JPS62290743A - Chlorinated polyethylene composition - Google Patents

Abstract

PURPOSE:To obtain a chlorinated polyethylene having high resilience as well as high tear strength and tensile strength, by blending a chlorinated polyethylene with a specified ethylene copolymer, an org. peroxide and a mercaptotriazine compd. in a specified ratio. CONSTITUTION:A chlorinated polyethylene (A) is blended with a copolymer (B) of a ethylene (1) with at least one comonomer (2) selected from the group consisting of an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid and its anhydride and a half ester of an unsaturated dicarboxylic acid, an org. peroxide (C) and a mercaptotriazine compd. (D) of formula I (wherein R is a mercapto amino group). The component B is used in an amount of 33-67wt% based on the combined amount of the components A and B. The component C is used in an amount of 0.1-10.0pts.wt. and the component D is used in an amount of 0.01-2.0pts.wt. per 100pts.wt. of the combined amount of the components A and B. The content of the comonomer in the component B is 1.0-20mol%.

Description

[Detailed description of the invention]

1-10 The present invention relates to (A) chlorinated polyethylene, (B) an ethylene copolymer of ethylene and a comonomer having a carboxylic acid group or its anhydride group, (C) an organic peroxide, and (D) a mercapto This relates to a 1:1 elementalized polyethylene composition consisting of a triazine-based compound, which has not only high repellency but also high tearability and tensile strength.
Another object of the present invention is to provide chlorinated polyethylene that has excellent processability and good mechanical properties (eg, flexibility).

[Since before the introduction of chlorinated polyethylene, technology has been used to blend ethylene-containing resins or rubbers such as low-density or high-density polyethylene, ethylene-propylene random or block copolymers, and ethylene-propylene copolymer rubber. is widely used, and the resulting composition can be used to coat electric wires,
electrical equipment. It is widely used in parts of electronic devices. However, among polymers containing ethylene and chlorinated polyethylene, compositions obtained by blending resinous materials can easily achieve improvements in mechanical strength, hardness, electrical properties, etc. , the rubbery properties are significantly reduced. Further, a composition in which ethylene-propylene copolymer rubber is blended with chlorinated polyethylene has good rubber properties and processability, but tearability and breaking strength are reduced. As mentioned above, the composition obtained by blending ethylene-containing resin or rubber-like material with chlorinated polyethylene has physical properties such as mechanical properties, hardness, electrical properties, and rubber properties. However, there is a problem in that it is not possible to obtain a composition with a good balance of these properties due to particularly high rebound resilience and reduced properties such as tearability. Based on these facts, the inventors of the present invention have found that they do not have these problems (defects), that is, they not only have good tear properties and rebound resilience, but also have well-balanced physical properties such as tensile strength, such as automobile bumpers, fashion bands, We have previously proposed a composition suitable for use in parts of electronic devices, electrical devices, etc. However, the composition is not completely satisfactory in terms of tearability. From the above, the present invention does not have these problems (defects), that is, it not only has good rebound properties, but also has well-balanced physical properties such as tensile strength, especially tear strength. The aim is to obtain extremely high compositions. . According to the present invention, these problems are solved by (A) chlorinated polyethylene. (B) at least one comonomer selected from the group consisting of (1) ethylene and (2) unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, their anhydrides, and halfesters of unsaturated dicarboxylic acids; ” [hereinafter referred to as comonomer (1)];
(G) an organic peroxide; and (D) a mercaptotriazine compound whose general formula is represented by the following formula (hereinafter referred to as blank space) CC (wherein R is selected from the group consisting of a mercapto group and an ami7 group), The composition ratio of the ethylene copolymer in the total amount of the chlorinated polyethylene and the ethylene copolymer is 33 to 67% by weight, and the composition ratio of the organic peroxide to 100 parts by weight of the total amount thereof is 0. 1-10.0 parts by weight, and the mercaptotriazine compound is 0.
This problem can be solved by a chlorinated polyethylene composition in which the comonomer (1) has a copolymerization ratio of 1.0 to 20 mol % in the ethylene copolymer. The present invention will be explained in detail below. (A) Chlorinated polyethylene The chlorinated polyethylene used in the present invention is obtained by chlorinating polyethylene powder or particles in an aqueous suspension, or
Alternatively, it can be obtained by chlorinating polyethylene dissolved in an organic solvent. (Preferably those obtained by chlorination in aqueous suspension) are generally amorphous chlorinated polyethylenes whose chlorine content is from 25 to 45% by weight, and especially whose IM element content is from 27 to 45% by weight.
45% by weight amorphous chlorinated polyethylene is preferred. Said polyethylene is obtained by homopolymerizing ethylene or copolymerizing ethylene with at most 20% by weight of α-olefin (generally having at most 12 carbon atoms). Its density is generally 0.91
0-0.970 g/cc. Further, its molecular weight is at least 30,000, preferably 50,000 to 700,000. Mooney viscosity (MS, 10
0°C) is usually 20 to 100, and particularly preferably 25 to 90. (B) Ethylene copolymer The ethylene copolymer used in the present invention is ethylene and comonomer (1), or these and "unsaturated carboxylic acid ester and/or vinyl ester having at most 30 carbon atoms" [Hereinafter referred to as “comonomer (2)”
It is a copolymer of Typical examples of comonomers (1) include acrylic acid, methacrylic acid, and crotons containing at most 2 carbon atoms.
5 unsaturated monocarboxylic acids as well as maleic acid, fumaric acid, tetrahydrophthalic acid, 4-methylcyclohexane-4-ene-1,2-carboxylic acid, itaconic acid, citraconic acid and bicyclo(2,2,1)- Hebuta-5-
4 to 50 carbon atoms, such as ene-2,3-dicarboxylic acid
unsaturated dicarboxylic acids and anhydrides of these unsaturated dicarboxylic acids. Among the above ethylene-based copolymers, are copolymers of ethylene and unsaturated dicarboxylic anhydrides, or copolymers of these with unsaturated dicarboxylic esters and/or vinyl esters? In the present invention, the dicarboxylic acid anhydride units of these copolymers are changed to dicarboxylic acid units or Hafester units by hydrolyzing and/or modifying the multi-component copolymers with alcohol. Ethylene copolymers obtained by replacing part or all of the unsaturated dicarboxylic anhydride units of a copolymer or multicomponent copolymer with dicarboxylic acid units or halfester units can also be preferably used. To carry out the hydrolysis, the ethylene-based copolymer is dissolved in an organic solvent (e.g., toluene) in the presence of a catalyst (e.g., a tertiary amine) to a
It can be obtained by reacting with water at a temperature of 0°C for 0.5 to 10 hours (preferably 2 to 6 hours, preferably 3 to 6 hours), followed by neutralization with acid. To perform alcohol modification, the ethylene copolymer can be obtained by the solution method or kneading method described later. The solution method is similar to the case of hydrolysis, in which the reaction is carried out in an organic solvent in the presence or absence of the above-mentioned catalyst (the reaction is slow in its absence).
2 minutes to 5 hours at the reflux temperature of the alcohol used in
Preferably from 2 minutes to 2 hours, preferably from 15 minutes to 1 hour.
time). On the other hand, the cross-wire method is usually 0.01 to 1.0 parts by weight (preferably 0.01 to 1.0 parts by weight) per 100 parts by weight of the ethylene copolymer.
05 to 0.5 parts by weight) of tertiary amine and dicarboxylic acid units in the copolymer.
twice the mole (preferably 1.0 to 2.0 times the mole) of the phase alcohol at a temperature higher than the melting point of the ethylene copolymer,
At a temperature below the boiling point of the alcohol used, a kneading machine such as the Banbury Mixer 1 extruder, which is commonly used in the rubber and synthetic resin fields, is used for several minutes to several tens of minutes (preferably 10 to 30 minutes). This method involves reacting while kneading. The saturated alcohol used in the above modification with alcohol is a linear or branched saturated alcohol having 1 to 12 carbon atoms, and includes methyl alcohol, ethyl alcohol, and -butyl alcohol. In the case of the above hydrolysis and in the case of modification with alcohol, the conversion rate to dicarboxylic acid and the halfesterization rate are both 0.5 to 100%, and 1O10 to
100% is desirable. The copolymerization ratio of ethylene in these ethylene copolymers is 50 to 99.98 mol%, preferably 80 to 99.8 mol%, and particularly preferably 65 to 8.0 mol%. In addition, the copolymerization ratio of comonomer (1) is 0.1 to 20
It is mol%, preferably 1.5 to 20 mol%, and 1.
5 to 15 mol% is suitable. If the copolymerization ratio of comonomer (1) in these copolymers is less than 1.0 mol%,
Poor adhesion to the filamentous objects described below. On the other hand, even if more than 20 mol % of the copolymer is used, although the features of the present invention are exhibited, it is not preferable from the production and economic standpoints, and furthermore, the proportion of the comonomer (2) is at most 30 mol. %, preferably 0.1 to 30 mol%,
Particularly suitable is 0.5 to 25 mol%. Using a copolymer in which the comonomer (2) copolymerization ratio exceeds 30 mol% in total is undesirable because the softening point of the copolymer becomes high and fluidity is impaired. Moreover, it is not favorable from an economic point of view. The ethylene copolymer of the present invention usually has a temperature of 500 to 3000K.
Ethylene and the comonomer (1) or comonomers thereof in the presence of a chain transfer catalyst (e.g. oxygen, organic peroxides, azo compounds, diazo compounds) at a temperature range of 40 to 300 °C under high pressure of g/c It is obtained by copolymerizing (2). A saturated or unsaturated hydrocarbon (for example, ethane, propane, propylene) is used as a chain transfer agent during this copolymerization. Of this chain transfer agent, a very small amount of unsaturated hydrocarbon is copolymerized. Melt flow index of the ethylene copolymer of the present invention (measured under condition 4 according to JIS K7210,
(hereinafter referred to as r MFRJ) is generally 0.001 to 10
00 g/10 minutes, and 0.05-500 g/
10 minutes is preferable, and 0.1 to 500 g for 710 minutes is particularly preferable. When these ethylene copolymers having an MFR of less than 0.01 g 710 min are used, moldability is poor. The method for producing these ethylene copolymers by copolymerization is well known. Furthermore, among the above-mentioned ethylene copolymers, the method of producing them by hydrolysis and/or modification with alcohol is also a well-known method. (C) Organic peroxide Furthermore, the organic peroxide used in the present invention is not particularly limited, but it is particularly desirable to have a decomposition temperature (temperature at which the half-life is 1 minute) of 120°C or higher, Especially 1
A temperature of 40°C or higher is preferable. Representative examples of suitable organic peroxides include 1. Ketone peroxides such as l -bis-tertiary-butylperoxy-3,3,5-)limethylcyclohexane, 2.5-
dimethylhexane-2; hydroperoxides such as 5-cybidroba-oxide, 2,5-dimethyl-2,
Mention may be made of peroxy esters such as 5-di-tert-butylperoxyhexane, diacyl peroxides such as benzoyl peroxide, and dialkyl peroxides such as dicumyl peroxide. Furthermore, polyfunctional substances such as triallyl cyanurate and triallyl in cyanurate, which are commonly used as crosslinking aids in the rubber field, may be blended. (D) Mercaptotriazine compound The mercaptotriazine compound used in the present invention is used as a vulcanizing agent or vulcanization accelerator in the rubber industry, and its general formula is the following formula [Formula (1)] This is what is shown as. (However, R is selected from the group consisting of a mercapto group and an amino group.) In this formula (II), the amine 7 group in R may have a hydrocarbon group having at most 20 carbon atoms. Representative examples of this mercaptotriazine compound include:
Examples include 1,3,5-) lithiocyanuric acid, l-hexylamino-3,5-dimethylcaptotriazine, 1-diethylamino-3,5-dimercaptotriazine, l-cyclohexylamino-3,5-dimercaptotriazine, etc. It will be done. This compound was published in Japanese Patent Publication No. 59-1009.
It is described in detail in the specification of Publication No. 9. (E) Composition ratio The composition ratio of the ethylene copolymer in the total amount (sum) of the chlorinated polyethylene and ethylene copolymer is 33 to 67% by weight (that is, the composition ratio of the chlorinated polyethylene is 67 to 67% by weight) 33% by weight), especially 35-65
% by weight is preferred. If the composition ratio of the ethylene copolymer in the total amount is less than 33% by weight, a composition that is flexible, tearable, and highly elastic cannot be obtained; on the other hand, if it exceeds 67% by weight, However, a highly elastic composition cannot be obtained. In addition, the composition ratio of the organic peroxide to 100 parts by weight of the total amount (total) of these is 0.1 to 10.0 parts by weight, preferably 0.5 to 10.0 parts by weight, particularly 0.5 to 10.0 parts by weight. 8.0 parts by weight is preferred. Total amount of these 1
If the composition ratio of organic peroxide to 0.00 parts by weight is less than 0.1 parts by weight, a composition with excellent mechanical properties cannot be obtained.On the other hand, if it exceeds 10.0 parts by weight, poor flexibility etc. There's a problem. Furthermore, for mercaptotriazine compounds, 0.01
~2.0 parts by weight, preferably 0.02 to 1.5 parts by weight, particularly preferably 0.1 to 1.2 parts by weight. When the composition ratio of the mercaptotriazine compound is 0.01 parts by weight, the crosslinking becomes too tight and it is difficult to control the crosslinking. On the other hand 2. If the amount exceeds 0 and H parts, the resulting crosslinked product will not have good tearability at high temperatures. (F) Mixing method, molding method, etc. Although the composition of the present invention can be obtained by uniformly blending the above-mentioned substances, fillers and dehydrochlorination prevention agents commonly used in the rubber and resin industries are also used. agent, plasticizer, oxygen. Oran, stabilizer against heat and light (ultraviolet m). Additives such as lubricants and colorants 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 such that blending is performed using a mixer such as an open roll, a dry blender, a Banbury mixer, and a Nigu mixer that are commonly used in the technical field. good,
Among these mixing methods, in order to obtain a more uniform composition, two or more of these mixing methods may be applied (for example, after mixing in advance with a dry blender, the mixture may be mixed using an open roll. How to mix). In these mixing methods, if melt-kneading is carried out at a relatively high temperature, part or all of the chlorinated polyethylene used may be crosslinked. Usually for this? It is necessary to carry out the test at 0'C or below. The composition of the present invention may be molded into a dust seal using molding machines commonly used in the rubber industry, such as extrusion molding machines, injection molding machines, compression molding machines, and calender molding machines. In addition, a method of manufacturing molded pieces while crosslinking by adding chlorinated polyethylene or the above-mentioned composition and generally crosslinking them in the rubber technology field, that is, a method of simultaneously proceeding crosslinking and molding, is applied to form the desired shape. It may be molded into a desired shape using a molding machine used for molding, such as an extrusion molding machine, an injection molding machine, a compression molding machine, or a calendar molding machine. -4''' and 1' Examples The present invention will be explained in more detail with reference to Examples below. In the Examples and Comparative Examples, the tensile strength (hereinafter referred to as
T'') and elongation (hereinafter referred to as rE8J) are JI
A11 was determined using a Schorper type tester according to SK-6301. In addition, the tear resistance test was performed on the seal 5K-630.
Measurements were made using JIS B type dumbbells in accordance with 1. In addition, the hardness test is performed using a JIS hardness meter (Shore A
), a JIS No. 3 dumbbell was manufactured as a test piece according to JIS K-6301, and the two dumbbells were stacked and measured. Furthermore, the impact resilience test was measured according to JIS K-6301. In addition, the abrasion resistance test was carried out using a taper abrasion machine according to JIS K-6301, and the amount of wear was measured using a grindstone H-22 at a load of Ikg and a rotational speed of 1000 times. Examples 1 to 6, Comparative Examples 1 to 9 Ethylene-butene-containing 3.0% by weight of butene-1
1 copolymer (density 0.940 g/c rn',
(average molecular weight approximately 200,000) was chlorinated in an aqueous suspension. Amorphous chlorinated polyethylene (chlorine content 30.2% by weight, Mooney viscosity (MS (100°C)) 1+4 70, hereinafter referred to as r CPE (1) J ) was produced. It also had a density of 0.925. Chlorinated polyethylene [chlorine content
30.2% by weight, non-quality, Mooney viscosity (MS (
100°(ri)2B, hereinafter referred to as r CPE(2) Jl◆4] was produced. As an ethylene copolymer, an ethylene-ethyl acrylate-maleic anhydride ternary copolymer with an MFR of 212 g 710 minutes [copolymerization ratio of ethyl acrylate 3
0.7% by weight, copolymerization ratio of maleic anhydride 1.7
% by weight, hereinafter referred to as "copolymer (a)"] and MF
Ethylene-methyl methacrylate-maleic anhydride ternary copolymer with R of 105 g 710 min [copolymerization ratio of methyl methacrylate 20.5% by weight, copolymerization ratio of maleic anhydride 3.1% by weight, hereinafter " Copolymer (b
)” was used. Furthermore, carbon black (manufactured by Showa Cabot Co., Ltd., trade name: Showblack N-330, average particle size: 30 nm, specific surface area: 80 m'/g, hereinafter referred to as "r CB") was used as a pigment. In addition, as a dehydrochlorination inhibitor, saponified magnesium [100 mesh pass, specific surface area 150]
r Mg0J] was used. Furthermore, dicumyl peroxide (hereinafter referred to as "DCP") was used as an organic peroxide, and triallyl isocyanurate (hereinafter referred to as "rTAIGJ") was used as a crosslinking auxiliary agent.
] was used. Furthermore, 1,3.5-mercapto-5-triazine [hereinafter referred to as "Azine (1)"] was used as a mercaptotriazine compound. Chlorinated polyethylene, ethylene copolymer, DCP and azine (1) whose blending amounts are shown in Table 1, and 2.0 parts by weight of TAI (1:, 5.0 parts by weight of Mg)
A sheet was formed while kneading O and 5.0 parts by weight of CB using oven rolls set at 50° C. for 20 minutes. Each sheet thus obtained was heated to a temperature of 18
A crosslinked sheet was produced by pressing for 10 minutes at 5°C and a pressure of 20 kg/cm'. The tensile strength and elongation of each of the obtained sheets were determined, as well as rebound resilience test 2, abrasion test, tear test, and hardness test. The results are shown in Table 2. (Hereinafter, blank space) In Comparative Examples 5, 8, and 9, crosslinked products were not obtained and measurement was impossible. The chlorinated polyethylene composition of the present invention exhibits the following effects. (+) Excellent rebound resilience. (2) High tear strength and various mechanical strengths. (3) Excellent weather resistance and durability. (4) #Good ozone properties. (5) #Excellent abrasion resistance. (6) #Good compression set property. The chlorinated polyethylene composition of the present invention exhibits the above-mentioned excellent properties and can be used in a wide variety of fields. Typical applications include general industrial parts (e.g., fenders, impact-resistant hard materials). and accessories (e.g. watch bands, fashion belts).

Claims (1)

[Scope of Claims] (A) Chlorinated polyethylene; (B) consisting of at least (1) ethylene and (2) unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, anhydride thereof, and half ester of unsaturated dicarboxylic acid. Ethylene copolymer with at least one comonomer selected from the group, (C) organic peroxide, and (D) mercaptotriazine compound whose general formula is represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where R is selected from the group consisting of mercapto groups and amino groups), and the composition ratio of the ethylene copolymer to the total amount of chlorinated polyethylene and ethylene copolymer is 33 to 67% by weight The composition ratio of the organic peroxide is 0.1 to 10.0 parts by weight based on 100 parts by weight of the total amount, and the mercaptotriazine compound is 0.1 to 10.0 parts by weight.
01 to 2.0 parts by weight, and the copolymerization ratio of the comonomer in the ethylene copolymer is 1.0 to 20 mol%.