are preferred. If the blending ratio of low molecular weight polyethylene is less than 0.01 part by weight with respect to 100 parts by weight of the total amount of chlorinated polyethylene and low density polyethylene, the composition has excellent shrinkage stability in terms of processability and heat resistance during molding. can't get it. On the other hand, if it exceeds 15 parts by weight, the heat resistance of the resulting composition will decrease. As mentioned above, transparency can be improved by further adding the nucleating agent to the composition. It is generally at most 5 parts by weight, and generally 3 parts by weight or less is sufficient, based on 100 parts by weight of the total amount of chlorinated polyethylene, low density polyethylene and low molecular weight polyethylene. Furthermore, stabilizers added to improve stability against heat and light are generally added in an amount of 10 parts by weight or less per 100 parts by weight of the total amount of chlorinated polyethylene, low density polyethylene and low molecular weight polyethylene. . Furthermore, 0.1 part by weight or more is added to exhibit sufficient stability. Above all,
0.5 to 5 parts by weight is desirable. (G) Manufacturing and molding method of chlorinated polyethylene composition Although the composition of the present invention can be obtained by uniformly blending the above-mentioned substances, it is also possible to obtain the composition of the present invention by uniformly blending the above substances. Additives such as mold release agents, oxygen, ozone and light (ultraviolet) stabilizers, binders, lubricants and colorants may be added depending on the intended use of the composition. In addition, sulfur vulcanizing agents, sulfur-releasing compound-based vulcanizing agents, amine-based vulcanizing agents, organic peroxide-based crosslinking agents and organic peroxide-based crosslinking co-agents commonly used in the rubber and resin industries. Additives may be added depending on the intended use of the composition. When producing the composition of the present invention, the blending (mixing) method may be to use a mixer commonly used in the art such as an open roll, dry blender, Banbury mixer, and kneader. Among these mixing methods, two or more of these mixing methods may be applied in order to obtain a more uniform composition (for example,
A method in which the mixture is mixed in advance with a dry blender and then mixed using an open roll). The composition of the present invention may be molded into a desired shape using a molding machine commonly used in the rubber industry, such as an extrusion molding machine, an injection molding machine, a compression molding machine, or a calendar molding machine. In addition, a method of manufacturing a molded product while vulcanizing (crosslinking) it by adding chlorinated polyethylene or the above-mentioned composition and vulcanizing (crosslinking) it in the rubber technology field, that is, a method of simultaneously proceeding vulcanization and molding, is applied. It may be formed into a desired shape. [] Examples and Comparative Examples The present invention will be explained in more detail below using Examples. In addition, in the examples and comparative examples, the tensile test was measured according to JIS K-6301. The elastic modulus test was performed using a Tensilon measuring machine (manufactured by Toyo Seiki Co., Ltd.) under conditions of a tensile speed of 5 mm/min and a chart speed of 600 mm/min. Furthermore, the autoclavability test was conducted at a temperature of 121℃ and a time of 20℃.
The shrinkage rate of the sample was measured using a retort processing apparatus under the conditions of 10 minutes. Further, transparency (HAZE) was measured using a transparency meter (Clarity Meter TM-ID). Further, in the flow rate test, the flow was measured under conditions of a temperature of 180° C. and a load of 21.6 kg in accordance with JIS K-6760. The ingredients used in the Examples and Comparative Examples have the following manufacturing methods, shapes, and physical properties, respectively. [Chlorinated polyethylene] As chlorinated polyethylene, the density is 0.950g/
Amorphous chlorinated polyethylene with a chlorine content of 40.4% by weight [ ^hereinafter referred to as "CDE (1) ”] and the density is
^Polyethylene (average molecular weight
Crystalline chlorinated polyethylene (hereinafter referred to as "CPE(2)") with a chlorine content of 30.2% by weight was obtained by chlorinating approximately 100,000 yen) by an aqueous suspension method. [Low-density polyethylene] Low-density polyethylene is a linear copolymer of ethylene and butene-1 with an MI of 15 g/10 min [density 0.920 g/cm ³ , hereinafter referred to as "L-LD(1)"] ]
and a linear copolymer of ethylene and hexene-1 with an MI of 50 g/10 min [density 0.925 g/cm ³ ,
Hereinafter referred to as "L-LD(2)"] was used. [Low molecular weight polyethylene] Also, as a low molecular weight polyethylene, it has a low softening point.
Low molecular weight homopolymer with a temperature of 117℃ [density 0.940
g/cm ³ , hereinafter referred to as "LPE(a)"], the softening point is 104
Oxidized homopolymer [density 0.930 g/cm ³ ,
Hereinafter referred to as "LPE(b)"] was used. [Rubber-like material] Furthermore, cis-1,4-butadiene rubber (styrene content: 25.0% by weight, hereinafter referred to as "BR") having a Mooney viscosity (ML ₁₊₄ ) of 43 was used as a rubber-like material. [Thermoplastic resin] Also, as a thermoplastic resin, vinyl chloride homopolymer (hereinafter referred to as "PVC") with a degree of polymerization of approximately 700 is used.
was used. [Stabilizer] Furthermore, as a stabilizer, epoxidized soybean oil with a molecular weight of approximately 1000 [manufactured by Adeka Argus Co., Ltd.] is used. Product name ADEKA SIZER 0-130S, specific gravity 0.982~
1.002, hereinafter referred to as ``stabilizer (1)''] and calcium-zinc complex [manufactured by Adeka Argus, trade name ADEKA Mark AO-40, specific gravity 2.3, hereinafter referred to as ``stabilizer (2)'']. . Examples 1 to 17, Comparative Examples 1 to 10 As the above composition components, “chlorinated polyethylene,
Rubber-like materials, thermoplastic resins (hereinafter referred to as ``chlorinated polyethylene, etc.''), low-density polyethylene, low-molecular-weight polyethylene, stabilizers, and nucleating agents in the amounts shown in Table 1 (all parts by weight) at 50% in advance.
Each was mixed for 10 minutes using a roll set at °C. Each of the obtained mixtures was melt-kneaded using a kneader in a temperature range of 120 to 150°C to produce a mixture (composition). Each composition was further melt-kneaded using a mixing roll to create a sheet. A pulverized product was prepared by pulverizing each of the sheets thus obtained. Each sheet was extruded using an extruder (tube-shaped die with a diameter of 4 mm, diameter 32 mm, L/D 20), the temperature of cylinder 1 was 130℃, and the temperature of cylinder 2 was 150℃.
℃, die temperature 180℃ and rotation speed 30 rotations/
Tubes were manufactured under the following conditions. Tensile test and elastic modulus test of each tube obtained. Autoclave tests, clarity tests and flow rate tests were conducted. The results obtained are shown in Table 2.

【table】

【table】

【table】

[Table] In Comparative Example 9, dehydrochlorination occurred during extrusion molding to produce tubes, and tubes could not be produced.

Claims (1)

[Scope of Claims] 1 (A) Amorphous or crystalline chlorinated polyethylene having a chlorine content of 20 to 50% by weight, (B) a density of 0.905 to less than 0.930 g/cm ³ and a melting point of 106 to 130℃, and the melt index is
0.01 to 100 g/10 minutes, and the number of side chain alkyl groups with 1 to 10 carbon atoms is substantially the main chain carbon atom
A composition consisting of low-density polyethylene whose molecular weight is 3 to 35 per 1,000, and (C) low-molecular-weight polyethylene whose molecular weight is 300 to 10,000, the low density accounting for in the total amount of chlorinated polyethylene and low-density polyethylene. The blending ratio of polyethylene is 1 to 25% by weight,
and a chlorinated polyethylene composition in which the blending ratio of low molecular weight polyethylene is 0.01 to 15 parts by weight based on 100 parts by weight of the total amount.