JPS5968354A - Chlorinated polyethylene composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent flexibility, dimensional accuracy, moldability, resistance to heat and weather, consisting of an amorphous or crystalline chlorinated PE, a specified ethylene copolymer and low- molecular PE. CONSTITUTION:Ethylene and 0.2-20wt% 3-12C alpha,beta-ethylenically unsaturated acid (anhydride) are copolymerized in the presence of a free radical-generating agent at 100-400 deg.C under a pressure of 140-150kg/cm<2> to obtain an ethylene copolymer. 0.01-15pts.wt. low-molecular PE having a softening point of 50- 140 deg.C, a specific gravity of 0.85-0.95 and an MW of 300-10,000 is blended with 100pts.wt. of the combined quantity of 99-70wt% amorphous or crystalline chlorinated PE having a density of 0.910-0.970g/cc, an MW of 50,000-700,000 and a chlorine content of 20-50wt% and 1-30wt% said ethylene copolymer.

Description

[Detailed Description of the Invention] ■Object of the Invention The present invention is directed to the use of chlorinated polyethylene, 0 ethylene, α, β-
The ethylene copolymer obtained by copolymerizing with an ethylenically unsaturated acid C) relates to a composition consisting of low molecular weight polyethylene, and is characterized by its flexibility and flexibility. This is the first thing to consider.

lI] Background of the Invention It has been known since before that thermoplastic resins are blended with lubricants, plasticizers, etc. (crosslinking agents, vulcanizing agents, vulcanization accelerators, vulcanization accelerator,
Comb elastomer compositions, such as plastic and rubber products, obtained by vulcanization or crosslinking by adding a cooling agent such as an anti-aging agent and heat treatment are used in a wide variety of fields. It is well known that this is the case. However, a thermoplastic resin composition with high rigidity has a large amount of plasticizer, stabilizer, etc. added thereto in order to produce appropriate flexibility and stability against heat. As a result, plasticizers, stabilizers, etc. bleed out, creating a safety problem. On the other hand, regarding rubber elastic compositions as well.

Since the elastomer itself has double bonds, it is necessary to improve heat resistance and weather resistance. For this reason, anti-foaming agents and the like are not added, but anti-aging agents also bleed, but they are made into vulcanized (cured) products using vulcanizing agents (cross-linking agents) etc. This process is necessary. Moreover, if the product is used for a long period of time, it has drawbacks such as a decrease in rubber elasticity due to deterioration of the elastomer. For these reasons, both thermoplastic resin compositions and comb elastomer compositions naturally have limitations in terms of use.

[]+[J Structure of the Invention Based on the above, the present inventors have searched extensively to obtain a composition with high flexibility and found that (2) the chlorine content is between 20 and 50% by weight. % amorphous or crystalline chlorinated polyethylene, 0 melt index (JIS
Measured according to Igu-6760 at a temperature of 190°C and a load of 2,16 Kq, hereinafter referred to as "M, 1.
α, β-ethylenically unsaturated, containing 3 to 12 carbon atoms in the molecule of ethylene and 0.2 to 20 tons) acid and/or
If it is an ethylene copolymer that cannot be obtained by copolymerizing chlorinated polyethylene or its anhydride, it is a composition consisting of low molecular weight polyethylene with a molecular weight of 300 to 10,000. The proportion of the ethylene copolymer in one amount of the polymer is 1 to 30% by weight, and
It has been discovered that a chlorinated polyethylene composition in which the blending ratio of low molecular weight polyethylene is o, oi to 15 parts by weight per 100 parts by weight of 1t is a composition with excellent flexibility, and the present invention has been achieved.

Effects of the invention Chlorinated polyethylene composition obtained by the invention
Not only does it have excellent flexibility, but it also exhibits the following effects (features).

(1) Good heat resistance.

(2) Has weather resistance.

(3) The accuracy of the molded product using the Ku1 method is very high.

(4) Not only is moldability good, but the shrinkage rate during molding is small.

(5) By adding a nucleating agent, a transparent molded product can be obtained.

(6) Even if heat treatment is performed, there is almost no shrinkage.

(Force: The elastic modulus of the molded product is low (elastomer-like).

(8) It is self-extinguishing.

(9) It can reversibly change from transparent to opaque as the temperature changes, and light shielding can be easily adjusted. That is, it is transparent at temperatures below 50°C, and
At temperatures above 0°C, it becomes opaque and exhibits the so-called temperature-sensitive effect.

Since the composition obtained by the present invention has the above-mentioned immediate effects, it 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 sets, etc. (2) Conduits for blood, body fluids, drugs, blood transfusions, blood collection, infusions, etc. (3) Backing (IL) For use in implantable devices or probes into living tissue. Medical utensils that are used by touching (5) Bags for infusions, blood transfusions, etc. The composition of the present invention can be used in a wide variety of ways as a temperature-sensitive material. Representative examples of its uses are shown below.

(+1) Covering the roofs of warehouses, etc. to protect goods due to temperature overload (2) Use tents for sunshades, sheets for sunshades (3) Window glass, partition boards for rooms, etc., blindfold boards ( 41m Fluoro sheet for industrial use and gardening (5) Corrugated sheet M for greenhouses, terraces, etc. Detailed description of the invention ^ Chlorinated polyethylene The chlorinated polyethylene that is not used in the present invention is obtained by chlorinating polyethylene powder or particles in an aqueous suspension. or by chlorinating polyethylene dissolved in an organic solvent (preferably not by chlorinating it in an aqueous suspension).In general, the chlorine content is Crystalline or crystalline chlorinated polyethylene with a weight ratio of 20 to 50% by weight, and particularly preferred is amorphous or crystalline chlorinated polyethylene with a chlorine content of 25 to 45% by weight.

The polyethylene is obtained by homopolymerizing ethylene or copolymerizing ethylene with at most 10 parts by weight of α-olefin (generally having at most 6 carbon atoms). Its density is generally 0.910~0
．． It is 970.9/cc. In addition, its molecular weight is 50,000~
It is 700,000.

σj Ethylene copolymer Also, the ethylene copolymer used in the present invention includes ethylene, an α, β-ethylenically unsaturated acid containing 3 to 12 carbon atoms in the molecule, and /-! It is obtained by copolymerizing J. takeso with anhydride. Representative examples of the unsaturated acids include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and isocrotonic acid, with acrylic acid and methacrylic acid being particularly preferred. The copolymerization ratio of the unsaturated acid in this copolymer is 02 to 20% by weight, generally 05 to 20% by weight.
I am in charge of the 0-layer department. Also, M, 1. 0.1~400. ￥
/10 minutes! [Crabs with a ratio of 1.0 to 400.9/10 minutes are the best. M, 1. 1) using an ethylene copolymer with a ratio of less than 0.1.9/10 minutes has poor fluidity
Furthermore, a product with adequate flexibility is not obtained. On the other hand, if an ethylene copolymer exceeding 400 g/10 minutes is used, it is not only impossible to obtain a product with good mechanical strength, but also the heat resistance of the product is poor.

The copolymerization ratio of the unsaturated acid and its anhydride in this ethylene copolymer is 0.2 to 20% by weight, especially 05 to 1% by weight.
6 weight section is the weight. When the copolymerization ratio of the unsaturated acid and its anhydride is less than 0.2 parts by weight, the composition has good moldability but poor flexibility. On the other hand, if it exceeds 20 parts by weight, the flexibility of the composition is good, but the tensile strength, transparency and surface 1? I! The eight sexes are inferior.

This copolymer combines ethylene and the unsaturated acid with a free radical generator (for example, an organic peroxide e1% adiazo compound)
as a catalyst, at 100 to 400°C (preferably 120 to 3°C)
00°C) under a pressure of 140 to 150"q/crrf,
It is manufactured by a second industry and is used in a wide range of applications.

0 Low molecular weight polyethylene Further, the molecule of the low molecular weight polyethylene used in the present invention is generally 300 to 10,000, and particularly preferably 1,500 to 9,000.

The low molecular weight polyethylene is a milky white, translucent powder.

It is in pellet form or liquid form.

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 positioning point of 100 to 1401.
11: emulsion type with a specific gravity of 0.90 to 095, (3) a copolymer type with a softening point of 60 to 110°C and a specific gravity of 090 to 095, and (4)
) Softening point is 100~140℃, specific gravity is 0.90~
There is an oxidized pomopolymer type that is 1.00.

Regarding low molecular weight polyethylene, please refer to Rubber Dai/Eftosha's ``Handbook of Plastic Compounded Chemicals'' (Rubber Digest, published in 1973), pp. 303-325, and also ``Fine Polymer &
Engineering Link Plastics'' (Kagaku Kogyo Nippo Co., Ltd., published in 1978), pages 96 to 102, describes their manufacturing methods and physical properties, which are not well known.
It is something that

a" Nucleating agent Although the composition of the present invention can be obtained by mixing chlorinated polyethylene, ethylene copolymer and low molecular weight polyethylene, transparency can be enhanced by further adding a nucleating agent. It is.

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 improves transparency by forming a large number of dispersed small crystals. Typical examples of this compound include organic carboxylic acids, aluminum salts of organic carbonic acids, dibenzylidenesorhitotalc, unsaturated fatty acid amides, and metal salts of stearic acid and Trichocystis stearic acid.

D Stabilizer Generally, when chlorinated polyethylene is exposed to light, heat during melt-kneading, heating, and use for a long time, it undergoes dehydrochlorination, discoloration, and deterioration, so chlorine-containing polymers are used to suppress stiffness. A stabilizer (dehydrochlorination inhibitor) known as a stabilizer is added to the solution.

When using the composition of the present invention 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. Based on the above, metal soaps (e.g. carunium stearate), evoquino derivatives, and composite stabilizers (powder, paste, liquid) that are harmless to the human body are recommended.
do. These stabilizers are well known from pages 266 to 297 of the aforementioned ``Handbook of Com Plastic Compounded Chemicals''.

a.) Blending ratio The blending ratio of ethylene copolymer to chlorinated polyethylene and ethylene copolymer in the silk of the present invention is 1 to 30% by weight, 1 to 25% by weight.
fj, '+ name is 11% and 2% to 25% weight is 38%. If the blending ratio of the ethylene copolymer to the total amount of Ji-hydrogenated polyethylene and ethylene copolymer is less than 1 part by weight, a product with poor fluidity of 9% and good mechanical strength cannot be obtained. On the other hand, if it exceeds 300 parts by weight, although the fluidity is good, the product becomes hard, making it impossible to obtain a product with appropriate flexibility, and furthermore, the resulting product has poor heat resistance. In addition, the blending ratio of low molecular weight polyfuridiene to 100 parts by weight of the combined Nl't of chlorinated polyethylene and ethylene copolymer is 0.01.
-15 double upper part, preferably 0.05 to 15 double upper part, and particularly preferably 0.1 to 12 double upper part. j) 1π
The blending ratio of low molecular weight polyethylene is 0 to 100 parts by weight of the combined amount of hydrogenated polyethylene and ethylene copolymer.
If the amount is less than 13 hours, it is impossible to create a composition with poor shrinkage stability in terms of processability and heat resistance during molding. On the other hand, if the 15-fold depression is exceeded, the heat resistance of the resulting composition decreases.

As mentioned above, transparency can be improved by further adding the nucleating agent to the composition. In general, at most 3 parts by weight per 100 parts by weight of the combined weight of chlorinated polyethylene, ethylene copolymer and low molecular weight polyethylene.
It is a part by weight, and generally 1 part by weight or less is sufficient.

Furthermore, the stabilizer added to improve the stability against heat and light is generally 15 parts by weight per 100 parts by weight of the combined weight of the chlorinated polyethylene, ethylene copolymer and low molecular weight polyethylene. The following are added.

Furthermore, in order to exhibit sufficient stability, more than the OIM amount is added. Particularly desirable is 0.5 to 12 fj parts.

0 Manufacturing and Molding Methods for Chlorinated Polyethylene Compositions It is clear that the compositions of the present invention can be obtained by uniformly blending the two substances Pj, and furthermore, the method generally used in the chlorinated polyethylene industry. Additives such as fillers, mold release agents, oxygen, meson and light (ultraviolet) stabilizers, binders, lubricants and I4 coloring agents may be added depending on the intended use of the composition. good. 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 aids are commonly used in the com industry and resin industry. Additives such as the following may be added depending on the intended use of the composition.

In preparing the composition of the present invention, the compounding (mixing) method includes mixing without mixing using mixers commonly used in the art such as open rolls, dry blenders, Banbury mixers, and Nigoo mixers. Yes. In order to obtain a more homogeneous composition, among the methods of mixing kowara, the mixing methods described in 1 and 2 above may be applied (for example, after mixing with a dry blender in advance). , the method of mixing using a mixing bowl/oven roll).

Composition Q of the present invention commonly used in the general com industry,! It may be molded into a desired shape using a molding machine such as an extrusion molding machine, an injection molding machine, a compression molding machine, or a calendar molding machine. chlorinated polyethylene or
A method of manufacturing a molded article by adding a composition as described in the following is generally used in the rubber technology field while applying pressure (crosslinking).
That is, the method of simultaneously proceeding vulcanization and molding may be performed for j months and then molded into a desired shape.

[VD Examples and Comparative Examples The present invention will now be explained in more detail with reference to Examples.

In addition, in the examples and comparative examples, the tensile test was conducted according to JIS
Measured according to Igu-6301.

The elastic modulus test was conducted using a Tensilon measuring machine (manufactured by Toyo Seiki Co., Ltd.) under conditions of a tensile speed of 5 mm/min and a Jartosbee-1 of 600 mm/min. Further, in the t-toclavability test, the shrinkage rate of the sample sheets was measured by using a retort processing apparatus once a month at a temperature of 121 DEG C. and a time of 20 minutes. - Transparency can also be measured using a transparency measuring device (Clarity Meter TM-TI).
E) was measured. Furthermore, the flow rate test is performed by JI
According to S K-6760, l:+'i ding j is 180
℃ and load is 21. (The flow was set to 5i for 11 under the condition of 5Kr.

In addition, the following manufacturing methods, formats, and materials used in the Examples and Comparative Examples are listed below.

[jpyrolyzed polyethylene]

As chlorinated polyethylene, Okiya is 0.950 gl
C7d polyethylene (average molecular weight approximately 250,000) is chlorinated by an aqueous suspension method to produce non-grade chlorinated polyethylene with a chlorine content of 40.4% by weight [hereinafter referred to as I'-CPE ( 1) By chlorinating polyethylene with a density of 0.926 GL and a density of 0.926 GL (average molecular year approximately 100,000) by an aqueous suspension method, a crystalline product with a chlorine content of 30.2 Chlorinated polyethylene [hereinafter referred to as r CPE (2) J]
woman using.

[Ethylene copolymer]

As an ethyl/one copolymer, the acrylic acid content is 3.5
Ethylene-acrylic acid copolymer [M, ■,
11 gl I 0 min, density 0.927 jj
/cnI, hereinafter referred to as rIi', AA(+)J], an ethylene-acrylic acid copolymer having an acrylic acid content of 132 parts by weight [to 1. T, 300gl
10 minutes, glance 111JJ' 0.927 gl,,1
, hereinafter referred to as [I2 A A (referred to as 21 J)] and an ethylene-methacrylic acid copolymer (M, 1.2.4.@/10 min, density 0.0. 942 glat, hereinafter referred to as [EI'vlAJ].

[Low molecular weight polyethylene]

i fc, the softening point is 117 as a low molecular weight polyethylene
Low molecular weight homopolymer [density 0.940 g
/cr! , hereinafter referred to as LI'E(a) J] and an oxidized homopolymer with a softening point of 104°C [density 0, 93
0,! i'/cnl, hereinafter I L I) E (
t)) J] was used.

[Rubber-like material]

Furthermore, Mooney viscosity (he'I L l
-1-4) is ・13/S1.4-7' Kujiencom (/S I4-containing iI4'90 heavy M section, hereinafter [L3R
J) is used for k.

[Heat resin]

1 loaf, heat riJ' 1Vinyl chloride with a degree of polymerization of about 700 as a Yilj resin? rξ autopolymer (hereinafter referred to as “PVC
”) was used.

[Stabilizer]

Furthermore, as a stabilizer, epoxidized oil having a molecular weight of about 1000 [manufactured by Ateca Argus Co., Ltd.] is used. Product name: Ateriki
Sizer 0-13O8, specific gravity 0.982-1. ,002
(hereinafter referred to as "stabilizer") was used.

Examples 1 to 16, Comparative Examples 1 to 9 The above composition components include "chlorinated polyethylene, rubber-like material % hot grade 1 plastic resin" (hereinafter referred to as "chlorinated polyethylene, etc.")
), ethylene copolymer, low-density polyethylene, and stabilizer in the amounts shown in Table 1 (all parts by weight) were mixed for 10 minutes using a roll preset at 50°C. .

The mixtures (compositions) are melted and kneaded using a kneader at a temperature range of 120 to 150°C.
was manufactured. Each of the compositions was further melt-kneaded using a mixing roll to create a notebook. A pulverized product was prepared by pulverizing each piece of f1g thus obtained. 7. Extruder (tube shape with 4 die diameters, diameter 32mm, L/D 20)
A tube was produced using ffi under the following conditions: the temperature of Rinder 1 was 130'C%, the temperature of Rinder 2 was 150C, the temperature of the die was 180C, and the number of revolutions was 30 revolutions/min. A tensile test, an elastic modulus test, an autoclave test, a transparency test, and a flow rate test were conducted on the unobtained fir tube. The results obtained are shown in Table 2.

In addition, in Example 9 of the ratio τ, dehydrochlorination occurred during extrusion molding to produce a tube, and it was not possible to produce a tube.

Patent applicant: Showa Denko Co., Ltd. Agent: Patent attorney Sei Kikuchi

Claims (1)

[Scope of Claims] 8. Amorphous or crystalline chlorinated polyethylene with a chlorine content of 20 to 50% by weight, σl, melt intex of 01 to 400g/10 minutes, and ethylene and 02%
α containing 3 to 12 carbon atoms in weight of ~20% by weight
, a composition comprising an ethylene copolymer obtained by copolymerizing a β-ethylene unsaturated acid and/or its anhydride, and a low molecular weight polyethylene having a molecular weight of 300 to 10,000. , the blending ratio of the ethylene copolymer in the total amount of chlorinated polyethylene and ethylene copolymer Q: l~30% by weight, the blending of low molecular weight polyethylene per 100 parts by weight of the maxim of Katsuko Noa et al. The proportion is 0.01 to 15 parts by weight of the chlorinated polyethylene composition.